toxicity and elemental contaminant concentrations of
TRANSCRIPT
U.S. Department ofthe Interior U.S. Geological Survey
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Site 1D# BreaK Other
Columbia Environmental Research Center
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Elemental Contamii ions of Groundwater, ore Waters, and Sur e iviissouri mver
s Re :e §0 Oniaha, Nebraska
USGS science for a changing world
113611 SUPERFUND RECORDS
Toxicity and Elemental Contaminant Concentrations of Groundwater, Sediment Pore Waters, and Surface Waters of the Missouri River
Associated wi th a Metals Refining Site in Omaha, Nebraska.
A report by:
Duane C. Chapman Ann L. Allert
James F. Fairchild Thomas W. May
Christopher J . Schmitt
United States Geological Survey Biological Resources Division
Columbia Environmental Research Center Columbia, MO
and
Edward V. Callahan Environmental Statistics
Fountain City, WI
Prepared for:
United States Environmental Protection Agency, Region VII Air, RCRA, and Toxics Division
726 Minnesota Avenue Kansas City, KS
lAG DW14952122-01-1
April, 2000
TABLE OF CONTENTS
Executive Summary ^ 1
Background and Purpose 1
Methods 2
Results and Discussion 8
Conclusions 15
Literature Cited 17
Figures
Figure 1. Location of sediment sampling sites 20
Figure 2. Results of hierarchical cluster analysis of element concentrations measured from sediment samples 21
Figure 3. Results of hierarchical cluster analysis of element concentrations measured from aqueous samples 22
Figure 4. Biplot of element concentration data measured from sediment samples 23
Figure 5. Biplot of element concentration data measured from
water samples 24
Tables
Table 1. Comparison of historical river water chemistry, CERC well water, and reconstituted river water 26 Table 2. Comparison of dissolved oxygen concentrations, conductivity, and pH measurements in the field with measurements made at CERC.,.27
Table 3. Water quality measurements taken before start of
Cer/oc/ap/)/7/a toxicity test 28
Table 4. Results of grain size analysis of sediments 29
Table 5. Concentrations of total recoverable arsenic, cadmium, lead and zinc in sediment samples... 30
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Table 6. Concentrations of arsenic, cadmium, lead and zinc in aqueous samples 31
Table 7. Concentrations of elements in sediment determined by semi-quantitative ICP-MS scan 32
Table 8. Concentrations of elements in water determined by semi-quantitative ICP-MS scan 34
Table 9. USEPA Water Quality Criteria for selected trace metals 36
Table 10. Calculated USEPA Water Quality Criteria Values for pore waters, river waters, and groundwater for selected metals 37
Table 11. Concentrations pf simultaneously extracted metals in sediments 38
Table 12. Molar concentrations of acid volatile sulfide and simultaneously extracted metals in sediments 39
Table 13. Calculated Toxic Units derived from estimated porewater concentrations of copper, cadmium, lead, zinc, nickel, and arsenic 40
Table 14. Calculated Toxic Units derived from measured porewater concentrations of copper, cadmium, lead, zinc, nickel, and arsenic 41
Table 15. Survival of Ceriodaphnia dubia exposed to sample and control water in a 7-day toxicity test 42
Table 16. Reproductive output of Ceriodaphnia dubia exposed to sample waters and reference waters in a 7 day toxicity test 43
Table 17. Historical water quality of Monitoring Well 19 and water quality of the well when sampled in this study 44
Appendices
Appendix A, Chemical Analysis Reports
Appendix B, Ancillary Data
EXECUTIVE SUMMARY
Surface waters, sediments, and sediment pore waters were collected from the Burt-Izard drain, which transects the ASARCO Omaha facility, and from the Missouri River adjacent to the facility. Groundwater was also collected from the facility. Waters and sediments were analyzed for inorganic contaminants, and the toxicity of the waters was evaluated wi th the Ceriodaphnia dubia 7-day test. Concentrations of several elemental contaminants of concern were highly elevated in the groundwater, but not in sediment pore waters. Lead concentrations were moderately elevated in whole sediment at one site, but lead concentrations in pore waters were low due to apparent sequestration by acid volatile sulfides.
The groundwater sample was highly toxic to Ceriodaphnia dubia, causing 100% mortality. Survival was reduced relative to controls (100% survival) at all dilutions. Even when diluted to 6 .25% with reconstituted river water, Ceriodaphnia survival was only 7 8 % in groundwater; however, Ceriodaphnia reproduction in the 6 .25% dilution was not significantly different from upstream porewater reference samples. Reproduction in pore water collected from one downstream site was somewhat reduced. This difference was significantly different from one upstream reference but not from the other. However, reduced reproduction at this site could not be attributed to measured elemental contaminants.
BACKGROUND AND PURPOSE
The American Smelting and Refining Company (ASARCO) Omaha facility, located at 500 Douglas Street in Omaha, Nebraska, was a primary lead refinery designed and operated to process lead bullion containing recoverable amounts of several different metals. Refinement was achieved using traditional pyro-metallurgical processes including addition of metallic and non-metallic compounds to molten lead to remove impurities. The Omaha plant produced refined lead and specialty metal by-products including antimony-rich lead, bismuth, dore (silver-rich material) and antimony oxide. The 23-acre facility, which lies along the Missouri River, was closed in July 1997. Remediation at the facility is being addressed under the state Remedial Action Plan Monitoring Act (RAPMA), a voluntary remediation program. Numerous buildings and structures remain on the site. The approved remediation plan calls for complete demolition of all site structures, regrading, and capping of the site.
Previous characterization and remedial design documents submitted by ASARCO on behalf of the Omaha plant have failed to clearly define the level of threat that previous releases and contaminated groundwater underlying the facility poses to biota living in the adjacent Missouri River. The potential threat stems from elevated levels of arsenic, lead, and other metals in the groundwater. Groundwater elevation data indicate that most of the underlying contaminated groundwater
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moves into the Missouri River. Lead concentrations in water surface grab samples collected periodically by ASARCO's contractor (Hydrometrics, Inc.) were somefimes higher than those collected immediately upstream from the site. In March 1997, ASARCO collected surface water and sediment samples from the Missouri River and a small on-site tributary (known as the Burt-Izard sewer outfall) and obtained analytical results. Elevated levels of inorganic contaminants in some river sediments have also been reported by Hydrometrics, Inc. Subsequent to this activity the Nebraska Department of Environmental Quality (NDEQ) made a final decision on the remedial plan for this site. The remedial plan does not specifically address groundwater or river sediments. The U.S. Environmental Protection Agency (USEPA) felt that further investigation of the elevated metal levels in the river sediments near the ASARCO refinery was warranted.
The USEPA entered into an agreement with the US Geological Survey, Biological Resources Division, Columbia Environmental Research Center (CERC) to perform this investigation. Specific objectives of this study were to determine the concentration, bioavailability, and toxicity of metals in the Missouri River adjacent to the site. In this report we present and discuss the findings of this investigation.
METHODS
Porewater Toxicity Testing
A porewater approach was undertaken to determine the bioavailability and toxicity of metals at the site. For many inorganic contaminants, ecological risk is associated with the free metal ion concentration in water. Pore water is the interstitial water between sediment particles. Because of restricted mixing within sediments, pore waters are in contact with sediments for a long time relative to surface waters. Consequently, porewater concentrations of sediment-associated contaminants are often elevated relative to overlying waters, and may represent a worst-case scenario in terms of ecological risk to aquatic organisms in overlying waters.
Because contaminants may be associated with sediments through a number of different mechanisms, not all sediment-associated contaminants are available for dissociation into pore waters-i.e., not all are equally bioavailable. For inorganic contaminants (metals and metalloids), such associations may be very loose, such as would represented by electrochemical attraction to the charged surfaces of clay mineral particles. These contaminants can be dislodged by changes in ionic composition or concentration of the surrounding water. On the other end of the availability spectrum are those elements of concern that may be part of the mineral phase itself. The metal sulfides-the ores refined at the ASARCO facil ity- represent
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this condition. These metals are only released to the liquid phase upon complete destruction of the mineral matrix (i.e., by digestion wi th strong acids) and are not generally considered to be biologically available (Tessier et al. 1979; Gorbas and Zhang 1994). Intermediate associations between elemental contaminants and sediment particles include sorption and other interactions wi th iron and manganese hydroxides; and complexation by sediment organic matter, including the humic and fulvic acids.
The analysis of bulk sediments for total metals generally involves the complete digestion of the matrix. Consequently, this method may include the measurement of metals and other elements that are not biologically available, and when used alone may overestimate ecological risk. We therefore also incorporated a method of dissociation (leaching sediments wi th a weak acid, 1-N HCI) that simulates
•relevant biological conditions (DiToro et al. 1992) for assessing and evaluating the
biological availability of sediment-associated contaminants at the ASARCO-Omaha facility and adjacent areas of the Missouri River. We considered this method,
I which does not consider those metals bound to acid volatile sulfides as bioavailable (DiToro et al. 1992), to be the most appropriate for assessing sediment-associated
I contaminants at the ASARCO facility. In addition, contaminated ground water
seeping into the river from beneath the ASARCO facility would first intersect the sediment pore water, which makes assessment of pore water highly appropriate for this study. Use of the porewater technique also allows testing wi th the Cladoceran Ceriodaphnia dubia, which is highly sensitive to metals but not to ammonia. The latter is a likely contaminant in urban environments that can confound test results wi th ammonia-sensitive organisms. The testing of pore water also eliminates the problem of grain size preference by the test organisms, which sometimes confounds whole-sediment toxicity tests.
Site Selection
Figure 1 represents a map of the site and the sampling locations. During a site visit in the spring of 1998, sandy sediments were found along the ASARCO waterfront. It was also determined that there were three likely paths of groundwater movement from the ASARCO facility into the river: 1) general seepage along the waterfront, 2) the Burt-Izard Drain, an open ditch running along the northern boundary of the site, and 3) the Chicago Street Drain, a now perforated storm drain traversing the property at a depth of about 2 m below the ground surface. Therefore, it was determined that sediment would be taken from one site within the Burt-Izard Drain (which is an open ditch or creek) and one at its confluence wi th the river. Two sites were to be sampled at the mouth of the Chicago Street Drain (which is a pipe buried at approximately 4 m depth). In addition, two sediment samples were to be taken just upstream of the ASARCO facility, one on the same (west) bank and one just upstream of the ASARCO facility on the opposite (east) bank. The upstream sediment sites were to function as reference sites. Sites along the waterfront of the facility were also selected for sediment sampling. At the time of sampling
nearly all of the sediment had been scoured from this outside-bend area. Consequently, sediment was collected as planned from the site within the Burt-Izard Drain (SED4) and at its mouth (SED5), and from the reference site across the river (SED2). However, there was no sediment to sample anywhere along the ASARCO waterfront. The sandy sediments that had been observed there in the spring had been removed by subsequent high water. The bottom along this outside bend of the Missouri River consisted primarily of rip-rap and slag. A search for an appropriate upstream same-side-of-river sediment sample was only successful after moving approximately 0.75 kilometers upstream. This sample (SED1) was collected from an eddy upstream of the outfall channel for Grace Street and North Interceptor. Sediment was found in two eddy areas downstream from the plant and these were sampled (SED24 and SED25). It was decided at the time of sampling that sites further downstream would be highly complicated by other potential inputs, and no further sediment sampling was conducted.
A sample from one of the monitoring wells near the river (MW19) was provided by ASARCO, which we analyzed and tested to determine the potential toxicity of ground water entering the river. In addition, two surface water samples were taken from the Missouri River. The river water samples served as additional references to verify that C. dubia was in fact adaptable to the water quality of the river and to verify that no upstream toxic releases occurred on that date that might confound the test.
Field Procedures
Sediment was collected on October 5, 1998. A Ponar dredge was used to sample sites over a meter deep, which includes all sites except SED4. A 10-cm diameter coring device (Onuf et al. 1996) was used at SED4. A Rockwell® PLGR global positioning system was used to record the position of sampling sites. Coordinates of sampling sites are given in Table A, Appendix B.
Pore water was extracted on site by means of pressure fi ltration using an apparatus similar to that described in Carr and Chapman (1995) and retained in an acid-washed polyethylene sample bottle. Nitrogen gas (analytical grade) was used as the source of pressure, and pressure in the extraction devices did not exceed 35 psi. Not all porewater extraction was completed before leaving the site, but extractions were completed within eight hours of sample collection. Between two and three liters of pore water were collected at each site. Surface water samples were collected by completely submersing the sample bottle, opening the lid and filling the bottle, and then recapping the bottle underwater.
Conductivity, pH, and dissolved oxygen were measured on each aqueous sample immediately after collection. Dissolved oxygen was determined with a YSI* model 57 dissolved oxygen meter and conductivity was determined using a YSI* S-C-T meter. Orion' 290A meters wi th a glass gel electrode were used to measure pH.
An 100 mL aliquot of each aqueous sample (pore, surface, or ground water) was filtered wi th a 0.45 pm polycarbonate filter and acidified with 1 % ultrapure nitric acid (v:v) for metals preservation. Two filtration blanks were also prepared using reverse osmosis water and preserved. One of these was collected before on-site filtration began and the other as the last filtration of the batch. Two aliquots of the sediment from which each pore water was extracted were also retained for metals analysis. All equipment which contacted sediment or sediment pore water was acid-washed prior to use. All aqueous samples to be used in toxicity tests were centrifuged (3000 g for 10 minutes) to remove fines after arrival at CERC. All samples, aqueous or solid-phase, were kept on ice or refrigerated (T<5°C) until use. Standard operating procedures for these and other procedures may be found in the Quality Assurance Project Plan For Sediment And Sediment Pore Water Sampling (USEPA and USGS 1998).
Laboratory Procedures
Rearing of test organisms
Based on data provided by Hydrometrics, Inc, it was determined that Missouri River water from the Omaha area is usually somewhat higher in potassium, sodium and sulfates than the CERC well water in which our test organisms are normally reared. Therefore, C. dubia were reared at the CERC for more than three months prior to the tests in a reconstituted water formulated to approximate that of the river. Reconstituted river water was made by addition of 180 mg of K2SO4 and 1980 mg of Na2S04 to 15L of CERC well water. The water chemistry of this reconstituted water is given in Table 1 . New reconstituted river water was made weekly and allowed to mix and aerate overnight before use. Culture techniques were similar to those described in USEPA (1994). Ceriodaphnia were fed a diet of fermented trout chow, yeast, and cereal leaves (YTC; USEPA 1994) and algae (Selenastrum capricornutum and Ankistrodesmus falcatus; 60:40 mix).
Toxicity tests
Toxicity tests were performed using the C. dubia 7-day survival and reproduction test (USEPA 1994). USEPA (1994) stipulates the use of a dilution series for. effluent toxicity testing, but not normally for environmental samples collected outside the mixing zone. We tested a dilution series of the groundwater sample (100, 50, 25, 12.5, and 6.25%) to determine the degree of toxicity of this water in the C. dubia test. We also tested a dilution series (100, 50, and 25%) of the porewater collected from within the Burt-Izard drain. Reconstituted river water was used as the diluent.
The hardness and alkalinity of surface water samples and some porewater samples were higher than expected, ranging from 250 mg/L to over 700 mg/L hardness as
CaCOg. Therefore, another reconstituted water, designed to reflect the chemistry of the surface waters collected on October 5, was also prepared from CERC well water and salts. This "Hard Recon" was tested as an additional treatment, to verify that C. dubia were tolerant of this very hard, alkaline, high-sulfate water. To make this second reconstituted water, 236 mg of CaS04, 34.8 mg of MgS04, and 129 mg NaHCOg were added per each liter of well water. Well water chemistry is described in Table 1.
A positive control dilution series (i.e., reference toxicant) consisting of three concentrations of NaCI in CERC well water (2.50, 1.25, and 0.613 parts per thousand) was also tested concurrently with the toxicity test. Lastly, a procedural control in CERC well water was also performed concurrently with the test. C. dubia used in the well water control were reared in well water instead of reconstituted river water.
The C. dubia toxicity tests were conducted according to USEPA (1994). Animals were exposed to 15 mL of the sample or the appropriate dilution in 30-mL glass beakers for seven days. One neonate, less than 12 hours old, was added to each beaker at the beginning of the test (day 0). There were ten replicates of each treatment. Waters were renewed daily. Endpoints, recorded daily, were lethality (absence of movement) and reproduction (number of neonates produced). Temperature in the test beakers was maintained at 25± 1°C by means of a temperature-controlled water bath. Test organisms were fed 1 mL of YTC and 1 mL of algae after renewal.
Sediment and Water Quality Measurements
Hardness, alkalinity, dissolved oxygen, pHr conductivity, nitrate 4-nitrite, sulfate, phosphate, chloride, calcium, and ammonia concentration of aqueous samples were measured after arrival at CERC. Hardness, alkalinity, calcium, and chloride were determined by titration. Dissolved oxygen was determined with a YSI® model 57 dissolved oxygen meter and conductivity was determined using a YSI® S-C-T meter. Orion® EA 940 meters with glass gel electrodes were used to measure pH. The Orion EA940 meters with an Orion® Model 95-12 ammonia ion selective electrode were employed for ammonia determinations. Sulfate, nitrate + nitrite, and phosphate concentrations were measured with a Hach® DR 2000 spectrophotometer. Dissolved organic carbon of sediment pore water was measured with a Technicon AAII®system. Sediment grain size was determined with the Bouyoucous Hydrometer Method. Standard operating procedures for these techniques can be found in USEPA and USGS (1998).
Daily during the test, water from exposure beakers (post-exposure) was collected for dissolved oxygen, pH and conductivity measurements. Hardness, alkalinity, and ammonia concentrations was also measured in the post-exposure water on day 4 and day 7. In order to have sufficient volume of post-exposure sample, water from
all replicates within a treatment was composited in a 250-mL beaker for these analyses.
Analytical Chemistry
Surface water, ground water, pore water, sediment, and aqueous and solid-phase blind quality assurance samples were analyzed at CERC for lead, zinc, arsenic, and cadmium by quantitative inductively coupled plasma - mass spectrometry (ICP-MS) analysis (May et al. 1997). These four metals were the contaminants of greatest interest. However, because of the possible presence of other toxic metals, a 64-element scan by semiquantitative ICP-MS was also performed. Sediments were also analyzed at CERC for acid volatile sulfides and simultaneously extracted metals (SEM-AVS). As noted in the introduction, SEM-AVS provides a measure of the bioavailability of certain metals (Di Toro et al. 1992). A complete listing of methods, QA/QC, and results of the metals analysis may be found in Appendix A; CERC laboratory report FY-99-32-03 and CERC laboratory report FY 99-32-04. As part of the quality assurance procedures CERC also analyzed "bl ind" water and sediment samples provided by USEPA.
Statistical Analysis
Survival data were evaluated wi th logistic analysis (Agresti 1990). Analysis of variance wi th rank transformation (Snedecor and Cochran 1989) was used to evaluate reproduction data. In the analysis of variance, total reproduction for each daphnid over the seven-day test (including those that died during the experiment) was the dependent variable. Experimentwise error rates for all pairwise comparisons were controlled at a = 0.05 wi th Tukey's method (Hochberg and Tamhane 1987).
The influence of metal concentrations on survival and reproduction was assessed wi th principal components analysis (Johnson and Wichern 1992). Principal components analysis was performed to find relationships between measured water quality and metals variables and the toxicity test data. Duplicate field water samples were taken at SED1 and an average of the resulting element concentrations was used to represent that site. Elements wi th at least half the observations above detection limit were included in the analysis. In addition, Br was excluded from sediment database since it had identical concentrations at each site where it was measured. Detection limit / 2 was used for analysis when a concentration was recorded as below detection limit. Concentration data from water samples from MW19 was excluded from analysis since concentrations found there were so high in relation to other sites that they unduly influenced the entire analysis. Concentrations were log transformed prior to analysis using the formula logio(x + 1). Thirty-nine elements from sediment samples were retained for analysis.
including: Al , As, Ba, Ca, Cd, Ce, Co, Cr, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ho, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, Pb, Pr, Rb, Sb, Sm, Sn, Sr, Tb, Ti , V, Y, Yb, Zn, and Zr. Thirty one elements from water samples were retained for analysis, including: A l , As, B, Ba, Br, Ca, Cd, Ce, Co, Cr, Cu, Fe, Ga, I, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sb, Sn, Sr, T i , U, V, W, and Zn.
In addition, a hierarchical cluster analysis was performed to evaluate similarity between sites in terms of elemental composition of water and sediment samples (Kaufman and Rousseeuw 1990).
RESULTS AND DISCUSSION
Site Locations
It was difficult to find sediment near the ASARCO facility. During the spring site visit, we had determined that we would not sample below the 1-480 bridge, just downstream of the ASARCO facility, because there was a large storm drain at that site that could confound the results. Because there were no sediments directly adjacent to the ASARCO facility, we were forced to forego that decision and collect sediments at alternate locations. However, it should be noted that at the time of sample collection, no water was entering the river through these drains, despite the heavy rain that had occurred during the previous night. These drains are very likely non-functional. Sites SED2 (reference site across the river), SED4 (upstream on the Burt-Izard Drain) and SED5 (mouth of the Burt-Izard Drain) were the only planned sites at which we were able to collect sediments. SED1 was moved approximately 0.75 kilometers upstream (above the confluence of the Grace Street and North Interceptor drain). Sites SED24 and SED25 were added in order to have sediments collected downstream of the facility. SED24 was collected directly under the 1-480 bridge, and SED25 was collected from an eddy 150 m downstream of the bridge. Figure 1 indicates the locations of the revised sediment sampling sites. Latitude and longitude of these sites are given in Appendix B, Table A.
Water Quality and Sediment Description
Field measurements of dissolved oxygen, conductivity and pH and initial measurements of these parameters at the laboratory are given in Table 2. Dissolved oxygen concentrations of pore water and groundwater increased between collection in the field and arrival at the lab. The pH values also increased slightly. Table 3 contains additional water quality measurements measured at CERC that were not also measured in the field.
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Table 4 gives the grain size analysis of the sediments. SED4 and SED5, collected from opposite ends of the Burt-Izard drain, were very different from the other samples. SED4 was alone in having a high percentage of particles larger than sand size, almost a third by weight. The remainder of SED4 was composed almost entirely of sand. SED4 also had the lowest moisture content and the lowest organic content, as determined by loss on ignition (LOI). Despite its proximity to SED4, SED5 differed to the other extreme, being the lowest in sand (26%), and highest in silt (52%) and clay (21%). SED5 was also the highest in moisture and more than double any other site in organic content (as indicated by LOI). Site SED4 was located within the Burt-Izard Drain, and probably received high runoff f lows during rain events, which would explain the large grain size and the presence of many particles of glass and what appeared to be road debris. SED5 was located in a low velocity eddy at the mouth of the Burt-Izard, which explains its different texture and consistency.
The monitoring well groundwater sample differed in many respects from the other water samples. Conductivity of the groundwater sample was near 3000 pmhos/cm^, which was five-fold higher than river water (600 |Jmhos/cm^). The conductivity of the groundwater sample stems largely from its very high chloride concentrafion (321 mg/L). In contrast, ammonia, nitrate + nitrite, sulfate, phosphate, and calcium concentrations were not highly elevated in the groundwater sample.
Although some pore waters were low in dissolved oxygen immediately after collection, all samples were well within concentrafions acceptable to C. dubia before the start of the toxicity test. Some pore waters were high in ammonia (notably SED4 and SED5) but such concentrations have not been shown to be toxic to C. dubia (Monda 1991). Daphnids are much less sensitive to ammonia than fish, while having a high sensitivity to other toxicants, which makes them an ideal organism for sediment porewater tesfing.
As noted in the introduction, organic material in the environment complexes and/or sorbs some contaminants, which renders them less bioavailable than contaminants less strongly bound to particulates (Tessier et al. 1979; Gobas and Zhang 1994). In all but SED5, porewater DOC concentrations were in the same range as the surface water samples, which is very low for pore waters (Table 3). SED5 porewater DOC concentration was quite high (15.2 mg/L), which is in concordance wi th the high LOI and fine texture of that sediment (Table 4).
Metals Concentrations
The results of the quantitative analysis of sediment are found in Table 5, and the quantitative analysis of aqueous samples is found in Table 6. The monitoring well sample (MW19) had strongly elevated concentrations of cadmium, zinc and arsenic.
but the lead concentration was not high (Table 6). Site SED25 had a somewhat elevated concentrafion of lead in the whole sediment (39.8 |Jg/g dry weight; Table 5), however whole sediment concentrations of cadmium, zinc, and arsenic were not remarkable. With the exception of MW19, none of these four elements were found in concentrations above the individual water quality in any aqueous sample. Recovery from the "blind" QA samples was very good. Quantitative analysis results were well within the control limits, and even the semiquantitative results were all within 25% of the USEPA value, and most were within 10%. USEPA values for these samples were provided to us after a draft version of this report was provided to USEPA, and are given in Appendix B, Table B.
Cadmium, zinc, arsenic, and especially lead were identified a priori as contaminants of concern at ASARCO-Omaha lead refinery. However, it is possible that unidentified elements (i.e., byproducts of lead refining processes or waste products from the ore-bearing material) could cause toxicity at these sites. Thus, we performed an additional, broad spectrum analysis of 64 elements in pore water, water, and sediment. These analyses were semi-quantitative in nature, but have sufficient accuracy to identify most potenfial elemental contaminants of concern should they be present in toxic concentrations. The results of the semiquantitative sediment analyses are presented in Table 7, and the semiquantitative analysis of aqueous samples is in Table 8. The groundwater from the monitoring well was high in many elements (Table 8). The semiquantitatively measured concentrations of metals in sediments were not remarkable, but verified the somewhat elevated level of lead (40 [ig/g) at SED25 identified in the quantitative analysis.
The USEPA chronic criteria for selected metals in water are found in Table 9. Many of the criteria are dependant on water hardness. Table 10 contains the criteria for the sediment pore waters, calculated using the measured hardness values. None of the sediment pore waters exceeded the USEPA water quality criteria of the quantitatively measured metals.
The high concentration of lead in SED25 sediment was not strongly reflected in the porewater, likely because of acid volatile sulfide (AVS) concentrations in SED25 sediment. Lead and certain other metals, measured as simultaneously extractable metals (SEM), are not biologically available when bound to AVS (Di Toro et al. 1992). One mole of AVS has the capacity to bind one mole of SEM. For a given total or SEM metal concentration, as the ratio of SEM to AVS becomes greater than one, a sharp increase in porewater metals is expected to follow, providing there is a moderate or high concentrafion of metal in the sediment (a SEM/AVS ratio greater than one can be inconsequential if both the AVS and SEM concentrations are very low). Concentrations of SEM may be found in Table 11, and a comparison of AVS and SEM concentrations can be found in Table 12. If the summation of the molar concentration of SEM minus the AVS concentration (bottom row, Table 11) is greater than one, then metals exceed the capacity for AVS sequestration and are assumed to be bioavailable.
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At equilibrium, different metals are selectively bound by AVS, depending on the solubility of the metal sulfide (Wildhaber and Schmitt 1996). Among the metals and metalloids of concern, mercury is the most strongly bound, fol lowed in order by silver, copper, cadmium, lead, zinc, nickel, arsenic, iron, manganese, and chromium. Therefore, for example, a high concentration of copper could bind all available AVS, leaving none to bind cadmium, lead or other metals less strongly bound by AVS. Wildhaber and Schmitt (1996) used AVS to estimate the porewater concentrations of metals, under the assumption that AVS limits the solubility of these elements. In our study, we did not measure simultaneously extractable mercury or silver. However, the molar concentration of these elements is likely to be low based on extant information, and mercuric and silver sulfides are usually not dissolved by SEM extraction. We therefore ignored these elements in our estimation of SEM binding by AVS.
