report: technology evaluation laboratory treatability

SDMS Document

B£[EC 113383

TECHNOLOGY EVALUATION LABORATORY TREATABILITY STUDY

CARROLL AND DUBIES SUPERFUND SITE FINAL REPORT

Prepared For:

ROBERT J. GLASSER Gould and Wilkie

One Chase Manhattan Plaza

New York, NY 10005 Attorneys for

Wickhen Products, Inc,

DEBRA L. ROTHBERG Periconi & Rothberg, P.C. 230 Park Avenue, Suite 615


Kolmar Laboratories, Inc.

Prepared By:

REMEDIATION TECHNOLOGIES, INC. 3040 William Pitt Way Pittsburgh, PA 15238

RETEC Project No.: 3-1644-150

OCTOBER 10,1994 400540



Prepared For:


One Chase Manhattan Plaza New York, NY 10005

Attorneys for Wickhen Products, Inc.




Prepared By:



OCTOBER 10,1994

^«00541



Prepared For:


One Chase Manhattan Plaza New York, NY 10005

Attorneys for Wickhen Products, Inc.




Prepared By:



Prepared By: 4^K2/i^^^^^.yY\fQlo.H^

Reviewed By: 'SOv„^^^?^>>^"~^v^^^

OCTOBER 10,1994 400542

TABLE OF CONTENTS

SECTION PAGE

1.0 INTRODUCTION 1-1

1.1 Backgroimd 1-1

2.0 FIELD SAMPLE COLLECTION 2-1

2.1 Sampling 2-1

2.2 Initial Sample Characterization 2-2

3.0 VAPOR EXTRACTION TESTING 3-1

3.1 Procedures 3-1

3.2 Results 3-9 3.2.1 Observations 3-9 3.2.2 Vacuum Monitormg 3-11 3.2.3 Photoionization Monitoring 3-16 3.2.4 Material Analyses 3-29 3.2.5 Vapor Analyses 3-33

3.3 Conclusions 3-36 3.3.1 Au- Flow Through Lagoon 3 and Lagoon 7 Materials 3-36 3.3.2 Dewatering of Lagoon Materials 3-37 3.3.3 VOC Removal from Lagoons 3 and 7 Materials Using

Vapor Extraction 3-37 3.3.4 Use of a Soil Amendment to Improve Treatment Efficiency 3-38

4.0 MINERALIZATION TESTING 4-1

4.1 Equipment Set-Up/Procedures 4-1

4.2 Results of Mineralization and Oxygen Uptake Rate Testing 4-3

4.3 Conclusions and Recommendations 4-7

5.0 SLURRY REACTOR TESTING 5-1

5.1 Equipment Set-up and Experimental Procedures 5-2

Technical Evaluation Laboratoiy Treatability Snidy-CanoU and Dubies Superfund Site-Final Report 71 O D ' ^ Vl ' ^ mpr/1644-150/101(»4 5:I5 f | U U U * i < ) i

TABLE OF CONTENTS (Continued)

SECTION PAGE

5.2 Results 5-4

5.3 Conclusions 5-19

6.0 PROJECT CONCLUSIONS/RECOMMENDATIONS 6-1

6.1 Conclusions 6-1 6.1.1 Vapor Extraction Conclusions 6-1 6.1.2 Mineralization Conclusions 6-2 6.1.3 Slurry Reactor Conclusions 6-2

6.2 Discussion 6-3

6.3 Recommendations 6-8

7.0 REFERENCES 7-1

LIST OF APPENDICES

APPENDIX A APPENDIX B APPENDIX C APPENDIX D

Grain Size and Bulk Density Data Plots of Daily Photoionization Readings SOPs Summary of Analytical Results - Solid and Aqueous Samples

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Technicai Evaluation Laboratory Treatabflity Study-Carroll and Dubies Superiund Site-Hnal Report mpr/1644-150/101094 5:15

LIST OF TABLES

TABLE PAGE

2-1 Initial Characterization Data (Detected Constituents) 2-3 3-1 Detected Constituents Lagoon 3 Vapor Extraction Columns 3-30 3-2 Detected Constituents Lagoon 7 Vapor Extraction Columns 3-31 3-3 Air Monitoring Results for Lagoon 3 Columns 3-34 3-4 Air Monitoring Results for Lagoon 7 Columns 3-35 4-1 Summary of Mineralization and Oxygen Uptake Rate Testing Data 4-4 5-1 Summary of Analytical Methods 5-1 5-2 Slurry Reactor Smdy Analytical Sampling Schedule 5-5 5-3 Lagoon 3 Slurry Reactor Solid Phase Analytical Results for Detected Compounds 5-7 5-4 Initial and Final Aqueous Samples from Lagoon 3 Slurry 5-11 5-5 Lagoon 7 Sliuxy Reactor Solid Phase Analytical Results for Detected Compounds 5-14 5-6 Initial and Final Aqueous Samples from Lagoon 7 Slurry 5-17 6-1 Biotransformation of Halogenated Aliphatic Compounds by Microorganisms . . . . 6-5 6-2 Chlorinated Solvents That Can Be Degraded by Pure Bacterial Cultures 6-7 6-3 Dehalogenation Mechanisms of Halogenated Xenobiotics in Aerobic Bacteria . . . 6-9

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Technical Evaluation Laboratoiy Treatability Study-CarroU and Dubies Superfund Site-Final Report iiq)r/1644-150/101094 4:47

LIST OF FIGURES

FIGURE PAGE

1-1 Evaluation Steps 1-3 3-lA Equipment Set Up for Bottom Vacuum Reading 3-2 3-lB Equipment Set Up for Top Vacuum Reading 3-3 3-lC Revised Equipment Set Up After 9/8/94 3-4 3-2 Colunm 3A Vacuum Readings 3-12 3-3 Column 3B Vacuum Readings 3-13 3-4 Columm 7A Vacuum Readings 3-15 3-5 Column 7B Vacuum Readings 3-17 3-6 Column 3A Initial Continuous Photoionization Readings for August 29, 1994 . . . 3-18 3-7 Column 3A Daily Interval and Spot Photoionization Measurements, 8/30/94 to

9/12/94 3-19 3-8 Column 3B Initial Contmuous Photoionization Readings for September 7, 1994 . . 3-21 3-9 Colimm 3B Daily Interval and Spot Photoionization Measurements, 9/08/94 to

9/21/94 3-22 3-10 Column 7A Initial Continuous Photoionization Readings for August 29, 1994 . . . 3-23 3-11 Column 7A Daily Interval and Spot Photoionization Measurements, 8/30/94 to

9/12/94 3-25 3-12 Column 7B Initial Continuous Photoionization Readings for September 7-

8, 1994 3-26 3-13 Coliram 7B Initial Continuous Photoionization Readings for September 8-

9, 1994 3-27 3-14 Column 7B Daily Interval and Spot Photoionization Measurements, 9/12/94 to

9/21/94 3-28 4-1 Results of Oxygen Uptake Rate Testing 4-5 5-1 Schematic of Bench-Scale Slurry Reactor 5-3 5-2 BTEX (GC) Concentrations in Solid Phase Lagoon 3 Slurry 5-8 5-3 Volatile Organics (GC/MS) Concentrations in Solid Phase Lagoon 3 Slurry . . . . 5-10 5-4 Microbial Counts Vs. Time Lagoon 3 Slurry 5-12 5-5 BTEX (GC) Concentrations m Solid Phase Lagoon 7 Slurry 5-15 5-6 Volatile Organics (GC/MS) Concentrations in Solid Phase Lagoon 7 Slurry . . . . 5-18 5-7 Microbial Counts Vs. Time Lagoon 7 Slurry 5-20

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Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Superfund Site-Final Report n5)r/1644-150/101094 5:22

1.0 INTRODUCTION

Pursuant to an agreement with the United States Environmental Protection Agency (U.S. EPA), Respondents to Admmistrative Order on Consent Index No. II CERCLA-00202 retained Remediation Technologies, Inc. (RETEC) to undertake an analysis of remediation altematives for treatment of organically impacted source area materials at the Carroll and Dubies Superfund Site in Deer Park, New York. As part of the evaluation of remediation altematives, RETEC performed an altemative remedial technology evaluation [RETEC, 1994a]. Based upon this preliminary screening, two potential altematives were identified: vapor extraction and bioslurry. These two altematives have been effective in treating similar constituents in similar materials.

The second level of evaluation performed by RETEC involved an analysis of the site-specific mixtures of constituents found in the lagoons to determine whether these materials are amenable to treatment using these technologies. This evaluation consisted of laboratory treatability testing.

This report presents the results of the Technology Evaluation Laboratory Treatability Study for the Carroll and Dubies Superfund Site. As per agreement with the U.S. EPA, earlier results have been provided to the Agency in the form of written updates.

1.1 Background

The need for a further evaluation of remediation altematives was identified following the completion of the low temperature thermal desorption (LTTD) treatability study [Blasland, Bouck, and Lee, 1994].

The Superfund Proposed Plan identifies Altemative 5, LTTD, as the preferred remedy for the site. However, the U.S. EPA recognizes that ..."Changes to the preferred remedy to another remedy may be made, if... additional data indicates that such a change will result in a more appropriate remedial action." RETEC has imdertaken, pursuant to agreement with the U.S. EPA, additional treatability studies of potential remedial altematives. These additional studies have been recommended because LTTD is not a proven technology for the materials contained within the lagoons at this site. In addition, LTTD presents a number of concems including environmental

400547 Technical Evaluation Laboratory Treaability Study-CarroU and Dubies Superfiind Site-Final Repon iiVr/1644-150/101094 3:58 1-1

emissions, and field scale implementability problems. Although the treatability test for LTTD did achieve reductions in organic concentrations, two significant problems with this technology were identified:

• The sludge matrix did not reach the target treatment temperature due to a high moisture content in the sludge.

• The thermally treated sludge could not be solidified due to the characteristics of the material.

A further review of the LTTD treatability report as ouflined in the Source Area Feasibility Study [Blasland, Bouck, and Lee, 1994], indicates that two separate LTTD units would be required to treat the various materials. The use of two systems, particularly the addition of a high temperature thermal desorption system, raises additional concems with air treatment, materials handling, site disruption, and energy requirements.

Based on these concems, the respondents, with the concurrence of the U.S. EPA, proceeded to evaluate altemative technologies. Figure 1-1 presents the sequence in which the altemative technologies will be evaluated in accordance with the existing remediation schedule for the site.

