C j O O > 20

RDT BRIEFING MEMOLover Ecorse Creek Dump (North Drive) Site

November 24, 1993

Purpose

The purpose of this Regional Decision Team briefing is to requestapproval to precede with a fund lead RemedialInvestigation/Feasibility Study at the Lower Ecorse Creek Dumpsite (formerly known as North Drive), located in Wyandotte,Michigan.

Background

The North Drive site in Wyandotte, Michigan, is a residentialarea built on a flood plain which was filled with an industrialwaste known to contain the compound ferric ferrocyanide, amongother materials. It has been suggested that the waste ismaterial called "gas wash" a product of the coal gas purificationprocess. The subsurface soils of several of the lots are knownto be contaminated with blue waste which contains cyanide. Theblue waste material has been routinely found two to three feetbelow the surface in a layer six inches thick. Blue staining wasalso found leaking through the basement walls of one residence.U.S. EPA has been contacted by numerous area residents withinformation about additional materials disposed of beyond "gaswash" and additional areas in Wyandotte and other communitieswhich were filled with similar industrial waste.

The site was referred to the United States EnvironmentalProtection Agency (U.S. EPA) in October 25, 1989, by the WayneCounty Health Department. U.S. EPA tasked its TechnicalAssistance Team on October 27, 1989, to conduct a siteinvestigation. Based upon the results of that investigation theAgency for Toxic and Disease Registry (ATSDR) made thedetermination that, "The levels of cyanide found in the soil dopresent an urgent public health threat. Steps to eliminate anydirect contact with the contaminated soil need to be takenimmediately." Subsequently, on December 1, 1989, U.S. EPAinitiated a removal action at a portion of the site, whichconsisted of capping areas of known contamination with 6 inchesor more of topsoil, and filling areas which had been excavated bya property owner with slag. These areas were then revegetated.Additional sampling was performed to determine the nature andextent of contamination, including water and air samples fromres idents' basements.

On August 13, 1993 ATSDR issued a Public Health Advisory for thesite. The advisory recommended that U.S. EPA implement thefollowing actions: 1) immediately dissociate the affectedresidents from the cyanide contamination, which is at levels ofhealth concern in residential subsurface soils; 2) implementpermanent measures to remediate the contamination as appropriate;

EPA Region 5 Records Ctr.

mi'235733

3) consider including the North Drive Site on the EPA NationalPriorities List or use other statutory or regulatory authoritiesas appropriate, take other steps to characterize the site andtake necessary action. They also recommended a door-to-doorwater utilization survey for the site area, and consideration ofplacing restrictions on digging into soils in the affected area.

On September 24, 1993, U.S. EPA signed an action memo committingadditional funds to the time-critical removal, for the purpose ofdissociating residents from the contamination leaking through thebasement walls at It would also fundrepairs to the existing soil cap and additional extent ofcontamination studies. U.S. EPA is also evaluating removal ofcontaminated soils from one of the affected properties. OnAugust 30, 1993, Region 5 proposed this site for inclusion onnext update of the NPL, based upon ATSDR's Health advisory. Itis expected that the site will become final before the end of thecalendar year.

Based upon the lack of evidence, and the urgent need to proceedwith a cleanup at this site to protect public health, we arerecommending to move ahead with a fund financed RI/FS. Noevidence exists to link any parties to the dumping that occurredin the area. A former resident of the North Drive area, hasstated that he remembers that green trucks, similar to trucksthat used to be used by the local gas company, now known asMichcon, dumped blue material along the Ecorse Creek near thecurrent site. This blue material may have been gas wash wastecontaining ferro-ferricyanide. Also a company called MichiganAlkali, now know owned by BASF, may have generated similar waste,but no evidence, other than anecdotal, exists to link eithercompany to the site. Based upon the available information, U.S.EPA offered BASF and Michcon the opportunity to perform theremoval action at the North Drive site. Neither party cooperatedand a fund financed removal commenced.

Risk

Based upon the most recent sampling, 3 to 70% (30% on average) ofthe cyanide complexes found at the site could be bioavailableupon ingestion as evidenced by data from the weak aciddissociable (WAD) method. The WAD method evaluates free cyanideusing acidic (pH 4.5) and boiling conditions. The ATSDR HealthAdvisory concluded that the site presents a serious immediatehealth risk based upon a worst case scenario that children wouldbe exposed to the highest level of WAD cyanide found insubsurface soils (1,262 ppm at 2-3 foot depth) continually over anumber of months at a maximum soil intake (5,000 mg/day) for apica child. Using a reasonable maximum exposure scenario used inSuperfund, where the highest value found near the surface (288ppm WAD CN) is used with a more typical soil intake value of 200mg/day for children we are below a level of exposure concern forany health impacts, using EPA's lowest existing reference dosefor hydrogen cyanide (0.02 mg/kg-bw-day). If a higher percentage

of cyanide is bioavailable (say 50% on average) upon ingestionthe health based criteria is reached. From the 3 to 70%bioavailability evidenced from current data, it appears that thecyanide complexes in the site soils are degrading, potentiallymaking all cyanide in the soil bioavailable and making theassumption of a higher percentage a reasonable one at this time.Further investigation into methods to test for cyanide arenecessary to accurately assess the bioavailability of cyanide atthis site.

At one residence where basement air data has been gathered, the cyanide exposure for 8 hours inside the

house with a four to six year old child for light to moderateactivity would be about 5 mg CN/day. This is, by itself, about10 fold EPA's safe dose for HCN. These levels also seem toindicate that the cyanide complexes are decomposing.

Although data only exists for the area of the removal action,interviews with former residents have indicated that the samematerial found at may have been used as fillmaterial all along the Ecorse Creek. Therefore, similar risks asdiscussed above may exist at other areas along the creek.

Community Concerns

Community Relations activities for the North Drive site,Wyandotte, Michigan began actively in June of 1993. Theseactivities have included meetings with the residents of theproperties affected by the removal. The activities also includedpress releases and interviews with the mayor, city council andneighboring residents to discuss the removal action.

On Sept 21-23, 1993 three days were spent in Wyandotte onCommunity interviews. We spoke with the Mayor and city council,and about a dozen other residents and neighbors. The mayor leftthe meeting saying we aren't telling him anything new and that hehasn't heard before. Other council members had various questionsinvolving building, remodeling, selling and buying property onNorth Drive. The residents on the removal site have expressedthat they would like some action taken; it has taken over threeyears to get to where we are today. They would like to selltheir property and move on with their lives. There is alsoconcern about what effects the contamination might have on apregnant woman and infants (there is pregnant woman living on-site now). Older residents in their 60's, 70's and 80's, whohave lived in the area all of their lives expressed a "so what"attitude. To paraphrase their concerns, "We've lived here allour lives and haven't been affected...we've played in the soilsand throughout the neighborhood...it hasn't been affectingus...why spend all that money for something that's not botheringus."

There has been considerable spuratic television an newspapercoverage of the site by the local media. On August 13, 1993

ATSDR released their health advisory. We did a release aboutremoval work starting on September 30, 1993. Several articlesappeared in the local papers and on TV for about two weeks thenstopped suddenly.

Congressman Dingell has been becoming more involved in the site.He has requested a briefing of his staff by the EPA. His mainconcern up to this point has been to get some action at the siteas quickly as possible. It could be expected that his involvedwill increase in the future due to the residential setting andpotential extent of the site.

Projected Cost/Schedule

Based upon a Intergovernmental Estimate prepared for the projectit is estimated that this RI/FS may cost approximately $941,680.It is estimated that the project would be completed by FY93 Q3.

Recommendation

Due to the great potential for human health impacts posed bycontamination at this site we are recommending that the RDTapprove commencement of a fund-financed RI/FS at the Lower EcorseCreek Dump site, and to obligate $941,000 for the action.

o

_JLJUL_1 LJLJUUUUUULJI u

1*

L» «

r~ni . ,r^

H II1 1

r~i

!l

il >XJ>>/

/'/

L,. U

^* / //*.

WYANDOTTETTTTi

CHI J L 1 •

^

jfcatf uui ctceCWO 000 100 lOM

[

f5

,J0~

k. -J(Z Jc1 1

1 l/~ 3 s|

*¥= \

,JU

(^ — 1In —

i5

1 IvMark A. Kowalewski cny Enqm««r

ft

}|

LJ[3

IL,A^JI

3 --TC]C^Ji

OJLJ3S

ilua

b' ~^^^ — iTr~l ^^_

s.v,±lE

Zd

,,j

•MJUKW.

sW"n

<3s

Potential Areaof Concern

FACT SHEET TEXT

NORTH DRIVE SITE

WYANDOTTE, MICHIGAN

DRAFT DATE: 5 NOVEMBER 1993

INTRODUCTION

The United States Environmental Protection Agency (U.S. EPA) is responsible for investigating

and overseeing the cleanup of hazardous contamination throughout the nation. In 1980,

Congress created the Superfund1 program, authorizing U.S. EPA to respond to releases of

hazardous substances, pollutants, and contaminants into the environment.