USEPA water quality criteria (and risk assessment in general) evaluate contaminants individually~not in combination, as they often occur in the environment. To evaluate complex mixtures in sediments, Wildhaber and Schmitt (1996) expanded upon the concept of "toxic units" first proposed by Sprague and Ramsay (1965). A toxic unit is one multiple of the USEPA water chronic criteria concentration in pore water. Because the toxicity of metals is often additive, the summation of the toxic units for each metal accounts for the cumulative toxicity of the mixture after all its components are scaled for toxicity. Therefore, if the summed toxic units for all metals in a pore water (measured or estimated) is one or greater, the sediment is assumed to be potentially toxic. The estimated toxic units of the sediment pore waters, calculated using the method of Wildhaber and Schmitt (1996), are presented in Table 13. In our study porewater element concentrations were measured directly and we were also able to calculate toxic units directly (Table 14). The two sets of results agree in that SED24, the only sediment to have an estimated total toxic unit value greater than one, also had the highest measured porewater toxic units. However, SED4, which had an esfimated toxic unit value of zero, had a somewhat high measured concentration of lead in the pore water, which was reflected by a lead toxic unit value of 0.86 and a total toxic unit value of 1.83 (Table 14).
Many measured porewater metal concentrations were above the limit of detection at sites that had enough sediment AVS to bind all metals. This may be due to deficiencies in the AVS and toxic units models, or it may also reflect the methodology of porewater collection. When pore water is collected in the field, a very small amount bf fines can pass through the filter. These fines can include solid-phase metals bound to sulfides. The fines are removed by filtration prior to acidification of the analytical sample and by centrifugation prior to toxicity testing. However, prior to removal of fines, dissolved oxygen concentrations may increase in the pore waters. This would oxidize sulfides and release metals to the pore water. Thus, we would see small increases in porewater metals concentrations. The porewater extraction method we employed is a preferred method for minimizing the amount of fines in collected pore water (Carr and Chapman 1995).
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However, some fines do pass through the 8 pm filter, and some sediment types wil pass more fines than others. The only porewater samples that contained any sediment visible to the naked eye prior to centrifugation were SED4 and SED5. The presence of these fines, although they were removed prior to analysis, may be partially responsible for the unexpectedly high concentration of metals in SED4 porewater.
Toxicity testing
C. dubia normally reproduces parthenogenetically, producing only fertile female offspring. Reproduction of a large number of male offspring is an indication of stress that can be caused by numerous environmental factors including changing light, temperature, or food (Barnes 1980). Identification of the sex of neonate ceriodaphnids is impossible without undue stress to the organism, so males are sometimes inadvertently included as test organisms. Presence of a large number of males in a test is an indication of a stressed population of test organisms and could invalidate the test. In this study, of 220 ceriodaphnids used in the test, only nine were identified as male. Seven of the nine were idenfified as having the same parent (all the offspring of that individual were male). Replicates stocked with male ceriodaphnids were excluded from all analyses.
Survival of ceriodaphnids was ^90% and reproducfion was high in the CERC well water, the Hard Recon, in the river waters, and in the upstream sediment (Tables 15 and 16). In the reconstituted river water, survival was somewhat reduced (75%) and reproduction was low compared to other references (8.75 young per female vs 31 - 39). This may stem partly from the fact that two male organisms were stocked into this treatment. Although these replicates were excluded from the analysis, the reduced sample size compromises statistical interpretation. All animals were cultured in this reconstituted river water and the cultures were highly successful. If there was any problem with the reconstituted river water, it occurred after the test was begun. Survival was 100% in the Hard Recon, which was made similarly to the reconstituted river water, but with a higher concentration of salts added, and 100% in the CERC well water procedural control, which was the source water of both the reconstituted river water and the Hard Recon. The chemistry of the reconstituted river water was intermediate between that of these two treatments, and the observed reduction in survival and reproduction in this treatment is therefore inexplicable.
In the positive controls (2.5, 1.25, and 6.125 part per thousand sodium chloride), survival was strongly reduced in the two higher concentrations, and reproduction was reduced in all three concentrations. This is within, but near the higher end, of the range of sodium chloride sensitivity seen in other Ceriodaphnia tests at our facility.
12
Survival and reproduction were significantly (p<0 .05) reduced in all but the lowest dilution (6.25%) of the groundwater sample, compared to the upstream porewater references SED1 and SED2. Reproduction was not reduced significantly in the lowest concentration of the groundwater sample.
Survival was 100% and reproduction was very high in both river water samples. Survival was ^ 9 0 % in all sediment pore waters. Reproduction in pore waters from the two sites associated wi th the Burt-Izard drain was not significantly reduced (Table 16). Because of a p/'/or/concerns that SED4 would be highly toxic, a dilution series was performed on pore water from this site. However, all concentrations, including the 100% porewater concentration, were not toxic. SED24, which had the highest porewater metal concentrations of any sample, was not significantly different in reproduction from the reference pore waters. Pore water from SED25 was significantly reduced in reproduction compared to SED1, but not significantly reduced compared to SED2. Metals concentrations in SED25 porewater were somewhat elevated compared to the references, but in no case did the concentrations of measured metals exceed the water quality criteria. The summation of measured porewater metal toxic units at this site was 0.88 (where a value of greater than 1 theoretically would be potentially toxic). Therefore, this site, which may have been marginally toxic, contained marginally high metals concentrations.
We expected groundwater influences on the sediment to be stronger in the Burt-Izard Drain than in the river sites. We did not find this to be so. A strong rain event, such as the one occurring the night prior to the sampling tr ip, could flush pore water from the large-grained sediments we found within the Burt-Izard drain. The result would be a short-term decrease in toxicity until the pore water regained equilibrium wi th the sediment particles, or until more groundwater intruded into the sediment at that site. However, this does not appear to have been the case at SED4, the sampling location lying within the Burt-Izard drain. Porewater ammonia was somewhat elevated at SED4 (Table 2), which would not be expected in the case of dilution wi th rainwater. Also, whole sediment concentrations of most elements were lower at SED4 (Table 7) than at most other sites. Therefore, sampling directly after a strong rain event does not seem to have been responsible for the lack of toxicity at this site, which would have been the site most likely to be affected by the rain event.
The daily water quality measurements associated wi th the toxicity tests are found in Appendix B, Table C.
Principal Components Analysis
As is expected, some element concentrations were highly correlated wi th each other. There are 741 pairs of elements from the sediment data and 465 pairs in
13
the water data, which are too many to list. Histograms of the correlation coefficients are shown in Figures A and B, Appendix B, Ancillary Data. Clearly some elements are strongly correlated with each other, especially in sediment samples. Therefore we make use of principal component analysis to develop a series of indices that summarize the element concentration data; i.e., the principal components are an attempt to develop an index of a sample's elemental composition.
Descriptions of the first three principal components for sediment numbers are listed in Table D, Appendix B. The first three components account for 73%, 17% and 6% of the sediment data variability, respectively. The first three principal components for water data are described in Table E, appendix B. Those components account for 47%, 23% and 11 % of the water data variability, respectively. The first sediment principal component is highly correlated with over half of the elements. This is possible since many of those elements were highly correlated to each other. In both cases the first principal component accounts for much of the variation in the data sets. The third principal component has few strong correlations with the element concentrations. In both datasets the principal components 4 and beyond are not meaningful.
The relation of principal components between sites are shown in Figures C through H, Appendix B. No strong patterns are obvious except that the first sediment principal component reflects the relatively low concentrations of many elements at SED4.
The relations between the principal components and Ceriodaphnia reproduction are shown in Figures I through N, Appendix B. It is not surprising that no strong relationship between reproduction and element composition is observed since, in general, reproductive rates did not differ between sites significantly. In particular none of the principal components adequately explain the low reproductive rates observed at SED25. Inspection of concentrations of individual element concentrafions similarly does not safisfactorily explain the low reproduction at SED25.
Cluster analysis
Hierarchical cluster analysis was used to evaluate similarities between sites, to see if sites differed in water quality depending on their location in the study. MW19 was excluded from the analysis because its high concentrations of many elements caused undue influence on the analysis.
Figure 2 shows the results for analysis of sediment data and demonstrates that SED1 and SED2 are very similar in elemental composifion, as are SED24 and
14
I I I
SED25. SED4 and SED5 do not group as closely. This is not surprising, despite their physical proximity, because of the physical differences between these two sites (Table 4). SED4 also stood out in the principal component analysis since its concentrations of most elements were noticeably lower that those of the other sites.
Figure 3 shows the results for analysis of the water data. Again, the data reflects the layout of the study sites. RW1 and RW2 are quite close together, as are the pairs (SED1, SED2) and (SED24, SED25). Again, SED4 and SED5 do not group closely to each other.
Similarity between sites in terms of elemental composition can also be inspected by the use of principal component plots (biplots). These plots simply plot each site in a two-dimensional graph using their first two principal component scores. Figure 4 shows the biplot from sediment samples. The same groupings observed in the cluster analysis are found here. SED1 and SED2 fall very close to each other. SED24 and SED25 are also fairly close, especially in respect to the first principal component. SED4 and SED5 are separated. Figure 5 shows this pattern one more time in the water data, with the addition of RW1 and RW2 being fairly close to each other. In summary, the cluster analysis shows us that samples that were similar in location and in type were also similar in water quality and in elemental composition at the time and under the hydrologic conditions that they were sampled. This is not surprising, but does serve as verification that sampling was correctly conducted and that sediments and sediment porewater chemistry varied according to location.
CONCLUSIONS
Water quality variables of surface and sediment pore water, including dissolved oxygen, hardness, alkalinity, temperature, pH, ammonia, sulfate, nitrate-H nitrite, chlorides, and calcium, were clearly within acceptable limits for Ceriodaphnia dubia growth and reproducfion.
The groundwater from the monitoring well (MW19) was highly toxic, and high in many toxic elements. It had to be diluted to a concentration of 6.25% with reconstituted river water before survival and reproduction were not significantly different from the references. Although this study was not intended to encompass the dilution rate of groundwater with river and sediment pore waters in situ, one would surmise that groundwater would be quickly and highly diluted (i.e., to <6.25%) as it enters the Missouri River.
15
Metals of toxicological concern were not highly elevated in sediments, sediment pore waters, or river waters. At the one site where lead was somewhat elevated in the sediment (SED25), it was present in the pore water at a concentration of less than one third of the USEPA chronic criteria for surface waters. Ceriodaphnia reproducfion may have been somewhat impaired at this site. Using the toxic units approach, based on measured porewater concentrations, metals concentrations in pore water at this site approached but did not exceed the concentration where chronic toxicity might be expected. Perhaps these marginally high concentrations of metals impacted Ceriodaphnia reproduction, or other unmeasured contaminants, such as organic chemicals, may have been involved. The reduction in reproduction was not clearly significant.
Sediments in large rivers such as the Missouri are in a constant state of f lux; they are deposited, re-suspended, and transported continuously. Transport of sediment in rivers is well-studied (Meade et al. 1990). Sediments that were present in the early spring were completely removed by higher f lows before the fall sampling trip. Much of the substrate on the ASARCO waterfront was solid slag at the time of the sampling tr ip. Weathering of slag and movement of groundwater should provide a constant source of lead and other contaminants from this site. However, the dilution factor of the Missouri River is immense, and apparently sediment does not linger long at the site before passing on downstream. A prolonged period of low f low could cause sediments to remain in place long enough for contaminants from the ASARCO site to reach toxic concentrations along the waterfront. However, the Missouri River is a navigable waterway, which requires the United States Army Corps of Engineers to maintain regular, annual periods of high f low for river traffic. Sediment accumulating during the winter low f low period apparently washes away during the fol lowing navigation season.
Our intent was to perform this study after a prolonged low-f iow period. Under such conditions, the net f low of groundwater from the ASARCO Omaha facility is most likely to be toward the Missouri River, and pore waters collected under such condifions would contain proportionately high concentrafions of groundwater originating on the site. During or following high water periods, the pore waters are more likely to be dominated by river water. Even after equilibration wi th the sediments, such pore waters would be expected to have much lower elemental concentrations than groundwater from the site. Unfortunately, the need for the data and information presented in this report necessitated that we conduct the study in the early fall of 1998, following a summer-long high water period resulting from record snowfall during the winter of 1997-1998. This contention is supported to a degree by earlier monitoring data for MW19, the one we sampled and tested. This well is the one closest to the Missouri River and therefore the one likely to be most influenced by river water. Monitoring samples taken between August of 1995 and January of 1998 had concentrafions of calcium, chlorides and sulfates averaging 2 to 5.3 times higher than they were during our study (Table 17). It could be that groundwater had in fact been diluted by river water prior to our arrival. However, the chloride concentrafion of MW19 water was over five times
16
that of the river water during this study, and the concentration of arsenic found in the water taken from MW19 (574 ug/L), was very close to the historical average arsenic concentration (598 MQ/L, Table 17).
Literature Cited
Agresti, A. 1990. Categorical Data Analysis. John Wiley and Sons. New York. 558pp.
Barnes, R.D. 1980. \nvertebrate Zoology. Saunders College. Philadelphia, PA, USA. 1089p.
Carr, R.S. and D.C. Chapman. 1995. Comparison of methods for conducting marine and estuarine sediment porewater toxicity tests - extraction, storage and handling techniques. Arch. Environ. Contam. Toxicol. 18:69-77.
DiToro, D.M., J . D. Mahony, D. J . Hansen, K. J . Scott, A.R. Carlson, and G. T. Ankley. 1992. Acid volatile sulfide predicts the acute toxicity of cadmium and nickel in sediments. Environ. Sci. Technol. 26: 96 -101 .
Gobas, F.A.P.C. and X. Zhang. 1994. Interactions of organic pollutants wi th particulate and dissolved organic matter in the aquatic environment, pp. 83 -92 in J.L. Hamelink, P.P. Landrum, H.L. Bergman, and W.H. Benson, eds. Bioavailability: Physical, Chemical, and Biological Interactions. Lewis Publishers, Boca Raton, LA. 239pp.
Hochberg, Y. and A.C. Tamhane. 1987. Multiple Comparison Procedures. John Wiley and Sons. New York. 450pp.
Johnson, R. A. and D. W. Wichern. 1992. Appl ied Multivariate Statistical Analysis. Srd edifion. Prentice Hall, Engelwood Cliffs, NJ. 642pp.
Kaufman L. and P.J. Rousseeuw 1990. Finding groups in data: an introduction to cluster analysis. J . Wiley, New York. 342 pp.
May, T.W., R.H. Wiedemeyer, W.G. Brumbaugh, and C J . Schmitt, 1997. The determination of metals in sediment pore-waters and in I N HCI-extracted sediments by ICP-MS. Atom. Spectr. 18:133-139.
Meade, R.H., T.R. Yuzyk, and T.J . Day, 1990. Movement and storage of sediment in fivers of the United States and Canada, pp. 255-280 in M.G. Wolman and H.C Riggs, editors. Surface Water Hydrology, Boulder, Co., Geological Society of America.
17
Monda, D.P. 1 9 9 1 . Toxicity of ammonia in sewage effiuent to aquatic macroinvertebrates. Masters Thesis, University of Missouri, Columbia, Missouri. 98pp.
Onuf, C.P., D.C. Chapman, and W . M . Rizzo. 1996. Inexpensive, easy to construct coring devices usable from small boats. Journal of Sedimentary Research. 66 :1031-1032.
Snedecor, G.W. and W.G. Cochran. 1989. Statistical Methods. 8** ed. Iowa State University Press. Ames, Iowa. 503pp.
Sprague, J.B., and B.A. Ramsay. 1965. Lethal levels of mixed copper-zinc solufions for juvenile salmon. J . Fish. Res. Bd. Can. 22 :425-432.
Tessier, A., P.G.C Campbell, and M. Bisson. 1979. Sequential extraction procedure for the speciation of particulate trace metals. Anal. Chem. 51 :844 -851 .
U.S. Environmental Protection Agency (USEPA). 1994. Short-term Methods for Estimating the Chronic Toxicity o f Effluents and Receiving Waters to Freshwater Organisms. EPA-600-4-91-002, Cincinnafi, Ohio. 246pp.
U.S. Environmental Protecfion Agency (USEPA) and U.S. Geological Survey (USGS). 1998. Quality Assurance Project Plan For Sediment And Sediment Pore Water Sampling. 26pp. plus appendices.
U.S. Environmental Protection Agency (USEPA). 1999. National Recommended Water Quality Criteria - Correction. EPA 822-Z-99-001.
Wildhaber, M.L. and C J . Schmitt. 1996. Estimating aquatic toxicity as determined through laboratory tests of Great Lake sediments containing complex mixtures of environmental contaminants. Environ. Monit. Assess. 41 :255-289.
18
Figures
Figure 1. Location of sediment sampling sites near the ASARCO facility in Omaha, Nebraska. SED1 is the site farthest north. SED2 is on the Eastern bank. SED4 is within the Burt-Izard Drain, and SED5 is in the Missouri River at the mouth of the Burt-Izard. SED24 is under the 1-480 Bridge and SED25 is the farthest south. Approximate boundary of ASARCO facility is indicated.
20
Se(dinnent
I I
12
10
8 _
6 _
4 _
Q LU CO
in O LU CO
•r-Q LU CO
CM Q LU CO
TT CNl Q IU CO
in eg Q LU CO
Figure 2. Results of hierarchical cluster analysis of element concentrations measured from sediment samples collected near the ASARCO facility in Omaha, Nebraska.
21
Water
Oi
10
8 _
6 -
4 _
2 J
m Q LU CO
•sf Q LU CO
River River Water Water 1 2
M- in CM CM Q Q LU LU CO CO
Q UJ CO
CM Q IU CO
Figure 3. Results of hierarchical cluster analysis of element concentrations measured from aqueous samples collected near the ASARCO facility, Omaha, Nebraska.
22
Se(diment
4 _
^ 2 J 0) c o Q. E o O (0 C2. 'o c •c CL T3
c 8
CO
0 _
SED4 o
1 1 1
SED5 o
SED1 o
o SED2
SED25 0
SED24 o
1 1 1
-15 -10 10 -5 0 5
First Principal Component
Figure 4. Biplot of element concentration data measured from sediment samples.
23
Water
6 _
4 _
c c O 9
E o O 15 g. o c •c Q.
8 0)
CO
-2
SED40
OSED24
SED^
River water 1 o
River water 2 o
1 1
OSED25
OSED1
1
SED5
o
-5 0 5
First Principal Component
Figure 5. Biplot of element concentration data measured from water samples.
24
I I I I I
Tables
Table 1 . Comparison of historical river water chemistry, Columbia Environmental Research Center (CERC) well water, and reconstituted river water. Historical averages of river water chemistry computed from unpublished Hydrometrics, Inc. data, and supplied to CERC by USEPA.
Sodium
^'eGDSs1:llutil(El?ijf
66.0
Potassium 7.9 2.2 7.9
Calcium 67.7 71.0 71.0
Magnesium 25.4 27.0 27.0
Chloride 17.1 21.0 21.0
Bicarbonate 184 188 188
Sulfate 212 47.0 145
Summation of identified salts
580 379 526
I 26 I
Table 2. Comparison of dissolved oxygen concentrations, conductivity, and pH measurements performed in the field wi th measurements made at CERC before the start of the toxicity test, including measurements on CERC reference waters and on dilutions of sample waters. MW19 is the groundwater sample from monitoring well 19. SEDx refers to pore waters collected from the various sediment sites. NaCI refers to the sodium chloride reference toxicant treatments and the concentration of NaCI added to reconstituted river water. Hard Recon refers to the reconstituted water made to reflect the water quality of the river waters.
River water 1
River water 2
SED1
SED2
SED4-100%
SED4-50%
SED4-25%
SED4-12.5%
SED5
SED24
SED25
MW19-100%
MW19-50%
MW19-25%
MW19-12.5%
MW19-6.25%
NaCI 2.5 Xo
NaCI 1.25 °/oo
NaCI 0.613 °/oo Reconstituted river water
Hard Recon
CERC Well water
, ' 7 Field Measurements' -' 'C";, I
Dissolved^. ^ Oxygen^f '' (mg/L) A
8.3
9.1
4.2
4.6
3.2
5.8
7.9
5.3
3.8
'.amm-,"i4.mhos/(5m |
600
600
690
800
600
800
580
650
2980
- 2 ^ =-; r^~.
8.83
8.02
7.34
7.62
7.58
6.99
7.58
7.73
7.42
g"!t M^a^urements/at'CE \
? Dissolved?
9.5
9.7
10.2
9.6
9.4
9.6
9.6
9.4
10.2
9.6
10.2
10.2
9.8
9.6
9.6
9.6
8.5
8.5
8.8
8.6
8.0
8.6
^gnhc^/afhlj
600 j
610
810
790
610
575
510
500
1310
710
900
3110
1400
1200
850
690
4620
2600
1510
510
580
341
8.34
8.33
7.75
8.07
7.92
8.14
8.17
8.18
7.61
8.30
7.88
8.25
7.98
8.08
8.15
8.16
8.19
8.19
8.19
8.17
8.26
8.48
2 7
Table 3. Water quality measurements taken before start of Ceriodaphnia toxicity test. MWT9 is the groundwater sample from Monitoring Well 19. SEDx refers to pore waters collected from the various sediment sites. NaCI refers to the sodium chloride reference toxicant treatments and the concentration of NaCI added to reconstituted river water. Hard Recon refers to the reconstituted water made to reflect the water quality of the river waters. Units are mg/L.
River water 1
River water 2
SED1
SED2
SED4
SED5
SED24
SED25
MW19
Reconstituted river water
Hard Recon
Well
3.3
7.9
8.2
1.2
15.2
4.6
6.6
6.5
1.2
fAlkaI>-.' SL.i„, i f f , , iX..
icaeieri)!
162
162
390
344
160
776
234
366
402
250
240
246
244
244
416
390
208
748
336
410
550
228
250
284
0.068
0.070
2.07
0.965
11.2
13.5
0.547
1.47
1.20
0.021
0.027
0.52
0.50
0.00
0.29
0.40
0.00
0.44
0.25
0.15
0.60
0.68
0.40
182
171
131
162
120
103
161
143
186
74.0
154
63.6
0.109
0.133
0.830
0.149
0.316
0.257
0.162
0.167
0.806
0.066
0.042
0.060
8.8
• 13.8
8.8
13.8
13.8
8.8
13.8
23.9
321
8.8
13.8
llfCa -
71.8
79.8
112
112
87.9
193
96.0
128
185
169
39.5
28
I \
Table 4. Results of grain size analysis of sediments collected in the Missouri River and in the Burt-Izard Drain, near ASARCO facility, Omaha, Nebraska. Percentages of sand, silt and clay determined by the Bouyoucous hydrometer method, larger particles separated by sieving.
- Samp I^-^v^fiV (iesignafibn;
SED1
SED2
SED4
SED5
SED24
SED25
-;::%;,llargeAl ' than Sahd.v.
0.0
0.0
32.0
0.0
0.0
1.5
f tUSand^;
47.5
63.0
66.0
26.3
86.5
81.3
42.0
29.0
1.0
52.0
10.5
12.8
10.5
8.0
1.0
21.8
3.0
4.5
:^r.frPercent^r-. '"Moisture >
28
27.8
18.2
41.8
20.6
22.1
' Loss*on. \ ignitiori:
1.4
1.5
0.80
3.7
0.8
1.3
29
Table 5. Concentrations (pg/g) dry weight of total recoverable arsenic, cadmium, lead and zinc in sediment samples from the Omaha, NE, ASARCO study. Measurements are from quantitafive analysis by ICP-MS.
-Element^
Arsenic
Cadmium
Lead
Zinc
"\^"EDI\
5.60
<0.27
8.40
39.0
rSED2;'
6.50
<0.27
7.10
34.5
2.90
<0.27
7.40
33.7
31% 7.80
0.43
19.7
77.2
5.90
<0.27
13.0
23.9
:"SEli(25!
6.90
<0.27
39.8
45.8
: EPA blind:/. - QA'sample "
4.60
0.78
7.00
41.0
0.31
0.27
1.10
5.10
^ MDL = method detection limit
30
Table 6. Concentrations (fag/L) of arsenic, cadmium, lead and zinc in aqueous samples from the Omaha, NE, ASARCO study. MW1 9 is the groundwater sample from Monitoring Well 19. SEDx refers to pore waters collected from the various sediment sites. NaCI refers to the sodium chloride reference toxicant treatments and the concentration of NaCI added to reconstituted river water. Hard Recon refers to the reconstituted water made to reflect the water quality of the river waters. Measurements are from quantitative analysis by ICP-MS.
' f Idehtif i(iatibh.^'i -=,
Filtration Blank 1
Filtrafion Blank 2
River water 1
River water 2
MW19
SED1 Pore water Dup.SEDI Porewater
SED2 Pore water
SED4 Pore water
SED5 Pore water
SED24 Pore water
SED25 Pore water
USEPA Blind Sample
MDL^
\iS^Arsenic|tf2l
< 0.07
< 0.07
2.70
2.70
574
30.7
30.4
15.6
23.1
56.3
4.00
7.70
13.3
0.07
aCits iCad mi umfes>j
1.00
0.03
0.79
0.52
21.5
0.15
1.20
0.67
0.67
0.49
1.10
0.77
18.10
0.02
cp^v-liead^-s'^
0.23
0.49
0.50
0.64
2.60
3.40
5.20
1.70
8.40
2.20
11.5
5.00
4.90
0.04
- " •* ^ »
•;Zinc >
8.20
2.60
11.3
4.20
1570
9.8
21.9
27.5
34.7
17.20
63.7
31.9
12.9
0.42
MDL = method detection limit
31
Table 7. Concentrations of elements in sediment from the ASARCO facility in Omaha, Nebraska determined by semi-quantitative ICP-MS scan. Units expressed as |ig/g dry weight.