These treatability studies focus on the treatment of organics. Treatability stodies conducted on inorganics have shown that the solidification/stabilization of these materials will meet proposed clean-up criteria [Blasland, Bouck, and Lee, 1994].

The overall objectives of the study conducted by RETEC are to:

• determine if the technologies are potentially effective in treating the lagoon materials in the source areas;

• determine, on a preliminary basis, limitations in applying the altemative technologies;

• provide a proof of concept level evaluation of the successful technologies, and;

• provide recommendations conceming the next steps in the remediation of the source area operable unit.

400548 Technical Evaluation Laboratory TreatahiliQ' Study-CarroU and Dubies Superfiind Site-Final Repon inpr/1644-150/101094 3:58 1-2

n C U R E 1-1 EVALUATION STEPS

® ®

Select Technology

1 '

RD/RA

Note: l)BoM Text Indicates Completed tasks si) LTTD Tteatabiliv coaq)Ieted on one system ^pe; other types are available

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Technical Evaluation Laboratory Treatability Study-CarroU and Dubies Superfund Site-Final Repon mpr/1644-150/101094 5:22 1-3

This report is divided into sections focusing on the individual aspects of RETEC's evaluation. Section 2.0 reviews the sample collection and initial characterization of the material. Section 3.0 reports the results of the vapor extraction testing. This testing included column studies of unamended material for evaluating in-situ application, and amended material for evaluating ex-sim applications. Section 4.0 presents the findings of the mineralization testing. This testing was implemented to determine if biological degradation was possible in the lagoon material. Section 5.0 reviews the results of the slurry reactor testing. Section 6.0 presents die project conclusions and recommendations.

It should be noted that Respondents intend to file an addendum to this report. The addendum will provide the U.S. EPA with the final SVOC data and amended column vapor VOC data. This data is not available at the time of this report.

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Technical Evaluation Laboratory Treatability Suidy-Canoll and Dubies Superfiind Site-Final Repon inpr/1644-150/101094 3:58 1-4

2.0 FIELD SAJVEPLE COLLECTION

Bulk samples of materials from Lagoons 3 and 7 were collected on August 16, 1994 for treatability studies. Lagoon 3 was chosen because it contains a representative mix of volatile organic compounds (VOCs), semivolatile organic compounds (SVOCs), and metals. Lagoon 7 was selected as a "worst case" material for treatment, because of its physical characteristics and the relatively high levels of constituents-of-concem in previous samples from this area.

2.1 Sampling

Sample Locations and Collection Methods

Grab samples were collected in each lagoon from a single sample location. A backhoe was used to excavate below the soil caps and into the lagoon materials. A photoionization device (HNu) was operated during sampling activities to monitor for organic vapors. When representative material was encountered, three 5-gallon sample buckets were filled at each location using a decontaminated shovel to lift materials directly out of the backhoe bucket. Following sample collection, the excavations were backfilled with the materials that had been temporarily staged.

Consistent with previous investigations, the excavated area in Lagoon 3 revealed a soil cap with a silty matrix and abundant shale fragments approximately 7 feet thick, below which was found a material described as black and gray sludge mixed with sand, silt and shale fragments. No organic vapors were detected with the HNu until a depth of 8 feet, where low readings of less than 1 ppm were detected. The sample was collected from a depth of 9 feet. The material collected was described as black moist sludge with abundant shale fragments, a sewage-like odor, and HNu readings of 3 to 5 ppm.

To collect the material from Lagoon 7, two test pits were excavated. The first test pit in Lagoon 7 went to a depth of 5.5 feet with no indication of sludge and no HNu detections. Fill was encountered, described as brown to gray sand and silt with abundant shale fragments. This pit was backfilled, and a second pit was initiated north of the first location. In the second pit, debris was encountered at 4 feet (clothing, fiimimre, metal), along with black, pink and gray

400551 Technical Evahuition Laboratory Treatability Study-Carroll and Dubies Superfund Site-Final Repon nipr/1644-150/101094 3:58 2-1

sludge material that exhibited HNu readings of 10 to 15 ppm. This material was collected from a depth of 5.5 feet for the treatability tests.

All six buckets of material were labeled and shipped, via 24-hour service to RETEC's Pittsburgh facility for the treatability studies. Upon arrival, all samples were logged in and placed in a refrigerated room (<40''F) until needed for the freatability tests. Chain-of-custody procedures were used for the collection and shipment of all samples.

2.2 Initial Sample Characterization

A single sample of Lagoon 3 material was collected and analyzed for VOCs and SVOCs by GC/MS. The sample was collected in the laboratory by opening one of the five-gallon buckets and filling a sample jar full of material from the top of the bucket (the material was not mixed before sampling). The bucket was then resealed immediately to minimize volatilization of the material.

Concentrations of compounds detected from this initial characterization of the materials are presented in Table 2-1.

An attempt was made to characterize both lagoon materials for grain size and bulk density. However, only a sieve analysis was performed on the material from Lagoon 7 using a modified ASTM D698 Method. The laboratory reported that the Lagoon 3 soil matrix was unsuitable for grain size or hydrometer testing and that the Lagoon 7 material was unsuitable for hydrometer testing. Composite samples were collected from all three buckets of each material for these analyses. Based on the sieve analysis, Lagoon 7 material was classified as a brown, silty sand with gravel. The grain size distribution was 25.7% gravel (material with a particle size greater than 4.75mm), 48.1% sand (material with a particle size between 4.75mm and 0.075mm),and 26.1% silt and clay (material with a particle size less than 0,075mm).

A distribution of the percentage of silt versus clay could not be obtained because the material was unsuitable for hydrometer testing. The wet density of Lagoon 3 material was 1.97 grams per cubic centimeter (gm/cc). The wet density of Lagoon 7 material was 1,09 gm/cc. The data sheets from grain size and bulk density tests are presented in Appendix A.

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Technical Evaluation Laboratoiy Treatability Sudy-CarroU and Dubies Superfiind Site-Final Repon-nipr/1644-150/101094 3:58 2-2

TABLE 2-1

EVrriAL CHARACTERIZATION DATA

(Detected Constituents)

Parameters

Total Solids %

BTEX

Benzene

Lagoon 3

68.5

Lagoon 7

42.3

7«g/Kg

160,000 83,000

Toluene 130,000 2,800,000

Ethylbenzene < 46.000 < 74,000

Total Xylenes

Cailorinated VOCs

Chloromethane

< 46,000 280,000

Mg« g

< 91,000 73.000J

Methylene Chloride <91,000 170,000

Tetrachloroethene 72.000 1.300,000

Trichloroethene

SVOCs

Bis(2-ethylhexy)phthalate

< 46.000 97.000

Mg/Kg

< 48,000 28,000J

2-Chloronaphthalene < 48.000 29.000J

Di-n-butylphthalate 190.000 990.000

Naphthalene < 48,000 42,000J

J - Compound was detected at a concentration below the sample detection limit. The reported value is an estimated quantity.

^ '400553

Technical Evaluation Laboratory Tteaability Study-CarroU and Dubies Superftind Site-Final Repon inpr/1644-lS0/101094 3:58 2-3

c 3.0 VAPOR EXTRACTION TESTING

Bench scale treatability testing was performed on two sample types from each lagoon for a total of four columns. One set of samples (Columns 3A and 7A) was prepared by sieving to remove rocks and debris. Another set of samples (Columns 3B and 7B) was sieved and mixed with wood shavings to make the texmre more porous.

These studies were designed to test the applicability of vapor extraction as a freatment approach for the lagoon materials. As outlined in the work plan [RETEC, 1994b], the objectives of the studies were:

• to determine if significant air flows could be obtained through columns of Lagoon 3 and Lagoon 7 materials,

• to determine if the lagoon materials could be dewatered through the use of vacuum,

• to determine if VOC removal from Lagoon 3 and Lagoon 7 materials is feasible using vapor extraction, and

• to determine if an amendment could alter the physical characteristics of Lagoon 3 and Lagoon 7 materials to improve freatment efficiency using vapor extraction.

3.1 Procedures

Equipment Set-Up

The experimental apparatus (for each soil colunm tested) is illustrated in Figure 3-1. It consisted of an open-ended glass tube 2 feet long, with an inside diameter of 1 7/8 inches, packed with test material to a height of 18". A mbber stopper was placed in the bottom of the mbe, a piece of screen and a piece of glass wool were placed inside the tube on top of the stopper, and tygon mbing was placed through the stopper and connected to a vacuum gage. The screen and glass wool prevented clogging of the mbing leading to the vacuum gage.

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Technical Evaluation Laboratoiy Treatability Study-Carroll and Dubies Superfund Site-Final Repon inpr/1644-lS0/101094 3:28 3-1

BLEED VALVE (OPEN)

—RUBBER STOPPER

— 1 -7 /8 " (LD . )

FLOW CONTROLLER (2 LPM MAXIMUM) U

1

BOTTOM VACUUM GAUGE

VACUUM PUMP CONDENSATE (17 LPM MAX FLOW) COLLECTOR

(272' HjO MAX VACUUM)

INTERFACE CABLE

r-^ ^

PHOTOIONIZATION DETECTOR COMPUTER FOR DOWNLOADING

PHOTOIONIZATION DATA

CARROLL AND DUBIES SUPERFUND SITE

3-1644-BB8

jgjgg^ M j ^ CAnn.F. i .4*-M<i ;

FIGURE 3-1A EQUIPMENT SET UP FOR

BOTTOM VACUUM READING

400555 NOT TO SCALE

IMEE VACUUM EXTRACTION STUDY

BENCH SCALE MODEL RCH PEHMSYlVtW*

IRAA-MO? In 3-2

BLEED VALVE (OPEN)

RUBBER STOPPER

FLOW CONTROLLER (2 LPM MAXIMUM)

v-_

TOP VACUUM GAUGE

TUBING (OPEN)

VACUUM PUMP CONDENSATE (17 LPM MAX FLOW) COLLECTOR

(272" H2O MAX VACUUM)

INTERFACE CABLE



40055B NOT TO SCALE

»/30/»4


3 - 1 6 4 4 - 8 8 8

r.>nnir.^M4-M0.