U.S. EPA has several internal programs to manage the complex task of cleaning up

contaminated sites. One of these programs, the Removal Program, was created to respond to

emergencies involving hazardous substances, pollutants, and contaminants. The Removal

Program was designed to minimize or eliminate any immediate danger when hazardous

materials threaten to contaminate the air, soil, or water, and endanger human health or the

environment In a typical U.S. EPA removal action, the contaminants are removed from the

area for treatment or disposal In a safe and approved manner. In some removal actions, the

threat can be removed by treating the contamination at the site.

This fact sheet provides information about U.S. EPA's investigations and recent actions

regarding the North Drive Site in Wyandotta, Wayne County, Michigan. The investigations

have been conducted by the U.S. EPA Region 5 Emergency Enforcement and Response

Branch (EERB), Response Section 1, of Grosse lie, Michigan.

Words appearing in bold type are defined in a glossary on page .

SITE DESCRIPTION

The North Drive Site Is located In a residential neighborhood In the City of Wyandotte, Wayne

County, Michigan. It consists of several residential properties along the south bank of the

Ecorse River, near the confluence of the river's north and south branches. The site Is

bordered on the north by the Ecorse River and further north by the Great Lakes Steel

Company; on the east by Fourth Street; on the west by Sixth Street; and on the south by

Emmons Street.

In the past, waste materials from an unknown source were dumped as fill in this area,

resulting In a layer of blue waste in the Surface and subsurface soils. Laboratory analysis

found that this waste contains a cyanide compound known as ferric ferrocyanlde, or

Prussian blue-a pigment that is commonly used In paints, dyes, and plastics. The full extent

of the waste layer is not known; however, studies indicate that the principal areas involved are

the properties at and the two adjacent vacant lots to the east on the north

side of the street. The waste layer has also been observed in the soil of the property at

on the south side of the street All inclusive, the site is estimated to involve an

area of approximately 40,000 square feet

SITE HISTORY

Prior to 1930, the land near the banks of the Ecorse River In Wyandotte consisted of

wetlands. Between the 1930s and 1966, the north and south branches of the river were

rechanneled in this area, and much of the wetlands were filled to create land for residential

development. The fill In many cases apparently consisted of waste material from local

industries, and was subsequently covered with soil. Later modifications to the river channel in

the early 1980s involved straightening the south bank of the river at the rear of several

residential properties in this area, reportedly using construction debris as fill.

A series of historical aerial photographs reveals the progress of the rechanneling. A 1937

photograph shows the wetlands and a small brook that flowed to the river between the present

locations of the properties at and . A 1951 photograph indicates that

much of the fill activity In the area along the river had taken place by that date. According to

the Wyandotte City Assessor's Office, the residence at was built in 1955; the

structure Is visible In an aerial photograph dated 1957. It is believed that the blue waste

material may have been dumped during the fill operations that took place prior to the

construction of the house at Local residents who lived nearby during the

years that the filling took place recall that the blue material came from a local Industry, and

was referred to as gaa wash, a by-product of the de-sulphuring of coal gas.

On October 3,1989, the current owner of the residence at called the Wayne

County Hearth Department (WCHD) to report that workers excavating to replace the driveway

on the property had encountered blue-colored soil. WCDH sampled soil from the driveway

and found elevated levels of cyanide. WCHD then referred the site to the U.S. EPA EERB.

U.S. EPA ACTIONS

On October 27,1989, U.S. EPA conducted a site assessment of and nearby

properties. U.S. EPA representatives observed that the sump at was heavily

stained with blue and white crystals, and contained blue water. According to the owner of the

residence, the blue water was especially noticeable after a heavy rainfall. Blue stains were

also visible on the basement walls, most prominentiy on the east wall. Outside the house,

stressed vegetation and stained soil were observed on the eastern portion of the property.

Blue stained soil was also visible in the soil where the driveway was being repaired. U.S.

EPA collected soil samples containing the blue waste, as well as samples of sump water from

the basements of two resldences- and . The samples were analyzed for

total cyanWe-a measurement of the concentration of cyanide that is present, whether it is

chemically bound to other substances or is free to react with other substances. Analytical

results showed elevated concentrations of cyanide in the soil samples, with the highest

concentration in a sample collected at a depth of 2 feet at The sump water

sample collected at contained total cyanide at a concentration of 2.4 parts per

million (ppm) and naphthalene at .041 ppm. The sump water sample collected at

contained total cyanide at 1.1 ppm.

The analytical results from this site assessment were transmitted to the Agency for Toxic

Substance and Disease Registry (ATSOR) for review and assessment ATSDR Issued Its

review on November 22.1989, concluding that the levels of cyankje found In the soil

presented an urgent public health threat. The agency further recommended that steps be

taken Immediately to eliminate the risk of persons coming Into direct contact with the

contaminated soil.

Following the ATSDR review, U.S. EPA Initiated an emergency response on December 4,

1989, to stabilize conditions at the site. The areas of known contamination were covered with

a cap of 6 Inches of dean topsofl, and the driveway and sidewalk, which had previously been

excavated by the property owner, were covered with slag. Additional topsoil was later spread

to cover an area that had become eroded. These actions eliminated the possibility of direct

contact with the blue waste material, and significantly reduced any threat until an extent-of-

contamination (HOC) study could be performed at the site to assess any dangers presented

by the presence of the cyanide-containing blue material.

U.S. EPA also began a search to identify companies which may have dumped the cyanide-

containing materials that have been found at the North Drive site. Such potentially

responsible parties (PRPs) are required under Superfund to clean up the contamination, or

pay the costs required for cleanup of the contamination at the site.

In April 1990, U.S. EPA conducted an EOC study to define the vertical and lateral extent of

the blue waste material, and to determine whether contaminants in the material were

spreading to surrounding soil. Post hole diggers were used to bore through the soil down to

the water table. The soil that was extracted with the boring was inspected to document the

approximate depth and thickness of the blue waste layer. In the boreholes where a distinct

layer was observed, soil samples were collected from soil below the waste layer to determine

whether contaminants from the waste layer were leaching to the surrounding soil. The blue

waste layer was found to extend Into the groundwater in many of the boreholes.

Groundwater samples were collected in two of these boreholes. Analytical results indicated

cyanide in samples of the soil below the blue waste layer and in groundwater samples,

confirming that cyanide had migrated from the blue waste material into the underlying soils

and the groundwater beneath the site. Chemical analysis of samples of the blue waste

material showed high levels of cyanide.

Further studies were performed to identify the cyanide-containing material and to determine

whether the cyanide could be released to the environment as free, or reactive, cyanide. In

January 1991 , a soil sample was collected at a depth of 2 to 3 feet. The sample was

subjected to x-ray diffraction analysis, a method that Is used to identify the chemical

constituents of a given substance, rather than measuring the concentrations of chemicals In

the substance. The analysis identified the blue waste material as ferric ferrocyanlde, a

chemical compound of iron and cyanide. Research to date indicates that the chemical bond \

between iron and cyanide is very strong, suggesting that the cyanide in ferric ferrocyanide J—

cannot be readily released to the environment <->

Sampling of water from residential sumps in May and June 1991 detected low levels of total

cyanide and did not detect reactive cyanide. Additional investigations were conducted in June vJc-

and July of 1991 to document the extent of blue-stained soil on th property v, ^ 'f~ <«-' '"*

and the adjacent vacant lots. Sampling was also conducted in October 1991 on two other V,i \?h *properties, and . Results showed little to no contamination on the V'<x

property. Analysis detected elevated levels of total cyanide but no reactive cyanide In \j

samples from .

Results of these studies showed consistent results for the measurement of total cyanide In soil

samples from the NorthDrjve site. Results measuring the concentrations of free and reactive

cyanide, however, were InransistentT^uldJdjiotjndicate conclusively whether the cyanide

present In the waste laye>1rMhe-soll'presents an environme_-t

'In June 1992, samples were collected for analysis by a new analytical method called weak ^^T

acid dissociable (WAD) cyanide analysis. WAD cyanide analysis is a method which attempts

to Identify in sample material that portion of cyanide which can easily be released to the

environment when exposed to weak addle conditions, similar to conditions present in the

environment Under a sampling plan developed in consultation with ATSDR and U.S. EPA's

Environmental Monitoring Systems Laboratory in Las Vegas, Nevada, U.S. EPA collected

WAD "

groundwater samples from basement sumps and soil samplesTkom the blue waste layer for

WAD cyanide analysis. Results Indicated elevated levels\of total dyanlde.

In December 1992, to determine whether cyanide was present near the ground surface of the

areas that had been capped with topsoil In the 1989 emergency response action, U.S. EPA

collected surface soil samples at the and properties. Results

Indicated high levels of total and WAD cyanide in natural soil eneath the previously installed

soil cap.

In January 1993, the owner of the residence at reported that a blue liquid and

a red-orange liquid were leaching into a basement closet. U.S. EPA preformed an emergency

response and a subsequent sampling visit Analytical results indicated elevated levels of total

and WAD cyanide in samples of the leaching liquid.