Element
Ag Al As Au B Ba Be Bi Br Ca Cd Ce Co Cr Cs Cu Dy Er Eu Fe Ga Gd Ge Hf Ho 1 In Ir K La Li Lu Mg Mn Mo Na Nb
'^SED1
<0.1 4000 6.00
0.3 1
200 <1 < 1 10
13000 0.6 20
5 8
<1 9 2
0.7 0.5
7000 3 2
<0.1 <0.1
0.3 <1 <1
<0.1 800
10 5
<0.1 5000 400 0.4 100 <1
.-, '- ' '
!'SED2^.f
<0.1 4000 7.00
0.2 2
200 < 1 <1 10
14000 0.3 20
6 9
< 1 6 2
0.7 0.5
8000 3 2
<0.1 <0.1
0.3 <1 < 1
<0.1 900
10 5
<0.1 5000 400 0.3
200 < 1
. :^V. . ' ; . . . -
f^SEoT:,
0.2 900 4.0 0.6 <1 30
<1 <1 10
45000 0.2 10 3
30 <1 30
0.6 0.2 0.2
11000 1
0.8 0.1
<0.1 <0.1
<1 <1
<0.1 200
5 < 1
<0.1 1000 200
9 100 <1
mm 0.2
7000 9
<0.1 2
200 <1 <1 10
16000 0.6 30 7
10 <1 20
2 1
0.6 10000
4 3
<0.1 0.1 0.4 <1 <1
<0.1 1000
10 7
0.1 4000
500 0.6 200 <1
feED24^
<0.1 3000
7.0 <0.1
< 1 400 <1 < 1 10
11000 <0.1
20 4 7
<1 3 1
0.6 0.4
6000 2 2
<0.1 <0.1
0.2 <1 < 1
<0.1 500
10 4
<0.1 4000
200 0.3
200 < 1
'SED25
0.1 3000
8.0 <0.1
< 1 300 <1 < 1 10
12000 0.2 20
5 8
< 1 5 1
0.6 0.4
7000 2 2
<0.1 <0.1
0.2 <1 <1
<0.1 500
10 4
<0.1 4000
300 0.3
200 <1
». USEPA <• Blind . QA •Sample
0.1 6000
5.0 0.8
3 90
< 1 < 1 10
88000 0.9 30 4 8
< 1 8 2
0.9 0.6
7000 4 3
<0.1 <0.1
0.3 < 1 <1
<0.1 600
10 5
<0.1 17000
500 0.8 100 <1
32
I I I
I I I I I I
-Element-
Nd Ni Os Pb Pd Pr Pt Rb Re Ru Sb Sm Sn Sn Sr Ta Tb Te Ti Tl Tm U V W Y Yb Zn Zr
j .?.-,^.:. ,-.-:*,-.„ : • . . : :
'X^S^X^-m:.' ':..-^'-
10 10
<0.1 10
<0.1 3
<0.1 9
<0.1 <1 0.2
2 0.1 0.1 50
<0.1 0.3
<0.1 70 0.1
<0.1 < 1 10
<0.1 8
0.7 60
2
yi<SB32:@
10 10
<0.1 6
<0.1 3
<0.1 9
<0.1 <1
<0.1 2
0.2 0.2 50
<0.1 0.3
<0.1 80 0.1
<0.1 <1 20
<0.1 8
0.7 50
3
^ S E i a 4 ^
4 30
<0.1 8
<0.1 1
<0.1 2
<0.1 <1 0.6 0.8
3 3
100 <0.1 <0.1 <0.1
30 <0.1 <0.1
<1 4
0.5 2
0.2 50
1
M&r.-^'f-i-.Mir.
10 20
<0.1 20
<0.1 4
<0.1 10
<0.1 <1 0.2
3 <0.1 <0.1
70 <0.1
0.4 <0.1
60 0.2 0.1 <1 20
<0.1 10
0.9 90
5
#SE[D2#
10 10
<0.1 10
<0.1 3
<0.1 4
<0.1 <1 0.4
2 0.1 0.1 30
<0.1 0.3
<0.1 90
<0.1 <0.1
< 1 10
<0.1 . 7 0.5 30
2
3M$^'^1i:ff.: «i^ i&^V-.; i7;-.:
i SED255;: ^f"''^?/'S5r.e'-V':='S
10 10
<0.1 40
<0.1 3
<0.1 6
<0.1 <1 0.5
2 0.2 0.2 40
<0.1 0.3
<0.1 70
<0.1 <0.1
< 1 10
<0.1 7
0.5 50
3
USEPA rBlinci;,-
r:^ample:i 10 10
<0.1 6
<0.1 4
<0.1 5
<0.1 <1 0.4
3 0.2 0.2
200 <0.1
0.4 <0.1
40 <0.1
0.1 < 1 10
<0.1 9
0.7 50
2
33
Table 8. Concentrations of elements in water from the Omaha, NE, ASARCO study determined by semi-quantitative ICP-MS scan. Units expressed as (ag/L unless otherwise specified.
;-i Element' '
Ag
Al
As
B
Ba
Be
Bi
Br
Caa
Cd
Ce
Co
Cr
Cs
Cu
Dy
Er
Eu
Fe
Ga
Gd
Ge
Hf
Ho
1
In
Ir
Ka
La
Li
Lu
' River" • water i
<0.1
8
4.2
63
63
0.25
<1
102
57
0.92
0.17
0.17
3.1
<1
3.2
<0.1
<0.1
<0.1
127
<0.1
<0.1
<0.1
<0.1
<0.1
1.7
<1
<0.1
5.4
0.11
45
<0.1
River water
^ - . 2
<0.1
<0.1
4.0
57
61
0.16
<1
103
56
0.61
<0.1
0.11
5.2
<1
4.4
<0.1
<0.1
<0.1
71
<0.1
<0.1
<0.1
<0.1
<0.1
1.8
<1
<0.1
5.7
<0.1
46
<0.1
SED'- "
<0.1
10
38.0
51
178
<0.1
<1
199
90
0.27
0.31
2.2
11
<1
3
<0.1
<0.1
<0.1
1520
0.22
<0.1
0.23
<0.1
<0.1
15
<1
<0.1
5.1
0.18
35
<0.1
-SED IS
<0.1
<0.1
39.0
46
177
<0.1
<1
196
84
1.3
0.1
2.3
16
<1
3.3
<0.1
<0.1
<0.1
1320
0.25
<0.1
0.28
<0.1
<0.1
28
<1
<0.1
5.6
<0.1
34
<0.1
<0.1
<0.1
19.0
90
130
0.15
<1
190
92
0.7
0.11
1.4
7.6
<1
4.4
<0.1
<0.1
<0.1
40
0.17
<0.1
<0.1
<0.1
<0.1
28
<1
<0.1
6.3
<0.1
48
<0.1
-SED.--
<0.1
18
28.0
95
144
<0.1
<1
121
54
0.75
0.63
1.2
5.6
<1
7.9
<0.1
<0.1
<0.1
742
0.13
<0.1
0.17
<0.1
<0.1
4
<1
<0.1
6.5
0.36
29
<0.1
<0.1
0.5
72.0
147
335
<0.1
<1
634
171
0.55
0.05
4.2
24
<1
3
<0.1
<0.1
<0.1
4210
0.33
<0.1
<0.1
<0.1
<0.1
56
<1
<0.1
8.4
<0.1
17
<0.1
t S E D , ^^24-v '
<0.1
22
5.6
52
117
<0.1
<1
138
80
1
0.19
0.86
9.2
<1
13
<0.1
<0.1
<0.1
238
0.11
<0.1
<0.1
<0.1
<0.1
11
<1
<0.1
5.1
0.11
40
<0.1
1 m "
<0.1
54
11
223
212
<0.1
<1
184
88
1.1
0.12
1.5
17
<1
4.6
<0.1
<0.1
<0.1
318
0.13
<0.1
<0.1
<0.1
<0.1
11
<1
<0.1
7
<0.1
40
<0.1
<0.1
39
771
6520
166
<0.1
<1
551
172
26
<0.1
11
16
2.4
20
<0.1
<0.1
<0.1
289
0.23
<0.1
0.27
<0.1
<0.1
5.8
<1
<0.1
92
<0.1
92
<0.1
' Filter -Blank
<0.1
2
0.10
<1
1
<0.1
<1
2.8
0.11
1.2
<0.1
<0.1
0.75
<1
3.9
<0.1
<0.1
<0.1
17
<0.1
<0.1
<0.1
<0.1
<0.1
<1
<1
<0.1
<0.1
<0.1
<1
<0.1
Filter " Blank
2 '
<0.1
0.84
0.15
<1
<1
<0.1
<1
2.3
<0.1
<0.1
<0.1
<0.1
0.44
<1
0.61
<0.1
<0.1
<0.1
17
<0.1
<0.1
<0.1
<0.1
<0.1
<1
<1
<0.1
<0.1
<0.1
<1
<0.1
USEPA ' : Q A ' sample
<0.1
82
16.0
<1
<1
5
<1
1.5
<0.1
20
<0.1
47
7.8
<1
5
<0.1
<0.1
<0.1
34
<0.1
<0.1
<0.1
<0.1
<0.1
<1
<1
<0.1
<0.1
<0.1
<1
<0.1
34 I
I I I I I I
7;;Elerri'ent" . -. • • ;H j - v : ^ i - . ' ' - ^ ' •
Mga
Mn
Mo
Naa
Nb
Nd
Ni
Os
Pb
Pd
Pr
Pt
Rb
Re
Ru
Sb
Sm
Sn
Sr
Ta
Tb
Te
Ti
Tl
Tm
U
v W
Y
Yb
Zn
Zr
' ;Rlyeir;; l; water-'j '..J •-.jl' SiJj V
23
17
3.2
67
<1
<0.1
3.7
<0.1
<1
<0.1
<0.1
<0.1
2.3
<0.1
<1
0.64
<0.1
<0.1
472
<0.1
<0.1
<0.1
1.4
<0.1
<0.1
4.2
2.4
0.14
<1
<0.1
21
<1
.liRiverj ' - i . "V ' ' - . ; •. -water -i
&2rn.: 22
5
3.3
72
<1
<0.1
2.2
<0.1
<1
<0.1
<0.1
<0.1
2.3
<0.1
<1
1
<0.1
0.47
522
<0.1
<0.1
<0.1
0.62
<0.1
<0.1
4.4
2.3
0.13
<1
<0.1
<1
<1
. .SEDr" ; -
38
4970
5.1
69
<1
0.14
7.2
<0.1
3.7
<0.1
<0.1
<0.1
3.1
<0.1
<1
0.84
<0.1
0.38
734
<0.1
<0.1
0.16
2.3
<0.1
<0.1
2.8
1.6
0.16
<1
<0.1
6.3
^'
•'sEDl|i;'; "-bupj'fe •: •"•;'..;;;.^fts.-;, >
36
4630
5.4
68
<1
<0.1
19
<0.1
5.6
<0.1
<0.1
<0.1
3
<0.1
<1
0.78
<0.1
0.51
739
<0.1
<0.1
<0.1
1.7
<0.1
<0.1
2.8
1.4
0.17
<1
<0.1
22
<1
feSEDiE ;
37
2800
4.8
77
<1
<0.1
6.2
<0.1
1.8
<0.1
<0.1
<0.1
4.4
<0.1
<1
2.4
<0.1
0.54
798
<0.1
<0.1
<0.1
1.2
<0.1
<0.1
6.2
1.6
0.26
<1
<0.1
26
<1
/••ii-- —:?.- i^^saJSK .f isEfeZKi! ;*;-r;faft5r. -?ySED - .SED'i f 'SED^ 1£|SED^ •;
. yf: sM ^2m \fmm *5SV "J-HA y ^ i i i ^ / J . W.'i'^J.ti:'i-. k-'-:;-:-X)iA
15
608
14
60
<1
0.29
4.7
<0.1
9.2
<0.1
<0.1
<0.1
3
<0.1
<1
8.2
<0.1
0.93
412
<0.1
<0.1
<0.1
1.7
<0.1
<0.1
4.1
1.8
0.44
<1
<0.1
37
<1
67
6820
6.8
94
<1
<0.1
10
<0.1
2.8
<0.1
<0.1
<0.1
3
<0.1
<1
1
<0.1
0.53
1172
<0.1
<0.1
0.14
2.9
<0.1
<0.1
<1
0.68
0.13
<1
<0.1
21
<1
32
1040
7.8
65
<1
0.1
8.9
<0.1
12
<0.1
<0.1
<0.1
2.7
<0.1
<1
4
<0.1
0.58
639
<0.1
<0.1
<0.1
1.8
<0.1
<0.1
5.5
2.8
0.11
<1
<0.1
67
<1
36
2160
10
87
<1
<0.1
19
<0.1
5.8
<0.1
<0.1
<0.1
3.3
<0.1
<1
12
<0.1
0.4
752
<0.1
<0.1
<0.1
4.9
<0.1
<0.1
7.4
3.2
0.32
<1
<0.1
44
<1
34
2660
56
532
<1
<0.1
14
<0.1
3
<0.1
<0.1
<0.1
134
0.78
<1
430
<0.1
1.4
1230
<0.1
<0.1
0.24
8.3
0.69
<0.1
5.6
2.2
13
<1
<0.1
2050
<1
f. Filfer^v., VBIanic' .
<0.1
4.9
0.2
<0.1
<1
<0.1
2.7
<0.1
<1
<0.1
<0.1
<0.1
<0.1
<0.1
<1
0.1
<0.1
<0.1
<1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<1
<0.1
<0.1
<1
<0.1
12
<1
;Filtec., '/"Blank '
<0.1
1.1
<0.1
<0.1
<1
<0.1
0.36
<0.1
<1
^ <0.1
<0.1
<0.1
<0.1
<0.1
<1
<0.1
<0.1
<0.1
<1
<0.1
<0.1
<0.1
0.14
<0.1
<0.1
<1
<0.1
<0.1
<1
<0.1
4
<1
./USEPA,: :v-:-' QA'••;.... '/isample .
<0 .1
52
<0.1
<0.1
<1
<0.1
34
<0.1
5.4
<0.1
<0.1
<0.1
<0.1
<0.1
<1
<0.1
<0.1
<0.1
<1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<1
25
<0.1
<1
<0.1
22
<1
^Concentration units lag/mL.
35
Table 9. USEPA Water Quality Criteria for selected trace metals or the hardness-based algorithms used to determine the criteria [taken from Wildhaber and Schmitt (1996) and USEPA (1999)] .
^ Element -.' \ ;
Arsenic
Cadmium
Copper
Lead
Nickel
Zinc
USEPA Chronic Criteri"a-;(^g/L)
190
g (0.7852[ln(hardness)l-3.490
g(0.8545|ln(hardness)l-1.702
Q (1.2730lln(hardness)l-4.705
g (0.8460|ln(hardnessll-1.1645
(0.8473|ln(hardness)l-K0.7614
36 I
Table 10. Calculated USEPA Water Quality Criteria Values for pore waters, river waters, and groundwater based on averaged measured hardness for selected metals. MW19 is groundwater from monitoring well 19, located on the ASARCO Omaha property. SEDx refers pore waters collected from the various sites. Units are |ig/L.
Site
MW19
River water 1
River water 2
SED1
SED2
SED4
SED5
SED24
SED25
Hardness (mg/L
CaCOa)
550
262
280
384
333
242
540
324
369
Cu
39.9
21.2
22.4
29.4
26.0
19.8
39.3
25.4
28.4 .
Cd.
4.3
2.4
2.5
3.3
2.9
2.3
4.3
2.9
3.2
Pb ,
27.9
10.8
11.8
17.6
14.7
9.8
27.2
14.2
16.8
Ni
666.9
356.1
376.7
492
436
333
657
426
476
Zn
449.3
239.7
253.6
331
294
224
442
287
320
37
Table 11. Concentrations of simultaneously extracted metals (iig/g) in sediments collected in the vicinity ofthe ASARCO lead refining facility in Omaha, Nebraska.
Field-I[JS=: ;•''-:
Arsenic
Cadmium
Copper
Lead
Nickel
Zinc
VSED;-
1.70
0.18
3.00
6.60
3.60
9.70
: SED;:
2.20
0.20
2.90
3.80
3.60
6.90
vi SED^ • , - . ; : , : < . . - . , •.VJ^v
0.48
0.17
3.50
26.10
3.00
79.80
sCSED ;
1.80
0.35
5.90
38.30
6.50
40.80
^SEcn;
1.80
0.099
1.10
9.20
1.90
5.80
SH^ED' --;:S25vv
2.30
0.19
3.30
43.2
3.10
23.80
. > ^ • - J . _
0.020
0.010
0.010
0.030
0.020
0.490
'MDL= Method detecfion limit
38
Table 12. Molar concentrations (fimol/g) of acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) in sediments collected in the vicinity ofthe ASARCO lead refining facility in Omaha, Nebraska.
FieldJO; ' r
AVS
Arsenic
Cadmium
Copper
Lead
Nickel
Zinc
SSEM
SSEM- AVS
S E P f "
1.60
0.023
0.002
0.047
0.032
0.061
0.148
0.313
-1.287
, 4 -?5-^'--^j V - ^ i ,
..§ED2;7:
0.095
0.029
0.002
0.046
0.018
0.061
0.106
0.262
0.167
8.40
0.006
0.002
0.055
0.126
0.051
1.221
1.461
-6.939
; VEP5" '
5.00
0.024
0.003
0.093
0.185
0.111
0.624
1.04
-3.96
' SEDZV.
0.015
0.024
0.001
0.017
0.044
0.032
0.089
0.207
0.192
:SED25
1.30
0.031
0.002
0.052
0.209
0.053
0.364
0.711
-0.589
39
Table 13. Calculated Toxic Units derived from estimated porewater concentrations of copper, cadmium, lead, zinc, nickel, and arsenic based on Wildhaber and Schmitt (1996).
h:f;:0Smm jfeSltew-y
SED1
SED2
SED4
SED5
SED24
SED25
i^R 0.00
0.00
0.00
0.00
0.02
0.00
0.00
0.00
0.00
0.00
0.19
0.00
MPBS
0.00
0.00
0.00
0.00
3.11
0.00
iiil r >.:;-.-. .:--:f • . ; ; : < ' • . • . • • • . t^ ! .y ] - ' . : . . : ^ , - i j -
0.00
0.00
0.00
0.00
0.01
0.00
SIS 0.00
0.02
0.00
0.00
0.02
0.00
w& 0.00
0.04
0.00
0.00
0.05
0.00
Total
0.00
0.07
0.00
0.00
3.40
0.00
40
Table 14. Calculated Toxic Units (measured porewater concentration / USEPA water quality criteria) for copper, cadmium, lead, zinc, nickel, and arsenic. Nickel and copper concentrations were obtained from semi-quantitative scan (Table 8). Cadmium, lead, zinc and arsenic concentrations were obtained from quantitative measurements (Table 6).
I^llll,gfjt Brnh-SiteJSS; SED1
SED2
SED4
SED5
SED24
SED25
^.ii'-eiiSiifi 0.1
0.17
0.40
0.08
0.51
0.16
mmBm mmmi::
0.20
0.23
0.29
0.11
0.38
0.24
Sig^ixie^Uiitsiplf l l i i i P
0.24
0.12
0.86
0.08
0.81
0.30
mMBM 0.05
0.09
0.15
0.04
0.22
0.10
W^MSPm M^BWi
0.03
0.01
0.01
0.02
0.02
0.04
immy:l!:t: ' : l '>ais>^-:"
0.16
0.08
0.12
0.30
0.02
0.04
Total 0.78
0.70
1.83
0.63
1.96
0.88
41
Table 15. Percent survival of non-male Ceriodaphnia dubia exposed to sample and control water in a 7 day toxicity test on samples collected in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska. Ceriodaphnia identified as male were excluded. MW19 is the groundwater sample from monitoring well 19. SEDx refers to pore waters collected from the various sediment sites. NaCI refers to the sodium chloride reference toxicant treatments and the concentration of NaCI added to reconstituted river water. Hard Recon refers to the reconstituted water made to reflect the water quality of the collected river waters.
- . , ''"' •' ""-"'hi--treatment 7;
" • ' ' ' ' " • . - , ' - ' '
MW19
River water 1
River water 2
SED1
SED2
SED24
SED25
SED4
SED5
Reconstituted river water
Hard Recon
NaCI
Well
J K 6 - 2 5 _ ^ ! ^
78
;5";i2.5.;-:>
30
90
. pjlutlon ',
: ' f '
0
89
100
t
•y 50
0
100
40
-
.100
0
100
100
100
90
100
100
100
90
75
100
0
100
4 2
Table 16. Mean reproductive output of Ceriodaphnia dubia exposed to sample waters and reference waters in a 7 day toxicity test. Reproductive output is the total number of young produced during the test, regardless of the individual's survival. Number of replicates are in parenthesis. Standard error of the mean is in brackets. Ceriodaphnia identified as male were excluded. Treatments significantly lower in reproduction than SED1 and SED2 are indicated wi th t w o asterisks ( ** ) . Treatments significantly lower than SED1, but not SED2, are indicated wi th a single asterisk (*). MW19 is the groundwater sample from Monitoring Well 19. SEDx refers to pore waters collected from the various sediment sites. NaCI refers to the sodium chloride reference toxicant treatments and the concentration of NaCI added to reconstituted river water. Hard Recon refers to the reconstituted water made to reflect the water quality of the river waters.
tiieatmielntffl^
: " - - ' ' • • " ' • • ' : • » » - • , - • ' ' • • • - . ' • .^ • • : ; ' •
SED1
SED2
MW19
RW1
RW2
SED24
SED25
SED4
SED5
Reconstituted River Water
Hard Recon
NaCI
Well
^ •6c253«^J:
20.56 (9) [5.27]
WSSz
7.6** (10) [5.17]
26.3 (10) [5.51]
'9^ifS[
0** (10) [0]
32.56 (9) [5.39]
1.11** (9) [0.73]
^;;-50%;;
0** (10) [0]
28.12 (8) [5.66]
0** (10) [0]
'i 100%
33.8 (10) [4.55]
26.1 (10) [2.28]
0** (10) [0] 48.44
(9) [4.5] 32.6
(10) [2.9] 32.4
(10) [2.55] 15.88*
(8) [3.35] 31.56
(9) [4.83] 23.5
(10) [3.36] 8.75**
(8) [3.95] 38.7
(10) [4.44] 0**
(10) [0] 31.2
(10) [2.13]
43
Table 17. Historical water quality of Monitoring Well 19 (MW19) and water quality of MW19 when sampled in this study (October 5, 1998). Historical water quality from unpublished data provided to USEPA by the Nebraska Department of Environmental Quality. All values in mg/L.
Date
August 1995
March 1996
May 1996
January 1997
May 1997
January 1998
Historical average
October 1998 (this study)
CalciiJm>. -Chioride',,
431
507
442
414
272
195
377
185
1396
1484
1709
1588
1136
1003
1386
321
• Sijlfate
789
1235
1167
979
864
900
989
186
Arsenic
0.260
0.770
0.390
0.660
0.680
0.830
0.598
0.574
44
U.S. Department of the Interior U.S. Geological Survey
Columbia Environmental Research Center
Toxicity and Elemental Contaminant Concentrations of Groondwater, Sediment Pore Waters, and Surface Waters of the Missouri River Associated with a IVIetals Refining Site in Qmaha, ISIebraska
Appendices A and B
USGS science foraclianging world
Toxicity and Elemental Contaminant Concentrafions of Groundwater, Sediment Pore Waters, and Surface Waters of the Missouri River
Associated wi th a Metals Refining Site in Omaha, Nebraska.
Appendix A: Chemical Analysis Reports
Duane C. Chapman Ann L. Ailert
James F. Fairchild Thomas W. May
Christopher J . Schmitt
United States Geological Survey Biological Resources Division
Columbia Environmental Research Center Columbia, MO
and
Edward V. Callahan Environmental Statistics
Fountain City, WI
Prepared for:
United States Environmental Protection Agency, Region VII Air, RCRA, and Toxics Division
726 Minnesota Avenue Kansas City, KS
lAG DW14952122-01-1
April, 2000
DETERMINATION OF ACID VOLATILE SULFIDE, SIMULTANEOUSLY EXTRACTABLE METALS,
AND TOTAL RECOVERABLE METALS DETERMINED BY QUANTITATIVE AND
SEMI-QUANTITATIVE ANALYSIS IN SEDIMENTS COLLECTED IN THE VICINITY OF
THE ASARCO SMELTER IN OMAHA, NE
Final Report FY99-32-04
Thomas May, Ray WiecJmeyer, and William Brumbaugh
U.S. Department of the Interior U.S. Geological Survey
Biological Resources Division Columbia Environmental Research Center
4200 New Haven Roaci Columbia, MO 65201
December 23,1999
PREPARED FOR
U.S. Environmental Protection Agency 726 Minnesota Avenue
Kansas City, Kansas 66101
lAG DW14952122-01
U. S. Geological Survey Biological Resources Division
Columbia Environmental Research Center 4200 New Haven Road
Columbia, MO 65201 -9634
TABLE OF CONTENTS
Sample H i s t o r y . . 3
Methods 3 - 5
Results anci Discussion. . 5
Quality Control 6-8
Tables:
Sample Data 9-12
Instrumental Calibration 13-17
Reference/Research Materials 18-21
Methoci Precision 22-29
Instrumental Precision 22-23
Spikes 30-33
Interference Checks 34-37
Blank Equivalent Concentrations. : . .• 38-40
Instrument Detection Limit , 41-42
Method Detection Limit and Limit of Quantitation 41-42
DETERMINATION OF ACID VOLATILE SULHDE, SIMULTANEOUSLY EXTRACTABLE METALS, AND TOTAL RECOVERABLE METALS DETERMINED
BY QUANTITATIVE AND SEMI-QUANTITATIVE ANALYSIS IN SEDIMENTS COLLECTED IN THE VICINITY OF THE ASARCO SMELTER IN OMAHA, NE
SAMPLE HISTORY:
A to t a l of s ix sediment samples collected from the v i c i n i t y of the ASARCO smelter in Omaha, NE, were received by the Inorganic Chemistry sec t ion of the Columbia Environmental Research Center (CERC) on 10/8/98. The samples were col lected on 10/5/98 in 4 oz glass j a r s and kept on ice for two days before transmission to the inorganic Chemistry Section. The sediments were t o be analyzed for percent moisture, loss on igni t ion , a c i d - v o l a t i l e sulf ide (AVS) and simultaneously extractable metals (SEM; As, Ni, Cu, Zn, Cd, and Pb) . In addi t ion , a t o t a l recoverable metals cjuantitative analysis (Zn, As, Cd, and Pb) and semi-quant i ta t ive scan was recjuested for the sediments. The objective of the analyses was to evaluate the p o t e n t i a l tox ic i ty by chemical measures. The purpose of t h i s repor t i s to provide analyt ical data for the samples which will help to quan t i t a t e the presence and b i o a v a i l a b i l i t y of cer ta in elemental contaminants.
METHODS:
Quality Control: Sediment samples were processed through the preparative and analytical flow scheme in one block with an associated BID (block initiation date) which included the following quality control for the preparation and determination of AVS and SEM: procedural blank, duplicate sample, 'one reference sediment, and one pre-extraction spike (blank) . During AVS determination, cjuality control also included an analysis spike (post-extraction) and a calibration check solution. Quality control parameters for SEM determinations by ICP-MS included a continuing calibration blank, independent calibration verification standard, laboratory control samples, duplicate analysis, analysis spike, interference check solution, and dilution percent difference. Additional alicjuants of sediment forming a second BID set were processed for the quantitative analysis and semi-quantitative metals scan by ICP-MS. Quality control for the cjuantitative analysis was the same as that described for the SEM determinations. For the semi-cjuantitative scan, quality control included procedural blanks, procedural blank spikes, sample replicates, reference materials, and sample spikes. Precision was determined by repeated runs of a laboratory control solution. All quality control results were tabulated to provide an overview of cjuality assurance and to facilitate interpretation.
3
Chemical P r e p a r a t i o n and A n a l y s i s , AVS and SEM: For AVS and SEM determination, each sediment sample was briefly homogenized in its collection container with a plastic scoop, following which a ~5 mL aliquant was taken for AVS determination. During the AVS determination on each sediment sample, a simultaneously extractable metals fraction was generated as described in standard operating procedure (SOP) P.197. This method was adapted from the EPA draft method 376.3 (4/91) written by Allen, Gongmin, Boothman, DiToro, and Mahony, and utilized a silver/sulfide electrode for determining AVS. Fifty mL of each extract was vacuum filtered through a ' 0.4 ^m polycarbonate membrane. A portion of each filtered SEM extract (10 mL) was subjected to a microwave oven nitric acid/hydrogen peroxide digestion utilizing 50 mL Zymark tubes as described in SOP P.246. Final dilution volume for the digestates was 50 mL in a matrix of 2% nitric acid. These samples were manually diluted 2X, and subsequent lOX dilutions were conducted where needed by a CETAC ASD-500 autodilutor. All SEM digestates were analyzed by inductively-coupled plasma-mass spectrometry (ICP-MS, SOP P.241). Masses monitored were Zn-66 and Zn-68, Ni-60 and Ni-62, Cu-63 and Cu-65, As-75, Cd-111 and Cd-114, and Pb-206+207+208. Masses reported were Zn-66, Ni-60, Cu-63, As-75, Cd-114, and Pb-206+207+208. Internal standards were Ge (50ppb), Rh (lOppb) and Th (lOppb), and standard calibrations were as follows: Zn - 50ppb, lOOppb, and 200ppb; Ni - lOppb, 2 0ppb, and 4 0ppb; Cu - lOppb, 20ppb, and 4 0ppb; As - 5ppb, lOppb, and 2 0ppb; Cd - 2ppb, 4ppb, and 8ppb; Pb - 5ppb, lOppb, and 20ppb. A second aliquant of wet sediment was taken for the determination of percent moisture (SOP P. 205) and loss on ignition (LOI, SOP P.229) at 500°C (percent of dry weight).