FIGURE 3-1 B EQUIPMENT SET UP FOR TOP VACUUM READING

WM[EC VACUUM EXTRACTION STUDY

BENCH SCALE MODEL PmSBURCH PgMNSYLVAWU NMlNfi NUHiDI pcvl

1f i i l4—M04

3-3

FLOW CONTROLLER (2 LPM MAXIMUM)

VACUUM PUMP (17 LPM MAX FLOW)

(272" HjO MAX VACUUM)

^ — ^ f(\ \ \ \ \ ^ 1 TOP VACUUM GAUGE \ \ I (PERIODICALLY INSTALLED

\ y TO TAKE READINGS)

BLEED VALVE (NORMALLY CLOSED-OPENED TO READ GAUGE)

^-RUBBER STOPPER

— 1-7/8"( I .D.)

BOTTOM VACUUM GAUGE

2nd BLEED VALVE (OPEN)

INTERFACE CABLE

r- H




3-1644-888

fiSSi Ctt) nLC:1«i ittslSL.

FIGURE 3-1C REVISED EQUIPMENT SET UP

AFTER 9 /8 /94

400557 NOT TO SCALE

WM£ VACUUM EXTRACTION STUDY

BENCH SCALE MODEL PITTSBURCB PtWraYLViUa*

1f?44-M0fi It) 3-4

Two tygon mbes were connected to a rubber stopper at the top of the soil column. Atmospheric air flow through one of the tobes was controlled by adjusting a screw clamp. This opening was a bleed valve, and was used to adjust the vacuum that was applied to the system. It was also used as a measuring point for the vacuum applied at the top of the soil column.

The other mbe at the top of the column ran through an in-line orifice flow controller that regulated air flow at 2 liters per minute, through a condensation collection flask, and to a vacuum pressure pump. As the tests progressed no water accumulated in the condensation flask, so the flask was removed.

The pump outlet was connected to a photoionization detector (Photovac Microtip HL-2000). The detector was connected to a portable computer, to which concentrations of airborne ionizable gases were periodically downloaded for averaging and graphing.

On September 8 (Day 11 for Columns 3A and 7A and Day 2 for Columns 3B and 7B), a bleed valve was added to the tabing at the bottom of each colunm to enhance air movement through the columns and the top bleed valve was closed. On September 11, both valves were operated to test the vacuum and organic vapor response. On September 12 (at the end of testing for Columns 3A and 7A, and on Day 6 for Columns 3B and 7B), the top bleed valve was again closed completely.

Sample and Column Preparation

Lagoon materials used in all four column tests were first wet sieved through a 1/4 inch screen to remove rocks and debris. Sieved material was used so that the relatively small-diameter columns could be packed with minimal gaps and bridging. The sieved materials were from the same batches that were used in the slurry reactor tests described in Section 5.0.

Initially, on August 29, two columns were set up, one each containing materials from Lagoon 3 and Lagoon 7 (Column 3A and Column 7A). These columns represented in-sim conditions. The materials were not amended, except for the initial screening process. The columns were packed 3 to 4 inches at a time, using a rubber stopper on a steel rod as a plunger, and a pocket penetrometer to compress the materials to the approximate density measured in the field (0.75 ton/ft^). The last day of operation for Columns 3A and 7A was September 12.

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Technical Evaluation Laboratory Treatability Study-CarroU and Dubies Superfund Site-Final Repon nipr/1644-150/101094 3:28 3-5

On September 7 two additional columns were set up with lagoon materials amended with fine-texmred wood shavings. The purpose of the amendment was to increase porosity. The amended columns, labeled as Columns 3B and 7B, represented a scenario where lagoon materials would be excavated, blended with an amendment, and treated with vapor extraction in engineered soil piles. These columns operated until September 21.

The shavings used were commercially available pine bedding (packaged by American Wood Fibers, Jessup, Maryland). Pine bedding was chosen because it was a namral material without chemical additives, had a porous texmre, water-absorbing properties, was inexpensive, readily available, and lightweight. The maximum particle size in the bedding mix was about 0.5 inches, and when shaken in a No. 8 sieve (a screen opening of about 1/10 inch), about 25% of the volume passed the sieve.

Columns 3B and 7B were packed with 15% by weight mixmres of shavings to sieved lagoon material. The shavings were mixed in by hand using a stainless steel spamla. Unlike Columns 3A and 7A, where the materials were packed into the columns at a density approximately representing undisturbed conditions. Columns 3B and 7B were filled without being compacted, because amended materials would not be compacted in an engineered soil pile configuration. The amended materials were gently shaken into the columns, to minimize bridging and voids.

Monitoring

Four types of monitoring were conducted during the operation of the vapor extraction test columns:

• vacuum monitoring,

• ionizable vapor monitoring using a photoionization detector,

initial and final constiment analysis of the lagoon materials, and

• initial and final volatile organic constiment analysis of the extracted vapor.

Vacuum Monitoring. The vacuum at the top and bottom of the columns was monitored and recorded periodically. The bottom vacuum was representative of the vacuum that could be propagated through die column. Using the bottom bleed valve, under dynamic flow conditions,

400559


the vacuum at the top of the column was representative of the vacuum that would be applied at

the vapor extraction wellhead.

When the bottom bleed valve was closed, and the top bleed valve open, air flow within the column would only occur in the headspace above the soil. As such, under steady state conditions, the vacuum at the bottom of the column should equal the vacuum in the headspace above the soil column. Under these operating conditions, the vacuum difference between the headspace and the bottom of the column is a measure of the ability of the soil to propagate a vacuum under no-flow conditions. Such a property is directly related to the ability of the soil to allow air flow through it.

When the top bleed valve was closed, and the bottom one open, air flow was allowed through the soil column. As such, the vacuum reading in the headspace is inversely related to the ability to allow air flow through it.

Photoionization Monitoring. Ionizable vapors and gases at the pvanp outlet were monitored with a Photovac Microtip 2000. This instrument does not distinguish between individual compounds, but displays readings that represent the total concentration of photoionizable chemicals present in the air sample. The detector's zero point was set to ambient air. The concentrations measured were indicative of the total concentration of volatile organic constiments in the air that was exiting the soil column. Minimum, maximum, and average readings were recorded by the Photovac data logger every 15 seconds. The results were downloaded to a computer to be reduced to averaged values for 5- and 30-minute intervals for plotting and interpretation.

Photoionization measurements were recorded continuously during the first approximately 24 hours of operation for Colmnns 3A and 7A. The initial continuous measurement period for Column 3B was approximately 12 hours, because of an equipment malfunction. Continuous readings were taken for the first 24 hours for Column 7B. Following a configuration change in the bleed valve system on the second day of operation, there was a second extended continuous monitoring period (18 hours) for Column 7B.

After the continuous monitoring period for each colunm was completed, daily interval monitoring periods of several hours were performed for the next two to six days. The data was downloaded to the computer for data reduction and plotting. After several days of interval

400560 Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Superfund Site-Final Repon. nipr/1644-150/101094 3:28 3-7

readings, when concentrations began to stabilize, spot readings were taken in lieu of interval

measurements.

Soil Analyses. For Columns 3A and 7A, with unamended lagoon materials, the initial analytical results are the same as those collected for the initial analyses of the slurry reactor materials (Section 5.0). Triplicate analyses were performed on the sieved materials used in both the slurry reactor and vapor extraction tests. The materials were analyzed for total solids, and VOCs and SVOCs usmg standard U.S. EPA GC/MS procedures (Section 5.0). For comparison purposes, the results of the triplicate analyses were averaged.

The initial amended mixtures used in Columns 3B and 7B were analyzed (single sample) for VOCs and total solids.

At the conclusion of operations, samples were collected for separate analyses firom the top, middle, and bottom of the material columns. Materials in Columns 3A, 3B, and 7B were divided evenly into thirds for the individual samples. In Column 7A, the material column had split, resulting at the end of operations in a space of about 3 inches between the top 3 inches of soil and the rest of the column. For the final analyses, the top 3 inches was sampled for the top portion, and the remaining soil column was split in half for the middle and bottom portions.

Vapor Analyses. Vapor samples were collected for analysis of VOCs, on the second day of operation after the system stabilized and at the end of operations. Vapor samples were collected with a syringe from the pump outiet mbing and were discharged into sealed and evacuated vials. The headspace was analyzed for chlorinated and non-chlorinated VOCs. Analyses were performed using a modification of U.S. EPA Methods 3810 (Headspace) and 8000 (Gas Chromatography).

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3.2 Results

3.2.1 Observations

Column 3A

Even following compaction, the Lagoon 3 unamended material had a relatively coarse and porous appearance in the column. During the first 48 hours of operation, the appearance of small voids and cracks in the material indicated fliat it was drying. Material separation, due to high initial vacuum also occurred. This high initial vacuum was due to a high resistance to flow. Condensation was not apparent in the vacuum lines, and water did not collect in the vacuum flask.

On September 8, within 12 hours after a bleed valve was added to the bottom of Column 3 A, the appearance of condensation on the glass at the top of the column was an indication that the material was drying out in response to the increased air flow. Within 22 hours, there was noticeable drying of the soil in the bottom half of the colunm.

On September 12, the height of the material column was measured at 18 inches, unchanged fi-om the original height. When the material was extruded from the glass column for sampling, it was very dry and hard and crumbled apart by hand.

Column 3B

The Lagoon 3 material mixed with the wood shavings was very porous and crumbly. After the bottom bleed valve was added to the column on Day 2, the mixmre began to dry noticeably. Within 12 hours, drying was indicated by a lighter appearance which extended up 9 inches fi'om the bottom of the colunm. Over the remaining days of operation, the mixture became visually drier throughout its length.

At the end of operations, the column was measured and found to have settled about 3/4 of an inch. The mixture crumbled apart as it was extruded from the glass column, and was very dry.

400562 Technical Evaluation Laboratory Treatability Study-CarroU and Dubies Superfimd Site-Final Repon mpr/1644-150/101094 3:28 3-9

Column 7A

The unamended material from Lagoon 7 was sticky and soft. Once vacuum was applied to the column, the material was pulled upward in the column several inches and separated into two pieces, with a space of 1 to 2 inches between the pieces. Within 30 hours, the physical appearance of the material indicated that the vacuum was drying it out. It began to settle, and shrink away firom the sides of the column in places. Other cracks and voids became evident.

After about a week, there was more drying and shrinkage, but only in the top piece of material near the vacuum source. There was condensation on the sides of the glass column and in the tobing, although no moisture accumulated in the condensation flask. When the bottom bleed valve was added to the column on September 8, there was an increase in condensation on the glass coIimm and in the mbing.