U.S. EPA has regularly provided updates on site conditions to WCHD, MDPH, MDNR, and the

Wyandotte emergency department

RECENT ACTIONS

On August 13,1993, ATSDR issued a Public Health Advisory regarding the North Drive site.

The advisory addressed the potential for residents of the area to become exposed to soil

contaminated with cyanide-containing compounds.

In September 1993, federal funding was approved under the Superfund Removal Program for

an emergency response to address the cyanide-containing material leaching into the

basement of the residence at U.S. EPA representatives met with local

officials and residents of the neighborhood surrounding the site to discuss the proposed

removal action and to assess community concerns.

The proposed removal action will Involve . The U.S. EPA EERB

expects construction activities to begin in (month) .

Unted Stales Region 5 Illinois. Indiana.Environmental Protection 77 West Jackson Blvd. Michigan, Minnesota,Agency _ Chicago, Illinois 60604 _ Ohio. Wisconsin

x°/EPA EnvironmentalNEWS RELEASE

Technical Contact: Bob(313) 692-7662

Media Contact: Dave Novak(312) 886-9840

For Imnediate Release: October 1, 1993

No. 93-SF81

EPA SET TO TACKLE CYANIDE AT WYANDOTTB SITE

U.S. Environnental Protection Agency (EPA) Region 5 has received approval

for investigating a cyanide-contaminated area in Wyandotte, HI. It involves

11 lots and 8 homes on North Drive, along Ecorse Creek.

The area soils contain low levels of cyanide which appear sporadically

throughout the 11 adjoining lots. Blue soils were found at depths of 2 to 3

feet.

"Our main concern is a hone where blue and red substances containing

cyanide are leaking through the basement foundation, staining the lower walls,

and collecting in the basement sump," said Bob Buckley, EPA's On-Scene

Coordinator and head of the technical investigation. "We've been involved at

the site since we were first contacted by the Wayne County Health Department

in 1989," he said. "Cur immediate goals are to stop the contaminants from

getting to area infants and from leaking into basements. Then we'll do soil

testing on the surrounding properties."

~ more —

e

"The are4 is also being considered for EPA's National Priorities List of

hazardous waste sites," said Deputy Regional Administrator David A. Ullrich.

"This would give us the authority for long-term, extensive toxicological

studies. We can then evaluate on-site treatment possibilities and the long-

term actions that may be necessary to remedy the problem."

EPA is handling the investigation in cooperation with the Agency for

Toxic Substances and Disea.se Registry, Michigan Department of Natural

Resources, the Wayne County Health Department, and other State and local

agencies.

Last week, EPA officials and government contractors began making plans

for testing and cleaning up the contamination. When residential access and

other agreements are obtained, extensive testing of the 11 lots will begin,

and the leaking basements will be looked into. Work in the neighborhood is to

begin almost immediately.

U.S. ENVIRONMENTAL PROTECTION AGENCYTECHNOLOGY SUPPORT CENTER

ENVIRONMENTAL MONITORING SYSTEMS LABORATORYP.O. BOX 93478

LAS VEGAS, NEVADA 89193O478

FACSIMILE LEAD SHEET

TO:

TBf PRK5DIVILLB

PHONE NUMBER/VERIFICATION NO: FAX TELEPHONE NUMBER

312-353-5541

OFFICE:

331-886-5122

FROM:

Kenneth W. Brown

PHONE NUMBER:

702-798-2270

FAX TELEPHONE NUMBER;

702-798-3146

DATE:

11-08-93

NUMBER OF PAGES INCLUDING COVER

23

COMMENTS:

octcaer 2, 1932

SUBJECT: Results of Cyanide Analysisfor the North Drive NPL 3ite

FROM: Kenneth W. BrownManager, Technology Support Center

TO: Bob BuckleyOn-Scene CoordinatorRegion 5

Bob, plaase find attached the report titled "Nortii DriveSpecialized Cyanide Analysis" by Jan £ric Kildufr, an LESCLV) Chemist. Edward and I hop« tha results of these sampleanalysis from the North Drive Site will be helpful to you andyour co-workers.

If you ne«d additional explanation and/or clarificationconcerning tha attached report, please give me a call at(702)793-2270 or Edward at (702)793-2626. If EMSL-LV can provideadditional technical support to you, please give me a call.

Attachment

oc:Edward Heithzar, QADPhil Galley, LESC

NORTH DRIVE SPECIALIZED C Y A N I D E ANALYSES

Jan Eric KilduffLockheed Environ menu! Science and Technology

9SS Kelly Johnton Or.Lu Vegu, Nevada 89119

Contract 68-CO-0049

Ttchiuctl Monitor(»j

KM Brown, Edward HeithmirQuality Aitunooe and Metboda Dtvdopnaeat Diviiioa

EaviroamfioUl Monitoring Syittmi LaboratoryP. O. Box 9347S, Lu Vegu, NV 89193-3478

TECHNOLOGY SUPPORT CENTER FOR MONITORING aad SITE CHARACTERIZATIONENVIRONMENTAL MONTTORINO SYSTEMS LABORATORY

OFFICE OF RESEARCH AND DEVELOPMENTU. S. ENVIRONMENTAL PROTECTION AGENCY

LAS VEGAS, NV 99119

NOTICE

This technical assistance report ha.s undergone i technical and/or q u a l i t v assurance review ar.C approval bypersonnel of (he EPA'ORD Environment:! Monitoring Syitems L^boniory »'. LAS Vepas (EMSL-I.V), Is forinternal Agency js« only. Distribution, application, and use of ihe dau conUiued herea ire u the discrtiion of

personael.

li

. „• : 4a«ri . : £— i' "SL i_ •

TABLE CF CONTENTS

Notice i i

Introduction 1

Approach 1

Procedure . . I

Resulu and Discussion 2

Conclusions tad Recommendations 3

Cyanide Soil Concentrations (Table I) 4

Cytniaa Witer tnd .Vir Conc;ntratioui (T*ble 2) 5

APPENDIX

RAW Analytical Data for North Driv* Soil Sample* (TabU 3) 7,3

Raw Analytical Data for North Drivt Water and Air Samples (Table 4) 9.10

Calibration Curvet for Ccloriractric Analyiet 11 to 16

Summary Data from Evaluation of Practice North Drive Soil Sampies (Table 5) 17

Summary Data from Evaluation of Synthetic Solution* (Table 6) 18

in

NORTH DRIVE SPECIALIZED CYANIDE ANALYSES

. INTRODUCTION

~^ic North Drive site in W;'s-iaoite. Michigan has «oil uid \vi.er potentially conaminajed «-nfl hignconcentrations of (hi mixed valence compound ferric ferrocyimdc otherwise known u Prussian Blue. Routineanalyses, using EPA metmxs 9010 hu produced ambiguous dita. Analyses for cytnids amenable to chlorinatiouwere nsa^inglass. Ai i consequence of these results, Robert I. 3owden. ChJef Emergency Response Branch.Region 5, requested Kenneth W. Brown, Manager Technology Support Crater at the Environmental MonitoringSystems Laboratory in Las Ve^as (EMSL-LV) to provide technical support for cyanide analyses. Ai thedivision coctractor. Lockheed waa requested to evaluate analytical protocols for cyanide »nd provide ipecialiudanalyses of cyanide in site-specific soil and grouad water sample* u part of the technical rapport.

IT. APPROACH

Analyses of sou and B.-ounawater samples from the North Drive me required cyanide a-ialyjes which distinguishbetween easily liberated cyaude .<od cyanide completed with inas:(ion meuls such u iron nickel and cobalt.The A3TM Standard test D 2036-S9C for Weak Acid Dissociable (WAD) cyinida and EPA Method 9010 fortotal cyanide were (he methods selected.

The complexity of there sample* required triplicate analyse*, interference checks and protocol verification of tbechosen analytical method* with synthetic solutions tad practice aoii samples. The WAD cyanide method wasevaluated for interferences from ferri- and/or ferrocyaoide. An ion chromatognphie (1C) method waa evaluatedfor its applicability to verify the presence of lulfide aad scrai-quantitate the cyaaide concentrations. Theinterference potential of culftd* in the colorimetrie determination of cyaaide was also evaluated. Practice soilsample* wen used to refine both analytical .method* aad address concerns with dimple homogeneity and highcyanide concentrations. A meeting with EMSL-LV personnel waa held to eaubUnb refined method proceduresbased upon the data obtained from taalyse* of the synthetic solutions and practice soil samples.

ITI. PROCEDURE

Th* ASTM Standard test D 2036-89C for Weak Acid Dissociable (WAD) cyuude was evaluated with sevensynthetic solutions. Five cyanide solutions obtained from potassium cyanide (XCN) 0.50 mg/L OT. pouuuiumferhcyaaide K.jFe(CN)« •' 5000 aad S.O mg/L CN*. tod potassium ferrocyanide K«Fe(CN\»t 500° *od 5-°mj/L CN' wore evaluated. A solution of 50.0 mf/L Na,S and a mixed solution of Kj=e<CN),, KCN sad Na, Sat 5.0. 0.5 and 50 mg/L respectively, were also eveluaisd. Each synthetic solution type was distilled intriplicate along with a spiked or unspiked prepiratioa blank and all solutions were analyzed coiorimetncaily.