Total R e c o v e r a b l e M e t a l s : A portion of each sample was lyophilized (SOP P.259) and then homogenized (SOP P.238d), following which a dried aliquant was digested (SOP P.281) in a sealed Teflon vessel in a microwave oven with HNO3 and H2O2 to prepare a digestate suitable for quantitative (P.241) and semi-quantitative scan (P.458) by ICP-MS. For both of these runs the samples were prediluted lOX with a CETAC ASD-500 autodiluter. Internal standards for the quantitative analysis were Ge (50ppb) and Rh (lOppb), and standard calibrations were as follows: Zn - 25ppb, 50ppb, and lOOppb; As -lOppb, 20ppb, and 40ppb; Cd - 2ppb, 4ppb, and 8ppb; Pb - 5ppb, lOppb, and 2 0ppb. Masses monitored and reported were the same as those described for the SEM analysis. For the semi-quantitative analysis, the external standard was a standard reference solution (Trace Metals in Drinking Water; Cat. No. CRM-TMDW, High Purity Standards, Charleston, SC) to which Pr, Tb, Tm, Ta, and Au were added at lOppb each to better represent the rare earth segment of the mass spectral range. Internal standards used for the semi-
4
quantitative run were Sc (lOppb), Rh (lOppb), and Th (lOppb). The accuracy of the semi-quantitative approach (TotalQuant®) is reported to be ± 30-50% by the manufacturer.
RESULTS AND DISCUSSION:
AVS a n d SEM: Percent moisture, LOI, AVS, and SEM results for sediment samples are indicated in Table 1. These results ranged as follows: moisture, 18.2 to 41.8%; LOI, 0.8 to 3.7%; ; AVS, 0.015 to 8.4 umole/g dry weight; simultaneously extractable metals in ug/g dry weight: Zn, 5.8 to 79.8; Ni, 1.9 to 6.5; Cu, 1.1 to 5.9; As, 0.48 to 2.3; Cd, 0.099 to 0.35; and Pb, 3.8 to 43.2.
SEM/AVS ratios and SEM-AVS differences were calculated for elements which are known to form sulfides less soluble than iron or manganese and are indicated in Table 2. Sediments having an SEM/AVS ratio > 1 and considerable positive SEM-AVS differences are considered potentially toxic to organisms in the acjuatic ecosystem. The .SEM-AVS difference is generally more meaningful for samples with low AVS because it better reflects the magnitude of SEM "metal excess." Two samples, CERC #18105 and #18111, contained low AVS concentrations (0.015 - 0.095 umole/g) and low SEM concentrations, and exhibited the only SEM/AVS > 1 (ESEM/AVS = 2.8 and 13.8 umole/g), but the SEM-AVS differences for these samples indicated that the magnitude of metal excess was small(< 0.2 umole/g).
Quantitat ive Analysis: Total recoverable concentrations of Zn, As, Cd, and Pb in sediment samples digested with HNO3/H2O2 (SOP P. 281) are indicated in Table 3. Concentration ranges for each element in ug/g dry weight were as follows: Zn, 23.9 to 77.2; As, 2.9 to 7.8; Cd, < 0.27 to 0.78; and Pb, 7.0 to 39.8.
Semi-Quantitative S c a n : Results of a semi-quantitative scan by ICP-MS of the HNO3/H2O2 digested sediments are indicated in Table 4. Concentrations of metals in sediments were generally consistent and comparable among field sites. In most instances, concentration differences were easily < lOX for a specific metal among field sites. Two exceptions to this were in CERC #18108, where Mo was much higher relative to the other samples (9 ug/g) , but Ba was much lower (30 ug/g). However, the remainder of the semi-quantitative, scan results were generally unremarkable.
QUALITY CONTROL:
C a l i b r a t i o n : Instrument calibration during cjuantitative analysis of sediment SEM extracts and sediment digestates by ICP-MS was verified by analyzing a continuing calibration blank and independent calibration verification standards, as indicated in Tables 5 and 6. Periodic runs of a laboratory control solution served to monitor calibration throughout the semi-quantitative (TotalQuant®) scan for sediments (Table 7) . In addition, a separate calibration solution was also ran at the beginning of the run, which exibited recoveries ranging from 95% to 134% (Table 8). A standardized Na2S solution confirmed calibration of the sulfide-specific electrode during AVS determination (Table 9).
C o n t r o l M a t e r i a l s : Results_ from the analysis of control materials are indicated in Tables 10-13. For SEM extracts and total recoverable digestate analyses, reference solutions (NIST 1643d and TMDW) were analyzed as ICP-MS laboratory control samples, and recoveries ranged from 90 - 102 percent (Tables 10-11) . A NIST 1645 river sediment was extracted with 1 N HCL, which resulted in good recoveries for Zn, Cd, and Pb, but poorer recoveries for Ni and Cu (Table 10) . Low recoveries for a partial digestion such as the IN HCl treatment are not unexpected because NIST certified ranges for sediment are based on recovery of metals from a "total" digestion procedure. These recoveries are consistent with previous IN HCl extractions performed by ECRC on sediments. Subjecting the same reference material to a total recoverable digestion resulted in recoveries of Zn, Cd, and Pb ranging from 95% to 100% (Table 11). Recoveries of elements from a reference sediment subjected to a total recoverable acid digestion and analyzed by a semi-quantitative scan are indicated in Table 12. Low recoveries for selected elements in the material (e.g. Na, Al, K, and Sb) is typical for the total recoverable digestion used, which yields incomplete solubilization of the refractory mineral phases (e.g. sand) of the sediment. Recoveries of sulfide (based on CERC historical data) from a IN HCl extract of NIST 1645 River Sediment are indicated in Table 13.
Analytical anci Method P r e c i s i o n : Analytical precision for the SEM extract and total recoverable cjuantitative analyses was measured by analyzing a sediment extract and total recoverable digestate twice at the instrument and determining the relative percent difference (RPD), which ranged from 0.001 to 7.7, as indicated in Tables 14 and 15. Analytical precision for the TotalQuant® scan on sediments was determined by repeated runs of a reference solution, which exhibited percent relative standard deviation (%RSD) values of < 13% (Table 7).
6
Method precision for SEM extracts was estimated in two ways: from the replicate extraction and microwave evaporative digestion of a sample (Tables 14 and 16) , and from the replicate microwave evaporative digestion alone (Table 16). Precision for a duplicate extraction and microwave evaporative digestion performed on sample #18107 exhibited poor RPD values ranging from 50% to 97% (#16230 SEM, Table 14) , indicating the more inhomogenous nature of this sediment. Another duplicate performed on sample #18109 produced improved RPDs, which ranged from 2.5% to 47%, depending on the analyte (Table 14). A replicate extraction and evaporative digestion (n=4) on sample #18113 SEM (Table 16), resulted in relative percent standard deviations (%RSD) ranging from 3.7% to 49%. Precision for a replicate microwave digestion alone on extract #18103 SEM MW indicated RSDs ranging from 2.3% to 10% (Table 16). A replicate total recoverable digestion and analysis (n=3) on samples #18104 and #18108 resulted in RSDs ranging from 4.0% to 39%, with the exception of Pb (Table 17). The 167 %RSD for Pb" from sample #18108 indicates a considerable sample inhomogenity for this element. Method precision from the duplicate preparation and analysis of sediment sulfide exhibited RPD values of 10% and 15% for two sediments (Table 18) . However, four replicates of a third sample resulted in a %RSD of 55% (Table 19) . The triplicate total recoverable digestion and analysis of sediment sample #18104 by semi-cjuantitative scan indicated RSD values < 30% for most elements, but poorer results for B, Cd, and Au (Table 20) . However, considerably higher %RSDs resulted for replicate digestion and analysis of sample #18108 (Table 21) , indicating a more marked inhomogeneity for this sample. Overall, the method precision results indicated the presence of considerable homogeneity discrepancies for some analytes among the sediment samples.
S p i k e s : SEM sample spikes were of two types: "analytical" (performed on a SEM extract during instrumental analysis) and "SEM" (sample or reagent blank spiked before extraction with HCl) . The recoveries for these spike types are indicated in Table 22, and ranged from 92 to 114% for both spike types. The recovery of spiked sulfide from reagent blanks ranged from 77% to 88% (Table 23). Spikes of reagent blank and sediment total recoverable acid digestates exhibited recoveries ranging from 91% to 104% (Table 24). Recoveries of elements from three spike types analyzed by a semiquantitative scan are indicated in Table 25. Percent recoveries ranged from 65% to 113%, depending on spike type and analyte.
ICP-MS I n t e r f e r e n c e Checks: Quantitative analysis by ICP-MS recjuires the analysis of two interference checks. A five fold dilution of a sediment extract (Table 26) indicated agreement 10% or better for all elements except As (16.1%) and Pb (12.3%). The same dilution on a total recoverable sediment digestate exhibited dilution percent differences < 10% for all analytes (Table 27) . Synthetic interference check solutions were analyzed with percent recoveries of analytes of interest indicated in Tables 28 and 29. Recoveries ranging from 83% to 118% indicate that the ICP-MS is adequately correcting for interferences.
Blank Equ iva len t C o n c e n t r a t i o n s : Blank equivalent concentrations (BEC) were computed for SEM procedural blanks for sediment (Table 30). The results indicate SEM BEC values less than the method detection limit (MDL) for As, but slightly above the MDL for all other analytes. BECs for the total recoverable cjuantitative analysis (Table 31) were less than their corresponding MDLs for all analytes. Mean BECs for a wide range of elements determined by semi-quantitative scan are indicated in Table 32.
Instrument Detection L i m i t s , Method De tec t ion L i m i t s , and Limi t s of Q u a n t i t a t i o n : Instrument detection limits, method detection limits, and limits of quantitation are indicated in Tables 33 and 34 for the SEM and total recoverable quantitative analyses. The method detection limit for sulfide was 0.003 umol/g dry weight.
Overall, the quality control results were considered to be acceptable based on specifications established by CERC.
Prepared By: Reviewed By:
Thomas May William Brumbaugh Ray Wiedmeyer
Approved By:
fOT( /Jim Petty Chief, Environmental Chemistry Branch
Table 1. Percent moisture, loss on ignition, acid volatile sulfide (umol/g), and concentrations of simultaneously extracted metals (ug/g) in sediments from the Qmaha, NE, ASARCO project.
ECRC # Field ID
18103 SED 1 A 18105 SED 2 A 18107 SED 4 A 18109 SED 5 A 18111 SED 24 A 18113 SED 25 A
MDL^
Matrix
Sediment Extract Sediment Extract Seditnent Exlract Sediment Extract Sediment Extract Sediment Extract
% Moisture
28.0 27.8 18.2 41.8 20.6 22.1
% LOI
1.4 1.5 0.8 3.7 0.8 1.3
AVS
1.6 0.095 8.4 5.0 0.015 1.3
0.003
Zn
9.7 6.9
79.8 40.8
5.8 23.8
0.49
Ni
3.6 3.6 3.0 6.5 1.9 3.1
0.02
Cu
3.0 2.9 3.5 5.9 1.1 3.3
0.01
As
1.7 2.2 0.48 1.8 1.8 2.3
0.02
Cd
0.18 0.20 0.17 0.35 0.099 0.19
0.01
Pb
6.6 3.8
26.1 38.3
9.2 43.2
0.03
^MDL = method detection limit (see Table 34).
Table 2. Ratio of SEM/AVS (a) and SEM-AVS difference (b) for zinc, arsenic, nickel, copper, cadmium, and lead.
a. SEM/AVS ECRC# Field ID Zn Ni Cu As Cd Pb
18103 18105 18107 18109 18111 18113
SED1 A SED 2 A SED 4 A SED 5 A SED 24 A SED 25 A
0.092 1.11 0.143 0.123 5.88 0.269
0.038 0.637 0.006 0.022 2.21 0.041
0.029 0.484 0.007 0.019 1.13 0.040
0.014 0.304 0.001 0.005 1.61 0.023
0.001 0.019 0.0002 0.0006 0.058 0.001
0.020 0.191 0.015 0.037 2.96 0.160
0.195 2.75 0.172 0.206
13.8 0.535
" I . = I[Cd.Cu,Ni,Pb.Zn] nMol/g -HAVS nMol/g.
b. SEM - AVS
ECRC# Field ID Zn Ni Cu As
^Z = Z[Cd,Cu.NI,Pb,Zn] nMol/g - AVS nMol/g.
Cd Pb
18103 18105 18107 18109 18111 18113
SED1 A SED 2 A SED 4 A SED 5 A SED 24 A SED 25 A
- 1.45 0.01
- 7.20 - 4.38
0.07 - 0.95
- 1.54 - 0.03 - 8.35 - 4.89
0.02 - 1.25
- 1.55 - 0.05 - 8.34 - 4.91
0.002 - 1.25
- 1.58 - 0.07 - 8.39 - 4.98
0.01 - 1.27
- 1.60 - 0.09 - 8.40 - 5.00 - 0.01 - 1.30
- 1.57 - 0.08 - 8.27 - 4.81
0.03 - 1.09
- 1.29 0.17
- 6.96 - 3.97
0.19 - 0.60
10
Table 3. Concentrations (ug/g dry weight) of total recoverable Zn, As, Cd, and Pb in sediment samples from the Omaha, NE, ASARCO study.
CERC# Field ID Zn As Cd Pb
18104 18106 18108 18110 18112 18114 18115
MDL^
SED1 B SED 2 8 SED 4 8 SED 5 8 SED 24 B SED 25 8
100
39.0 34.5 33.7 77.2 23.9 45.8 41.0
5.1
5.6 6.5 2.9 7.8 5.9 6.9 4.6
0.31
< 0.27 < 0.27 < 0.27
0.43 < 0.27 < 0.27
0.78
0.27
8.4 7.1 7.4
19.7 13.0 39.8
7.0
1.1
a MDL = method detection limit (see Table 34).
11
Table 4. Concentrations of elements in sediment from the Omaha, NE, ASARCO study determined by semiquantitative scan. Units expressed as ug/g dry weight.
Ele
Li Be B
Na Mg Al K
Ca Ti V Cr Mn Fe Co Ni Cu Zn Ga
• Ge As Br Rb Sr Y Zr Nb Mo Ru Pd Ag Cd In Sn
SED1 B CERC# 18104
5 <1
1 100
5000 4000
800 13000
70 10 8
400 7000
5 10 9
60 3
<0.1 6.00
10 9
50 8 2
<1 0.4 <1
<0.1 <0.1
0.6 <1 0.1
SED 2 B CERC# 18106
5 <1
2 200
5000 4000
900 14000
80 20
9 400
8000 6
10 6
50 3
<0.1 7.00
10 9
50 8 3
<1 0.3 <1
<0.1 <0.1
0.3 <1 0.2
SED 4 8 CERC# 18108
<1 <1 <1 100
1000 900 200
45000 30 4
30 200
11000 3
30 30 50
1 0.1 4.0 10 2
100 2 1
<1 9
<1 <0.1
0.2 0.2 <1
3
• • •
SED 5 8 CERC# 18110
7 <1
2 200
4000 7000 1000
16000 60 20
. 10 500
iOOOO 7
20 20 90 4
<0.1 9
10 10 70 10 5
<1 0.6 <1
<0.1 0.2 0.6 <1
<0.1
SED 24 B CERC# 18112
4 <1 <1 200
4000 3000
500 11000
90 10 7
200 6000
4 10 3
30 2
<0.1 7.0 10 4
30 7 2
<1 0.3 <1
<0.1 <0.1 <0.1
<1 0.1
SED 25 B CERC# 18114
4 <1 <1
200 4000 3000
500 12000
70 10 8
300 7000
5 10 5
50 2
<0.1 8.0 10 6
40 7 3
<1 0.3 <1
<0.1 0.1 0.2 <1 0.2
100 CERC# 18115
5 <1
3 100
17000 6000 600
88000 40 10 8
500 7000
4 10 8
50 4
<0.1 5.0 10 5
200 9 2
<1 0.8 <1
<0.1 0.1 0.9 <1 0.2
Ele
Sb Te 1
Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er
Tm Yb Lu Hf Ta W Re Os Ir Pt Au Tl Pb Bi U
•
SED1 8 CERC# 18104
0.2 <0.1
<1 <1
200 10 20
3 10 2
0.5 2
0.3 2
0.3 0.7
<0.1 0.7
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
0.3 0.1 10
<1 <1
IH 1
SED^ 8 CERC# 18106
<0.1 <0.1
<1 <1
200 10 20
3 10 2
0.5 2
0.3 2
0.3 0.7
<0.1 0.7
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
0.2 0.1
6 <1 <1
H •
SED 4 8 CERC# 18108
0.6 <0.1
<1 <1 30
5 10
1 4
0.8 0.2 0.8
<0.1 0.6
<0.1 0.2
<0.1 0.2
<0.1 <0.1 <0.1
0.5 <0.1 <0.1 <0.1 <0.1
0.6 <0.1
8 <1 <1
B H
SED 5 8 CERC# 18110
0.2 <0.1
<1 <1
200 10 30 4
10 3
0.6 3
0.4 2
0.4 1
0.1 0.9 0.1 0.1
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
0.2 20
<1 <1
, BB
SED 24 8 CERC# 18112
0.4 <0.1
<1 <1
400 10 20
3 10 2
0.4 2
0.3 1
0.2 0.6
<0.1 0.5
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
10 <1 <1
IB
SED 25 8 CERC# 18114
0.5 <0.1
<1 <1 300
10 20
3 10 2
0.4 2
0.3 1
0.2 0.6
<0.1 0.5
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
40 <1 <1
• i 1
100 CERC# 18115
0.4 <0.1
<1 <1 90 10 30 4
10 3
0.6 3
0.4 2
0.3 0.9 0.1 0.7
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
0.8 <0.1
6 <1 <1
• i m
Table 5. Concentrations of elements in a continuing calibration blank (CCB) and independent calibration verification staridard (ICVS) ran every 10 samples throughout the SEM quantitative analysis. Results expressed as |jg/mL.
BID" & R u n #
10/23/98 Run #1
10/23/98 Run #2,
10/23/98 Run #3
10/23/98 Run #4
10/23/98 Run #5
Element
Zn As Ni Cu Cd Pb
Zn As Ni Cu Cd Pb
Zn As Ni Cu Cd Pb
Zn As Ni Cu Cd Pb
Zn As Ni Cu Cd Pb
CCB"
-0.05106 0.01203 0.00418 0.00019 -0.00010 -0.00026
-0.02524 0.06115 0.00191 -0.00063 -0.00044 -0.00043
-0.01052 0.04539 -0.00081 -0.00626 0.00038 0.00166
-0.06284 0.05797 -0.00177 -0.00184 0.00237 0.00271
-0.03143 0.06807 -0.00122 -0.00510 0.00051 0.00422
ICVS
72.2 7.2
25.2 25.9
6.8 6 7
73.3 7.5
24.6 25.3
7.1 6.5
71.0 7.6
25.1 26.1
7.0 6.4
73.2 7.6
24.3 24.8
7.0 6.4
71.5 7.4
24.4 25.1
7.0 6.6
"BID & Run # = Block Initiation Date: a date
% Rec
(ICVS)'
96. 103. 101. 103.
97. 95.
98. 108.
98. 101. 102.
94.
95. 108. 100. 105. 101.
9 1 .
98. 108.
97. 99.
101. 9 1 .
95. 106.
98. - 101.
100. 94.
assigned
BID" & Run #
10/23/98 Run #6
10/23/98 Run #7
to each member of
Element
Zn As Cd Pb
Zn As Cd Pb
a group of
CCB"
-0.01921 -0.03375 -0.01028 -0.00640
-0.01376 -0.01882 -0.01060 -0.00673
ICVS
69.8 7.6 7.1 6.8
68.2 7.1 6.8 7.1
samples that will identi
% Rec
(ICVS)'
93. 108. 101.
97.
91 . 102.
97. 101.
fy the sample as a member of the group or "block"; run # refers to # of times CCB or ICVS analyzed in analytical mn.
"acceptance criteria for CCB is +/- 3 X IDL for each element
'acceptance criteria for ICVS = +/-10% (90% -110%).
ICVS = 75ppb for Zn, 25ppb for Ni and Cu, and 7ppb for Cd and Pb.
13
Table 6. Concentrations of elements in a continuing calibration blank (CCB) and independent calibration verification standard (ICVS) ran every 10 samples throughout the total recoverable quantitative analysis. Results expressed as ng/mL.
BID" Ele CCB" % Rec
ICVS (ICVS)'
Run#1
Run #2
Run #3
Run #4
11/13/98 11/13/98 11/13/98 11/13/98
BID"
11/13/98 11/13/98 11/13/98 11/13/98
BID"
11/13/98 11/13/98 11/13/98 11/13/98
BID"
11/13/98 11/13/98 11/13/98 11/13/98
Zn As Cd Pb
Ele
Zn As Cd Pb
Ele
Zn As Cd Pb
Ele
Zn As Cd Pb
-0.01532 0.01846 0.00037 0.00657
CCB"
-0.02339 -0.00660 0.00009 0.00361
CCB"
-0.02557 0.00132 -0.00009 0.00280
CCB"
-0.03214 0.00288 -0.00038 0.00315
68.0 35.9
5.9 6.0
ICVS
69.0 35.7
5.8 5.8
ICVS
69.5 35.8
6.0 5.9
ICVS
68.4 35.4
6.1 6.0
97. 103. 99. 99.
% Rec (ICVS)'
99. 102. 97. 96.
% Rec (ICVS)'
99. 102. 100. 98.
% Rec (ICVS)'
98. 101. 102. 99.
BID" Ele CCB" ICVS % Rec (ICVS)'
Run #5
Run #6
11/13/98 11/13/98 11/13/98 11/13/98
BID"
11/13/98 11/13/98 11/13/98 11/13/98
Zn As Cd Pb
Ele
Zn As Cd Pb
-0.01485 -0.00331 -0.00049 0.00038
CCB"
-0.02802 -0.00411 -0.00021 0.00228
72.0 36.0
5.9 5.7
ICVS
72.8 36.8
6.0 5.8
103. 103. 98. 95.
% Rec (ICVS)'
104. 105. 99. 97.
1
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample
as a member of the group or "block."
"acceptance criteria for CCB is +/- 3 X IDL for each element.
'acceptance criteria for ICVS = +/-10% (90% -110%). ICVS = 70ppb for Zn; SSppb for As; 6ppb for Cd and Pb.
14
Table 7. Percent relative standard deviation from repeated analysis of Trace Metals
in Drinking Water Standard^ during the semi-quantitative sample run. Results expressed in ng/mL.
Element
Li Be Na Mg . Al K Ca V Cr Mn Fe Co Ni Cu Zn As Rb Sr Mo Ag Cd Sb Te 8a Pr Tb Tm Ta Au Tl Pb 81 U
Run#1
22. 22.
6704. 9685. 135.
2589. 34904.
31. 21. 40. 103. 26. 62. 21. 71. 82. 10.4
259. 102. 2.0 10.4 10.5 3.2 50. 10. 11. 11. 11.6 10.9 11. 42. 9.0 11.
Run #2
21. 21.
6750. 10144. • 128. 2628. 35582.
32. 22. 41. 118. 27. 61. 20. 71. 82. 10.4
263. 102. 2.0 9.8 9.8 2.9 49. 10. 10. 10. 9.4 8.6 10. 37. 8.1 10.
Run #3
19. 21.
6446. 10089.
130. 2679. 34069.
30. 20. 40. 96. 25. 58. 19. 64. 74. 9.8
261. 99. 2.1 10.6 10.7 3.2 59. 11. 11. 11. 10.9 10.8 11. 42. 8.7 11.
Actual Cone
20. 20.
6000. 9000. 120.
2500. 35000.
30. 20. 40. 100. 25. 60. 20. 70. 80. 10.
250. 100. 2.0 10. 10. 3.0 50. 10. 10. 10. 10. 10. 10. 40. 10. 10.
Mean Cone
21. 21.
6633. 9973. 131.
2632. 34852.
31. 21. 40. 106. 26. 60. 20. 68. 79. 10.2
261. 101. 2.0 10.3 10.3 3.1 53. 10. 11. 11. 10.6 10.1 10. 40. 8.6 10.
SD
1.9 0.4
164. 250. 3.6 45. 758. 1.0 0.9 0.7 11. 1.2 1.8 1.0 4.1 4.6 0.3 2. 1.8 0.0 0.4 0.5 0.2 5.6 0.7 0.7 0.8 1.1 1.3 0.5 2.8 0.5 0.4
% RSD
9. 1.9 2.5 2.5 2.7 1.7 2. 3.3 4.3 1.6 11. 4.6 3.0 5. 6. 5.8 3.3 OJ 1.8 1.3 4.1 5.0 5.8 10.6 6.9 6.5 7.1 10.3 127 5.1 7. 5.3 4.0
High Purity Trace Metals in Drinking Water, Cat # CRM-TMDW. Charleston, SC; Pr, Tb, Tm, Ta, and Au manually added to represent rare earth region of the mass spectral range.
15
Table 8. Recovery of elements from a laboratory control sample^ with semi-quantitative analysis.
Element
Be Al V Cr Mn Co Ni Cu Zn As
Ag. Cd Sb Ba Tl Pb
Actual Cone
50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50.
Meas Cone
64. 58. 51. 53. 50. 54. 54. 57. 67. 61. 51. 55. 56. 49. 47. 49.
% Rec
129. 115. 103. 106. 100. 107. 109. 114. 134. 122. 101. 109. 111.
97. 95. 97.
"SPEX Claritas PPT Instrument Check Standard 1 (GL-ICS-1); SPEX CertiPrep, Inc., Metuchen, NJ
16
Table 9. Performance of a standardized Na2S solution used for instrument calibration verification during AVS determination.
BID" Ele. Run Ref. Actual Meas Meas % Error % Error' ISOP Oper Date Material Cone Cone 1 Cone 2 1 2 Init.
10/23/98 S 10/27/98 Na2S 19.2 18.6 19.1 -3.12 -0.52 P.197 WGB 10/23/98 S 10/28/98 Na2S 19.2 19.1 18.6 -0.52 -3.12 P.197 WGB
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
ISOP = instrumental standard operating procedure.
17
Table 10. Recoveries of elements from reference solutions and an HCl extracted reference sediment material (SEM quantitative analysis).