When operation ceased, the total length of the column was still 18 inches, although the top 3 inches had separated from the remaining 15 inches by a gap of 3 inches. When the material was extruded firom the glass for san^ling, it was wet and sticky. The material at the top of the column was slightly drier than the rest of the material. A small amount of water had collected at the bottom of the glass column.

Column 7B

The wood shavings and Lagoon 7 material mixmre blended fairly well and the mixture was crumbly. Setding was visible in the glass column within the first day of operation. Twelve hours after adding the bottom bleed valve to die system, a noticeable drying firont, indicated by a lighter color, was evident on the bottom 8 inches of the soil column. The mixmre in the column continued to dry during the remaining days of operation.

At the end of operations, the material in the glass column had setded 1 1/2 inches. The material fell apart as it was pushed out of the mbe, and was described as very dry.

400563

Technical Evaluation Laboratoiy Treatability Study-CarroU and Dubies Superfund Site-Final Repon mpr/1644-150/101094 3:28 3-10

3.2.2 Vacuum Monitoring

Column 3A

Vacuum readings at die top and bottom of Column 3A were monitored for a 12-day period. The change in daily average vacuum readings over time in Column 3A are illustrated in Figure 3-2. The vacuum measurements at the top of the colunm were obtained by opening the bottom line, and allowing air flow through the soil column. A high vacuum reading under these conditions indicates that a large pressure drop occurs across the soil column; therefore, the soil colunm presents significant resistance to air flow, or low air permeability. Conversely, a low vacuum in the headspace when air is flowing through the column indicates that the soil column possesses a high permeability to air flow. Initially, the vacuum at the top of the column, the end at which the vacuum was applied, was relatively high, indicating resistance to air flow through the column. The vacuum reading at the bottom of the colunm was relatively low, indicating limited air movement from the bottom of the column toward the top. Within 4 to 6 days of operation, the vacuum measurements indicated that vacuum was becoming uniform through the column.

The readings on September 9 were taken simultaneously by opening the bottom line and closing the top line. Under these flow-through conditions, the difference in top and bottom vacuum values (approximately 5" of water column) represents the vacuum loss across the soil column.

These vacuum readings show that a vacuum can be propagated through the material. The vacuum data indicates that significant air flow can be obtained through unamended Lagoon 3 material. These conclusions are consistent with the porous appearance of the unamended Column 3A material, and the visual appearance of drying during the operation of the column.

Column 3B

Average daily vacuum readings are available for the initial and final three days of operation for Column 3B (Figure 3-3). No vacuum readings were taken during the period of September 10 to September 18.

400564

Technical Evaluation Laboratory Treatability Suidy-CarroU and Dubies Siqierfiuid Site-Final Repon inpr/1644-150/101094 3:28 3-11

\

Figure 3-2 Column 3A Vacuum Readings

35

30

25

I 2°

o Sg I S

10

Adjustment in Bleed Line Configuration

J_ 08/29 08/30 08/31 09/01 09/02 09/03 09/04

Day 09/05 09/06 09/07 09/08 09/09

Vacuum at top of column Vacuum at bottom of column

o o en

1^

u Figure 3-3

Column 3B Vacuum Readings

I v>

I

g.

I

Tl

I I

O o Of

^

"6

30

25

20

15

10

5 -

09/07 09/08

Adjustment in Bleed Line Ctmfiguration

_L

09/09 09/10 09/11 09/12 09/13 09/14 Day

09/15 09/16 09/17 09/18 09/19 09/20 09/21

-» Vacuum at top of column -»- Vacuum at bottom of colunm

Following the adjustment of the bleed valve arrangement on the second day of column operation,

top and bottom vacuum readings came closer together and dropped (September 9). At the end

of the monitoring period on September 19, 20, and 21 , vacuum readings from the top and the

bottom of the column were relatively close, indicating significant air flow through the column.

The vacuum readings for the amended Column 3B at the end of the monitoring period were

somewhat lower (2 to 5 inches of water column), compared to the final readings for the

unamended Column 3A (6 to 11 inches of water column), indicating less resistance to air flow and

improved air movement as a result of the amendment.

Column 7A

As Figure 3-4 illustrates, the top and bottom average daily vacuum readings for Colunm

7A never intersected. The readings were brought closer together with an adjustment in the bleed

line opening on the third day of operation, and an adjustment in the configuration of the system

on the eleventh day of operation. However, at the end of the monitoring period, there was no

indication of uniform vacuum propagation, and thus limited air flow, between the top and bottom

of the column.

V~ Spot vacuum readings early in the operation of Colunm 7 A (at about 30 hours) reflected

the physical changes of drying and shrinkage of the lagoon material. The vacuum at the bottom

of the column had risen to 18 inches of water, and the vacuum at the top of the column had

dropped to 60 inches of water. The changes in vacuum were probably due to the increase in voids

and shrinkage caused by drying. However, the vacuum at the bottom of the column could not be

sustained consistently.

As Figure 3-4 indicates, the behavior exhibited by the material in Colunm 7A is

qualitatively similar to that exhibited by the material in Column 3A. Namely, a decrease in

headspace vacuum occurred, likely associated with progressive drying of the column material.

The main difference between Columns 7A and 3A is that the headspace vacuum values for

Column 7A indicate a much lower permeability of die colunm material to air flow. A lower

permeability is also indicated by the higher vacuum difference between the bottom of the colunm

and t te headspace measured under flow-through conditions (approximately 20" of water column,

on September 9).

4Q0567

Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Superfund Site-Final Repon mpr/1644-150/101094 3:28 3-14

I? -I Figure 3-4

Column 7A Vacuum Readings

I 4 I

B

ca

I

I

51

180

160

140

120

8 100

£ 60

40

20

08/29

^justment in Bleed Line enings

_u


08/30 08/31 09/01 09/02 09/0} 09/04 Day

09/05 09/06 09/07 09/08 09/09

Vacuum at top of column Vacuum at bottom of column ]

o o to

In conclusion, air flow through unamended Lagoon 7 material was limited, except through the formation of cracks and voids that developed with vacuum application and subsequent drying. Limited air flow through unamended Lagoon 7 material is consistent with its dense, samrated consistency.

Column 7B

As Figure 3-5 illustrates, average daily vacuum readings are available for the initial and final three days of operation of Column 7B.

On the first day of column operation, the top and bottom vacuum readings were fairly close. When the bleed line configuration was adjusted, the top and bottom vacuum readings diverged. By the last three days of monitoring, on September 19, 20, and 21, the top and bottom readings were relatively close but variable.

The limited data indicates there was similar vacuum at the top and bottom of the column, and dius air flow through the column, at the end of the operational period. The addition of wood shavings to the Lagoon 7 material appeared to have improved its permeability to air, compared to the unamended material.

3.2.3 Photoionization Monitoring

Column 3A

Figure 3-6 and Figure 3-7 illustrate the pattem of photoionization readings over the operational period of Colunm 3A. Figure 3-6 shows five-minute and then 30-minute average readings over the initial continuous monitoring period of about 24 hours. There were variable readings during the first 12 hours, with averages ranging firom 4 ppm to greater than 50 ppm. After the initial 12 hour period, readings stabilized in the range of 3 to 5 ppm. Figure 3-7 shows daily interval averages and spot readings for the remainder of the operational period. Plots of daily photoionization readings for August 30 and 31, and September 1, 2, 4, and 6 are found in Appendix B. The readings were low, near zero, and steady up until the second bleed valve was added to the column on September 8. At that time, a peak in average readings exceeding 100 ppm indicated that the increased an- flow allowed by the second bleed valve resulted in increased removal of VOCs from the colunm. Even more interesting is the high spike of 480 ppm noted

400569 Technical Evaluation Laboratoiy Treatability Smdy-CarroU and Dubies Superfund Site-Final Repon nipr/1644-150/101094 3:28 3-16

i r r t i .

Figure 3-5 Column 7B Vacuum Readings

II CA I

CI

I

I

30

25

20

15

10


J_ _L _L I _L J_ _L _L

09/07 09/08 09/09 09/10 09/H 09/12 09/13 09/14

Day 09/15 09/16 09/17 09/18 09/19 09/20 09/21

• Vacuum at top of column Vacuum at bottom of column

o o C I -a o

t if S B

Figure 3-6 Column 3A Initial Continuous Photoionization Readings for August 29,1994

60

C3

I I I

50

I

M

I I

40

I I 30

'

20

10

4 ^

o O

-a

± 325 650

Time (minutes) 975 1300

AveragesJ 5 & 30 Minute Interval

o g l § Ul sr

I I I

I

8'

500

450

400

350

E Q. e- 300 c o I 250

o O

200

150

100

50

O o CI <1 to

Figure 3-7 Column 3A Daily Interval and Spot Photoionization Measurements, 8-30-94 to 9-12-94

08/30 08/31 09/01 09/02 09/03 09/04 09/05 09/06 09/07 09/08 09/09 09/10 09/11 09/12 Day

Interval Average

A - Spot Measurement

during a spot reading on September 11. The increased air flow and the drying which increased air permeability in the colunm soil, would account for this spike. A spot reading on September 12, the final day of operation, showed that the concentration had dropped to less than 50 ppm.

Column 3P

Figure 3-8 illustrates the initial continuous monitoring period for Column 3B, which was cut short by equipment difficulties to about 12 hours, and Figure 3-9 illustrates the trend in daily interval averages and spot readings over the rest of the operational period. Plots of daily photoionization readings for Column 3B for September 8 and 9 are found in Appendix B. Similar to the trend seen in Column 3A, there was initial variability in the readings, with excursions in the range of 30 to 40 ppm, and average readings dropping to near 0 ppm (lower than was observed during the same period for Column 3A, which averaged around 5 ppm). On September 8, near the end of the second day of operation for this column, a bleed valve was added to the bottom of the column which increased air flow. There was an increase in average organic vapor readings in the 30 to 40 ppm range, gradually declining over the operational period to 0 ppm.

A comparison between the photoionization readings for the unamended (Column 3A) and V amended (Column 3B) tests does not show a clear advantage for VOC removal from Lagoon 3

material with the addition of the wood shavings. The initial continuous monitoring profiles, where both columns were operated with the same bleed valve configuration, are similar. The more sustained removal for Colimm 3B over an approximate 10-day period could be a result of the bleed valve configuration as well as the addition of the amendment.