Twelve sec* of triplicate analysis of the North Drive practice soil umplee were performed according to theWAD cyanide (5 sets) and EPA Method 9010 cyanide (7 sets) methods. Results from these evaluations wereused to reflae the analytical methods prior to analysis of tbe North Drive samples.

r

The ASTM WAD cyaaide aad EPA total cyaaide methods were used with the following modifications. SoilMunples were prepared u slurries in amber bottle* with 0.01 M NaOH. Triplicate sample* were taken from theslurry mixture. Sufficient sample was taken to ensure an uaslurriod soil sample size of 0.1 (ram which is s tea-fold reduction in sample size normally required by each method. Water aaomloe consisted of either 250 mL or100 mL aliquots. diluted to a final volume of 500 mL with deioniied water, dapeadcot on the number of

1

ar.Uv:cs rcaiired for the. part icular sample. Quality arriuronce requiremer.u .-.pecifu-d 2 .oii and or.c vn^cr rp i ice•c l.C mg cymij f t for eacn rr.etnoa. Th: 1C was u««i (c irulvz«: ire sc<-uober solutions tr.d de:cnrunc ai u t ion

:~Rciors necessary for appl icat ion of the cclonmetnc mrtnod. IV.rnary qL*.ii ucion for cvm:de used iht manual^olonmetnc analysis outlined in ASTM 2G36-S9C. One triplicate :ct of to^il cvtr.ide w.aiys&s w*$ dist i l led oru:

hour after recharging me icrunber with fresh N»CH s o l u t i o n . Authent ic Pruvsiin alue sample*by ths AS7M WAD and EPA 'yOlO methods for compir»tiv« -jjrpo»e«. Specific details of the

and QA requirement are dcv:rib«d in the Quality Assurance Prefect Plan (QAPjP).

IV. RESULTS AND DISCUSSION

A. InUrferencA Check* and Protocol Venfication

ASTM WAD cyanide method -act the percent recovery md relajiv* standard deviation (RSD) requirement!4* specified u> :QC Technical Work Plan (TWP) for $ynthetic toluttoas (Table 6, Appendix I). Two wlutioruwfire evuluated it unceatratioot 1000 time* in excess of the specified tnxmm to determine (he ir;erterencts dt,eto high-iron cyanide complete*.

Analysis of the practice soil samples (Table 3, Appaiidix) determined t 10 fold reduction LQ simple siie wunecessary to remain below maic.mum recommended cyanide concentrations for '.he method* Problems withsample homogeaeity required the soili b« homogeoized into a slurry with water. AnaJys.s of the North Drive

tubstiruted 0.01 M NaOH to ensure better cyanide stability.

One liability/ S1 inxrferenc* study was completed. The study consisted of spiking a portion of cyanide distillatesolution with Na,S to yield a 500 mg/L S'1 sclutton. After 24 hours the spiked acd unspikcd solutions wereanalyzed colorimttncally. The cyanide valuea for both solutions were unchanged from the previous day.

B. North Drive Soil and Water Sample*

Soil md water sample* collected June 22 tad 23, 1992 wen itored cold and in the dtrk until analyse*conducted from August 20 to September 3 were complete. Summary data for the cyanide concentration! in thetoil camples are reported in Table 1. Summary data for cyanide concentration* in the water umplea arereported in T»ble 2. Complete analytical result* are in the Appendix (Tables 3 and 4). Samples from stationS106, S107, S109 were scrubber solution* from air sampling. Sample* $106 and S109 had leaked all solutionduring stupmant, 5 siL remained in S107. Colonmetnc analysis indicated < 10 ppb cyanide present,

The sot! sample* ranged from • dry garden soil to a dark blue siudge typical of a river or lake bottom. Soilsample* slumea wen prepared in sufficient quantity to allow aliqucts to be drawn for total, WAD and spikesamples from on* container. After homogeoization the tlurrie* appeared uniform in color and texture with theconsiiteacy of syrup. Slurries were stored cold tod in the dark except whiie measuring out sample*. Slurrieswere remixed prior to talcing sample*. Between two and three set* of multiple distillations »ere completeddaily. Precaution* were taken to tainimiie expofurt of the aample* to light during the distillation* using an•luououm foil covered fume hood sash. Toe hood wall* were covered with a dark grey plastic to minimumreflected light

Distillate* were analyzed within 36 to 48 noun. During the protocol validation stage sufficient preparationblanks were run to demonstrate the method* free from cootaounale* and interferences, thua only on* WAD andone total cyanide method blank was analyzed to confirm the punty of the ie*gent*. Recoveries of spikedreagent blanks (1.0 mg cyanide) were deemed *uffiewnt indicators of proper method performance. The first setof oolorimMric aoalyte* were performed at 540 am, on the shoulder of the Umbda^ at 578 am normally usedfor this analyst*. There wax a concern that the high abaorbance of the sample* would not yield linear resultsabove 100 ppb with the spectrophotomeier. Reeoverie* of the ICV and CCV at 105 and 104%, respectively acd

an R: = O.S932 for the 0 to 200 ppb curve indicated the data were acceritMble. Hie rerrvuninc colonmeincanalyses were performed at S"1! nti

Hi* 1C method for analysis ol CN' and S!' determined thai in the presence of cxc&ss i-', the sens i t iv i ty of the:lcctrochem:cal detector for cyanide1- was severely reduced and unstable. When S~ was abseni. ne 1C cyanidecalibration remained stable. The 1C was configured to rncasura a concentration range from Approximately 02to 10 ppra, ihe expected cyanide concentration of dittillaiu after d i lu t ion In all samples the S"1 concentration•.vas leu than 0.2 ppm. Due to a somewhat noisy baseline the 1C yielded positive results ( < 0.15 ppra) evenwith eluam blanks.

Several samples had RSD's vn excess of 25% by either the Toul or WAD cyanide method but not both. It issuggested thil heterogeneities to the flumec due to small stones and organic dcbns co-jpled with an extremelysmall urople sii» tony have contnbuted to the error. Large RSO's were teen in some water sample* to whichpaniculate was present. Effort! were taken to obtain a representative water sample but settling may haveoccurred wbile taJong sample ahquois.

For aoit sample SlOO, the scrubber was collected (u specified in the protocol) after a one hour collection ume.New scrubber wu added and distillate collected for an additional hour. The cyanide concentration for thesecond hour wu 73% of the value obtained after the first hour. The result demonstrates the method does notcompletely recover all cyanide and that it is time as well as concentration dependent. Keating raws duringdistillation, gu flow-rates through the scrubbers and sample size all have an influence en the reported cyanidevalue. Tie protocol did not specify collection, of distillates for an additional hour in the WAD cyamdeanalyses. In general, the reported concentrations for total cyanide are suspected to be low. Because of timeconstraints total and WAD cyanide analyses used a single calibration curve. The totaJ cyanide method requiresa stronger ionic strength NaOH scrubber solution which may have inhibited color development of the distillates.resulting in an estimated maximum decrease of 10% below the actual values for total cyanide.

The WAD and total cyanide analyse* of 0.1 gram samples of Prussian Blue wero used to compare the high soilcyanido concentrations to the pun suspect compound. The WAD cyanide concentration for Prussian Blue wasapproximately equal or lower in concentration than in the highest soil samples. This ii not unreasonable as thehistory (exposure to sunlight during processing and packaging) ii unknown. Toe cyanide values obtained fromthe total cyanide method wu a minimum of 6 fold higher than any soil or water sample.

V. CONCLUSIONS AND RECOMMENDATIONS

The values obtained for the WAD cyanide analysis of the North Drive soil and water samples are representativeof the quantity of easily liberated cyanide present in those samples. The reliability of the data ia supported bythe percent RSD of the triplicate analyse* aad the spike recoveries. The total cyanide analyses also hadreasonable RSD'i and spike recoveries. However, aa demonstrated by the additional 1 hour distillation, thetotal cyanide value* in only reprosenutive of the total cyanide that can be recovered in a one hour distillation.The percent of total cyanide present in the sample that this represents is currently unknown. Although notexperimentally verified in this work, it might be expected that one hour WAD distillations also do not recoverall cyanide* that could be released with longer distillation time.

Further investigations are required to find a more suitable method to obtain total cyanide values in soil andwater samples which is time and concentration independent. On* potential method would utilize ligandexchange of that free and weak cyanide metal compiexae with the moat stable metal cyanide complex whichcould then be analyzed colorimetncally or by 1C. The 1C method for cyanide U rapid and reasonably precise.Further refinement of the method utilizing pulsed electrochemical detection is required. This technique shouldallow the quantitation of both cyanide and lulflde without lose in souativiry because of its ability to maintain aclean electrode surface.