BID
10/23/98 10/23/98 10/23/98 10/23/98 10/23/98 10/23/98
10/23/98 10/23/98 10/23/98 10/23/98 10/23/98 10/23/98
10/23/98 10/23/98
- 10/23/98 10/23/98 10/23/98 10/23/98
Analysis Date
11/5/98 11/5/98 12/3/98 12/3/98 11/5/98 11/5/98
11/5/98 11/5/98 12/3/98 12/3/98 11/5/98 11/5/98
11/5/98 11/5/98 12/3/98 12/3/98 11/5/98 11/5/98
Reference Material
NIST 1643d" NIST 1643d" NIST 1643d" NIST 1643d" NIST 1643d" NIST 1643d"
TMDW TMDW' TMDW' TMDW' . TMDW' TMDW'
NIST 1645'* NIST 1645" NIST 1645" NIST 1645" NIST 1645" NIST 1645"
Element
Zn As Ni Cu Cd Pb
Zn As Ni Cu Cd Pb
Zn As Ni Cu Cd Pb
Actual Cone"
72.48 +/- 0.65 56.02 +/- 0.73 58.1 +/- 2.7 20.5 +/- 3.8 6:47 +/- 0.37 18.15+/-0.64
70 +/- 7 80 +/- 8 60 +/- 6 20 +/- 2 10 +/- 1 40 +/- 4
1720+/-170 (66)
45.8 +/- 2.9 109+/-19
10.2+/-1.5 714+/-28
Meas. Cone
73.9 58.1 54.8 20.7
6.4 18.4
62.2 82.3 56.3 19.0 10.2 37.5
1482. 27.7 13.0 52.3 7.4
675.
% Rec
101. 102. 99.
100. 100. 100.
99. 100. 100. 100. 100. 100.
96. e
30. 58. 85. 98.
ISOP
P.241 P.241 P.241 P.241 P.241 P.241
P.241 P.241 P.241 P.241 P.241 P.241
P.241 P.241 P.241 P.241 P.241 P.241
Oper Init.
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
Concentrations of NIST 1643d and TMDW are ng/mL; concentrations of NIST 1645 are ug/g dry wgt.
NIST 1643d = National Institute of Standards and Technology Standard Reference Material Trace Elements in Water 1643d. Concentration results in ug/L. Solution used as instrumental laboratory control sample.
"TMDW = Trace Metals in Drinking Water laboratory control solution, Cat # CRM-TMDW; concentration results in ug/L. Solution used as instrumental
laboratory control sample. NIST 1645 River Sediment = National Institute of Standards and Technology SRM 1645 River Sediment extracted with 1 N HCl; concentration results in
ug/g dry weight.
"percent recovery not calculated because of non-certified value.
Table 11. Recoveries of elements from reference solutions and a reference sediment used as laboratory control samples (total recoverable quantitative analysis).
BID
11/13/98 11/13/98 11/13/98 11/13/98
11/13/98 11/13/98 11/13/98 11/13/98
11/13/98 11/13/98 11/13/98 11/13/98
Analysis Date
12/2/98 12/2/98 12/2/98 12/2/98
12/2/98 12/2/98 12/2/98 12/2/98
12/2/98 12/2/98 12/2/98 12/2/98
Reference Material
NIST 1643d" NIST1643d" NIST 1643d" NIST 1643d"
TMDW' TMDW' TMDW' TMDW'
NIST 1645" NIST 1645" NIST 1645" NIST 1645"
Element
Zn As Cd Pb
Zn As Cd Pb
Zn As Cd Pb
Actual Cone.".
72.48 +/- 0.65 56.02 +/- 0.73 6.47 +/- 0.37 18.15+/-0.64
70 +/- 7 80 +/- 8 10+/-1 40 +/- 4
1720+/-170 (66)
10.2+/-1.5 714+/-28
Meas. Cone.
64.5 57.4 6.16
18.0
58.9 77.8 9.80
41.0
1651. 72.8 10.8
652.
% Rec
90. 101. 100. 100.
93. 100. 100. 100.
100. e
100. 95.
ISOP
P.241 P.241 P.241 P.241
P.241 P.241 P.241 P.241
P.241 P.241 P.241 P.241
Oper. Init.
RHW/TWM RHW/rWM RHW/TWM RHW/TWM
RHW/TWM RHW/TWM RHW/TWM RHW/TWM
RHW/TWM RHW/TWM RHW/TWM RHW/TWM
"Concentrations of NIST 1643d and TMDW are ng/mL; concentrations of NIST 1645 are ug/g dry wgt.
" N I S T 1643d = National Institute of Standards and Technology Standard Reference Material Trace Elements in Water 1643d. Solution used as laboratory control sample.
' T M D W = Trace Metals in Drinking Water laboratory control solution. Cat # CRM-TMDW; solution used as a laboratory control sample.
" N I S T 1645 = National Institute of Standards and Technology Standard Reference Material 1645: river sediment
"percent recovery not calculated because of non-certified value.
19
Table 12. Recovery of elements from a sediment reference material (semi-quantitative analysis).
Element Units
Na Mg Al K
Ca V Cr Mn Co Ni Cu Zn As Cd Sb Hg Tl Pb U
ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry ug/g dry
Meas. Cone.
1293. 7387. 5953.
541. 31653.
18.8 31465.
819. 8.81
45.6 126.
1916. 84.5 10.8 21.0
1.11 1.31
669. 0.91
Cert. Mean
5400. 7400.
22600. 12600.
(29000) 23.5
29600. 785.
10.1 45.8
109. 1720. (66)
10.2 (51)
1.10 1.44
714. 1.11
Upper Limit
5500. 7600.
23000. 13100. 31900.
30.4 32400.
882. 107 48.7
128. 1890.
72.6 11.7 56.1
1.60 1.51
742. 1.16
Low/er Limit
5300. 7200.
22200. 12100. 26100.
16.6 26800.
688. 9.50
42.9 90.0
1550. 59.4
8.70 45.9
0.60 1.37
686. 1.06
% Rec
24. 100. 27.
5. 100. 100. 100. 100. 93.
100. 100. 101. 116. 100. 46.
100. 96. 98. 86.
20
Table 13. Concentration of sulfide in a reference sediment. Measured concentrations (Meas. Cone.) expressed as ug/g. j
BID" Ele.
Meas. QC # Cone.
Reference Material Matrix
Upper Low er Pass/ Prep Prep Limit Limit Fail SOP Init. ISOP"
Oper. Init.
10/23/98 61 237. NIST 1645 sediment 240. 160. P.197 JWA P.197 WGB
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
"iSOP = instrumental standard operating procedure.
'NIST 1645 River Sediment = National Institute of Standards and Technology SRM 1645 River Sediment extracted with 1 N HCl; concentration results in
ug/g dry weight.
21
Table 14. Method precision from the duplicate extraction, digestion, and analysis of sediments (SEM quantitative analysis).
BID" Sample ID Matrix Element Rep 1 Rep 2 Diff" Mean RPD' ISOP" Oper. Init.
10/23/98
10/23/98
10/23/98
18107 SEM" 18107 SEM" 18107 SEM" 18107 SEM" 18107 SEM" 18107 SEM"
18109 SEM' 18109 SEM' 18109 SEM' 18109 SEM' 18109 SEM' 18109 SEM'
18113Analysis3 18113 Analysis^ 18107 Analysis" 18107 Analysis" 18113 Analysis^ 18113AnaIysis3
Sediment extract Sediment extract Sediment extract Sediment extract Sedinient extract Sediment extract
Sediment extract Sediment extract
. Sediment extract Sediment extract Sediment extract Sediment extract
Sediment extract Sediment extract Sediment extract Sediment extract Sediment extract Sediment extract
Zn As Ni Cu Cd Pb
Zn As Ni Cu Cd Pb
Zn As Ni Cu Cd Pb
78.7 0.48 2.97 3.52 0.17
26.1
40.3 1.82 6.47 5.89 0.35
38.3
105. 10.1 17.1 16.4
0.84 22.3
31.9 0.29 1.27 1.22 0.07
52.1
30.6 1.78 6.24 6.26 0.56
27.3
114. 10.2 16.9 16.3 0.89
22.4
46.8 0.19 1.70 2.30 0.10
26.0
9.74 0.04 0.23 0.36 0.21
11.0
8.41 0.18 0.15 0.05 0.05 0.04
55.3 0.38 2.12 2.37 0.12
39.1
35.5 1.80 6.35 6.07 0.45
32.8
110. 10.2 170 16.4 0.87
22.4
85. 50. 80. 97. 85. 66.
27. 2.5 3.6 6.0
47. 34.
77 1.7 0.9 0.3 5.3 0.2
P. 197 P.197 P.197 P.197 P.197 P.197
P.197 P.197 P.197 P.197 P.197 P.197
P.197 P.197 P.197 P.197 P.197 P.197
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
"Diff = Dup 1 - Dup 2. 'RPD = relative percent difference, calculated as Diff/Mean X 100; acceptance criteria +/-10%. "iSOP = standard operating procedure used for instrumental analysis of sample, here CERC SOP P.197. "two aliquants of sample 18107 extracted with 1N HCl followed by microwave evaporative digestion; units ug/g. 'two aliquants of sample 18109 extracted with 1 N HCl followed by microwave evaporative digestion; units ug/g. ^duplicate instrumental analysis of extract 18113; units are ug/L. "duplicate instrumental analysis of extract 18107; units are ug/L.
Table 15. Relative percent difference from the duplicate analysis of a sediment digestate (total recoverable quantitative analysis).
BID" Matrix Ele Dup 1 Dup 2 Diff" Mean RPD' ISOP" Oper. Init.
11/13/98 sediment digestate" 11 /13/98 sediment digestate" 11 /13/98 sediment digestate" 11/13/9'8 sediment digestate"
Zn
As
Cd
Pb
69.9
22.7
4.05
14.7
70.0
22.7
4.14
14.4
0.12
0.00
0.09
0.25
70.0
22.7
4.09
14.6
0.2
0.001
2.2
1.7
P.241
P.241
P.241
P.241
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the
"Diff = Dup 1 - Dup 2.
""RPD = relative percent difference, calculated as Diff/Mean X 100; acceptance criteria +/-10%.
"iSOP = standard operating procedure used for instrumental analysis of sample (C5.212).
"two aliquots of pore water sample #18104 (SED 1 B) spiked with SOppb Zn, 20ppb As, 4ppb Cd, and lOppb Pb and analyzed separately at the instrument (analysis duplicate).
23
Table 16. Percent relative standard deviation from the replicate extraction and/or evaporative digestion of samples for zinc, arsenic, cadmium, and lead (SEM quantitative analysis).
BID" Ele. Matrix Rep 1 Rep 2 Rep 3 Rep 4 Mean Units SD" Prep. Oper.
%RSD' PSOP" Init. ISOP" Init.
10/23/98
10/23/98
"
Zn 18113 SEM' As Ni Cu Cd Pb
Zn 18103 SEM MW^ As Ni Cu Cd Pb
22.8 2.29 3.15 .3.34 0.191
43.2
9.67 1.70 3.55 2.96 0.181 6.63
23.0 2.40 3.11 5.06 0.166
35.2
11.5 1.82 3.68 3.05 0.195 6.33
21.2 2.18 2.96 3.86 0.229
77.5
117 1.83 3.49 2.91 0.197 6.49
27.5 2.28 3.23 3.30 0.194
27.0
... — — — — —
23.6 2.29 3.11 3.89 0.195
45.7
11.0 1.78 3.58 2.97 0.191 6.48
ug/g ug/g ug/g ug/g ug/g ug/g
ug/g ug/g ug/g ug/g ug/g ug/g
2.70 0.089 0.114 0.821 0.026
22.2
1.13863 0.076 0.096 0.070 0.009 0.147
11. 3.9 3.7
21. 13. 49.
10. 4.3 2.7 2.3 4.7 2.3
P.197 P.197 P.197 P.197 P.197 P.197
P.197 P.197 P.197 P.197 P.197 P.197
JWA JWA JWA JWA JWA JWA
JWA JWA JWA JWA JWA JWA
P.197 P.197 P.197 P.197 P.197 P.197
P.197 P.197 P.197 P.197 P.197 P.197
WGB WGB WGB WGB WGB WGB
WGB WGB WGB WGB WGB WGB
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
SD = standard deviation.
'%RSD = percent relative standard deviation.
PSOP = standard operating procedure used for chemical preparation of sample.
"iSOP = standard operating procedure used for instrumental analysis of sample.
four aliquants of sample 18113 extracted with 1 N HCl followed by microwave evaporative digestion; units ug/g.
^three aliquots of SEM extract 18113 subjected to microwave evaporative digestion; units ug/g.
Table 17. Percent relative standard deviation from triplicate preparation and analysis of a sediment sample (total recoverable quantitative analysis). ,
BID"
11/13/98
11/13/98
11/13/98
11/13/98
11/13/98
11/13/98
11/13/98
11/13/98
*
Ele.
Zn
As
Cd
Pb
Zn
As
Cd
Pb
Matrix
18104'
18104'
18104'
18104'
18108^
18108^
18108^
18108«
Rep 1
39.0
5.6
0.14
8.4
33.7
2.9
0.1
7.4
Rep 2
35.0
5.4
0.1
8.3
43.4
2.3
0.1
1134.
Rep 3
40.2
5.9
0.16
9.4
38.5
1.6
0.1
21.4
Mean
38.1
5.6
0.14
8.7
38.5
2.3
0.11
388.
Units
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
ug/g
SD"
2.742
0.223
0.015
0.617
4.841
0.639
0.042
646.
%RSD'
7.2
4.0
10.
71
13.
28.
39.
167.
PSOP"
P.281
P.281
P.281
P.281
P.281
P.281
P.281
P.281
Prep.
Init.
JWA
JWA
JWA
JWA
JWA
JWA
JWA
JWA
ISOP"
P.241
P.241
P.241
P.241
P.241
P.241
P.241
P.241
Oper.
Init
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
SD = standard deviation.
'%RSD = percent relative standard deviation.
"PSOP = standard operating procedure used for chemical preparation of sample.
"iSOP = standard operating procedure used for instrumental analysis of sample.
sample 18104 digested in triplicate and analyzed.
^sample 18108 digested in triplicate and analyzed.
25
Table 18. Relative percent difference from the duplicate analysis of samples for AVS.
Analysis Date
10/23/98 10/23/98
Ele.
S S
Matrix
18107 AVS 18109 AVS
Dup 1
8.385 4.976
Dup 2
7.609 4.302
Mean
7.997 4.639
Units
umol/g umol/g
Diff^
0.776 0.674
RPD"
10. 15.
PSOP
P.197 P.197
Prep. Init.
JWA JWA
ISOP'
P.197 P.197
Oper. Init
WGB WGB
"Diff = Dup 1 - Dup 2. "RPD = relative percent difference, calculated as Diff/Mean X 100; acceptance criteria +/-10%
'iSOP = standard operating procedure used for instrumental analysis of sample.
26
Table 19. Percent relative standard deviation from the replicate extraction of sediment for AVS.
BID"
10/23/98
Ele.
S
Matrix
18113 AVS'
Rep 1
1.291
Rep 2
0.501
Rep 3
0.502
Rep 4
0.535
Mean
0.7
Units
umol/g
SD"
0.39
%RSD'
55.
PSOP"
P.197
Prep.
Init.
JWA
ISOP"
P.197
Oper.
Init.
WGB
"BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
SD = standard deviation.
'%RSD = percent relative standard deviation.
PSOP = standard operating procedure used for chemical preparation of sample.
"iSOP = standard operating procedure used for instrumental analysis of sample,
'four aliquants of sample 18113 extracted with 1 N HCl followed by sulfide detemiination.
27
Table 20. Percent relative standard deviation in elemental concentrations from replicate^ sediment samples (semi-quantitative analysis).
Ele Rep1 Rep2 Rep 3 Mean SD RPD Ele Repi Rep2 Rep 3 Mean SD RPD
Li Be B
Na Mg Al K
4.9 0.269 1.0
146. 4696. 4187.
802. Ca 12917. Ti V
Cr Mn Fe Co Ni
Cu Zn Ga Ge As Br Rb Sr Y
Zr Nb Mo Ru Pd Ag Cd In
Sn
69.6 14.5 8.4
353. 7235.
5.4 13.3 8.9
56.3 3.0 0;073 6.5
11.1 87
45.0 7.9 2.4 0.109 0.354
0.0 0.026 0.040 0.634 0.014 0.140
5.0 0.316 0.6
155. 4774. 4084.
811. 13405.
71.8 13.8 7.6
344. 6962.
5.4 127 7.4
46.1 3.1 0.075 6.4
11.8 8.4
42.7 8.1 27 0.128 0.298
0.0 0.016 0.036 0.241 0.014 0.219
5.1 0.351 1.5
136. 4631. 4351.
817 13384.
73.5 14.9 8.5
353. 7729.
5.9 14.1 7.4
51.5 3.3 0.078 6.8
13.3 9.0
44.7 7.9 2.5 0.096 0.347
0.0 0.032 0.034 0.257 0.010 0.196
5.0 0.312 1-1
146. 4701. 4207.
810. 13236.
71.6 14.4 8.2
350. 7309.
5.6 13.3 7.9
51.3 3.1 0.075 6.5
12.1 87
44.1 7.9 2.5 0.111 0.333
0.025 0.037 0.378 0.013 0.185
0.111 0.041 0.446 9.6
72. 135.
7.4 276.
2.0 0.554 0.468 5.5
389. 0.249 0.722 0.873 5.1 0.169 0.002 0.184 1.1 0.340 1.3 0.094 0.181 0.016 0.031
0.008 0.003 0.223 .0.002 0.040
2. 13. 42.
7. 2. 3. 1. 2. 3. 4. 6. 2. 5. 4. 5.
11. 10. 5. 3. 3. 9. 4. 3. 1. 7.
14. 9.
32. 8.
59. 18. 22.
Sb 0.158 Te 0.034
I 0.101 Cs 0.684 Ba 231. La 12.3
21.4 3.4
11.8 2.3
0.105. 0.122
Ce Pr Nd Sm Eu Gd Tb Dy Ho Er
Tm Yb Lu Hf Ta W Re Os
Ir Pt
Au TI
Pb Bi U
0.500 2.4 0.304 1.7 0.271 0.688 0.093 0.650 0.091 0.071 0.002 0.014 0.0 0.0 0.0 0.012 0.267 0.109
11.3 0.071 0.532
0.030 0.073 0.676
200. 12.0 23.1 3.5
11.9 2.5 0.488 2.4 0.304 17 0.269 0.688 0.091 0.642 0.085 0.083 0.002 0.012 0.0 0.0 0.0 0.0 0.020 0.105 6.8 0.065 0.528
0.044 0.098 0.737
208. 12.8 237 3.5
12.1 2.3 0.505 2.4 0.305 17 0.275 0.709 0.094 0.691 0.088 0.076 0.002 0.014 0.0 0.0 0.0 0.0 0.052 0.110 8.3 0.074 0.559
0.128 0.036 0.090 0.699
213. 12.4 22.7 3.5
12.0 2.3 0.498 2.4 0.304 17 0.272 0.695 0.093 0.661 0.088 0.077 0.002 0.013
0.027 0.007 0.015 0.033
16. 0.408 1.2 0.076 0.181 0.116 0.009 0.020 0.001 0.035 0.003 0.012 0.001 0.026 0.003 0.006 0.000 0.001
0.113 0.134 0.108 0.002 8.8 2.3 0.070 0.005 0.540 0.017
21. 20. 17. 5. 8. 3. 5. 2. 2. 5. 2. 1. 0. 2. 1. 2. 1. 4. 3. 8. 1. 8.
119. 2.
26. 7. 3.
hre^^miots ^ ^£RC ^ ^ ^ 4 ( S g ^ ^ ) s^^^e ly c ^ ^ ^ d ai^^^lyzi
Table 21. Percent relative standard deviation in elemental concentrations from replicate^ sediment samples (semi-quantitative analysis).
Ele Repi Rep2 Rep 3 Mean SD RPD Ele Repi Rep2 Rep 3 Mean SD RPD
Li Be
8 Na Mg AI K
1.0 0.080 0.278
96.7 1214. 871. 190.
Ca 45454. Ti V
Cr Mn
32.9 3.9
32.5 177.
Fe 10728. Co Ni
Cu Zn Ga Ge As Br
Rb Sr Y
Zr Nb Mo Ru Pd Ag Cd In
Sn
2.7 28.9 27.3 51.1
1.0 0.110 3.7
12.3 1.9
98.4 2.4 1.2 0.187 9.5 0.002 0.017 0.222 0.239 0.002 3.0
1.1 0.049 1.3
129. 1332. 1527.
192. 29082.
74.5 3.6 3.5
62.6 3028.
1.6 3.4 5.7
60.4 0.941 0.043 27
10.0 1.9
72.2 3.7 2.1 0.059 1.3 0.0 0.016 6.6 0.179 0.028 1.8
0.894 0.079 0.435
113. 975. 816. 161.
45671. 26.8 3.5 4.3
84.4 3690.
1.4 3.4 73
50.4 0.660 0.036 17
11.6 1.4
82.5 2.2 1.3 0.096 4.5 0.0 0.015 0.204 0.234 0.002 4.7
1.0 0.069 0.678
113. 1174. 1071.
181. 40069.
44.7 3.7
13.5 108.
5815. 1.9
11.9 13.5 54.0 0.880 0.063 2.7
11.3 17
84.4 2.8 1.5 0.114 5.1 — 0.016 2.3 0.217 0.011 3.2
0.106 0.018 0.562
16.2 182. 396.
17.2 9516.
25.9 0.183
16.5 61.0
4267. 0.698
147 12.0 5.6 0.196 0.041 1.0 1.2 0.262
13.2 0.793 0.485 0.066 4.1 —
0.001 3.7 0.033 0.015 1.4
11. 26. 83. 14. 15. 37.
9. 24. 58.
5. 123. 56. 73. 37.
124. 89. 10. 22. 65. 36. 11. 15. 16. 29. 32. 58. 81. —
6. 157
15. 141. . 45.
Sb Te
I Cs Ba La Ce Pr
Nd Sm Eu Gd Tb Dy Ho Er
Tm Yb Lu Hf Ta W Re Os
Ir Pt
Au TI
Pb Bi U
0.646 0.030 0.080 0.132
34.0 5.0
10.3 1.3 4.2 0.817 0.153 0.772 0.099 0.556 0.086 0.231 0.035 0.226 0.030 0.037 0.007 0.526 0.0 0.0 0.0 0.0 0.644 0.032 8.2. 0.052 0.541
0.758 4.7 0.041 0.122
85.5 7.6
10.9 1.9 5.9 1.1 0.169 1.0 0.142 0.762 0.122 0.327 0.045 0.299 0.039 0.067 0.002 0.037 0.0 0.0 0.0 0.0 0.321 0.030
992. 7.3 0.476
0.382 0.017 0.049 0.117
26.0 4.9 7.2 1.2 4.0 0.688 0.132 0.690 0.087 0.503 0.076 0.208 0.028 0.193 0.028 0.034 0.002 0.040 0.0 0.0 0.0 0.0 0.098 0.032
21.5 0.053 0.565
0.595 1.6 0.057 0.124
48.5 5.9 9.5 1.5 4.7 0.884 0.151 0.836 0.109 0.607 0.095 0.256 0.036 0.239 0.032 0.046 0.004 0.201 — — — — 0.354 0.031
341. 2.5 0.527
0.193 2.69 0.021 0.008
32.3 1.51 1.96 0.355 1.01 0.236 0.019 0.186 0.029 0.137 0.024 0.063 0.009 0.054 0.006 0.018 0.003 0.282
— — — — 0.274 0.001
564. 4.17 0.046
32. 171. 37.
6. 67. 26. 21. 24. 21. 27. 12. 22. 27. 23. 25. 25. 24. 23. 18. 40. 80.
140. — —
• —
— 78.
2. 166. 169.
9.
^Throo aitnr rnfe nf CPRC #18108 /SED 4 B) seoaratelv dloested and analyzed.
Table 22 . Percent recovery of elements from a spiked blank and sediment extract (SEM quantitative analysis).
BID"
10/23/98 10/23/98 10/23/98 10/23/98 10/23/98
10/23/98 10/23/98 10/23/98 10/23/98 10/23/98 10/23/98
Ele.
Zn As Cu Cd Pb
Zn As Ni Cu Cd Pb
Spk Type
Blank SEM Blank SEM Blank SEM Blank SEM Blank SEM
18103-Analytical 18103-Analytical 18111 -Analytical 18111 -Analytical 18103-Analytical 18103-Analytical
Matrix
Sed. Ext. Sed. Ext. Sed. Ext. Sed. Ext. Sed. Ext.
Sed. Ext. Sed. Ext. Sed. Ext. Sed. Ext. Sed. Ext. Sed. Ext.
Analysis Units
ug/L ug/L ug/L ug/L ug/L
ug/L ug/L ug/L ug/L ug/L ug/L
Spk Amt."
ug
200. 10. 20. 10. 20.
10. 1. 2. 2. 0.4 1.
Vol.
(L)
0.100 0.100 0.100 0.100 0.100
0.100 0.100 0.100 0.100 0.100 0.100
Effective' Cone.
2000. 100. 200. 100. 200.
100. 10. 20. 20.
4. 10.
Bkgd." Cone.
64.2 0.53 1.05 0.48
14.4
44.6 6.32 4.88 1.97 0.71 2.63
Total" Cone.
2000. 107. 198. 104. 198.
138. 17.2 24.3 21.0
5.27 12.8
% Rec'
97. 107. 99.
103. 92.
94. 109. 97. 95.
114. 101.
Spk/8kgd
31. 188. 190. 210.
14.
2. 2. 4.
10. 6. 4.
ISOP
P.197 P.197 P.197 P.197 P.197
P.197 P.197 P.197 P.197 P.197 P.197
Oper. Init.
JW/VWGB JW/VWGB JW/VWGB JW/VWGB JWAAVGB
JW/VWGB JWAAWGB JWAAA/GB JWA/WGB JWA/WGB JWA/WGB
"BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
as a member of the group or "block."
Spike Amt. ug = the absolute microgram (ug) amount of the spike which was added to a sample.
'Effective Cone. = the Spike Amt (ug) divided by the total solution volume, units ug/L.
Bkgd Cone. = the measured concentration of the sample prior to spiking, units ug/L.
"Total C^nc. = the measured concentration of the spiked sample (spike + background, units ug/L.
'% Rec. = percent recovery: [(Total Cone. - Bkgd Cone.)/Effecfive Cone. * 100]
Table 23. Percent recoveries of sulfide in a blank AVS extract.
BID" Ele. Spike Form
Amt." uMoI
Matrix Total uMol' Meas.
Bkgd." uMol
Spk/Bkdg" Spk/Bkgd" SD
% R E C ' PSOP Prep. Init.
ISOP Oper. Init.
10/23/98 10/23/98 10/23/98
S S S
NaS NaS NaS
307 307 307,
Blank Blank Blank
236.8 264.3 2707
0.0 0.0 0.0
00
00
00
n/a n/a n/a
77. 86. 88.
P.197 P.197 P.197
JWA JWA JWA
P.197 P.197 P.197
WGB WGB WGB
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
Amt uMol = the absolute uMol amount of the spike in the form listed in column 3 which was added to a sample.
"Total uMol Meas. = the micromoles (uMol) of the analyte in the sample spike measured by the instrument (spike + background),
"skgd (uMol) = background amount of the blank in pMol.
"Spk/Bkgd = the ratio of the spike amount added (column 4) divided by the mean sample background concentration (column 7).
'%REC = Total uMol Meas. (column 6) - Bkgd. uMol (column 7) divided by the Amt. uMol (column 4) X 100.
°N/A = not applicable; standard deviation of background was 0.0.
31
Table 24. Percent recovery of elements from a spiked blank and spiked sediment digestates (total recoverable quantitative analysis).
BID"
11/13/98 11/13/98 11/13/98 11/13/98
11/13/98 11/13/98 11/13/98
11/13/98 11/13/98 11/13/98
Ele.