Column 7A

The photoionizable vapor results for the initial continuous monitoring period for Column 7A are shown in graphical form in Figure 3-10. Readings were initially high, exceeding 300 ppm. The initially higher readings for Column 7A con^>ared to Column 3A, are consistent based on the higher VOC concentrations that have been measured in Lagoon 7 material compared to Lagoon 3 material. Within 2 hours, readings averaged around 100 ppm, dropping to the 20 to 40 ppm range within 6 hours. At the end of the initial monitoring period, readings had stabilized to around 30 ppm.

400573 Technical Evaluation Laboratory Treatability Soidy-Carroll and Dubies SuperAmd Site-Final Repon nvr/1644-150/101094 5:22 3-20

m S 9 1 l l it l l

H J

i

1

Ul 1 i^> 1

1 Mt\ 40

35

30

25

1 ^^ c i ° § c o O

15

10

1

5

1 M ^ i \

O 0

o c C I

1 Figure 3-8 | 1 Column SB Initial Continuous Photoionization Readings for September 7,19941

1

1 100 200

1 ••"^

1

1

UU

1

300 400 500 600 700 Time (minutes)

• 5 Minute Averages 1

if

f

I

CA

I I 3

Figure 3-9 Column 3B Daily Interval and Spot Photoionization Measurements, 9/8/94 to 9/21/94

40

30

E a. 3>

1 20

c o O

10

0

* (—1 A

o o C l

09/08 09/09 09/10 09/11 09/12 09/13 09/14 09/15 09/16 09/17 09/18 09/1 Day

09/20 09/21

fe

Interval Averages I

A - Spot Measurement

^1 5§' ° l l i Ul

•5" CO

I I §•

CO

R

350

300

250

200

150

100

Figure 3-10 Column 7A Initial Continuous Photoionization Readings for August 29,1994

50 -

- • - « - » •

O o CT

sen

_L -L J_

100 200 300 400 500 600 700 800 Time (minutes)

900 1000 1100 1200 1300 1400

5&30 Minute Interval Averages I

Figure 3-11, which shows the available daily average interval and spot measurements for the duration of Colunm 7A operation, is incomplete because of equipment failure. Plots of daily photoionization readings for August 30 and 31, and September 1 are found in Appendix B. It can be seen that during the first few days of operation, the average readings stabilized in the range of 10 to 20 ppm, and had dropped down to near 0 ppm on September 8 when the bottom bleed valve was added. As had been observed for Column 3A, a high spot reading of about 80 ppm was observed not immediately after adding the bottom bleed valve, but a few days later, when increased drying in the soil column was evident.

Colwmn 7B

Two initial continuous monitoring periods were performed for Colunm 7B, the first (Figure 3-12) for an approximate 24-hour period on September 7 and 8, and the second (Figure 3-13) for an 18-hour period on September 8 to 9. Figure 3-12 shows average concentrations up to ahnost 750 ppm at the beginning, tapering off rapidly, and then jumping to greater than 2,500 ppm when the bottom bleed valve was added to the column.

About an hour and a half elapsed before the second round of continuous monitoring began V again (Figure 3-13); by then readings were down to the 700 ppm range. Over the next 18 hours,

there was a steady decline in organic vapor concentrations, which stabilized around 150 ppm. Interval readings began again on September 12. The average daily reading on that day (Figure 3-14) was in the range of 20 to 30 ppm. For the remainder of the operational period, as illustrated by Figure 3-14, there was a steady decline in total organic vapor concentrations, approaching zero on September 21.

In conclusion, the organic vapor removal efficiency, as measured by the organic vapor monitoring from the amended Lagoon 7 material (Column 7B) was improved, compared to the unamended Lagoon 7 material (Column 7A). This conclusion is based on the information shown in Figure 3-12, compared to Figure 3-10. In the first 200 minutes, organic vapors in the range of 150 ppm to almost 750 ppm were removed fi"om Column 7B, while in the same time period in Column 7A, organic vapors in the concentration range of 50 ppm to 350 ppm were being removed.

Plots of daily photoionization readings for Column 7B for September 12, 13, 14, 15, and

16 are found in Appendix B.

I 400577 Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Superfund Site-Final Repon mpr/1644-150/101094 3:28 3-24

4 2 § | § Ol K

a

CO

I

I §••

CO

S'

Figure 3-11 Column 7A Daily Interval and Spot Photoionization Measurements, 8/30/94 to 9/12/94

E a. Q.

O

•? c

s c o o

100

80

60

40

20

O o Cl -a 00

08/30 08/31 09/01 09/02 09/03 09/04 09/05 09/06 09/07 09/08 09/09 09/10 09/11 09/12 Day

I n te rva l A v e r a g e

A - S p o t Measurenf ient |

bi

ll o » S a

§ •3

I I

I

I CO

S"

I

Figure 3-12 Column 7B Initial Continuous Photoionization Readings for September 7-8,1994

2750

2500

2250

2000

-g- 1750 Q. Q.

c* 1500 o

•g I 1250 c O 1000

200 400 600 800

Time (minutes) 1000 1200 1400

o Cl CP

5 & 30 Minute Interval Averages

1 ^

ft w Ul <

o § S g Ul sr

f CO

.1

I

I CO

S

I 1

Figure 3-13 Column 78 Initial Continuous Photoionization Readings for September 8-9,1994

800

600

E Q. Q.

I 400 « u c o O

200

_L _L

o o ct CO

o

100 200 300 400 500 600 700 Time (minutes)

800 900 1000 1100 1200

30 Minute Interval Averages I

n S E. o E »— a. | §

C3

I

Figure 3-14 Column 7B Daily Interval and Spot Photoionization Measurements, 9/12/94 to 9/21/94

40

30

E Q.

I 20 s c o O

10

O C l CO

09/12 09/13 09/14 09/15 09/16 09/17 Day

09/18 09/19 09/20

_ A _

09721

Interval Average I

A - Spot Measurement I

V- -3.2.4 Material Analyses

Lagoon 3 Results

Table 3-1 summarizes the analytical information on the Lagoon 3 materials. The initial analysis for Column 3A is the same as the analysis performed on the sieved sample used in the slurry reactor (Section 5.0). The Colunm 3A results show that all of the VOCs detected in die initial sample were reduced to concentrations below the detection limit in the t)ottom, middle, and top of the column after treatment. Assuming that the average detection limit is the final concentration, the percent reductions are benzene 97%, tetrachloroethene 93%, toluene 98%, and total xylenes 74%. This reduction is consistent with the general observations that air flow was achieved through the unamended Lagoon 3 materials. The results for Column 3A also show a significant moisture loss of about 22%, as indicated by the increase in the average solids concentration. The greatest moismre reduction was in the bottom of the column, which is consistent with the visual appearance of the column drying from the bottom up over the operational period.

The final samples for Column 3B were collected for analysis on September 21. The single sample analysis for the Lagoon 3 material mixed with wood shavings shows concentrations considerably lower than the initial value for Column 3A, more than can be accounted for by dilution with the wood shavings. This may be due to sample variability (the initial Column 3A sample was analyzed in triplicate, while a single initial sample was collected for Column 3B), or to losses of volatile constiments through additional mixing and handling.

The Column 3B results show that all of the VOCs detected in the initial sample were reduced to concentrations below the detection limit in the bottom, middle, and top of the column after treatment. Minimum percent reductions, assuming that the average detection limit is the final concentration, range firom 51% to 93%. The percent reductions may be artificially low, skewed by the relatively high detection limits in the final samples compared to the initial concentrations. That is, even though the calculated percentage reductions are lower for Column 3B con^ared to Column 3A, there is not a technical reason that the reductions would be lower.

Methylene chloride, which was not detected in the initial sample, was reported at an estimated value below the quantitation limit in the final top sample only. The fact that it was

400582


TABLE 3-1 DETECTED CONSTITUENTS •

LAGOON 3 VAPOR EXTRACTION COLUMNS

SAMPLE ID

. RATCSAMM-EP

COLUMN 3A 1

(Ltgoon 3, unamended) I

Inilial, avg.'

08/|»»4 Q

[%. : "m ' : . i [ ' - ' f : / ^ . i i ^ ^^^

k m So!Mi.?4 1 71,81 _

|Ben2ene

rrdracbkiraelhaK

Toluene

lxjte!S}.!S»1

SAMPLE |D

. . BATE SAMPLER

24,667

9,967

44,333

2.m —

Iniliaf

.09/07/94 JQ

TplslSolids.% . . 1 85,7| 1

;:-::,.r.:.::::-^;:^:;:;:l^'-.;H:;:;iv.;^;-;;-:::::r Benzene

Toluene

Xylenei. total

1,900

S.000

9,800

1.300

—

Final-Bonom

<»/M/M Q

Final-Middle

09/14/94 1 0

Final-Top

. m»l9i ].Q ^ ^ -• G.«VMll««i P i i w i i ^ r t f ^ >•"' '*-

_.?16|„^ L 9 2 , ! j . „ | m \ ^

< 630

< 630

< 630

< -_ - 630 —

Final-Boltum

< 680

< 680

< 680

< 680 ._-

< 690

< 690

< 690

< 690 ....

COI .UMN3B '

(^.agoon 3, amended)

Final-Middle I Fnial-Top

. ._ IQ IQ " ^ ••• :;Co»veat(t«il P w i m ^ n •••'•'•?:*-i '?::' ^^^ ^

1_J,_... _ .L_l j.__ i^;;;; VoiMB«bif i i«fci ' f l i i /kfy:: : :^ '*:^;: : : :" ' ;^r^:;v ' : ; !--; :- ' -

-

_

Final-Avg.'

09/14«4 SI-

Perecni Reduction'

. mmmrn'm-mmm^ti^m^^^i

9361,.

< 667

< 667

< 667

< 667 -

Final-AvB.

: : : ^ Q \ '-y:"!~i\Vith^-'fvX~.-

l_. • • r r r :h-: . - ' iS^i'r.

— 1

__,._ _ ._ 1 \:vS:}-\:-y:-:::m-/:-v:-..-- \

97%

93%

98K

-74%

r -

• y V : " • • : • • • : • ' : • : : • - : • ' : :

o o CO CO

Q: Data Qualifier column J: Compound detected below quantitation limit. Value repoited is estimated.