Ttble 1, Cyanide Concentrations' ird Spike Recoveries from N o r t h D r . v e soils

!Sample

ID(*)

S99

S99

SLOG

S100X'

Si 00

SI 00

S101

S101

S101

S102

S102

S102X'

S102PBS*

S102

S103

S103

S103

3104

S104

PBIuaP

PBIuaT*

PBlueW*

BlueWS*

Method'

Total

WAD

Total

Total

Total -S

WAD

Total

WAD

WAD-S

Total

ToUl-S

Total

Total-S

WAD

Total

WAD

WAD-S

Total

WAD

Total

Total-S

WAD

WAD-S

SSampie

3

3

3

3

3

3

3

3

3

3

3

I

1

3

3

3

3

3

3

2

1

2

1

[CM]*

< 21

< 22

7,936

5,772

16.452

< 34

3,573

429

5,665

13.144

18,758

7,807

oa

411

9,002

1,262

(.035

13,440

415

77.681

76,717

916

9,753

% RSD

oa

na

0.8

10.4

6.2

01

5.7

14.4

13.8

3.0

10.8

na

na

47.0

40.5

4.3

19.5

1.7

25.1

8.3

na

7.8

na

PercentSolidi

68.7

•

63.0tr

•

•

58.6

•

•

43.9

•

•

0

43,9

29.7

•

•

31.2

•

100

100

100

100

CNSpikeManirtig)

0

0

0

c1.0

0

0

0

1.0

0

1.0

0

1.0

0

0

0

.847

0

0

0

1.0

0

1.0

CNSpike

Recovery ji(%) J

na

at

01

na

101

oa

na

oa

48

oa

71

na

110

na

na

na

91

na

01

ni

45'

na

89

•Coootamtioa reported In *u received" unple, Not eomcted for % aolida.*Tbi "-S* deootea a ipikad uoaple.•Samplt* (with ID'i 3100T_X2) distUltd 1 additional hour with freth acrubber solution.'Sample it a preparation blank tpikod with 1.0 mf of cyanide.•Authentic Pnuaiaa Blua ample.'Calculated from Sample ID I PBIueTA.

rab!« 2. C;inide Concentrations and Spike Recoveries from North Dnve incl Air Simples.

SampleID(*)

S107»

S89

S89

S89

SS9WPB

8-26TP3

8-26TPBS'

S90

S90

S91

S91

S91

S91

S92

S92

S92

Method*

fiB^Si

Toul

Toul

ToUl-S

WAD

WAD

Toul

Total

Toul

WAD

Total

ToUl-S

WAD

WAD-S

Toul

WAD

WAD-S

Sample

ssssem

i3

3

3

I

1

1

3

3

3

3

3

3

31

3

3

Avenge[CN]

(mg/L)ssamsss

< 0.010

0.914

4.180

< 0.010

< O.OiO

< 0.010

3.197

.583

0.370

1.241

9.201

< 0.010

6.775

2.758

< 0.010

4.150

% RSD

BaiBSS

na

23.2

5.0

na

na

oa

ca

na

7.5

10.3

3.6

na

3.3

l.l

na

6.8

CNSpikeMass

SBBS

0

0

S473

0

0

0

8473

0

0

0

1.0

0

1.0

0

0

1.0

CNSpikeConeimg/L)

0

0

33S9

0

0

0

3.389

0

0

0

6.67

0

6.67

0

0

4.0

CNSpike

Recovery

na [1

na

94

na

na

tu

94

na

oa

oa

119

na

102

na '

na ,

104

The '•£* deootea a tpikad aaopl*.^Sanpl* cnnaiited of 5 mL of §crubb«r wlutioa.•Sample ia a preparation blank spikad with 1.0 mg of eyiaide.

APPENDIX

Table 3. Haw Analytical Data for Cyanide Analysis of North Drive SoH Sample*

sue. coc PATES(if) ML tt». OMlttMl AMlyntf

1 8SO T71C6S An, 25 Aug 25

2 ass trass An2s AH 2*a aos 171*90 AH2S Anas

4 so* i7i5s» AH at 6»pts ast in*** AH at SHI8 8M 1715641 Augai 8>p1

7 8100 171651 AufllO Aug 210 8IM 171551 AH 20 AHtlS SIM 171861 AH 20 AHtl

1O SIM' 171(51 *H *• *»S*111 SlOf 1MC51 AH 30 AH 2112 8100- 171*61 AugM AH 21

IS SIM 17I5S1 S»p2 Sup*17 SMO 1716*1 aopf awS

10 SIM 17UB1 a*pt »o*>s

10 6100 171541 8op2 S*p320 SMS 171901 Sip 2 C«pS21 SIM 171661 Sap* Sop a

22 S10I 171662 Aug25 AH 2523 SIOI 171*62 AH 2ft AH 2ft24 8101 1715*2 AH 2ft AH 2*

?r> 5101 171652 Aug 31 Sip 120 SIOI 171*62 AH 31 Copl27 S101 171SS2 AH at Sipl

2* atOI 171*62 Aug 31 Scp 12* 8101 17106X AH at Sipl30 8101 171*62 AH 31 Sip t

31 S102 171663 Am to Aug 2132 SIM 171SS3 AH IS AH 2133 SIM 171*63 AH IS AH 21

34 S142 I7ISS* Aim 24 Aug 2*3ft SI02 171*93 AMQ 24 AH 24

tern Anil, bmpln Cyw.ltte

Ht IMhod ID C«K4NM»*on

1 Total 9B8TA <22

2 Total 800TB <21a Total 8MTC <10

1 WAD 800WA < 10

2 WAD SOSWB <1»a WAD aotwc <io

1 ToUl BIOOTA 7101f Total 8100TB 7075a Total S100TC 7073

1 Total K1SOTAX2 *30S

2 Total SfOOIBXl <SSSa Total 5I007CX2 4H51

1 Total 8IOOT8AA ITASO

2 Total StSOTCBB I90UJ total SIMTSCC 15794)

1 WAD S100WA <3«2 WAD 8MOWB < 333 WAD 5100WC <31

1 ToUl 8101 TA 3S422 Ttfol 8101 IB 37003 Total 810ITC 31*7

1 WAD SIOIWA 3102 WAD StOtWB 4Ma WAD 6101WC 4*»

1 WAD S101WSA 01*22 WAD SI01WSB 9103a WAD 8IOIW8C 5M1

1 Tort SI02TA IJI11

2 Total S102TB 136513 Total 8102TC 1277*

1 ToUl 8102TSC 17204)1 Total SMZT8B 110021 Total 3I07T8A 21003

CM fip*N> (M SpiktMMan Cuo» ftacowofy

*Rg» (iH*47) f»)

0 0 n«0 0 no0 0 m

0 O IM

0 O no0 0 r.m

U 0 n>0 0 na0 0 no

0 O (>•

» 0 n«0 0 ••

1.0 0437 HMtt

IJO SISt S*4A

1.0 7M* 102*

0 O nm

0 0 Ml

0 0 no

0 0 n*

0 0 M

0 0 M

O 0 IK

0 0 no0 0 no

1 12200 &3«

0 0 n.0 0 MO O no

1 I7«0 4«<*1 1520 61*

M»«» Pi(C«nl MBIO PvrcunlRec«lrad Sl-jcry Stuny Solid** *

(0) <*) to)

O.1I20 74 7DU OHM *134Mt.

0.1213 7470* 0 I«M 0170*0.1300 7470* 01763

0.1177 74 70tt d ISflB

0 1100 74 70* 0.1*63OHM 7470% 01404

O.IICi* 73.74U 0 IM5 M.OUtt

01004 7374* 0 I4IJ 03.40*01223 7374* 0.105001100 7374* 015*50 1004 73.74H * 144301223 7374* 0 US*

0 1CC.1 7374,4 ft.1437

01234 7374* 0.1094

0 1301 73 74* * 174M

01113 73 Ji<rt O 1510

01 IM 73/4* 01626012*1 73.74* 0.1737

0.1236 71. ta^ 31784 lltCSt0.1IJB /a 4»*t 01570 0030** 1071 73 11* 0 1447

O 04107 7.->'4<"> O l l d O

00*50 73,-U* O.I 100O.M21 734** O.I II 7

OCCI0 73 48tt 0 t!l^

ooaei '34** o uo*O IOOS ;34** 0 I3«*

0.1224 U.A3H 01713 71 «m01203 0*63* 01763 M 5OW01000 MOM* 01545

o i ui oa w.« o I4W201174 MU<* 0. 17IO

D 1301 0*03* 0 IBia

Scufbkor SoMu n

by 1C Colo .

0 134 «.0 OIJ

0127 <QOIO0120 <OOIO

0 127 « oo in

O < O U i O0 <OOIO

4.02 JO/5

15t 341*

40O 3IM

2^0 ? 4»l

257 2431

t 20 3 155

722 7 4 / 2

5 «O 7 ••;

57* (211

029 <OIM6D 34 <00 16

017 <00lfl

1 It 1 8 JB

It* 1 754

1 3* 1 451

o 2je o ru• 2fli 0141

0217 01*4

2U1 ? }•>»

2*4 1 »$«

221 J 01 B

7 18 S 41 .