Zn As Cd Pb
Zn Cd Pb
Zn Cd Pb
Spk Type
18106-Analytical 18106-Analytical 18106-Analytical 18106-Analytical
Blank - Method Blank - Method Blank - Method
18014-Method 18014-Method 18014-Method
Analysis Units
ng/mL ng/mL ng/mL ng/mL
ug/g ug/g ug/g
ug/g ug/g ug/'g
Spk Amt." (ng) or (ug)
(ng) 500. 200. 40.
100.
(ug) 1000.
100. 1000.
(ug) 1000. 100.
1000.
Vol (mL) or Wgt (g)
(mL) 10. 10. 10. 10.
(g) 0.5 0.5 0.5
(g) 0.503 0.503 0.503
Effective' Cone.
50. 20. 4.
10.
. 2000. 200.
2000.
1988. 199.
1988.
Bkgd." Cone.
17.2 3.1 0.12 3.54
1.01 0.10 0.25
38.08 0.14 8.71
Total" Cone.
62.5 22.8 4.00
12.9
2065. 209.
2067.
2081. 203.
1945.
% Rec'
91. 98. 97. 94.
103. 104. 103.
103. 102. 97.
ISOP
P.241 P.241 P.241 P.241
P.241 P.241 P.241
P.241 P.241 P.241
Oper. Init.
RHW/TWM RHW/TWM RHW/TWM RHW/TWM
RHW/TWM RHW/TWM RHW/TWM
RHW/TWM RHW/TWM RHW/TWM
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
as a member of the group or "block."
"Spike Amt. = the absolute nanogram (ng) or microgram (ug) amount ofthe spike which was added to a sample (CERC# 18106 and 18104 used for spiking).
'Effective Cone. = the Spike Amt (ng or ug) divided by the total solution volume (mL) or dry weight (g); units ng/mL or ug/g.
Bkgd Cone. = the measured concentration of the sample prior to spiking, units ng/mL.
"Total Cone. = the measured concentration of the spiked sample (spike + background, units ng/mL).
/% Rec. = percent recovery: [(Total Cone. - Bkgd Conc.)/Effective Cone. * 100]
32
Table 25. Recovery of elements from blank and sample spikes (semi-quantitative analysis).
Analysis Spike: Spiked
Element
Be V Cr Mn Co Ni Cu Zn As -Ag Cd Sb Ba Tl Pb
Spike Amt (ug/L)
50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50.
Blank Method Spike: Spiked
' Element
1 ' 1 Fe
Cu
1 " 1 Cd
Pb
_ Sediment 1 Spiked ' Element
1 ^ 1 Fe
Cu
1 ^^ 1 Cd
Pb
•
Spike Amt (ug)
10000. 10000.
500. 1000.
100. 1000.
Bkgd Cone
0.11 5.47 • 3.93
135.17 2.72 6.31 2.58 27.19 3.74 0.06 0.10 0.24
131.20 0.03 18.43
Wgt (g)
0.5 0.5 0.5 0.5 0.5 0.5
Method Spike": Spike
Amt(ug) Wgt(g)
10000. 10000.
500. 1000.
100. 1000.
0.503 0.503 0.503 0.503 0.503 0.503
Total Cone
53. 51. 49.
181. 48. 56. 51. 84. 59. 49. 52. 50.
179. 39. 57.
Effective Cone ug/g
20000. 20000.
1000. 2000.
200. 2000.
Effective Cone ug/g
20000. 20000.
1000. 2000.
200. 2000.
% Rec
106. 92. 89. 92. 91. 99. 97.
113. 111. 99.
103. 100. 95.. 77. 77.
Bkgd Cone
0.59 13.96 0.15 2.18 0.11 0.34
Bkgd Cone
4207.08 7308.69
7.90 51.29
0.38 8.79
Total Cone
21015. 15761.
979. 2217.
218. 1750.
Total Cone
20653. 21333.
826. 1946. 205.
1304.
•
Spk/Bkgd Ratio
33937. 1433. 6818.
916. 1754. 5803.
Spk/Bkgd Ratio
4.8 2.7
127. 39.0
530. 228.
% Rec
105. 79. 98.
111. 109. 87.
% Rec
82. 70. 82. 95.
102. 65.
"CERC #18104 (SED 1 B) used for spiking.
33
Table 26. Interference check using dilution percent difference (SEM quantitative analysis).
BID"
10/23/98
10/23/98
10/23/98
10/23/98
10/23/98
10/23/98
Run Date
11/05/98
11/05/98
12/03/98
12/03/98
11/05/98
11/05/98
Matrix
Type
Sed. Ext."
Sed. Ext."
Sed. Ext."
Sed. Ext."
Sed. Ext."
Sed. Ext."
Element
Zn
As
Ni
Cu
Cd
Pb
Undiluted
Sample
83.3
12.4
18.1
157
1.4
45.5
Diluted
Sample"
8.53
1.45
3.83
3.34
0.15
5.11
% Diff
2.5
16.1
6.2
6.2
9.6
12.3
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
"dilution factor = 10 for 11/05/98 mn date, 5 for 12/03/98 run date.
'dilution % difference acceptance criteria = +/-10%; concentrations exceeding +/-10%. indicative of suspect interferent.
"sediment extract used for dilution check was from sample 18103.
"sediment extract used for dilution check was from sample 18113.
34
Table 27. Interference check using dilution periient difference (total recoverable quantitative analysis).
BID"
11/13/98 11/13/98 11/13/98 11/13/98
Run Date
12/2/98 12/2/98 12/2/98 12/2/98
Element
Zn As Cd Pb
Undiluted
Sample
84.7 24.
4.3 19.8
Diluted
Measured
17.9 5.0 0.88 4.0
Sample
" Final
89.3 25.
4.4 20.2
% Diff
5.5 4.2 2.2 2.1
"BID
b .-I
Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
dilution factor = 5 (1+4).
'dilution % difference acceptance criteria = +/-10%; concentrations exceeding +/-10%. indicative of suspect interferent.
"sample #18110 (SED 5 B) spiked with SOppb Zn, 20ppb As, 4ppb Cd, and lOppb Pb and used for dilution check.
35
Table 28. Recovery of elements from an interference check solution^ (SEM quantitative analysis).
BID Run Date Cone (ppb) Cone (ppb) Dilution
Element measured actual Factor % Rec'
10/23/98 10/23/98 10/24/98 10/25/98 10/23/98 10/23/98
11/05/98 11/05/98 12/03/98 12/03/98 11/05/98 11/05/98
Zn As Ni Cu . Cd Pb
100. 100. 200. 100. 50.
100.
22. 18. 33. 19. 12. 17.
5 5 5 5 5 5
110. 92. 83. 95.
118. 83.
"High Purity ICP-MS Solution AB in 2% nitric acid, Charleston, SC; CAT # ICP-MS-ICS.
suggested acceptance tolerance 80% -120%.
I 36 I
Table 29. Recovery of elements from an interference check solution' (total recoverable quantitative analysis).
Cone (ppb) Cone (ppb) Dilution BID Run Date Element measured actual Factor % Rec."
11/13/98 11/13/98 11/13/98
-.11/13/98
12/2/98 12/2/98 12/2/98 12/2/98
Zn As Cd Pb
19.2 17.0 11.1 19.7
20. 20. 10. 20.
5 5 5 5
96. 85.
111. 99.
"High Purity ICP-MS Solution AB in 2% nitric acid. Charleston, SC; CAT # ICP-MS-ICS.
'suggested acceptance tolerance 80% -120%.
37
Table 30. Blank equivalent concentrations for the SEM procedure (SEM quantitative analysis).
BID Blank Type Element
Solution Concentration (ng/mL) Rep 1 Rep 2 Rep 3
10/23/98 SEM-MW" Zn As Ni Cu Cd Pb
14.7 0.059 7.33 0.198 0.098 3.00
117 0.147 6.70 0.205 0.095 2.80
12.1 0.113 6.13 0.228 0.092 2.85
Dry Weight Equivalent Concentration (ug/g) Rep 1 Rep 2 Rep 3 Mean Std Dev
1.84 0.007 0.916 0.025 0.012 0.38
1.46 0.018 0.838 0.026 0.012 0.35
1.51 0.014 0.767 0.029 0.012 0.36
1.61 0.013 0.84 0.026 0.012 0.36
0.21 0.0056 0.075 0.0020 0.0004 0.014
"SEM-MW= Rep 1 extracted with 1N HCl and then subjected to evaporative boildown; Rep 2 and Rep 3 are aliquots of the Rep 1 SEM extract taken prior to the evaporative boildown and then subjected to the boildown.
38
Table 31. Blank equivalent concentrations for total recoverable quantitative analysis.
BID Blank Solution Concentration (ng/mL) Type Element Rep 1 Rep 2 Rep 3
11/13/98 Method" Zn As Cd Pb
4.4 0.084 -0.99 3.37
-2.6 0.045 0.21 0.33
13.4 0.19 0.23 0.13
Dry Weight Equivalent Concentration (ug/g) Rep 1 Rep 2 Rep 3 Mean Std Dev
0.87 0.017 0.20 0.67
-0.53 - 0.009
0.043 0.07
2.68 0.038 0.047 0.03
1.01 0.015 0.096 0.25
1.61 0.0237 0.0889 0.363
"Method= triplicate reagent blanks subjected to acid digestion (P.281).
39
Table 32.. Blank equivalent concentrations (ug/g dry weight) of elements in digestion blanks analyzed with sediment (semi-quantitative analysis).
Ele
Li Na Mg A! K
Ca Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Rb Sr Y Zr Nb Mo Ru Pd Ag Cd In Sn
BEC B lk l
0.016 89.2
9.3 1.0 8.3
20.6 - 0.022
0.078 0.378 0.008
12.3 0.004 0.106 0.354 1.9 0.000 0.000 0.048 0.004 0.064 0.000 0.024 0.000 0.070 0.000 0.000 0.070 0.246 0.000 0.408
BEC Blk 2
0.004 19.0
1.3 0.3 5.3
17.3 0.024 0.024 0.204 0.002
20.2 0.000 0.030 0.048 0.15 0.000 0.000 0.042 0.002 0.028 0.000 0.004 0.000 0.026 0.000 0.000 0.018 0.044 0.000 0.116
BEC Blk 3
0.004 102.
1.9 0.428 6.9
13.8 0.006 0.030 0.192 0.012 9.4 0.004 0.036 0.038 4.5 0.000 0.000 0.072 0.002 0.126 0.000 0.004 0.002 0.020 0.000 0.000 0.012 0.052 0.000 0.068
Mean BEC
0.008 70.1 4.2 0.59
6.8 17.2 0.003 0.044 0.258 0.007
14.0 0.003 0.057 0.147 2.2 0.000 0.000 0.054 0.003 0.073 0.000 0.011 0.001 0.039 0.000 0.000 0.033 0.114 0.000 0.197
Ele
Sb Te Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Er
Tm Yb Lu Hf Ta W Re Os Ir Pt Au Tl Pb Bi U
BEC B l k l
0.214 0.000 0.000 0.018 0.008 0.018 0.000 0.004 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.004 0.000 0.000 0.000 0.000 0.000 0.716 0.006 0.842 0.002 0.000
BEC Blk 2
0.052 0.000 0.000 0.000 0.002 0.006 0.000 0.002 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.184 0.000 0.120 0.002 0.000
BEC Blk 3
0.026 0.000 0.000 0.000 0.000 0.004 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.000 0.000 0.000 0.000 0.000 0.084 0.000 0.072 0.000 0.000
Mean BEC
0.097 0.000 0.000 0.006 0.003 0.009 0.000 0.002 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.000 0.000 0.000 0.000 0.000 0.328 0.002 0.345 0.001 0.000
40 I
Table 33. Instrument detection limits, method detection limits, and limits of quantitation for SEM (SEM quantitative analysis).
BID Run Date" Element Std Cone" Blk SD 1 ' Blk SD 2 Blk SD 3 IDL" MDL" L O Q ' ISOP Oper. Init.
10/23/98 10/23/98 10/23/98 10/23/98 10/23/98 10/23/98
05/08/98 05/08/98 05/08/98 05/08/98 05/08/98 05/08/98
Zn As Ni Cu Cd Pb
0.0 0.0 0.0 0.0 0.0 0.0
0.041772 0.007909 0.0247
0.015674 0.015171 0.020417
0.0284181 0.0137351 0.8161418 0.0950397 0.0057909 0.0231045
0.10850 0.00938 0.00661 0.00738 0.00303 0.00364
0.179 0.031 0.847 0.118 0.024 0.047
0.490 0.023 0.017 0.011 0.010 0.033
1.62 0.08 0.06 0.04 0.03 0.11
P.241 P.241 P.241 P.241 P.241 P.241
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
"date of 3rd non-consecutive day analysis, following which IDL was computed.
concentration of low level standard used in analysis in ppb, which was reagenfblank or 0 cone standard,
'standard deviation from analysis of 0 standard (reagent blank) 7 consecutive times in one day.
IDL = instrument detection limit (ng/mL), computed as 3 X mean of standard deviations.
"MDL = method detection limit (ng/mL), computed as 3 X (SDb + SDj ) where SDb = standard deviation of a blank (n = 3) and
SDj = standard deviation of a low level sample or spiked sample (n = 3); units are ug/g dry weight.
LOQ = limit of quantitation (ug/g dry weight), computed as 3.3 X the MDL.
41
Table 34. Instrument detection limits, method detection limits, and limits of quantitation for the analytes of interest (total recoverable quantitative analysis). ,,
BID Run Date" Element Matrix Std Cone" B I k S D I ' Blk SD 2 Blk SD 3 IDL" MDL" LOQ' ISOP Oper. Init.
11/13/98 11/13/98 11/13/98 11/13/98
5/8/98 5/8/98 5/8/98 5/8/98
Zn As Cd Pb
sediment sediment sediment sediment
0.0 0.0 0.0 0.0
' 0.04177 0.00791 0.01517 0.02042
0.02842 0.01374 0.00579 0.02310
0.10850 0.00938 0.00303 0.00364
0.179 0.031 0.024 0.047
5.11 0.31 0.27 1.12
16.9 1.04 0.88 3.71
P.241 P.241 P.241 P.241
RHW/TWM RHW/TWM RHW/TWM RHW/TWM
date of 3rd non-consecutive day analysis, following which IDL was computed.
"concentration of low level standard used in analysis in ppb, which was reagent blank or 0 cone standard,
'standard deviation from analysis of 0 standard (reagent blank) 7 consecutive times in one day.
IDL = instrument detection limit (ng/mL), computed as 3 X mean of standard deviations.
"MDL = method detection limit (ng/mL), computed as 3 X (SDt, + SDg ) where SD5 = standard deviation of a blank (n = 3) and
SDg = standard deviation of a low level sample or spiked sample (n = 3).
' L O Q = limit of quantitation ng/mL, computed as 3.3 X the MDL.
42
QUANTITATIVE AND SEMI-QUANTITATIVE DETERMINATION OF METALS IN WATER SAMPLES FROM THE VICINITY OF THE
ASARCO SMELTER IN OMAHA, NE
Final Report FY99-32-03
Thomas May, Ray Wiedmeyer, and Bill Brumbaugh
U.S. Department of the Interior U.S. Geological Survey
Biological Resources Division Columbia Environmental Research Center
4200 New Haven Road Columbia, MO 65201
December 7, 1999
PREPARED FOR
U.S. Environmental Protection Agency 726 Minnesota Avenue
Kansas City, Kansas 66101
lAG DW14952122-01
U. S. Geological Survey Biological Resources Division
Columbia Environmental Research Center 4200 New Haven Road
Columbia, MO 65201-9634
TABLE OF CONTENTS
Sample H i s t o r y 3
Methods 3-4
Results and Discussion 4-5
Quality Control ' 5-6
Tables:
Sample Data . .7-11
Instrumental Calibration. . . . 12, 21
Reference/Research Materials 13 , 21
Method Precision 22
Instrumental Precision 15, 19-20
Post-Digestion Spikes. . 14, 23
Instrument Detection Limit 18
Method Detection Limit and Limit of Quantitation .18
Interference Checks 16-17
Quantitative and Semi-Quantitative Determination of Metals in Water Samples from the vicinity of the ASARCO Smelter in Omaha, NE
SAMPLE HISTORY:
A total of 13 water samples was received by the Inorganic Chemistry section of the Columbia Environmental Research Center (CERC) on 10/8/98. Once received by the Inorganic Section, the samples were assigned a Batch # (491) and. CERC identification #s (18091 - 18102 and 18116). The samples were collected on October 5, 1998 by Duane Chapman, Steve- Olson, Barry Poulton, and Mark Laustrup. The samples were filtered through a 0.45 um membrane with a Geotech filtration unit, placed in 4 oz precleaned polyethylene bottles, and preserved by acidification with nitric acid (1% v/v) . Another group of 9 water samples were received on 10/23/98, which consisted of post-test porewaters and CERC well water, RO water, or reconstituted water made from those sources. These samples were assigned a Batch # (4 94) and CERC •identification #s (18201 - 18209) . For both groups of samples, analyses requested included a quantitative analysis for zinc, arsenic, cadmium, and lead, and a semi-quantitative analysis for a comprehensive list of elements. The purpose of this report is to provide analytical data for evaluating the presence and bioavailability of certain elemental contaminants.
METHODS:
No further chemical preparation was conducted on the samples prior to instrumental analysis. Samples were first subjected to a semiquantitative analysis by ICP-MS (SOP P.458) to indicate concentrations of other elements of interest, to reveal the presence of unexpected elements, to determine optimal dilutions for quantitative analysis, and to identify samples appropriate for QC purposes in the cjuantitative run. All samples were prediluted lOX because of matrix components, while one sample recjuired further dilution (50X) due to high sodium levels. A multiple-element control solution (Trace Metals in Drinking Water, High Purity CRM-TMDW) was used as the external standard to which 5 other elements were added (Pr, Tb, Tm, Ta, and Au) to better represent the rare-earth region of the mass spectral range. All samples were delivered to the ICP-MS by a CETAC ASX-500 autosampler system coupled with a Gilson peristaltic pump. The internal standards were Sc, Rh, and Th (all -lOppb) delivered via peristaltic pump into the sample line. The semi-cjuantitative scan is reported to be H 3 0% to 4-50% in accuracy by the manufacturer. The final elemental list reported was dependent upon individual element behavior as judged by cjuality control results.
For the quantitative analysis run, the analysis was conducted with a PE/SCIEX Elan 6000 ICP-MS, which was set up and optimized according to the manufacturer's specifications and described in ECRC SOP P.241. Samples were delivered to the ICP-MS as described above for the semi-quantitative scan. All samples were prediluted lOX, with one sample requiring 50X. The internal standards were Ge (50 ppb) for Zn and As, Rh (10 ppb) for Cd, and Bi (10 ppb) for Pb, which were metered into the sample line via peristaltic pump. Calibration standards for analysis were dependent on the analyte: Zn- 25, 50, and 100 ng/mL; As- 10, 20, and 40 ng/mL; Cd-2, 4, and 8 ng/mL; and Pb- 5, 10, and 20 ng/mL. Masses monitored included Zn-66 and Zn-68, As-75, and Cd-111 and Cd-114. Lead was monitored and reported as the sum of three isotopes (Pb-2 06 + Pb-207 + Pb-208) . Only one mass was reported for Zn and Cd (Zn-66 and Cd-114).
RESULTS AND DISCUSSION:
Quant i ta t ive Analysis : Concentrations of Zn, As, Cd and Pb in water samples determined by quantitative ICP-MS analysis are indicated in Table 1. Table la consists of those samples generated during the ASARCO field sampling effort, whereas Table lb includes samples provided at CERC following the field sampling event. The "post- test" porewaters (#18205 - #18208) were taken from containers from which an aliquot was taken for daily toxicity testing. The remainder of the samples (#18201 - #18204 and #18209) were CERC well water, RO water or reconstituted water (Recon) made from those sources. Highest concentrations of Zn, As, and Cd were found in sample #18099 (Table la) , which was water taken from the well on the ASARCO smelter site. The highest concentration of Pb was found in a sediment porewater sample (#18095). As a general group, the sediment porewater samples (#18091 - #18096) contained the next highest concentrations of analytes, followed by river water (#18097 and #18098), and finally the filtration blanks (#18100 and #18101). One of these blanks (#18100) showed signs of apparent Zn and Cd contamination. Sample #18116 was a reference water solution provided by the U.S. EPA. Results for the field duplicate porewater sample (#18091 and #18102) exhibited excellent agreement for As, good agreement for Pb, but poorer agreement for Zn and Cd. Analyte concentrations in post-test porewaters (#18206 - #18208, Table lb) were generally lower than concentrations in pre-test porewaters (Table la) . Greater reductions were observed for Zn and Pb concentrations in post-test waters than for Cd. Dilution concentrations of 6.25% MW19 (#18205, Table lb) agreed reasonably well when compared to 6.25% of the concentrations obtained for the full strength pre-test sample (#18099, Table la).
I I I I I
Semi-Quantitative A n a l y s i s : Results from the semi-quantitative scan (Table 2) revealed that the ASARCO well water sample contained considerably higher concentrations of numerous elements (Li, B, Na, K, Ca, Ti, Co, Ni, Cu, Zn, As, Br, Rb, Sr, Mo, Cd, Sb, Cs, and W) when compared with concentrations of these elements in the remaining samples. Concentration results for the field duplicate (#18091 and #18102) showed good agreement for most elements, with the exceptions of Ni, Zn and Cd. As a general rule, where measurable concentrations of elements were present, porewater samples (#18091 - 18096) contained higher concentrations than did river water (#18097 and #18098) . This was markedly apparent for Mn and Fe, but much less so for most of the remaining elements. There was good agreement between concentrations of Zn, As, Cd, Pb determined by quantitative analysis and by semi-quantitative scan. The most problematic element was Zn, especially for concentrations below 10 ppb.
QUALITY CONTROL:
Each sample block processed through the analytical flow scheme was assigned a BID (block initiation date), which included the following quality control for the quantitative determination of Zn As, Cd, and Pb by ICP-MS: duplicate analyses, dilution check, reference solutions, analysis spikes, an interference check, and calibration checks. For the semi-quantitative scan, the following quality control was included: a calibration check, an analysis spike, and a precision check. All quality control results were tabulated to provide an overview of quality assurance and to facilitate, interpretation.
Quanti tat ive Analysis: A calibration blank and an independent calibration verification standard were analyzed every 10 samples to confirm the calibration status of the ICP-MS (Table 3). Results from the analysis of two reference solutions are indicated in Table 4, with elemental recoveries ranging from 85% to 107%. Recovery of the elements from an analysis spike ranged from 99% to 115% (Table 5). Precision from the duplicate analyses of a water sample is indicated in Table 6 and ranged from 0.2 to 3.5 relative percent difference (RPD), depending on the analyte. As a check for potential interferences, a water sample was spiked with each analyte then diluted 5X, with the results being compared to the undiluted sample (Table 7). Dilution percent differences ranged from 1.7 to 9.3. A synthetic solution containing high concentrations of Al, Ca, Fe, Mg, Na, P, K, S, C, Mo, and Ti was analyzed to observed the effects of these interferences on Mn, Ni, Cu, Zn, As, Ag, and Cd (Table 8) . Recoveries ranged from 85% to 114%. Finally, the instrument detection limits, method detection
limits, and limits of cjuantitation for each analyte are indicated in Table 9.
Semi-quantitative A n a l y s i s : The multi-element reference solution (CRM-TMDW) that was used as the external standard in semi-quantitative analysis was also analyzed as a sample after every 10 samples to determine precision for the analytical run. The percent relative standard deviation (%RSD) ranged from 0.7% to 15%, depending on the element (Tables 10 and 11) . Recoveries of elements from a Spec calibration check standard are indicated in Table 12 and ranged from 85% to 123%, with the exception of Zn and As in Run #1 (170% and 137%). The relative percent differences (RPD) in elemental concentrations from a field duplicate porewater sample are indicated in Table 13. RPDs are < 40 for most elements having measurable concentrations. Poorer RPDs were noted for Ni, Zn, Cd, I, and Ce. Finally, results of an analysis spike are indicated in Table 14. Recoveries ranged from 84% to 138% for most elements, but poorer recoveries were observed for Zn (205%) and As (150%) in Run #1 and Mn (205%) in Run #2.
Overall, the cjuality control was considered within acceptable limits as specified by CERC.
Prepared By: Reviewed By:
Thomas W. May' William G. Brumbaugh Ray Wiedmeyer Research Chemist Research Chemists
Apprpved By:
Jim Petty Chief, Environmental Chemistry Branch
Table 1. Concentrations (ng/mL) of Zn, As, Cd, and Pb in water samples from the Omaha, NE, ASARCO study.
a. Samples from ASARCO field sampling.
CERC# Field ID Water Type Zn As Cd Pb
18100 18101 18097 18098 18099 18091 18102 18092 18093 18094 18095 18096 18116
Filtration Blk 1 Filtration Blk 2 RW1 RW2 MW19 SED1 C SED 1 C Dup. SED 2 0 SED4C SED5C SED 24 C SED 25 C 001
RO RO river river vyell
porewater porewater porewater porewater porewater porewater porewater reference
8.2 2.6
11.3 4.2
1570. 9.8
21.9 27.5 34.7 17.2 63.7 31.9 12.9
<0.07 <0.07
27 27
574. 30.7 30.4 15.6 23.1 56.3 4.0 7.7
13.3
1.0 0.03 0.79 0.52
21.5 0.15 1.2 0.67 0.67 0.49 1.1 0.77
18.1
0.23 0.49 0.50 0.64 2.6 3.4 5.2 17 8.4 2.2
11.5 5.0 4.9'
MDL" 0.42 0.07 0.02 0.04
"MDL = method detection limit (see Table 9).
b. CERC/ASARCO Post Test and Other Samples
CERC#
18201 18202 18203 18204 18205 18206 18207 18208 18209
MDL"
Field ID
ASARCO 1 ASARCO 2 ASARCO 3 ASARCO 4 ASARCO 5 ASARCO 6 ASARCO 7 ASARCO 8 ASARCO 9
Water Type
CERC Well Post Test River Recon Post Test Hard Recon Post Test
NaCI Post Test MW19 6.25% Post Test
Sed 25 Post Test Sed 5 Post Test Sed 4 Post Test
RO water BioEast
Zn
21.3 2.1 17 0.0
-76.6 1.0 1.2 7.2 3.3
1.2
As
1.0 0.85 0.80 0.22
31.3 87
26.2 11.6 0.53
0.60
Cd
0.45 0.18 1.4 0.51 1.5 0.36 0.63 0.48 1.3
0.10
Pb
0.37 <0.27 < 0.27 <0.27 <0.27 <0.27 <0.27 <0.27 <0.27
0.27
MDL = method detection limit (see Table 9).
Table 2. Concentrations of elements in water from the Omaha, NE, ASARCO study determined by semi-quantitative scan. Units expressed as ug/L unless otherwise specified.