(I ] Other volatile conaiiluems were analyzed but not delected above Ihe method detection limit using GC/MS analyses. [2] Numerical average of three analyses, irone or iwo of the three analyses were repoited as below the method detection limit,

then the detection limit was used lo compute the average. [3] Average of bottom, middle, and lop concentrations. (4] Percent reduction calculated as:

Initial (Concentration - Final Concenwration Inilial ConcenUation

(S] Based on single analysis of Lagoon 3 material blended with IS% by weight wood shavings.

r

il 11 Ki

•3

i •3'

.1

R

I a.

O O cn GO

TABLE 3-2 DETECTED CONSTITUENTS'

LAGOON 7 VAPOR EXTRACTION COLUMNS

SAMPLE ID

P 4 T E S f ^ > 4 r t { : p

COLUMN 7A

(Lagoon 7, unamended)

Inilial, avg. '

08/18/94 _ r Q

. I loiai Solids. %

Benzene

TeiiachloroetheiK

Toluene

Trichloroelhene

Xylenes, tola! _ .

.

SAMPLE ID

BATE SAMPLED

. 4 0 5 |

•

150,000

!,S33,333

4,133,333

143,333

330,000 —

Final-Bottom

0 ? / ! l / ? l _ . Q Final-Middle

_ 09/14/94 I Q Final-Tog

Qimm. I Q Cki ive i i t lda i l>anui« fen:^ :

,, ..48.21 1 - 4 5 . 5 1 1 52.51 1 y p l i « t e O r M B J n ( i i i r t { t V ^ ^ - ^ i - v - : ' : ; - --•^' ^

J?,ooo 1,500,000

[ 3,700,000

, 110.000

37Q.QOO

46,000

s s o j m 2,200,000

64,000

_ L ~ . 180,000

< !?o,ooo _ 970,000

2,300,000

< 120,000

- 270,000

-

COLUMN 7 B

(Lagoon 7, amended)

Inilial <

Q?/07/?l„.I__ | - . - : ; : : - : ; ^ ^ F . - : , : : : ; ; ; : , : ; ; - . ; ; : : : ; : • - • ' - : : : - . ; : = ; • • ; -

IT<8»! Solids. % 1 52.61J

Benzene

Telracbloroelheiie

Toluene

Trichtoroelhene

Xylsnsj. !9t t l

_ 120,000

1 ^ , 0 0 0

3,400,000

91,000

360.000

-

Final^Bollom

IQ. Final-Middle

[Q Final-Top

r : . : " :].Q Cwvwr t lKMl r a n w i c t m ^ • ^ • • ••• • • • '•

i;:v; yitiiniit orMnintPi/kfV •:;,:• -r ::

• —

-^ - . - --

Final-Avg •

09/M/94 J Q

- _ 4S7 l

8 I , » 7

1,116,667

2,733,333

98,000

^ 273,333

Percent Reduction'

: : ; * ; " • ; ; ' : ; ; • • : : • : • . ; . , ; : : ! : : , • • ' ; : ; ; ' ,

; : • : : : > : : : : : , : , ( ) : : • : : : • . . : . • • : • ' •

46%

27%

34%

3 1 %

_ 17%

_ _ „ _ . . . . _ _

Finaf-Ave.

1 • • • - ; • ^ : : ; - . , ; , ;

~

-

Notes:

Q: Data Qualifier column

J: Compound delected below quamilalion limit. Value repoited is estimated.

[ 1) Chher volatile constiluents were analyzed but not detected above tlie method deteclion limit using GC/MS analyses.

(2) Numerical average of three analyses. If one or Iwo of the three analyses were rcpodcd as below the method detection limit,

then the detection limit was used lo compute Ihe average.

(3] Average of bolioni, middle, and lop concentrations.

|4 | PerceM reduction calculated as:

Initial Concentration - Final Concentralion

Inilial Concentralion

[5] Baud on single analysis of Lagoon 7 material blended with 15% by weight wood shavings.

V measured in a final sample but not in the initial sample could be a fimction of the detection limit. Methylene chloride is also a common laboratory contaminant. Because of the imcertainty of these results, a percentage reduction has not been calculated for this constiment.

The pattem of moisture reduction is uniform throughout the length of the column, for an average reduction (reflected by an increase in the total solids concentration) of about 12%. This is consistent with visual observations of relatively rapid drying over the length of the column during operations.

Lagoon 7 Reswlts

The analytical results for Lagoon 7 materials are summarized in Table 3-2. All of the VOCs detected in the initial analyses were also detected in the treated Column 7A. The detected concentrations of benzene, tetrachloroethene, toluene, trichloroethene, and total xylenes were lowest in the middle portion of the treated column. The highest detected concentrations of tetrachloroethene, toluene, and xylenes were found in the bottom portion. Greater reduction in VOC concentrations nearest the vacuum source (near the top of the column) would be predicted for this low permeability material. Looking at average values for the treated column, percent reductions were estimated to range from 17% to 46%. This limited reduction is consistent with the general observations that only limited air flow could be generated through the column of unamended Lagoon 7 material. The average moisture reduction (indicated by the increase in total solids) was about 8% for Column 7A. The greatest moismre reduction was noted in the top portion of the column.

The final samples for Column 7B were collected for analysis on September 21. The single sample analysis for the Lagoon 7 material mixed with wood shavings shows concentrations in the range that would be predicted with a 15% dilution with the wood shavings.

The Column 7B results show that benzene, trichloroethene, and total xylenes were reduced to below detection limits in the top, middle, and bottom samples. Tetrachloroethene and toluene were detected in the treated material, but in concentrations significantly lower than the initial sample. Percentage reductions for all constituents exceed 99%, assuming that the detection limits for benzene, trichloroethene, and total xylenes represent the final concentration. The concentrations of detected constituents were similar throughout the column, indicating uniform

4005S5 Technical Evaluation Laboratoiy Treatability Study-Carroll and Dubies Superfiind Site-Final Report nq)r/1644-150/101094 3:28 3-32

removal. Constituent reductions for Column 7B are the highest calculated reductions of all the

columns.

The moisture was reduced 41% on average for the column, compared to the initial sample, based on an increase in total solids. Moisture removal was fairly uniform through the column. This is the highest moisture reduction of all the columns.

3.2.5 Vapor Analyses

Lagoon 3 Results

Vapor analyses were performed to characterize the organic vapors that were being removed firom Lagoon 3. The results are presented in Table 3-3. The sample collected fi-om Column 3 A on Day 2 (August 30) found only one VOC above the detection limit, tetrachloroethylene at a concentration of 0.005 ppm by volume. At the time the sample was collected, total organic vapor readings from the photoionization detector were averaging 2.7 ppm. On Day 14 (September 12), a second sample was collected. At this time, the bleed valve configuration on the column had been changed, and the total organic vapor reading was 45 ppm. Three constituents were measured above the detection limit, two alkanes, nonane and decane, and tetrachloroethylene. These results show that total organic vapor readings were a reasonable indicator of specific volatile constiments. That is, when the organic vapor reading was low, only one constiment was detected, and when the organic v^wr reading was higher, three constiments were detected in higher concentrations.

The Day 2 air sample for Colimm 3B was collected on August 8. A photoionization reading near the time of the sample collection is not available. Measurements taken within 4 hours of san^le collection were in the range of 30 to 40 ppm. The constiments detected, nonane, decane, and tetrachloroethylene, were the same as were detected on Day 14 for Column 3A, and were found in similar concentrations.

Lagoon 7 Results

The Lagoon 7 air analysis results presented in Table 3-4, like the Lagoon 3 results, show

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Technical Evaluation Laboratoiy Treatability Study-CarroU and Dubies Superfiind Site-Final Report inpr/1644-150/101094 3:28 3-33

TABLE 3-3

AIR MONITORING RESULTS FOR LAGOON 3 COLUMNS

COLUMN ID

SAMPLE ro

Pentane

Hexaoe

Heptane

Octane

Nonane

Decane

Benzene

Ethylbenzene

Toluene

Xylenes, m&p-

Vinyl chloride

Methylene chloride

tians-1.2,-Dichloroethylene

Chloroform

1,1,1-Trichloroethane

Caiboo tetrachloride

Tiichloroethylene

Tetrachloroethvlene

COLUMN 3A

(Lagoon 3 Mateiial)

Dav2 0.. Pay 14 _QJ

COLL^MN 3B

(Lagoon 3 Material amended with sawdust)

P»Y2 0 Pay 14 0 Alkanes C5-C10 (DDDIV)

<

< < < < <

0.07

0.07

0.07

0.07

0.07

0.07

< 0.07

< 0.07

< 0.07

< 0.07

0.15

0.51

< < < <

0.07

0.07

0.07

0.07

0.09

0.89

(1)

a) 0)

(1)

0)

m BTEX (Dl)iliv>

< < <

< <

0.07

0.07

0.07

0.07

0.07

< 0.07

< 0.07

< 0.07

< 0.07

< 0.07

< < <

< <

0.07

0.07

0.07

0.07

0.07

0)

(I)

<i)

(1)

rn CUisrinated Volatlie Oreaiilcs (vpmvV

< < < < < <

<

3

2

0.1

0.005

0.005

0.005

0.005

p.005

< 3

< 2

< 0.1

< 0.005

< 0.005

< 0.005

< 0.005

0.008

< < <

< < < <

3

2

0.1

0.005

0.005

0.005

0.005

0.015

C)

0)

0)

(1)

0)

(1)

(1)

0)

(DAnalytical results not yet available. Q: Qualifier Column.

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Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Superfiind Site-Final Report inpr/1644-150/101094 5:22 3-34

TABLE 3-4

AIR MONITORING RESULTS FOR LAGOON 7 COLUMNS

COLUMN ID

SAMPLE ro

COLUMN 7A

(Lagoon 7 Material)

Dav2 0 Dav 14 O 1

(Lagoon

Pay

COLUMN 7B

7 Material amended with sawdust)

2 0 Dav 14 O

Alkanes CS-ClOYppmv) 1

Pentane

Hexane

Heptane

Octane

Nonane

Decane

Benzene

Ethylbenzene

Toluene

Xylenes, m&p-

Xvlenes. o-

Vinyl chloride

Methylene chloride

trans-1,2.-DichlotoethyIene

Chloroform

1.1.1-Trichloroethane

Caibon tetrachloride

Trichloioethylene

Tetiachioroethvlene

<

< < < <

0.07

0.07

0.07

0.07

0.07

0.09

< 0.07

< 0.07

< 0.07

< 0.07

< 0.07

< 0.07

< 0.07

0,10

< 0.07

0.62

4.81

7.60

(I)

(1)

0)

(1)

(1)

rn

BTEXfDi>tnv> 1

< <

0.07

0.07

0.34

< <

0.07

0.07

, . Chlorinal

< <

< < < <

3

2

0.1

0.005

0.005

0.005

0.008

0.093

< 0.07

< 0.07

< 0.07

< 0.07

< 0.07

ted Volatile OrsaBlcs (n

< 3

< 2

< 0.1

< 0.005

< 0.005

< 0.005

< 0.005

0.009

0.37

0.63

46.03

1.67

4.65

(1)

0)

0)

(I)

tn

pmv) 1

< < <

3

2

O.I

0.016

0.057

< 0.005

0.696

17.530

0)

(1)

(t)

0)

(t)

0)

0)

ni

0)AnaIytical results not yet available.