OM 0522

M* 5 4 1 7

7 70 ; «Jt

• 40 4405

II 11 11 1*4

Volvno tutor Ci.nr

0 26

• 2S

o ?i

076

02S

925

D2S

02S

02S

« 25

0 25

075

r. / •0 i?s

0 25

075

U2S

025

u 25

U ?5

IS

', 25

I 25

I 25

il OJ

27 03

2703

2311

2111

21 tl

4U

40

40

20

1? &

50

SO

1«-I i

I 8

j J

I 47

-2:?

144V

IC4 2

15.' I

I J25

20544

> II

4 II

4 14

I«U 3

I 10 1

/ e-. j/i n 2*I tl Bfl

20 11 .• » 1

20 »' I

rc Kit*

I J J

101 3

^)0 I VJ O

50 IM 1tO 144 0

Table 3. Raw Analytical Data for Cyanide Analysis ol North Drive Soil Samples - Continued

SUI. COC DATES(f») No. No. DIatlllad Aaalyzad

37 6102 171563 Aug 20 Aug 21

30 na M Aug 19 Aug 21

3» Sl*2 171583 Aug 27 Am 2748 8102 171*53 Aug 27 Aajg2741 8102 171*63 Aug 27 Aaaj27

42 S103 171544 Aug 20 Aug 2743 6M3 I71S44 Aug 2* Aug 2744 SM3 171*44 Augl* Aug 27

45 SIM 171*44 Aug 27 Aug 2740 8IH 171*44 Aug 27 Aug 1747 8108 171844 Aag27 Aug27

41 S103 171544 Aug 27 Aug 2748 8IM 171*44 Aug 27 Aug 27M SIM 171*44 Aug 27 Aug 27

51 8104 1715*4 Aug 24 Aug 2562 6104 1715*4 Aug 24 Aug 2563 8104 171*04 Aug 24 Au«2S

54 SI04 1716*4 Aug 31 Sop 199 81*4 1719*4 Atfg31 *a*150 8104 171504 Aug 31 Sapl

57 na na Sap 3 Sap 3M na na fta»3 Sop3

M na •• Sap 3 tap 3

60 M na fiap3 Sap 3•1 M na Sap 3 Sap 3

«2 na m S«p 3 Sap 3

Sam Anal. Sampla Cyanlda(I) IteMwJ ID ConconMtton

1 Total SI02TSAX ?«07

1 Total S102TP8S 433

1 WAO B102WA 390.6t WAD B18IWB 637.0a WAD S102WC 267.2

1 Total 3103TA 51822 Total 8M8TB 0381* Total 8103TC 12433

1 WAO S10JWA 12172 WAD 81MW8) 12Ma WAD 8103WC 1208

1 WAD 8I03WSA M532 WAO 81*3*98 «22*a WAO S1MW8C *023

1 ToUl 61WTA 135401 Total 8I04TB 136*0a Total S104TC 13114

1 WAD S104WA 4371 WAD S104WB 80*3 WAD 6I04WC 301

1 ToUl PBtunTA 731352 Tola) PBtaoTB 1Z20O

1 Tulal PeiualSA 78717

1 WAO PBluaWA 0872 WAO PBfcaWB MS

1 WAD PBIuaWSA *7&3

CM Sp*» CN SalkaoMajuj Cone Hacowary(mg) (rnoAg) (H)

1 733O 6.0%

1 "4.0 mg 1 100lfc

0 0 .11• 0 M

0 0 na

0 0 na0 • M

• • Ha

• 0 na0 ft na0 0 na

•J47 7333 106*•J47 7317 074k0.147 7530 10241

0 0 na0 0 na0 • na

0 o nt0 0 naO 0 n«

0 0 na

0 0 M

1 «167 45H

0 0 na0 0 na

1 8000 Ol<*

M««» Ptrram Ma«l PaicanlRooaivad Sicily S)UH| SolMt*'

(•) (4») (H)

0 I3«J3 fliOol* O IDM

na nil na na

o.oeeo ei.u4t 0.142100040 M.03H 0.1360

• 1166 Mftttt 01*13

01252 11 »\>V> 01521 6600%

0 1247 11 *544 0 1522 00 10%

0.1277 11 96H 0.1550

O.I (OS aijfi&St 0.1340

OHM 11054* 01462

0.1323 0105% 01*14

01165 11 »5<A 0 1410

OtIS* 11064* 0.1413

0.1124 (I.06H 01372

0005O 05 734k 01445 S5 504k

01114 Ob 734k 01005 S2 3CVk

0 1007 65 734k 0 1664

0.0904 &S 73% 0 137£,

00*40 06.134k 0 12*1

00873 66734* 01324

Oil II na n* na

01011 na na na

0 1220 na na na

01013 nt na na

0 1204 na na na

0.1007 na na na

Concanliaiiur.

Scuibbat Solubcn Sciubbn

by 1C Cclor Vii.una

(mg/L) (mo/l ) (I)

4 M i .:i7 0 2b

4M 43S1 0?S

0 53 0 20S 0 2i

423 0349 025

070 0173 025

733 3 2 4 4 02

751 5150 0?

046 7037 07

0.67 C 568 0 2S

0.06 0 022 0 25

• S» 0035 025

316 4131 OTi>

1 40 2 1<5 0 25

313 4013 025

3.26 & 147 0 2b

4.45 005« 025

025 5734 02S

02m u ii* o ?•>0241 0172 fl 2S

0210 0 IDS 0 25

20 34 32 708 0 ?S

7540 134/2 025

20 1 37 4/2 0 TS

0 U 0 3B2 0 i S

050 0437 0?S

418 3 U2U 0 il

fmctoi

2J «l

rjQ

21 57

21 5?

2157

M 6 7

6607

•007

4

4

4

25

iO5050

; o^ 02 0

200

;ao

3333

28 VI

7 M

I? 71

O O t

41 <V3

4/ II

142

151 «9

U)S SJ

1I&4I

100 S2

121 1

114 7

/» 01

15 82

I 1 I'j

13 12

!]/ i

an 810* itl 1 hour aJUr adding haah acutbbar sotoKon.

•Mai arin«d In oualical* lor «wch toil l»p«

Table 4. Raw Analytical Data for Cyanide Analysis of Not in Drive Water and Air Samples

8UI. COG DATfcS(«•) Na». Ma Ol*taM AjMriyzBd

83 888 17154* Aug 2* Anf2784 888 171848 *aj28 Ana, 27*S 988 17154* AttfjH A«g27

0* SI* 171541 Aug 20 Amjj787 8*8 17154* tag 18 Aug 278* 8*8 171548 Aug I* A>**7

7* na na Aug 20 Aug 2771 no M AjifjM AM027

72 5*8 17154* Aug 31 Sap t78 888 171848 AMD 31 8aaj174 888 171848 Au| 31 8aa> 1

75 na n« Aug 27 Aug 27

» 9*0 17154* Aug 20 Aug 27•4 808 171540 Ajjfjta A«fl27•S 8M 171940 Aug 20 Anaj 27

00 SflO 1/1540 Auflll Sap 1•7 8*0 17184* *aj31 Sap 1•0 6*0 17154* Ajpj31 Sapl

•0 801 I7IS43 Aug 24 Aug 2i88 881 171843 Aat)M Aug 7*81 8*1 171543 Aug 24 taffS

•2 SOI I7IM3 Sap 2 *>«P 3•3 881 171543 Bap 2 Sap 304 801 171543 8»p2 Sap 3

06 SOI 171543 Sap 2 Sup 380 881 171843 Sap 2 Sap 387 8*1 171*43 Sap 2 Sap 3

Sam Anal. Sampla Cyanidap) Ua4had ID Conoanaiajton

t Total SHTA 0.1*02 Total SUfB IJM• Total SOorC 0780

1 Total 6*BTSA 3O632 ToM 8*91 SB 43773 Total StOTSC 4.2*1

1 Total l-MTPfl OJOOO1 Taut B-28IP8S 3187

1 WAD StBWA O«02t 8MD SMVta O.M3s WAD SMWC oooo

1 WAD S*»WPU OOCO

1 Total SCOT A O8S4

f Tola* 8001B OS01

3 Total S90TC OSOS

1 WAD SUOWA 03M

2 WAD 800WB 0402

3 WAD 800WC 03S5

1 ToUl I7IS43VA 1 140

2 Total IT1543TB 1.2*3

3 Total 171543TC 1 MI

1 loul SBITSA 1 8^7

2 lotol SO USB 0237

3 lolaJ SOI1SC 0511

1 WAD SttlWA <OOIO

2 WAO 801 WB <0010

3 WAD SftlWC <OOIO

CN Sail* CNfipikut

fclMa Cone Ratn«ai|f

(maj {maAo) I1*)