Element
Li Be B
Na^ Mg^ Al K"
Ca^ Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Br Rb Sr Y Zr Nb Mo Ru Pd Ag Cd In Sn
F B I ECRC#
18100
< 1 <0.1
<1 <0.1 <0.1
2 <0.1 0.11 <0.1 <0.1 0.75
4.9 17
<0.1 2.7 3.9 12
<0.1 <0.1 0.10
2.8 <0.1
<1 <1 <1 <1 0.2 <1
<0.1 <0.1
1.2 <1
<0.1
F8 2 ECRC#
18101
< 1 <0.1
<1 <0.1 <0.1 0.84
<0.1 <0.1 0.14 <0.1 0.44
1.1 17
<0.1 0.36 0.61
4 <0.1 <0.1 0.15
2.3 <0.1
<1 <1 <1 <1
<0.1 <1
<0.1 <0.1 <0.1
<1 <0.1
•1 •
001 ECRC#
18116
. <1 5
<1 <0.1 <0.1
82 <0.1 <0.1 <0.1
25 7.8 52 34 47 34
5 22
<0.1 <0.1 16.0 1.5
<0.1 <1 <1 <1 <1
<0.1 <1
<0.1 <0.1
20 <1
<0.1
• • •
MW19 ECRC#
18099
92 <0.1 6520
532 34 39 92
172 8.3 2.2 16
2660 289
11 14 20
2050 0.23 0.27 771 551 134
1230 <1 <1 <1 56
<1 <0.1 <0.1
26 <1 1.4
RW 1 ECRC#
18097
45 0.25
63 67 23
8 5.4 57 1.4 2.4 3.1 17
127 0.17
3.7 3.2 21
<0.1 <0.1
4.2 102 2.3
472 <1 <1 <1 3.2 <1
<0.1 <0.1 0.92
<1 <0.1
RW2 ECRC#
18098
46 0.16
57 72 22
<0.1 5.7 56
0.62 2.3 5.2
5 71
0.11 2.2 4.4 <1
<0.1 <0.1
4.0 103 2.3 522 <1 <1 <1 3.3 <1
<0.1 <0.1 0.61
<1 0.47
SED 1 C ECRC#
18091
35 <0.1
51 69 38 10
5.1 90
2.3 • 1.6
11 4970 1520
2.2 7.2
3 6.3
0.22 0.23 38.0 199 3.1 734 <1 <1 <1 5.1 <1
<0.1 <0.1 0.27
<1 0.38
SED 1 C Dup ECRC#
18102
34 <0.1
46 68 36
<0.1 5.6 84 1.7 1.4 16
4630 1320
2.3 19
3.3 22
0.25 0.28 39.0 196
3 739 <1 <1 <1 5.4 <1
<0.1 <0.1
1.3 _. <1
0.51
SED2C ECRC#
18092
48 0.15
90 77 37
<0.1 6.3 92 1.2 1.6 7.6
2800 40 1.4 6.2 4.4 26
0.17 <0.1 19.0 190 4.4 798 <1 <1 <1 4.8 <1
<0.1 <0.1
0.7 <1
0.54
• • 1
SED4C ECRC#
18093
29 <0.1
95 60 15 18
6.5 54 1.7 1.8 5.6
608 742 1.2 4.7 7.9 37
0.13 0.17 28.0 121
3 412 <1 <1 <1 14
<1 <0.1 <0.1 0.75
<1 0.93
SED5C ECRC#
18094
17 <0.1
147 94 67 0.5 8.4 171 2.9
0.68 24
6820 4210
4.2 10 3
21 0.33 <0.1 72.0 634
3 1172
<1 <1 <1 6.8 <1
<0.1 <0.1 0.55
<1 0.53
SED 24 C ECRC#
18095
40 <0.1
52 65 32 22 5.1 80 1.8 2.8 9.2
1040 238 0.86
8.9 13 67
0.11 <0.1
5.6 138 27 639 <1 <1 <1 7.8 <1
<0.1 <0.1
1 <1
0.58
SED 25 C ECRC#
18096
40 <0.1
223. 87 36 54
7 88
4.9 3.2 17
2160 318 1.5 19
4.6 44
0.13 <0.1
11 184 3.3 752 <1 <1 <1 10
<1 <0.1 <0.1
1.1 <1 0.4
Table 2. Concentrations of elements in water from the Omaha, NE, ASARCO study determined by semi-quantitative scan. Units expressed as ug/L unless otherwise specified...(cont'd).
Element
Li Be B
Na" Mg" AI K"
Ca" Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Br Rb Sr Y . Zr Nb Mo Ru Pd Ag Cd In Sn
3r> . . t »:-
ASARCO 1 ECRC#
18201
19 <0.1
34 16 21 37 2.4 26
0.63 1.27 0.68
<0.1 <1
<0.1 <0.1 0.81
6.9 <0.1 <0.1 <0.1
95 3.6
250 <1 <1 <1
<0.1 <1
<0.1 0.27 0.23
<1 <0.1
ASARCO 2 ECRC#
18202
19 <0.1
46 20 22 2.8 2.9 77
<0.1 17 3.2 1.0 20
<0.1 <0.1
0.6 28
<0.1 <0.1 <0.1
110 3.0
299 <1 <1 <1
<0.1 <1
<0.1 <0.1 0.13
<1 <0.1
ASARCO 3 ECRC#
18203
20 <0.1
39 53 25 2.0 2.4 62
0.16 0.97
17 <0.1
21 <0.1 <0.1
17 17
<0.1 <0.1 <0.1
137 3.8
296 <1 <1 <1
<0.1 <1
<0.1 <0.1
1.2 <1
<0.1
ASARCO 4 ASARCO 5 ECRC#
18204
17 <0.1
33 230 20
2-1 2.8 65
<0.1 2.9
0.87 <0.1 .
4.8 <0.1 <0.1 0.37
6.0 <0.1 <0.1 <0.1
175 3.4
279 <1 <1 <1
<0.1 <1
<0.1 <0.1 0.42 <1
0
ECRC# 18205
23 <0.1 284
53 24
0.98 8.1 86
<0.1 1.6
0.85 192 47
0.29 <0.1
1.9 93
<0.1 <0.1
33 168 12
356 <1 <1 <1 2.4 <1
<0.1 <0.1
1.4 <1
<0.1
ASARCO 6 ECRC#
18206
49 <0.1
183 83 35
2.9 7.6 102 1.1 2.8 3.4
3210 48 1.0 2.4 17 1.6 0.1
<0.1 8.4 231 4.1 901 <1 <1 <1 6.1 <1
<0.1 <0.1 0.63 <1
<0.1
ASARCO 7 ECRC#
18207
20 <0.1
106 87 64 3.4 9.2 140 1.0 1.1 4.6
4190 <1 3.4 2.9 1.1 2.5
<0.1 <0.1
31 747 3.5
1130 <1 <1 <1 6.3 <1
<0.1 <0.1 0.52
- <1 <0.1
ASARCO 8 ECRC#
18208
34 <0.1
76 57 14
6.6 78 58
0.86 1.7 1.8
452 113 0.8 2.2 2.2 6.6
<0.1 <0.1
13 159 3.4 375 <1 <1 <1 18
<1 <0.1 <0.1 0.41 <1
<0.1
ASARCO 9 ECRC#
18209
<1 <0.1
<1 <0.1 <0.1
6.1-<0.1 <0.1 0.27 1.76
<0.1 1.64 120
<0.1 <0.1
1.0 21
<0.1 <0.1 <0.1
21 <0.1
<1 <1 <1 <1
<0.1 <1
<0.1 2.1 1.1 <1
<0.1
Table 2. Concentrations of elements in water from the Omaha, NE, ASARCO study determined by semi-quantitative
Element
Sb Te 1
Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er
Tm Yb Lu Hf Ta W Re Os Ir Pt Tl Pb Bl U
FB1 FB2 001 MW19 ECRC# ECRC# ECRC# ECRC#
18100 18101 18116 18099
0. <0.
< <
<0. <0. <0. <o.-<o.-<o.-<o.-<0. <0. <0. <o.-<o.-<0. ' <0. ' <0 . ' <o.-<0. ' <o.-<0. ' <0 . ' <0.1 <0.1
< 1 < 1 <1
1 <0. 1 <0. 1 < 1 < 1 < 1 <0. 1 <0. 1 <0. 1 <o.-1 <0. 1 <0. ' 1 <0 . 1 <0. I <0. 1 <0. 1 <o.-
<o.-<0. ' <0. ' <0. ' <o.-<0. ' <0. ' <o.-<0. ' <0.1 <0.^
< 1 < 1 <1
1 <0. 1 <0. 1 < 1 < 1 < 1 <0. 1 <o. 1 <0. 1 <o.-1 <0. 1 <o.-1 <o.-1 <0. 1 <0. 1 <0. 1 <o.-1 <o.-
<0. ' 1 <o.-
<0. ' I <0. '
<0. ' <o.-<0. ' <0 . ' <0.1 <0.1
5. < 1 <1
1 430 1 0.24 1 5.8 1 2.4 1 166 1 <0.1 1 <0.1 1 <0.1 1 <0.1 I <0.1 1 <0.1 I <0.1 1 <0.1 1 - <0.1 1 <0.1 1 <0.1 1 <0.1 1 <0.1
<0.1 I <0.1
<0.1 13
0.78 <0.1 <0.1 <0.1 0.69
1 3 <1 5.6
RW 1 ECRC#
18097
0.64 <0.1
1.7 <1 63
0.11 0.17 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.14 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 4.2
RW 2 SED 1 C ECRC# ECRC#
18098 18091
1 <0.1
1.£ <1 61
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.13 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 4.4
0.84 0.16
! 15 <1 178
0.18 0.31
<0.1 0.14
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.16 <0.1 <0.1 <0.1 <0.1 <0.1
37 <1 2.8
SED 1 C Dup ECRC#
18102
0.78 <0.1
28 <1 177
<0.1 0.1
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.17 <0.1 <0.1 <0.1 <0.1 <0.1
5.6 <1 2.8
SED 2 0 ECRC#
18092
2.4 <0.1
28 <1 130
<0.1 0.11 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.26 <0.1 <0.1 <0.1 <0.1 <0.1
1.8 <1 6.2
SED 4 0 ECRC#
18093
8.2 <0.1
4 <1 144
0.36 0.63 <0.1 0.29 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.44 <0.1 <0.1 <0.1 <0.1 <0.1
9.2 <1 4.1
SED 5 C ECRC#
18094
1 0.14
56 <1
335 <0.1 0.05 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.13 <0.1 <0.1 <0.1 <0.1 <0.1
2.8 <1 <1
SED 24 C ECRC#
18095
4 <0.1
11 <1 117
0.11 0.19 <0.1
0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.11 <0.1 <0.1 <0.1 <0.1 <0.1
12 <1 5.5
SED 25 C ECRC#
18096
12 <0.1
11 <1
212 <0.1 0.12 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.32
<0.1 <0.1 <0.1 <0.1 <0.1
5.8 <1 7.4
Table 2. Concentrations of elements in water from the Omaha, NE, ASARCO study determined by semi-quantitative scan. Units expressed as ug/L unless otherwise specified...(cont'd).
Element
ASARCO 1 ASARCO 2 ASARCO 3 ASARCO 4 ASARCO 5 ASARCO 6 ASARCO 7 ASARCO 8 ASARCO 9 ECRC# ECRC# ECRC# ECRC# ECRC# ECRC# ECRC# ECRC# ECRC#
18201 18202 18203 18204 18205 18206 18207 18208 18209
Sb Te
1 Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er
Tm Yb Lu Hf Ta W Re Os Ir Pt Tl Pb Bi U
0.68 <0.1
1.4 <1 48
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 <1
<0.1 <0.1
17 <1 68
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 <1
<0.1 <0.1
1.6 <1 55
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 <1
<0.1 <0.1
1.7 <1 60
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 <1
22 <0.1
2.0 <1 71
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 . <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.94 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 <1
15 <0.1
4.6 <1 193
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.28 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 5.5
0.61 <0.1
6.6 <1 198
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
0.1 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 <1
6.8 <0.1
8.1 <1 118
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.44 <0.1 <0.1 <0.1 <0.1 <0.1
<1 <1 4.5
0.6 <0.1
3.2 <1 <1
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.11 <0.1
<1 <1 <1
11
Table 3. Concentrations of elements in a continuing calibration blank (CCB) and independent calibration verification standard (ICVS) ran every 10 samples. Results expressed as ng/mL.
a. Analysis # f
Run#1
BID'
b. Analysis #2 '
% Rec
Ele COB' ICVS (ICVS)"
% Rec
BID" Ele CCB' ICVS (ICVS)"
10/15/98 10/15/98 10/15/98 10/15/98
Zn As Cd Pb
0.01077 -0.00522 -0.00093 0.00050
32.9 36.2
6.0 5.9
94. 104. 100. 98.
Run#1 11/23/98 11/23/98 11/23/98 11/23/98
Zn As Cd Pb
-0.01297 0.06907 -0.00096 -0.00002
65.1 34.1
5.8 6.3
93. 97. 97.
105.
BID"
% Rec
Ele CCB ' ICVS (ICVS)" BID' Ele CCB'
% Rec
ICVS (ICVS)"
Run #2
Run #3
Run #4
10/15/98 10/15/98 10/15/98 10/15/98
BID"
J 10/15/98 10/15/98 10/15/98 10/15/98
BID"
\ 10/15/98 10/15/98 10/15/98 10/15/98
Zn As Cd Pb
Ele
Zn As Cd Pb
Ele
Zn As Cd Pb
0.01551 -0.01791 -0.00191 0.00117
CCB'
0.05946 0.01378 -0.00091 0.00152
CCB'
0.05362 -0.04520 -0.00095 0.00223
32.6 36.1 6.0 5.9
ICVS
32.9 36.2
5.9 5.8
ICVS
33.2 36.5
6.0 5.9
93. 103. 101. 98.
% Rec (ICVS)"
94. 103. 98. 96.
% Rec (ICVS)"
95. 104. 99. 98.
Run #2
Run #3
Run #4
11/23/98 11/23/98 11/23/98 11/23/98
BID"
11/23/98 11/23/98 11/23/98 11/23/98
BID"
11/23/98 11/23/98 11/23/98 11/23/98
Zn As Cd Pb
Ele
Zn As Cd Pb
Ele
Zn As Cd Pb
-0.05107 0.05426 -0.00056 -0.00159
CCB'
-0.09241 0.06539 -0.00143 -0.00179
CCB'
-0.07363 0.085043 -0.00131 0.002406
64.7 34.8
5.8 6.3
ICVS
63.4 35.2
6.5 5.9
ICVS
67.6 33.8
6.0 6.0
92. 99. 96.
106.
% Rec (ICVS)"
91. 100. 109. 98.
% Rec (ICVS)"
97. 97.
100. 101.
"Analysis #1 = CERC #18091 -18102, 18116; Analysis #2 = CERC #18201 -18209.
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
'acceptance criteria for CCB is +/- 3 X IDL for each element.
"acceptance criteria for ICVS = +/-10% (90% -110%). ICVS = 35ppb or 70ppb for Zn; 35ppb for As; Sppb for Cd and Pb. I
12 I
Table 4. Recoveries of elements from reference solutions used as laboratory control samples in the quantitative analysis of water samples.
BID
10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98
10/15/98 10/15/98 10/15/98 11/23/98 11/23/98. 11/23/98
Analysis Date
10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98
10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98
Reference Material
NIST 1643" NIST 1643" NIST 1643" NIST 1643" NIST 1643" NIST 1643"
TMDW" TMDW" TMDW" TMDW" TMDW" TMDW"
Element
Zn As Cd Zn As Cd
Zn As Cd Zn As Cd
Actual Cone
72.48 +/- 0.65 56.02 +/- 0.73 6.47 +/- 0.37
72.48 +/- 0.65 56.02 +/- 0.73 6.47 +/- 0.37
70 +/- 7 80 +/- 8 10+/-1 70 +/- 7 80 +/- 8 10+/-1
Meas. Cone.
72.8 60.6
6.50 60.8 55.3
6.44
59.6 79.1
9.66 56.4 75.0
97
% Rec
100. 107. 100. 85.
100. 100.
95. 100. 100. 90.
100. 100.
ISOP
P.241 P.241 P.241 P.241 P.241 P.241
P.241 P.241 P.241 P.241 P.241 P.241
Oper. Init.
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
i RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
NIST 1643d = National Institute of Standards and Technology Standard Reference Material Trace Elements in Water 1643d. Concentration results expressed as ng/mL. Solution used as laboratory control sampli
" T M D W = Trace Metals in Drinking Water laboratory control solution. Cat # CRM-TMDW; concentration results in ng/n Solution used as laboratory control sample.
13
Table 5. Percent recovery of elements frorn a spiked water sample.
BID"
10/15/98 10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98 11/23/98
Ele.
Zn As Cd Pb Zn As Cd Pb
Spk Type
Sample - Analytical Sample - Analytical Sample - Analytical Sample - Analytical Sample - Analytical Sample - Analytical Sample - Analytical Sample - Analytical
Water Type
river river river river
river recon river recon river recon river recon
Analysis Units
ng/mL ng/mL ng/mL ng/mL ng/mL ng/mL ng/mL ng/mL
Spk Amt."
ng
500. 200.
40. 100. 500. 200.
40. 100.
Volume (mL)
10. 10. 10.
• 10. 10. 10. 10. 10.
Effective' Cone
50. 20.
4. 10. 50. 20.
4. 10.
Bkgd." Cone.
1.2 0.3 0.10 0.05
- 0.14 0.07 0.02
- 0.04
Total" Cone
58.2 23.2
4.4 10.1 49.5 20.7
4.1 10.0
% Rec'
114. 115. 107. 101. 99.
103. 103. 101.
ISOP
P.241 P.241 P.241 P.241 P.241 P.241 P.241 P.241
Oper. Init.
RHW/TWN)I RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block.'
as a member of the group or "block."
Spike Amt. ng = the absolute microgram (ng) amount of the spike which was added to a sample (CERC# 18097 and 18202 used for spiking).
Effective (Done. = the Spike Amt (ng) divided by the total solution volume, units ng/mL.
Bkgd Cone. = the measured concentration of the sample prior to spiking, units ng/mL.
"Total Cone. = the measured concentration of the spiked sample (spike + background, units ng/mL).
% Rec. = percent recovery: [(Total Cone. - Bkgd Cone.)/Effective Cone. * 100]
14
Table 6. Relative percent difference from the duplicate analysis of water.
BID" Matrix Ele
Water
Type Dup 1 Dup 2 D i f f Mean RPD' ISOP" Oper. Init.
10/15/98
10/15/98
10/15/98
10/15/98
11/23/98
11/23/98
11/23/98
11/23/98
water"
water"
water"
water"
water'
water'
water'
water'
Zn
As
Cd
Pb
Zn
As
Cd
Pb
pore water
pore water
pore water
pore water
river recon
river recon
river recon
river recon
59.1
25.2
4.40
11.0
49.9
207
4.1
10.1
59.7
25.5
4.41
11.2
49.1
20.0
4.0
10.3
0.55
0.31
0.01
0.21
0.79
0.70
0.01
0.28
59.4
25.4
4.40
11.1
49.5
20.3
4.05
10.2
0.9
1.2
0.2
1.9
1.6
3.5
0.2
2.8
P.241
P.241
P.241
P.241
P.241
P.241
P.241
P.241
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
RHW/TWM
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the
"Diff = Dup 1 - Dup 2.
'''RPD = relative percent difference, calculated as Diff/Mean X 100; acceptance criteria +/-10%.
'iSOP = standard operating procedure used for instrumental analysis of sample (C5.212).
"two aliquots of pore water sample #18093 (SED 4 C) spiked with 50ppb Zn, 20ppb As, 4ppb Cd, and lOppb Pb anc analyzed separately at the instrument (analysis duplicate).
'two aliquots of pore water sample #18202 (River Recon) spiked with SOppb Zn, 20ppb As, 4ppb Cd, and lOppb Pb analyzed separately at the instrument (analysis duplicate).
15
Table 7. Interference check using dilution percent difference.
BID"
10/15/98 10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98 11/23/98
Run Date
10/15/98 10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98 11/23/98
Water Type
pore water" pore water" pore water" pore water" river recon" river recon" river recon" river recon"
Element
Zn As Cd Pb Zn As Cd Pb
Undiluted _ Sample
103.5 43.
7.8 18.3 43.9 20.2
4.4 10.0
Diluted Measured'
22.6 8.8 1.63 3.73 9.51 3.87 0.80 2.04
Sample ' Final
113.1 44.
8.1 18.6 47.6 19.4 4.0
10.2
% Diff
9.3 2.8 3.9 17 8.3 4.3 8.0 1.7
BID = Block Initiation Date: a date assigned to each member of a group of samples that will identify the sample as a member of the group or "block."
"dilution factor = 5(1 +4).
'dilution % difference acceptance criteria = +/-10%; concentrations exceeding +/-10%. indicative of suspect interferent.
"sample #18092 (SED 2 C) spiked with 50ppb Zn, 20ppb As, 4ppb Cd, and lOppb Pb and used for dilution check.
"sample #18202 (River Recon) spiked with SOppb Zn, 20ppb As, 4ppb Cd, and 10ppb Pb and used for dilution check.
16
Table 8. Recovery of elements from an interference check solution^
BID Run Date Cone (ppb) Cone (ppb) Dilution
Element measured actual Factor % Rec'
10/15/98 10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98 11/23/98
10/15/98 10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98 11/23/98
Zn As Cd Pb Zn As Cd Pb
18.5 17.0 10.8 22.0 17.3 16.0 10.6 22.7
20. 20. 10. 20. 20. 20. 10. 20.
5 5 5 5 5 5 5 5
93. 85.
108. 110. 87. 80.
106. 114.
"High Purity ICP-MS Solution AB in 2% nitric acid, Charleston, SC; CAT # ICP-MS-ICS.
"suggested acceptance tolerance 80% -120%.
17
Table 9. instrument detection limits, method detection limits, and limits of quantitation for the analytes of interest.
BID Run Date" Element Matrix Std Cone." B I k S D l ' Blk SD 2 Blk SD 3 IDL" MDL" LOQ' ISOP Oper. Init.
10/15/98 10/15/98 10/15/98 10/15/98 11/23/98 11/23/98 11/23/98 11/23/98
5/8/98 5/8/98 5/8/98 5/8/98 5/8/98 5/8/98 5/8/98 5/8/98
Zn As Cd Pb Zn As Cd Pb
water water water water water water water water
0.0 • 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.04177 0.00791 0.01517 0.02042 0.04177 0.00791 0.01517 0.02042
0.02842 0.01374 0.00579 0.02310 0.02842 0.01374 0.00579 0.02310
0.10850 0.00938 0.00303 0.00364 0.10850 0.00938 0.00303 0.00364
0.179 0.031 0.024 0.047 0.179 0.031 0.024 0.047
0.42 0.07 0.02 0.04 1.22 0.60 0.10 0.27
1.4 0.24 0.06 0.15 4.0 2.0 0.3 0.9
P.241 P.241 P.241 P.241 P.241 P.241 P.241 P.241
RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM RHW/TWM
"date of 3rd non-consecutive day analysis, following which IDL was computed.
"concentration of low level standard used in analysis in ppb, which was reagent blank or 0 cone standard,
'standard deviation from analysis of 0 standard (reagent blank) 7 consecutive times in one day.
IDL = instrument detection limit (ng/mL), computed as 3 X mean of standard deviations.
"MDL = method detection limit (ng/mL), computed as 3 X (SDb •*" SDg^)''^ where SDb = standard deviation of a blank (n = 3) and
SDg = standard deviation of a low level sample or spiked sample (n = 3).
'LOQ = limit of quantitation ng/mL, computed as 3.3 X the MDL.
18
Table 10. Percent relative standard deviation from repeated analysis of Trace Metals in Drinking Water Standard^ during the semi-quantitative sample run. Results expressed in ng/mL.
Element
Li Be Na Mg Al K Ca V Cr Mn Fe Co Ni Cu Zn As Rb Sr Mo Ag Cd Sb Te Ba Pr Tb Tm Ta Au Tl Pb Bi U
Run#1
18. 19.
5736. 8637. 117.
2250. 33237.
30. 20. 38. 77. 24. 55. 20. 67. 80. 9.3
247. 96. 1.9 9.5 10.0 3.0 49. 9. 9. 9. 10.0 10.5 10. 39. 8.1 10.
Run #2
19. 18.
6140. 9130. 120.
2484. 35648.
30. 19. 41. 102. 26. 60. 20. 69. 82. 10.5
262. 98. 2.0 9.4 9.8 3.2 50. 10. 10. 9. 9.6 8.9 10. 31. 7.8 10.
Run #3
19. 19.
6104. 9014. 128.
2491. 33452.
31. 20. 39. 100. 24. 56. 21. 70. 81. 9.6
249. 97. 1.9 9.6 10.2 3.2 51. 10. 10. 10. 9.3 10.4 10. 41. 8.6 10.
Actual Cone
20. 20.
6000. 9000. 120.
2500. 35000.
30. 20. 40. 100. 25. 60. 20. 70. 80. 10.
250. 100. 2.0 10. 10. 3.0 50. 10. 10. 10. 10. 10. 10. 40. 10. 10.
Mean Cone
18. 19.
5993. 8927. 122.
2408. 34112.
30. 20. 40. 93. 25. 57. 20. 69. 81. 9.8
252. 97. 1.9 9.5 10.0 3.1 50. 9. 10. 10. 9.6 9.9 10. 37. 8.2 10.
SD
0.6 0.3
224. 258. 5.6
137. 1334.
0.7 0.3 1.5 14. 0.9 2.6 0.4 1.5 0.9 0.6 8. 0.7 0.0 0.1 0.2 0.1 1.3 0.3 0.3 0.3 0.3 0.9 0.3 5.1 0.4 0.2
% RSD
3. 1.5 3.7 2.9 4.6 5.7 4. 2.4 1.6 3.7 15. 3.8 4.6 2. 2. 1.1 6.1 3.2 0.7 2.6 1.4 2.1 3.7 2.6 2.6 3.5 3.6 3.3 9. 3.0 14. 4.5 2.5
"High Purity Trace Metals in Drinking Water, Cat # CRM-TMDW, Charleston, SC; Pr, Tb, Tm, Ta, and Au manually added to represent rare earth region of the mass spectral range.
19
Table 11. Percent relative standard deviation from repeated analysis of Trace Metal in Drinking Water Standard^ during the semi-quantitative sample run. Results expressed in ng/mL.
Element
Li Be Na Mg AI K Ca V Cr Mn Fe Co Ni Cu Zn As Rb Sr Mo Ag
. Cd Sb Te Ba Pr Tb Tm Ta TI Pb Bi U
Run#1
21. 22.
6847. 10016.
127. 2608. 33190.
30. 20. 39. 70. 22. 57. 20. 67. 75. 9.6
221. 97. 1.8 8.9 97 2.8 48. 9. 10. 10. 12.0 10. 42. 9.2 11.
Run #2
22. 21.
5977. . 9134.
115. 2730. 37892.
32. 21. 44. 93. 26. 65. 21. 74. 82. 11.
256. 104. 2.0 10. 10. 2.8 51. 9. 10. 9. 11. 10. 39. 8.6 10.
Run #3
22. 21.
6022. 9303. 115.
2792. 35923.
33. 21. 44. 93. 25. 68. 22. 78. 84. 11.
265. 107. 2.0 10. 10. 2.9 52. 10. 10. 10. 11. 9.
40. 8.7 11.
Actual Cone
20. 20.
6000. 9000. 120.
2500. 35000.
30. 20. 40. 100. 25. 60. 20. 70. 80. 10.
250. 100. 2.0 10. 10. 3.0 50. 10. 10. 10. 10. 10. 40. 10. 10.
Mean Cone
22. 21.
6282. 9484. 119.
2710. 35668.
32. 21. 42. 85. 24. 63. 21. 73.. 80. 10.6
248. 103. 1.9 9.7 10.1 2.8 50. 10. 10. 10. 11.1 10. 40. 8.8 11.
SD
0.5 0.6
489. 468. 7.2 94.