Q: Qualifier Column.

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Technical Evaluation Laboratoiy TreatabiliQ' Smdy-CanoU and Dubies Superfiind Site-Final Report mpr/1644-150/101094 5:22 3-35

a good correlation between the photoionization readings and the number and concentrations of VOCs detected. The relevant photoionization readings were:

Column 7A, Day 2 (August 30): 25 ppm

• Column 7A, Day 14 (September 12): 3.3 ppm

Column 7B, Day 2 (September 8): 730 ppm

Table 3-4 shows that decane and toluene were detected on Day 2 in Column 7A, and tetrachloroethylene was detected on Day 14. On Day 2 of Column 7B operation, alkanes, BTEX, and chlorinated VOCs were all detected in significant concentrations.

3.3 Conclusions

Final soil and air analytical results for Columns 3B and 7B are not yet available. Conclusions about the constiment reduction in these columns, and changes during operations in constiments in the vapor phase, will be made when that information is complete. Based on the existing information, conclusions can be made that address the original objectives of the vapor extraction tests.

3.3.1 Air Flow Through Lagoon 3 and Lagoon 7 Materials

The vacuum measurements for Lagoon 3 material without an amendment (Column 3A) clearly showed that uniform vacuum can be developed over time through the material column, indicating air flow. The amended Lagoon 3 material (Column 3B) also indicated significant air flow at the end of the operational period. Air flow through imamended Lagoon 7 material (Column 7A) was limited, and was the result of voids and shrinkage channels. Similar vacuum was measured at both the top and the bottom of the amended Lagoon 7 material (Column 7B) by the end of the operational period, indicating air flow. The visual appearance of drying of the soil firom the bottom upward in Colimins 3A, 3B, and 7B over the operational period was also an indication of air flow.

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Technical Evaluation Laboratoiy Treatability Study-Carroll and Dubies Superfund Site-Final Report nipr/1644-150/101094 3:28 3-36

3.3.2 Dewatering of Lagoon Materials

Columns 3A, 3B, and 7B became visibly drier during vapor extraction and the moismre analysis of Column 3A after treatment showed a 22 % reduction in moisture, while there was about an 8% reduction in moismre in the treated Column 7A. Moisture analyses are not yet available for treated Columns 3B and 7B.

3.3 J VOC Removal from Lagoons 3 and 7 Materials Using Vapor Extraction

VOC removal was demonstrated in two ways during these tests, by the appearance of VOCs in the air pumped through the columns, and in the reduction in the concentrations of VOCs in the treated soils compared to the untreated soils.

VOCs were measured both as total organic vapors using a photoionization detector and through constiment analysis in air exiting from all four columns. The concentrations and identities of the VOCs varied with the lagoon materials, operating conditions, and the period of operation.

Reductions ranging from 74% to 98% for individual VOCs were measured in Column 3A. All VOCs in the initial sample were reduced to below detection limits in the final samples. Percentage reductions were calculated by assuming the detection limits were the final concentrations. In Column 3B, all VOCs were also reduced to below the detection limits. However, calculated minimum percent reductions were apparently lower than for Column 3A, ranging from 51% to 93%. There is not a technical reason that the reductions in Column 3B would be lower than in Column 3A. These results reflect the fact that the initial concentrations for Column 3B were lower, and closer to the detection limits for the final samples, than the initial concentrations in Column 3A.

Percentage reductions of VOCs in the unamended Column 7A materials ranged from 17% to 46%. In the amended Column 7B, however, calculated reductions exceeded 99% for all five of the VOCs detected in the initial sample, indicating that the addition of the amending agent improved VOC removal using vapor extraction.

400590 Technical Evaluation Laboratory Treatability Smdy-CarroU and Dubies Superftuid Site-Final Report mpr/1644-150/101094 3:28 3-37

3.3.4 Use of a SoU Amendment to Improve Treatment EfHciency

Vacuum readings, total organic vapor readings, the visual observations of column drying, and VOC reductions in Column 7B indicate that treatment efficiency of Lagoon 7 material would be io^roved with the use of a soil amendment to modify the texmre of the material to be treated. An amendment would not be required to treat Lagoon 3 material using vapor extraction.

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Technical Evahiation Laboratory Treatability Soidy-CarroU and Dubies Superftind Site-Final Report sq>r/1644-lSO/101094 3:28 3-38

4.0 MINERALIZATION TESTING

Benzene mineralization tests were initiated to verify that microorganisms in Lagoon 3 and Lagoon 7 materials are capable of biodegrading the organic constiments-of-concem under liquid/solids treatment conditions. In these tests, **C-benzene was added to slurries of the test materials and the production of "CO2 measured over time (COj is the ultimate product of aerobic benzene biodegradation). Benzene is used as an indicator because it has been previously found in samples from both Lagoon 3 and Lagoon 7 in significant concentrations. Anything which inhibits biodegradation, such as sample biotoxicity due to excessive metals or chlorinated solvent toxicity, or the absence of appropriate microorganisms, produces a negative result in these mineralization tests.

4.1 Equipment Set-Up/Trocedures

Prior to initiating the mineralization tests, microbial seed inocula were developed from each of the Lagoon 3 and Lagoon 7 materials. Seed development helps ensure that indigenous microorganisms are metabolically active prior to initiation of biodegradation tests. To develop the seed, sludge samples were suspended in a nutrient solution at very low solids loadings (1 % solids). After three days of incubation, the presence of microbial activity in the seed cultures was verified using oxygen uptake rate (OUR) measurements. These measurements are a non-specific measure of aerobic microbial activity. The higher the OUR, the higher the microbial activity in a sample (OUR values range from less than 1.0 for inactive samples to over 1(X) for samples with high levels of biodegradable constiments). Based on the measured OURs, microorganisms were metabolically active in both seed inocula.

Once microbial activity in the seed inocula had been verified, benzene mineralization tests were initiated. These tests were set-up for each lagoon material following the laboratory workplan (duplicate biologically active test reactors at 10% and 20% solids and duplicate sterile control reactors at 20% solids). Each reactor was pH neutralized, and amended with inorganic nutrients and microbial seed at the start of testing. The ^*C-benzene radiotracer used for testing was obtained from SIGMA Chemical Company with a radiochemical pmity of 98%. Therefore, for benzene mineralization to be significant, it must exceed 2%. Benzene mineralization was monitored by trapping and quantifying "CO2 produced during biodegradation of the '*C-benzene

400592 Technical Evaluation Laboratory Treatability Study-CairoU and Dubies Supeifimd Site-Final Repoit mpT/1644-lS0/101094 3:58 4-1

radiotracer. The "CO2 was trapped using an alkaline ttapping agent and quantified using scintillation counting procedures as described in RETEC SOP #543 (Appendix C).

Additional Tests to Evaluate Microbial Inhibition

The original Scope of Work for the Lagoon 3 and Lagoon 7 materials was limited to screening of mineralization activity in the untreated materials (before initiation of slurry treatment). However, preliminary data from those tests demonsfrated low rates of benzene mineralization. To determine what was responsible for the low observed mineralization rates, the scope was modified to include the following two components:

Muieralization Testing: Benzene mineralization activity in initial Lagoon 3 and Lagoon 7 materials (per original workplan) was compared with that in samples collected from the bench-scale liquid/solids reactors after seven days of operation.

Oxygen Uptake Rate Testing: Oxygen uptake rates measured in dilutions of the untreated Lagoon 3 and Lagoon 7 materials were compared to those in the partially treated materials from the bench-scale reactors (after seven days of freatment).

The same mineralization tests performed on the initial Lagoon 3 and Lagoon 7 materials were repeated on samples collected from the bench-scale liquid/solids reactors after seven days of active treatment. The second set of mineralization tests was performed to differentiate between inhibitory factors which are readily removable (chlorinated volatile organics) and those which are more difficult to remove (metals, high salinity levels or other non-volatile sludge characteristics).

OUR measurements were added to provide additional information on potential inhibitory agents and the extent of inhibition. Oxygen uptake rate measurements are used commonly by RETEC to ttack levels of total microbial activity. The measurements are performed according to RETEC SOP #502 (Appendix C). As aerobic microorganisms biodegrade organic constiments, oxygen is consumed. High OUR values indicate high rates of microbial activity. Factors which inhibit microbial activity produce low OUR values.

The tests conducted on lagoon materials involved measuring OURs over a range of solids loadings (2.5%, 5%, 10%, 15% and 20% solids). All test reactors were amended with microbial seed and inorganic nutrients 24 hours prior to OUR measurement. Normally, increasing the

400593 Technical Evaluation Laboratoiy Treatability Study-CairoU and Dubies Supeifund Site-Final Repoit mpr/1644-150/101094 3:58 4-2

quantity of biodegradable organic matter (by increasing the loading rate in a liquid/solids reactor) produces an increase in measured OURs. However, when inhibitory factors are present, oxygen uptake rates fail to increase, and in some cases decline with increasing solids loadings. By measuring OURs at several solids loadings, the presence or absence of inhibitory factors was determined. As with the mineralization tests, the OUR measurements were performed both on the initial lagoon materials as well as on the samples from the bench-scale liquid/solids reactors to determine the type of inhibitory factors present (i.e., chlorinated volatile organics or other less-easily removed constiments).

4.2 Results of Mineralization and Oxygen Uptake Rate Testing

Table 4-1 summarizes the results of mineralization and OUR tests performed on the initial and partially freated Lagoon 3 and Lagoon 7 materials.

Benzene mineralization was clearly inhibited in the untteated lagoon materials. In the Lagoon 3 materials, benzene mineralization activity was significant at the 10% solids loading, but not at the 20% loading. In the Lagoon 7 materials, benzene mineralization activity was not significant at either of the solids loadings tested.