0 0 na

0 0 na

0 0 na

OM73 33102 ttl<M

•.0473 8.30*2 *m

• J473 3M92 tOIH

0 0 na

0*473 33102 813S*

0 na <u0 na naO na. M

0 na n i

0 n« na

0 na na0 na na

O na n4

O na na

0 na n*

0 na 'ia

0 na na

0 na n*

i 067 licit

1 007 HIM

1 007 122Mi

0 na iij

0 na na

0 na na

Samp.*

Valuma

025

025

0250

0250

0250

• 250

0 100

o too0 100

U2S«

Q2SO

0250

0250

0 2M

0250

• 250

0 250

0 ?50

U <U1

0 ISO

o iso

C 250a 250

Scrubhei Sulutiui

ConcaniralkM

by 1C- G.,ki

0 a» i 101

1 78 1 U2

1 85 DM

i67 S472

033 S2S2

0 133 <0 010

430 3M7

o 13 ooaiO 13 0001

0 II 0 COJ

nd" < 0.0 to

0«B 0(17

001 07 JO

027 OC4I

0 4b 0 3^4

• .54 O 402

• 42 0 555

1 3'j 1 I4U

t 52 1 203

1*2 1 393

1 42 5 JH

482 5542

4«2 V707

C 203 ^ U O i O

• 1»S <001»

0200 <0010

Sctubbur CJii -iron

(U

c ;-0 ?0 2

025

025

0 25

02i

025

S5!>0

IS7

12 S

12 5

u ^5 3J JJ i

0 2b 3J 333

* ?5 13 33 )

o ;:,

02S

I ib

I 25t 25

lag/in L|

1 101

1 U2

D.MI

• a;,!S4T?

S2S2

<0 010

3007

OUOI

0001

OCOJ

0 I

02o ?

0 2

02

02

0?

02

0«

025

075

II 70

II 71

11 .'8

21 n34 41

34 4t

125

4JO

1 ,?b

1 25

1 25

84 ?2

UnaII 19

,41 /

lit I

152 3

j<-y

"•*

0 U20 §3

2 4S

O 13

n/o;IJ2 •!>

I I 3 S 9

\l I «140 t121 1

I I I AH

86 ?i

I I I 4 5

I'D 4

I6t i

171 7

J ' ,

4 42

4 M

VakJM by 1C bal«w . 15 ppm dua to inlrgraiwn of teaahna naiaa

• ral -

Table 4. Raw Analytical Data for Cyanide Analysis ot Noil/i Drive Water and An Samples - Continued

Sui.in >*•

to s»r0* Ml

100 Ml

101 &B2

IK an103 802

W4 SO?

109 Mtita au

no SMMl flit112 SW

IU SI07

CCC

NDi

171541

I71S43

171S43

I7IS44I7IS44I7IS44

171544

I7IM4171544

171544I7IM4171*44

171547

DATESDtelNtad

Sap 2Sap 2

Sap I

Aug IB

AM| M

Anal*

Sapl

Sapl

«HH

Sap 2lap 2Sap 2

na

Analynd

Gap 38ap38a,3

Autf 21AUI 21Au|2l

Saplfi»pi•apt

Sap 3••paSapa

Sap 12

S*m Anal|«) Uattuxl

1 WAD

2 WAD

a WAD

1 Totalt Totala Total

1 WAD

2 WADa WAD

1 WAD

X WADa WAD

1 Total

Eanipta Cyar«d»O Cunc ••nation

saiwsAa»iwsaSOIWSC

I7IB-I4TAIN544TBI7IS44TC

K«:rWA

802WB

auwc

M2WSAA

BOtWBBB

S02WSCC

S107

70JO«.Ht

0.000

2 71»

2 70S

t.TBt

OC06

0004 "

0001

30204J4X

4200

<OOIO

<-N Splk«Man C

fcM> (m<

1

1

1

0

0

0

0

«0

tt1

0

EHtaj)

0«7

00?

&S7

n^

atna

<u

na

na

4

4

4

rvi

CM Lpik«i

^^T'101M

IOO<HM%

..*

na

M

na

M

na

oathtoo*I07H

na

Vakma

tLL

0 ISO

0 ISO

O.ISO

o^'-o02500250

0 100

0 100

0 100

«24002SO

0250

Otui

Sciubfcar S

»v ir, •(m>lt

3.

313 7

2 flJ2 14221

0 1310 1120 133

3M321J04

,i.l

iGluflOll

IttonCi tu.

I'-noA-l

4 :il

40133 ess

2 7ltt2 78bZ7»l

,,002

01020003

3»a4342

4210

< 0 UIU

VuluiH*

(1)

02S

025

025

a ^s02S02b

il ?borb025

C2SC26

0.75

4J LOS

?*-

^s21

102020

1?^

1 251 25

2'j

2S

25

.'II

Cmic

(up/ml |

l<« 7'160 blIM St

ui nUSi

1*0

1 14

1 23

204

l i J .1717171 2

U -13

1 1u

'

^I

.-

i ' i

!'f ii:ri

VaktMky 1Cto«lu* ISppw«>!•«• bito0iMion«4

Sample Mats a

o DPD25 DPD Std

50 ODD Std1.00 CM Std' 50 &pfc Std200 000 Std

0.0060.0560.0890.1630.2153.31C

2.01310.0493: oass0.15790.2303

/

Sample iD

ox,

Measd Cyanide RecvdAbsorb Cone. or

(A) {0001 Oil FflC

cv 100 ppoOCV 100 pp3Blank

S102TAS102TBS102TC

S102TFSS

S102TSA

S102TSAX2

S100TA. S100TB

S100TC

S100TAX2S100TBX2STOOTCX2

171544TA171544TA171544TA

0.1650.1640.006

0.1990.2020.170

0.140

0.221

0.272

02100.2000.222

0.1640.1610.206

0.2100.2090.213

'04.19-4.93

128.36: 30.43^08.33

37.62

143.55

178.78

'35,96129.05"44.24

104.19102.12! 32.50

1 36.96135.27138.03

105%104%

505050

50

'so

23.81

27.0327.0327.03

23.8123.8123.81

202020

tt'

0.06

o ;o <o w 100 120 iao 2co

CttOmTOtOfl \PpD]

3 ft Cafeota Data —iRLw

Regression Output;ConstantStd Err of Y EstR SquaredNo. of ObservationsDegrees of Freedom

0.01313330.01025830.9932830

64

X Coefficients)Std Err of Coef.

O.OQ1448Q0.0000595

Notes:Used coiorimetrlc method per ASTMAbsoroance measured at 540 nm, shoulderof 578 nm peak resulting in 50% decreaseIn absorbance for a given concentration.

11

3amoieAbsoroance

a Caic a~ i *\ r « * n i- m •*

.. .J.IL/I U iiUi ' . j i ^,

0 ppo

25 POD S:d30 ppo StC

'CO ppO StdKSOPPD Std2CO ppp Std

0.33.3.0.3-

010129243459683876

Meas'dSample ID

:cv 100 ppaEiank

S102TSBS102TSC

S101TAS101TBS101TC

S104TAS104TBS104TC

S99TAS99TBS99TC

171543TA171543TB171543TC

Absorb

3.

(A)

3540.01

0.0.

0.0.0

0.0.0.

750706

658630524

467546518

0.0120.0120.

0.0.0.

012

419438604

: 0200J 12863 23713.4543C.5714

3.8886

CyaniaeCone.(POO)

-6.91-2.31

•88.09157.96

146.91140.46116.05

102.93121.12114.87

-1.84-1.84-1.84

91.8896.25

111.45

C 3 r

;s(-i

a ? -

u[<Vb

flecvd .15 -or

OilFac < .^

•77%

ai '

12 -

ai -50.0

50.0

12.5

12.3

12.5

50.0SO.O

50.0 CoSt(

1.25 R,1.25 No

1.25 De

X <1.25 Sti1.261.25

' 'n»:iK * . )20C'0;

" SOUVM ~ 9^9^993 /

.'

y/

''/

/i /i /' // i

//

/I 1 1 1 1 1 1 1 L _ 1 1 1 ' I I I 1 1 . 1 1

0 20 '0 50 M IX 12C '40 'BO '» XC

CcAdMrotn fpcD)

G CN CArata Ooto — 'Sdft

Regression Output:nstant 0.0200105 IJErrotYEst 0.01059071Squared 0.9991993 i. of Observations 8 !grees of Freedom 4 i

:oefftcient(8) 0.0043427 !jErrofCoef. 0.0000614

Notes:Used colorimetric metnod per ASTM

*ICV aged, concentration suspect, ICVreanalyzed by 1C and coiorlmetrlc methodto oomfirm value.