2361. 1.6 0.8 3.1 14. 17 5.3 1.0 5.5 4.8 0.9 23. 5.3 0.1 0.6 0.4 0.1 2.1 0.2 0.1 0.2 0.8 0.4 1.2 0.3 0.4
% RSD
2. 3.0 7.8 4.9 6.1 3.5 7. 5.1 3.8 7.3 16. 7.1 8.4 5. 7. 6.0 8.2 9.4 5.2 6.1
" 6.4 4.1 3.2 4.2 2.3 1.4 2.1 6.9 4.1 3. 3.5 3.5
High Purity Trace Metals in Drinking Water, Cat # CRM-TMDW, Charieston, SC; Pr, Tb, Tm, Ta, and Au manually added to represent rare earth region of the mass spectral range.
20
Table 12. Recovery of elements from a laboratory control sample^ with semi-quantitative analysis.
Run#1 Run #2
Element
Be Al V Cr Mn Co Ni Cu Zn As Ag Cd Sb Ba Tl Pb
Actual Cone
10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10. 10.
Meas Cone.
12. 9.
10. 9.
10. 10. 11. 11. 17. 14. 10. 11. 12. 11. 11. 10.
% Rec .
123. 85. 98. 95.
101. 102. 107. 112. 170. 137. 97.
115. 115. 113. 107. 103.
Element
Be Al V Cr Mn Co Ni Cu Zn As Ag Cd Sb Ba Tl Pb
Actual Cone
50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50.
Meas Cone
52. 47.' 53. 51. 53. 47. 55. 55. 57. 52. 43. 47. 49. 46. 47. 49.
% Rec
103. 94.
105. 103. 106. 95.
109. 111. 115. 103. 86. 94. 98. 93. 94. 99.
"SPEX Claritas PPT Instrument Check Standard 1 (CL-ICS-1); SPEX CertiPrep, Inc.. Metuchen, NJ
21
Table 13. Relative percent difference in elemental concentrations from a duplicate field pore water sample (semi-quantitative analysis).
Element
SED 1 C SED 1 C Dup 18091 18102 Repi Rep2 Diff Mean RPD
Li Be
B Na" Mg"
Al K"
Ca" Ti V
Cr Mn Fe Co Ni
Cu Zn Ga Ge As Br Rb Sr Y
Zr Nb Mo Ru Pd Ag Cd In
Sn
35 <0.1
51 69 38 10. 5.
90 2.3 1.6 11
4969 1518
2.2 7.2 3.0 6.3
0.22 0.23
38 199.00
3.1 734.000
<1 <1 <1 5.1 <1
<0.1 <0.1 0.27
<1 0.38
34 <0.1
46 68 36
<0.1 6.
84 17 1.4 16
4628 1322
2.3 19
3.3 22
0.25 0.28
39 196 3.0 739 <1 <1 <1 5.4 <1
<0.1 <0.1
1.3 <1
0.51
1.0
5.0 1.0 2.0
0.50 6.0
0.60 0.20
5.0 341 196
0.10 12
0.30 15.700
0.03 0.05
1.0 3.0
0.10 5.0
0.30
1.0
0.13
34.5 3.
48.5 10. 68.5 1. 37.0 5.
5.4 87.0
2.0 1.50 13.5
4799 1420
2.3 13.1 3.2
14.2 0.24 0.26 38.5 198 3.1 737
9. 7.
30. 13. 37.
7. 14. 4.
90. 10. 111. 13. 20.
3. 2. 3. 1.
5.3 6.
0.79 131.
0.45 29.
Element
Sb Te
1 Cs Ba La Ce Pr
Nd Sm Eu Gd Tb Dy Ho Er
Tm Yb Lu Hf Ta W Re Os
Ir Pt Tl
Pb Bi U
SED1 C 18091 Rep1
0.84 0.16
15 <1 178
0.18 0.31 <0.1 0.14
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.16 <0.1 <0.1 <0.1 <0.1 <0.1
37 <1 2.8
SED 1 C Dup 18102 Rep2
0.78 <0.1
28 <1 177
<0.1 0.10 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 .<0.1 <0.1 <0.1 <0.1 <0.1 0.17 <0.1 <0.1 <0.1 <0.1 <0.1
5.6 <1 2.8
Diff
0.06 —
13 —
1.0 —
0.21 — — — — — — — — — — — — — —
0.01 — — — — —
1.9
0.0
Mean
0.81 —
21.5 —
178 —
0.21 — — — — — — — — — — — — — —
0.17 — — — — —
4.7 —
2.8
RPD
7. — 60. —
1. —
102. — —
— — — — — — — — —
— 6.
— — — — — 41. — 0.
Table 14. Recovery of elements from a spiked water sample (semi-quantitative analysis).
Run #1
Spiked Element
Be AI V Cr Mn Co Ni Cu Zn As Ag Cd Sb Ba Tl Pb
Spike Amt (ug/L)
50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50.
Bkgd Cone
0.00 0.00 0.22 0.42 0.57 0.01 0.25 0.46 0.00 0.42 0.03 0.06 0.17 6.45 0.00 0.09
Total Cone
67. 57. 53. 53. 52. 53. 57. 57.
103. 76. 52. 60. 59. 55. 43. 42.
% Rec
134. 113. 106. 105. 103. 106. 113. 114. 205. 150. 104. 120. 118. 97. 87. 84.
Run #2
Spiked Spike Bkgd Total Element Amt (ug/L) Cone Cone % Rec
Be Al V Cr Mn Co Ni Cu Zn As Ag Cd Sb Ba Tl Pb
50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50. 50.
0.00 6.06 1.76 0.04 1.64 0.00 0.00 1.02
20.6 0.00 0.00 1.05 0.60 0.38 0.00 0.69
54. 45. 56. 55.
104. 55. 58. 60. 69. 62. 69. 53. 54. 63. 50. 51.
109. 78.
108. 110. 205. 110. 115. 118. 97.
124. 138. 104. 107 125. 100. 101.
23
Toxicity and Elemental Contaminant Concentrations of Groundwater, Sediment Pore Waters, and Surface Waters of the Missouri River
Associated wi th a Metals Refining Site in Omaha, Nebraska.
Appendix B: Ancillary Data
Duane C. Chapman Ann L. Allert
James F. Fairchild Thomas W. May
Christopher J . Schmitt
United States Geological Survey Biological Resources Division
Columbia Environmental Research Center Columbia, MO
and
Edward V. Callahan Environmental Statistics
Fountain City, WI
Prepared for:
United States Environmental Protection Agency, Region VII Air, RCRA, and Toxics Division
726 Minnesota Avenue Kansas City, KS
lAG DW14952122-01-1
April, 2000
TABLE OF CONTENTS
FIGURES
Figure A. The distribution of correlation coefficients calculated from concentrations of all pairs of elements measured in sediment samples 1
Figure B. The distribution of correlation coefficients calculated from concentrations of all pairs of elements measured in aqueous samples 2
Figure C. Comparison of the first principal component calculated from element concentration data of sediment samples between study sites 3
Figure D. Comparison of the second principal component calculated from element concentration data of sediment samples between study sites 4
Figure E. Comparison of the third principal component calculated from element concentration data of sediment samples between study sites 5
Figure F. Comparison of the first principal component calculated from element concentration data of water samples between study sites 6
Figure G. Comparison of the second principal component calculated from element concentration data of water samples between study sites 7
Figure H. Comparison of the third principal component calculated from element concentration data of water samples between study sites 8
Figure I. Relationship of the first principal component calculated from element concentration data of sediment samples wi th mean Ceriodaphnia reproductive rates from a 7-day toxicity test on pore waters 9
Figure J . Relationship of the second principal component calculated from element concentration data of sediment samples wi th mean Ceriodaphnia reproductive rates from a 7-day toxicity test on pore waters 10
Figure K. Relationship of the third principal component calculated from element concentration data of sediment samples wi th mean Ceriodaphnia reproductive rates from a 7-day toxicity test on pore waters 11
Figure L. Relationship of the first principal component calculated from element concentration data of aqueous samples with mean Ceriodaphnia reproductive rates from a 7-day toxicity test 12
Figure M. Relationship of the second principal component calculated from element concentration data of aqueous samples with mean Ceriodaphnia reproductive rates from a 7-day toxici ty test 13
Figure N. Relationship of the third principal component calculated from element concentration data of aqueous samples with mean Ceriodaphnia reproductive rates from a 7-day toxici ty test 14
TABLES
Table A. Latitude and longitude of sampling stations 16
Table B. "True" values for element concentrations in EPA blind quality assurance samples 17
Table C. Water quality during 7-day Ceriodaphnia toxicity test of river water, sediment porewater, and groundwater 18
Table D. Correlation of concentrations of elements found in sediment samples wi th the first three principal components calculated from those numbers 22
Table E. Correlation of concentrations of elements found in water samples wi th the first three principal components calculated from those numbers 23
I
Appendix B, Figures
I I I I
Sediment Sample
30 -
B 20 o
c 0) o
CL
10 -
0 -
-1.0 -0.5 0.0 0.5
Pearson Correlation Coefficient
1.0
Figure A, Appendix B. The distribution of correlation coefficients calculated from concentrations of all pairs of elements measured in sediment samples collected in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
Water Sample
20 i
15 -
to o
o 10 -
0) o i _
Q.
-0.5 0.0 0.5
Pearson Correlation Coefficient
Figure B, Appendix B. The distribution of correlation coefficients calculated from concentrations of all pairs of elements measured in aqueous samples (river water, groundwater, and sediment pore water) collected in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
Sediment Sample
SED5
SED4
SED25
SED24
SED2
SED1
-10
1 r -5 0
First Principal Component
Figure C, Appendix B. Comparison of the first principal component calculated from element concentration data of sediment samples between study sites in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
I
Sediment Sample
SED5
SED4
SED25
SED24
SED2
SED1
-4 -2 0 2
Second Principal Component
Figure D, Appendix B. Comparison of the second principal component calculated from element concentration data of sediment samples between study sites in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
Sediment Sample
SED5
SED4
SED25
SED24
SED2
SED1
-1 0 2
Third Principal Component
Figure E, Appendix B. Comparison of the third principal component calculated from element concentration data of sediment samples between study sites in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
Water Sample
SED5
SED4
SED25
SED24
SED2
SED1
River water 2
River water 1
I I . r
0 2 4
First Principal Component
6
I I I
Figure F, Appendix B. Comparison of the first principal component calculated from element concentration data of water samples between study sites collected in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
Water Sample
SED5
SED4
SED25
SED24
SED2
SED1
River water 2
River water 1
I I I
-2 0 2
Second Principal Component
Figure G, Appendix B. Comparison of the second principal component calculated from element concentration data of water samples between study sites in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
Water Sample
SED5
SED4
SED25
SED24
SED2
SED1
River water 2
River water 1
1 \ \
-2 0 2
Third Principal Component
Figure H, Appendix B. Comparison of the third principal component calculated from element concentration data of water samples between study sites in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
Se(diment
30
3 a. "5 O (U
.> o 3
TJ O 1— Q . 0) a: c CO (U
25
20
-5 0
First Principal Component
Figure i. Appendix B. Relationship of the first principal component calculated from element concentration data of sediment samples wi th mean Ceriodaphnia reproductive rates from a 7-day toxicity test on pore waters collected from those sediments. Samples were taken in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
Se(diment
30
3
s-3
o .> "S 3
T3
9 C3. Ct: c (U
25
20
T
- 6 - 4 - 2 0 2 4 6
Second Principal Component
Figure J , Appendix B. Relationship of the second principal component calculated from element concentration data of sediment samples with mean Ceriodaphnia reproductive rates from a 7-day toxicity test on pore waters collected from those sediments. Samples were taken in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
10
Se(diment
30
3
a-3 o 0)
.> t> 3
T3 e a 0) cr c (0 0)
25
20
oSED5
SED25
0
1 1
SED24 o
o SED4
•
1
o SED1
o SED2
1 1
-2 -1 0 ' 1
Third Principal Component
Figure K, Appendix B. Relationship of the third principal component calculated from element concentration data of sediment samples with mean Ceriodaphnia reproductive rates from a 7-day toxicity test on pore waters collected from those sediments. Samples were taken in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
11
Water
45
40
3
B-
> ts 3
T3
e Q.
a: c
30
25
20
15
o River water 1
River water 2
o
1
•
SED1 SED24 °
°o SED4
SED2 o
SED25 0
I l l l
SED5 o
1 1
- 2 0 2 4
First Principal Component
8
Figure L, Appendix B. Relationship of the first principal component calculated from element concentration data of aqueous samples (river water and sediment pore water) wi th mean Ceriodaphnia reproductive rates from a 7-day toxicity test on those samples. Samples were taken in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
12
Water
45
40
3
s-a> .> "G 3
• D
2 Q. O)
Q::
c (Q 0)
30
25
20
15
River water 2
o
SED5 o- ^
1 .1
o River water 1
SED1 o
SED2 o
1
S f 24 SED4
o
SED25 o
1 1
- 4 - 2 0 2 4
Second Principal Component
Figure M, Appendix B. Relationship of the second principal component calculated from element concentration data of aqueous samples (river water and sediment pore water) with mean Ceriodaphnia reproductive rates from a 7-day toxicity test on those samples. Samples were taken in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
13
Water
45
40
3
B-
> t3 3
T3
2 Q. 0)
C (Q 0)
30
25
20
15
o River water 1
SED1 o
SED4 o
River ^ water 2
SED24 o
SED2
o
SED5 o
SED25
o
-4 -2 0 2
Third Principal Component
4
Figure N, Appendix B. Relationship of the third principal component calculated from element concentration data of aqueous samples (river water and sediment pore water) wi th mean Ceriodaphnia reproductive rates from a 7-day toxicity test on those samples. Samples were taken in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
14
Appendix B, Tables
I I
Table A, Appendix B. Latitude and longitude of sampling stations, in the vicinity ofthe ASARCO lead refining facility, Omaha Nebraska. Data collected using a
Rockwell ® PLGR global positioning system.
Sedl
Sed 2
Sed 4
Sed 5
RW1
RW2
Sed 24
Sed 25
ls?f: ; :.r. fi - ?S V?; v ji5i ^ i VLatitude
mm^i^mm^m^^mmm w;?'"Deg,v:- ?:
41
41
41
41
41
41
41
41
^ ^ \ j m r i %
16
15
15
15
15
15
15
15
^M!^e&^^"::.,
12
48
52
49
48
33
37
33
5Si^Sv:^^^"'?#f^A/esf-':';:>;§^''^ •
•^SSPegS-^¥
95
45
95
95
95
95
95
95
:f;:-i5;=;Miri^- ::\'.
55
15
55
55
55
55
55
55
*-v";4Secv,-'-:
15
60
30
26
14
22
11
22
•'.•('ETitir \
±5.5
±6.6
±5.2
±15.0
±45.0
±14.0
±6.3
±6.3
I I
16
Table B, Appendix B. "True" values for element concentrations in EPA blind quality assurance samples. The values on this page were provided to CERC after all analyses were complete and the first draft of this report was provided to EPA.
Parartietei'; L-!'^hi'>r~~"--'-''-yp-^
Aluminum
Arsenic
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganes e
Nickel
Lead
Selenium
Vanadium
Zinc
:§kj- {\ig/i-)'.^}t
57.5
11.3
4.01
164.01
45
7.5
3.81
37.5
0.43
48.5
31.1
4.6
0.6
24.0
10.5
^ ^ S i^Parameteri
Ant imony
Barium
Beryllium
Cadmium
Chromiu m
Lead
Nickel
Selenium
Zinc
Mercury
0.30
69
0.32
1.0
7.5
5.8
15
0.5
43
0.001
17
Table C, Appendix B. Water quality during 7-day Ceriodaphnia toxicity test of river water, sediment pore water, and groundwater collected in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska. Measurements were taken on pooled replicates after exposure to Ceriodaphnia. M W 1 9 is the groundwater sample from Monitoring Well 19. SEDx refers to pore waters collected from the various sediment sites. NaCI refers to the sodium chloride reference toxicant treatments and the concentration of NaCI added to reconstituted river water. Hard Recon refers to the reconstituted water made to reflect the water quality of the river waters.
CERC well water
Reconstituted river water
Hard Recon
River water 1
River water 2
SEDI
10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98
r-;?pissolved:;^
;^':(riig/L-y:-'•. 7.30 7.90 8.00 7.96 7.67 7.79 7.60 7.77 7.00 7.90 8.10 7.15 7.78 7.13 7.50 7.80 7.80 8.10 7.63 7.87 7.30 7.40 7.90 7.80 7.89 7.72 7.79 7.25 7.30 7.90 8.00 7.88 7.65 7.83 7.35 7.40 7.70 7.50 7.50 7.63 7.56 7.44
i'TjeniperaturB:
22.9 22.2 22.3 21.8 23.8 23.0 24.5 22.6 23.4 22.0 21.7 23.0 23.5 24.8 22.6 22.7 22.1 21.7 24.1 23.8 24.3 23.4 22.1 22.3 21.8 22.9 23.7 24.9 23.6 22.2 22.0 21.8 23.4 23.4 25.5 23.2 22.6 22.6 22.3 22.7 24.3 24.1
^ . ' • : - ^ • , ^ ^ ? • • ' • • i . r - y .
•':]iCbnductiyrty.ii:; ^•-;'(ixmhos/cfh)-.'l-
420 434 386 421 400 395 423 510 562 520 521 522 496 522 690 673 658 717 683 669 654 810 768 720 776 798 743 755 800 784 724 752 826 748 755 900 790 793 806 811 784 764
.• ' • , ' i * 'pHv' '
»'^-S 8.51 8.64 8.46 8.25 8.36 8.45
8.41 8.66 8.21 8.31 8.39 8.40
8.47 8.66 8.44 8.39 8.45 8.53
8.55 8.76 8.48 8.45 8.49 8.57
8.54 8.76 8.49 8.39 8.49 8.58
8.41 8.60 8.34 8.36 8.47 8.47
'•i;-:':!.vAlkallnit>^^f|i^
146
174
205
214
226
239
192
182
174
184
422
296
;i(iTig/L;aS;GaG.03Jf
190
219
256
253
284
283
286
276
266
274
322
305
<0.10
>0.10
<0.10
>0.10
<0.10
>0.01
<0.1
>0.1
0.119
0.119
0.545
0.15
0.14
0.29
0.56
0.51
0.88
20.2
16.3
19.3
13.3
13.3
9.3
18
Table C, Appendix B, continued. 1 ;?>•«'-HP'-r-j^."^' fifC'Treatmeiit':,
SED2
SED4 12.5%
SED4 25%
SED4 50%
SED4 100%
SED5
''^•'.Date
10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 , 10/14/98 10/15/96 10/16/98
..Dissolved-:• 'oxygen,'. "(mg/L)
7.40 7.80 7.90 7.70 7.72 7.74 7.55 7.40 8.10 8.00 7.80 7.79 7.75 7.21 7.60 7.90 7.90 7.80 7.62 7.93 7.09 7.10 7.60 7.90 7.60 7.45 7.73 7.00 7.30 7.70 7.90 7.80 7.49 7.62 7.32 7.30 7.70 9.70 7.80 7.81 8.00 7.35
i emperature
23.4 22.3 22.4 22.3 22.6 24.4 24.3 23.4 22.3 22.1 22.1 22.7 23.8 24.6 23.1 22.1 22.2 22.3 22.8 23.8 24.5 23.5 22.4 22.5 22.5 22.9 24.4 25.1 23.6 22.5 22.3 22.3 22.9 24.7 24.9 22.8 22.7 22.1 22.0 22.6 23.1 24.3
Conductivity'.^ '" (nmhos/cm) '-.
810 775 792 714 820 790 766 590 553 514 529 602 524 531 590 595 550 558 603 566 572 680 680 635 615 697 633 622 700 747 701 782 734 721 695
1100 1069 1465 1045 1035 1016 989
8.37 8.58 8.34 8.33 8.45 8.44
8.36 8.65 8.39 8.40 8.37 8.46
8.40 8.65 8.39 8.39 8.39 8.43
8.51 8.78 8.53 8.48 8.44 8.55
8.40 8.64 8.41 8.37 8.36 8.42
8.46 8.59 7.82 8.43 8.53 8.53
|r,^?.AIkalinity";''^.V,. ^mg/L'as CaCOi)cj
168
257
202
204
225
209
250
176
204
381
V,- "HardnessV'i > ' (mg/L as da to i ) .
232
297
270
243
270
256
294
233
390
379
.V.,NHj;N^' ^\(mg/L) .
4.1
0.393
0.464
— —
5.28
^(mg/L)' -
0.37
0.52
0.78
: >? c i . . ' '(mg/L) '
13.3
27.1
24.2
19
Table C, Appendix v:s;,VTreatmentf;:'.'t.-
SED24
SED25
MW19 6.25%
MW19 12.5%
MW19 25%
MW19 50%
MW19 100%
NaCI 25%
10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98
10/10/98
10/10/98
10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98
B, continued. SfsDIsisblvedf /
7.60 7.90 7.80 7.80 7.72 7.97 7.31 7.60 8.00 7.70 8.06 7.65 7.84 7.45 7.40 8.10 7.80 7.02 7.66 7.95 7.40 7.40 8.10 8.10-8.15 7.81 7.89
7.60
7.10
7.40
7.80 7.80 7.80 8.07 7.67 7.71 7.15
^ :T<9mperature'
22.8 22.7 22.4 22.0 22.8 23.0 24.3 22.4 22.2 22.3 21.8 22.8 22.9 24.2 22.9 22.3 22.3 21.8 23.0 23.1 24.4 23.2 21.9 22.2 21.5 23.3 23.5
22.7
23.1
23.0
23.2 22.8 22.2 21.8 23.1 24.3 24.4
ScojiidiiKtiyity^^i; % (Jjirihosi/cSTiyu '
790 869 818 875 845 864 804 910 929 903 893 902 873 892 760 744 738 734 770 710 736 950 931 977 955 982 922
1090
1710
4200
1500 1702 1649 1694 1776 1787 1693
8.47 8.86 8.48 8.54 8.50 8.60
8.42 8.61 8.37 8.38 8.45 8.46
8.44 8.71 8.37 8.46 8.41 8.51
8.41 8.77 8.44 8.57 8.47 8.52
8.68
8.73
8.72
8.30 8.59 8.35 8.31 8.40 8.44
\i'\?-:'^':-->:--,yr:'--.i^i^ivfS'S^
;rKmg/^as';eapC)i)f?:
264
219
278
276
230
213
270
244
216
250
S/' xHardhesisVKvv
270
321
322
307
296
259
320
300
260
286
-St^HiirNll;
0.182
0.423
0.088
0.093
<0.1
M t i g / t y i ^
0.43
_»_ _
lilciip
16.3
20
Table C, Appendix B, continued. mM
.yrfvJi'eatmehtiJ^T.
NaCI 50%
NaCI 100%
.^•.•?Date:;--
10/10/98 10/11/98 10/12/98 10/13/98 10/14/98 10/15/98 10/16/98 10/10/98 10/11/98
e.j-pjssplveclSj
4SH(iTt"g<t:)'':-:'i,. 8.00 7.80 7.80 8.02 7.88 7.80 7.81 8.20 8.00
»w-i,ff.-;,-r-''.r-"--'ii-Srernperaturq.
23.3 22.8 22.1 21.7 22.5 24.1 24.3 23.5 23.2
.ponductiyi^Jy •.'(p.mho.s/cm)'';':|;
2710 2810 2760 2870 3040 2990 2850
5100
5240
''s'-'ftSSS ;?Mi m ^ i 8.28 8.59 8.36 8.32 8.41 8.43
8.35
8.55
i a ^ ^ ^ y c a l i r i i t y ; ^ ^ Mifig/L'as-CaCOam
204
f~S.y-'H0ne$s$jH Vftg/L^asieaCOV):' /•>'i^^-.'.>-3'''>?'^,>-j;,
250
288
%;NH3-NV|V' :^f,(nig/L)>t
<0.1
^;!m'Kin''^'»i*?v.5
'~JjrngA#S||
21
Table D, Appendix B. Correlation of concentrations of elements found in sediment samples wi th the first three principal components calculated from those numbers. Correlations wi th absolute values greater than 0.8 are in bold. Sediments were collected in the vicinity of the ASARCO lead refining facility, Omaha, Nebraska.
: Elenlent
Y
Li
Pr
Tb
Al
Er
Sm
Gd
Nd
La
Eu
Ce
K
Mg
Yb
Ho
Ga
Rb
V
As
.-:, PCI
1
1
0.99
0.99
0.98
0.97
0.96
0.96
0.96
0.96
0.96
0.96
0.96
0.95
0.94
0.93
0.92
0.91
0.91
0.9
PC2.
-0.01
0.03
-0.03
-0.02
0.19
0.21
0.10
0.10
-0.25
-0.25
0.26
0.12
0.22
-0.21
0.32
0.34
0.37
0.32
0.21
-0.04
- vPCS'--^
0
0
-0.12
-0.13
-0.03
-0.08
-0.2
-0.2
0.02
0.02
0.07
-0.21
0.19
0.18
0.08
0.08
0.11
0.17
0.02
-0.42
iJEfeiment.;:
Co
Ba
Zr
Ti
Dy
Mn
Na
Cd
Pb
Zn
Fe
Cu
Sr
Ni
Sb
Ca
Cr
Mo
Sn
PCI
0.9
0.85
0.85
0.83
0.82
0.74
0.62
0.44
0.29
0.29
-0.46
-0.5
-0.56
-0.66
-0.73
-0.87
-0.89
-0.94
-0.97
PC2
0.39
-0.51
0.31
-0.52
0.42
0.62
-0.29
0.79
-0.07
0.91
0.84
0.85
0.83
0.63
-0.32
0.48
0.44
0.33
0.21
PC3:.:. '- •;;••
-0.08
-0.1
-0.38
0.16
0.39
0.1
-0.47
0.21
-0.82
-0.18
-0.19
-0.11
-0.03
-0.29
-0.53
-0.03
-0.05
-0.05
-0.01
22
Table E, Appendix B. Correlation of concentrations of elements found in water samples wi th the first three principal components calculated from those numbers. Correlations wi th absolute values greater than 0.8 are in bold.
EIertient =:
Co
Ba
Br
Ga
Ca
Cr
1
Sr
Mn
As
Mg
K
1 Fe
Ni
Na
Ti
^ • • ' • P ^ l - ' - -
0.98
0.97
0.96
0.95
0.93
0.92
0.91
0.87
0.86
0.86
0.82
0.76
0.73
0.71
0.7
0.67
t:-':PC2-.i •
0.06
0.23
-0.25
-0.15
-0.24
0.07
-0.08
-0.3
0.33
-0.01
-0.35
-0.03
0.08
0.42
-0.32
0.49
•:rt--PC3:F
-0.12
-0.02
0.01
-0.18
0.2
0.22
0.09
0.33
0.03
-0.42
0.4
-0.09
-0.34
0.45
0.47
0.42
Elernerit
8
Rb
Mo
Zn
Pb
Sn
Sb
W
AI
Ce
Cd
Cu
U
V
Li
¥ PGIi :i . : . ..
0.58
0.51
0.4
0.36
0.34
0.3
0.08
0.06
-0.09
-0.18
-0.26
-0.27
-0.62
-0.67
-0.78
•-. :PG2^-,::;
0.31
0.24
0.85
0.71
0.83
0.45
0.91
0.7
0.86
0.68
0.68
0.67
0.52
0.49
0.07
' • •. PC3:.-i 1
0.27
0.1
-0.27
0.17
-0.16
-0.63
0.09
-0.29
0.25
-0.65
0.61
-0.16
0.41
0.51
0.44
23