AosorcanceSample ;D eas a ;alc d

0 PPD25 ppo Sta50 opo Std

100 PPQ Std" 50 ppo Std200 ppD Std

0.0070.126C.2400.4780 6960874

0.01940.12920.23890.45840.67730.8973

Samoie iD

icv 100 ppD*ccvioo opoBlank8-26TPB8-26TPBS8-27WPB

S103TAS103T3S103TCS90TAS90TBS90TCS89TAS89TBS89TCS89TSAS89TSBS89TSC

S103WAS103WBS103WCS103WSAS103WSBS103WSC

S102WAS102WBS102WC

MMS'd

Absorb(A)

0.3820.4700.007O.OC50,4580.020

0.2330.4050.542O.BflS0.6030.51 B0.4330.6250.3780.6500.7160.688

0.6440.7020.7160.7460.5260.724

0.0510.0730.046

Aaeti 1000 cam toiks** Spike Sol••Spike Sol**Splke Sol

0.3720.3940.408

CyanideCone.(ppb)82.60

'02.65-2.83-3.2999.92

0.13

48.6637.84

119.05147.07132.95113.6994.22

1 37.9681.69

143.661 58.69152.31

142.29155.50158.69166.53115.41160.52

7.1912.216.06

solution80.3285.3488.53

<VbPecva

orDM Pac

•83%103%

'.2540

i 25

68.6766.6766.675.5565.5565.55611.7611.7611.7634.4834.4834.48

4

44

252525

28.5728.5728.57

101010

ntvt-m *Sow

i j

i!12 h

ai

0 20 40 60 80 100 120 140 160 '30 20C

Regression Output:ConstantStd Err of Y EatR SquaredNo. of ObservationsDegree* of Freedom

0.01942110.01886940.9975163

64

X Coefficients)Std Err of Coef.

0.00438950.0001095

Notes:Used colorlmetric method per ASTM

* ICV prepared fresh from extremely smallmass of KCN. Weighing error suggested.

• 'Average for spike soln. - 847.28 ng/ml826TPBS; S89TSA.B.C: and S103WSAScrubbers in series S103T. 590T. SB9T, & S89TSdiluted to 200 rather than 250 ml.

13

-osornanceSample iO

3 ppo25 ppo Std50 ppD Srd

1CC ppo Std1 50 ppD Std

Sample 10

iCv 100 ppdccv 100 ppoBlank

S90WAS90WB390 WC

S99WAS99WBS99WC

SI 01 SWAS101SWBS101SWCS101WAS101WBstoiwc

S104WAS104WBS104WC

SB2WAS92WBS92WC

S89WAS89WBS89WC

^eas d

0.00511690.2690.47B0.774

Meas'dAbsorb

(A)0.4120.4870.002

0.6290.712

0.63

0.0040.0120.008

0.5750.6

0.5160.3290.3650.422

0.4080.4420.278

0.0260.0250.029

0.0220.0230.031

Calc'd i.xwHi-'-'-i

3.Q'.890.1420 : . ; ( - : •••«»« jsj'C0.2651 ;.

3oot: -&®£0.5113 .jL ••*«•-'

07576 "' :

3;l"s/fe /

/Cyanide Pecvo ;$(. /

Cone. or \ /fppdi -5il Fac « . . , , /'

79.82 '85% \ "'' / 395.06 102% i \ /-3.44 Hh /

123.89 2.857 ^[ / \140.75 2.857 j /124.10 2.857 i /

"r /- /1 L'/ 1

-3.03 1.25 I /-1.41 1.25 c.ih /-2.22 1.25 )/ !

. i * i i ' i i i i i i : i ' : i i i i '

112.93 ,20 0 2C *0 60 50 'X 120 i<0 :ffl 'M97.70 20

100.95 20 CononMbA ippb)

62.97 2.0 3 a Cdtnta Data — 'J?l«70.28 2.081.86 2.0 '

Regression Output:79.01 2.0 Constant 0.018931085.92 2.0 StdErrofYEst 0.027800252.61 2.0 R Squared 0.9934486

No. of Observations 51.44 1.25 Degrees of Freedom 31.23 1.252.04 1.25 X Coeff icient(s) 0.0049241

Std Err of Coef. 0.00023080.62 1.250.83 1.282.45 1.25

Notes:Used colorimeirtc metnod par ASTM

*ICV prepared fresh from solid KCN.

AosortanceiC Mcas a

' ODD25 ppO Std50 pco Std

ICO ppo StdiSOppoStd200 ppO Std

0.0040.1 OS3 1980.4080.5710728

Talc'a

J.C1610.1074Z 19863.3811C36363.7461

:.9r

13 h^ i'JBTB : '

Sample iO

iCV 1 00 ppCccv iCOppo

Mees'dAbsorb

(A)0.4030.4060.002

CyanideCone.:ppb)

105.39'06.81

-3.87

Pecvdor

C.I Fas106%

•07<M>

•15 -

1*1-

S91TSAG91TSB391TSCS91WA391WBS91WCS91WSA391W8BS91WSC

> S100WAI S100WB! S1QOWC

PBlu«T8A

PBIueWAPBIueWB

PBIuaWSA

0.5980.6230.6410.0030.000•0.0020.6320.6020.595

'59.42' 66.26171.20-3.59-442-4.96

168.73160.51'58.59

33.3333.3333.33

1.251.251.28

252525

3100TSAS100TSBS100TSC

0.6980.7340.768

'86.81198.87205.44

40

40

40

0.0010.0010.001

1.14U41.14

0.700

0.0690.064

0.518

187.36

11.7513.12

2.02.02.0

S92WSAAS92WSBBS92W8CC

PBIueTAPBIueTB

0.5760.6600.041

0.6130.627

153.11173.66171.20

163.53167.36

25.025.026.0

200200

200

33.33333.333

0 20 43 60 80 :00 120 140 160 :8C 20C

Cwmroi'M (ppb)

3 CM CflMrafin Don — 'JU«

Regression Output:Constant 0.0161158StdErrotYEst 0.0177551R Squared 0.9968221No. of Observations 8Degrees of Freedom 4

X Coefficients) 0.0038C01Std Err of Coat. 0.0001030

Notes:UMd coiorlmetric method per ASTM

*!CV prepared fresn from solid KCN.

'37.50 28.571

is

'-0V 2*5 Er ' '-- _

Calibration Curve VI

Sememoei 12, :992

Calibration Curve Regression Cutout

Cone. Absom.(ppd) (578nm

0 0.00010 0.03650 0.177

100 1348230 ' 0.695

Constant:StdErr of Y EstiR Sauareo•Mo. of Observations.Degrees of FreeaonX Coefficient(S)Std £rr of Coef.

0.001364 ,

0.001493 i0 999979 >

5 :3 I

0.003469 •0 000003 i

Sample Analysis

Sample 10 Absorp.(578nrm

ICB 0.002ICV 0.1813107 0.003

Cone. Dilution | Cone.(OPtj) ; Pactor 'ppO)

flec's '! iRPO's i

0.18 ' |51.77 |0.47 20 1 9.43

CCV 0.178*1 50.90 1 IICCB 0.001 -0.10 I !

1 104% Reci1 11102% Rec!I i

ICV true value: SOppoCCV true value: SOppo

ICV Source: Stock Cyaiude Solution *92083CCV Source: C.amde Standard LAL#fli01872234

"salt 5. Sjrnmary Oa'a I.'QTI Evaiuat on of Practice Norxn Dnvi Soil Samples.

Distill SamcieDate '0

Scruober AVQ SpikeAverage Sample Cone. Spike unapikea ^ecva.

Mass Cone. vfl RSO Avg. Mass Cone. Sample Percent<g) 'mg/kgj (mg/kg) 'ma) ma/kg; 10 (%)

TOTAL CYANIDES

Jun-18 T

Jun-18 T2

Jun-18 T3t

Jun-30 T4

jun-18 TS

Jun-19 T3S*

Jun-30 T4S

0.984

0.284

0.290

0.206

0.951

0.254

0.109

•482

587

2322

5487

1545 .

3819

5979

WEAK ACID

Jun-10 WA01

Jun-i 1 WA02

. Jun-11 WA03

Jun-11 WA02S

Jun-12 WA03S

1.124

1.118

1.341

1.422

0.254

1S7.9 '

228.2

1186

390.8

387

15% 5.8

97% 0.84

9% 2.7

8% 4.5

3% 5.9 0.25 263 T 24%

8% 4.71 0.25 970 T3 154%

15% 2.6 0.25 2289 T4 22%

DISSOCIABLE CYANIDES

18% 0.62

19% 1.01

41% 5.4

26% 2.2 0.25 176 WAD2 93%

14% 39% 0.05 197 WAD1 82%

'Burton 2v«lu««

17

L D = .23

Tible 6. Summary Dau for Analysis of Synthetic Cyanide Solutions byWAD Cyanide Analysis.

SolutionComponent*

KCN

K,Fc<CN),

K,Fe<CN),

K<Fe<CN)4

K«Fe<CN)«

N^S

KCN',

Prepared

ICNT(mg/L)

0.5

5000

5

5000

5

Ok

0.5

Sample<*)

3

3

3

3

3

3

3

Averagi[CN1

(mf/L)

0.4T7

45.9?

<0.20

599

< 0.20

<0.20

0.53

%RSD

7.1

9.0

ni

4.0

oa

na

6.4

%Recovery

95.4

0.92

< 4.0

12.0

< 4.0

< 4.0

105

•Concentration of cyanide species u CM"."Interference check with 50 mg of Na,S addad.•A 3 component mixture consisting of 50 Of of NajS and 5.0 mg of K,Fe(CNV

II