The results of OUR tests performed on the imfreated materials (Figure 4-1) confirmed that significant inhibition was present in both samples prior to liquid/solids freatment. In the Lagoon 3 materials, the inhibition was evident at solids loadings greater than 10%. In the Lagoon 7 materials, the inhibition was observed at all solids loadings tested and microbial activity was reduced to exttemely low levels at solids loadings of 10% to 20%.

In contrast to the tests performed on the initial lagoon materials, both mineralization and OUR test results indicated that seven days of liquid/solids freatment was sufficient to remove microbial inhibition. Significant levels of benzene mineralization activity were demonsfrated for both Lagoon 3 and Lagoon 7 materials at 10% and 20% solids loadings. In the OUR tests, no inhibition of microbial activity was detected.

400594 Technical Evaluation Laboratory Treatability Study-CarroU and Dubies Superfiind Site-Final Repon n4>r/1644-lSO/101094 3:S8 4-3

TABLE 4-1

SUMMARY OF MINERALIZATION AND OXYGEN UPTAKE RATE TESTING DATA

PARAMETERS UNITS

BENZENE MINERALIZATION TESTING

Cumulative Mineralization (SOP #543)"' 20% Solids % Mineralization 10% Solids % Mineralization

Conclusion of Testing Microbial Inhibition Yes/No Inhibition Threshold % Solids

LAGOON 3 MATE3UALS

Untreated (As

Received)

0.4 31.9

Yes 10%

Partially Treated"'

2.5 8.4

No

LAGOON 7 MATERIALS

Untreated (As

Received)

0.08 0.44

Yes 10%

Partially Treated"'

21.56 7.9

No

OXYGEN UPTAKE RATE TESTING

Measured OURS (SOP #502)™ 20% Solids mg/Oz/L/hr 15% Solids mg/Oj/L/hr 10% Solids mg/Oj/L/hr 5% Solids mg/Oj/L/hr

2.5% Solids mg/O^/LAir

Conclusions of Testing Microbial Inhibition Yes/No Inhibition Threshold % Solids

27 58 78 55 28

Yes 10%

153 106 82 63 NT

No

2 2 24 34 32

Yes 5%

114 125 44 24 19

No

NOTES: NT = Not Tested SOP: RETEC standard operating procedure.

Mineralization testing performed over a 14-day test period using reactors seeded with acclimated inoculum, amended with inorganic nutrients and pH neutralized. Mineralization testing performed using reactors which were seeded with acclimated inoculum, amended with inorganic nutrients and pH neutralized 24 hours prior to testing. The material used for the tests was collected from the liquid/solids slurry reactor after seven days of treatment.

HI

Bl

(31

400595 Technical Evaluation Laboratory Treatability Smdy-CarroU and Dubies Supeifimd Site-Final Report n^r/1644-150/101094 3:58 4-4

Figure 4-1 Results of Oxygen Uptake Rate Testing

200

i 1

too -

50 -

Lagoon 3 Materials

^

k

^

k

r

[ ^ ^

Inhibition Tlveshold for Untreated Materials

X "" ^ ^ ^ ^ ^

y

y /

^ ^

- - K ^

' 1 \

S 10 IS

Solids Loadings (% solids) 20

200

Lagoon 7 Materials I MWWBBBBWIWIKSnimSBr^MiWtoU'i-ti iTlliWi'l 1

5 10 IS Solids Loadings (% solids)

20

Measured OURs in Measured OURs in Partially Treated Materials Untreated Materials

25

400596 When inhibition is not present there is generally a linear relationship tietween oxygen uptake and solids loadings.

4-5

The mineralization and OUR data suggest that the chlorinated organic concentrations initially present in Lagoon 3 and Lagoon 7 materials were the source of the microbial inhibition initially measured. That chlorinated organics were responsible for the observed inhibition is suggested principally by two factors. First, the inhibition is not likely due to concentrations of metals or other non-volatile constiments, because these constiments would not be removed during short-term liquid/solids treatment (less than seven days). If these factors were the cause of inhibition, tests on the imtreated and partially treated materials would have indicated similar levels of inhibition. Second, previous experience with liquid/solids treatment of sludges indicates that the concentrations of BTEX and other semivolatiles in the lagoon materials are not sufficient to result in microbial inhibition. Therefore, the chlorinated organic concentrations in the lagoon materials were considered within the range that is generally toxic to aerobic microorganisms, but would also would be removed during the early stages of liquid/solids treatment due to volatilization processes.

Because the concepmal design for application of liquid/solids treatment at the Lagoon 3 and Lagoon 7 areas includes a provision for capture and treatment of volatile emissions, the initial inhibition of microbial activity due to chlorinated organic toxicity does not necessarily mean that bioremediation of these materials would be unsuccessful. Rather, the data indicate that successful bioremediation could be completed in one of two ways. First, treatment could be performed at solids loadings low enough to minimize microbial inhibition. For Lagoon 3 material, this would involve operation of batch reactors at initial solids loadings of 10% or less. Lower solids loadings would be required for Lagoon 7 material. Second, a two-phase treatment scenario could be used. During the first treatment phase, aeration and mixing equipment would be used to reduce chlorinated organic concentrations to a level which does not inhibit biodegradation activity. Ehiring this initial treatment phase, microbial activity levels in the material would be very low and constiment removal would be dominated by physical transfer processes. Then, after the chlorinated organic concentrations had been reduced to non-inhibitory levels, a second treatment phase could be initiated during which biological processes would significantly contribute to constiment removal. An acclimated microbial seed could be introduced into the treatment reactors at the beginning of the second treatment phase to maximize microbial activity levels and minimize acclimation or lag periods.

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Technical Evaluation Laboratory Treatabtli^ Siudy-Canoll and Dubies Supeifund Site-Final Report. inpr/1644-150/101094 3:58 4-6

, 4.3 Conclusions and Recommendations

Specific conclusions of mineralization and OUR testing include:

Significant inhibitory factors are present in untreated Lagoon 3 materials, and to a greater extent in Lagoon 7 materials

Treating the materials for seven days in bench-scale liquid/solids reactors removed the observed inhibition, suggesting that volatile chlorinated organic constiments were the source of the inhibition.

After removing the inhibitory factors, high levels of benzene mineralization and oxygen uptake were maintained in the materials, indicating that biodegradation of organic constiments was taking place.

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Technical Evahiation Laboratoiy Treatability Snidy-CarroU and Dubies SupeiAind Site-Final Report mpr/1644-150/101094 3:58 4-7

5.0 SLURRY REACTOR TESTING

The section presents the experimental procedures, results, and conclusions from the laboratory slurry reactor smdies on lagoon materials collected from the Carroll and Dubies site in Port Jervis, NY. Studies were conducted on materials from Lagoon 3 and Lagoon 7 to determine if biosluny treatment of volatile and semivolatile organic compounds is applicable for the lagoon materials. The slurry reactor smdies were performed according to the general procedures discussed in RETEC SOP #701, "Biological Slurry Reactor Testing" (Appendix C). Table 5-1 presents the analytical methods used for all samples. Routine operational monitoring throughout the smdies included: pH, dissolved oxygen (D.O.), temperamre, and nutrients. The microbial enumerations (microbial counts) were performed according to methods cited by [Clark, 1985] and [Shiaris, et. al., 1983].

TABLE 5-1

SUMMARY OF ANALYTICAL METHODS

I PARAMETER

pH

j Total Suspended Solids (TSS)

1 Total Organic Carbon (TOC)

1 Oil and Grease (O&G)

1 Ammonia Nitrogen (NH3-N)

1 Nitrate Nitrogen (NO3-N)

Orthophosphorus

BTEX

Volatile Organic Compounds (VOCs)

Semivolatile Organic Compounds (SVOCs)

WATER METHOD

SW9040

EPA 160.2

SW9060

SW9070

EPA 350.1

SW9200

EPA 365.2

SW 8020

SW8240

SW 8270

SOIL METHOD

SW9045

. . . .

Walkley-Black I

SW9071

EPA 350.1

SW9200

EPA 365.2

SW 8020 1

SW 8240 1

SW 8270 1

SW: SW 846-Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, Third Edition, EPA, September, 1986.

EPA: Methods for Chemical Analysis of Water and Wastes EPA 600/4-79-020, March, 1983 and its i^xiates.

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Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Superfiind Site-Final Report n4>r/1644-150/101094 3:58 5-1

5.1 Equipment Set-up and Experimental Procedures

Two slurry reactors were operated, one for Lagoon 3 material and one for Lagoon 7 material for a period of three weeks. -The experimental apparatus used is illustrated in Figure 5-1. Each reactor consists of a 7-gallon heavy-duty glass vessel with a side port from which samples were obtained. Oxygen was initially provided to the reactors by the introduction of humidified air. However, air caused the reactors to foam excessively. The air was removed shortly after start-up and was replaced with a 30% solution of hydrogen peroxide (H2O2). H2O2 was added to the reactors periodically using a pump and automatic timer. The addition of the H2O2 resulted in the maintenance of a sufficient concentration of dissolved oxygen in the reactors without producing excessive foaming. Each slurry was continuously mixed to keep solids in suspension. The reactors were covered by a plexiglass plate with a stoppered access port in the top which was used for the addition of nutrients or for pH adjustment when needed.

On Day 17 of operation, the H2O2 pumps to each reactor were shut-off and humidified air was again supplied as the oxygen source to determine if air would again cause excessive foaming. Between Day 17 and Day 20, the slurry reactor containing Lagoon 7 material foamed excessively.

To load the slurry reactors, Lagoon 3 and Lagoon 7 materials were wet sieved through a 1/4 inch screen and mixed with buffered, deionized water to the targeted solids concentration by weight. The Lagoon 3 slurry reactor was operated at approximately a 20% solids concentration by weight. Due to the low solids content and high contamination in Lagoon 7 material, the Lagoon 7 slurry reactor was operated at approximately a 10% solids concentration by weight. Enough buffered water and lagoon material was used so that the initial volume of each reactor was approximately 25 L. Dissolved oxygen was maintained at concentrations greater than 3.0 mg/L. Nutrient concentrations, measured as ammonia nitrogen, nitrate nitrogen, and orthophosphate, were maintained at greater than 20 mg/L. Nitrogen and orthophosphate concentrations were checked periodically using test kits, and stock solutions of these nutrients were added to the reactors as needed. The pH was maintained in the neutral range of 7.0 to 7.5 and adjusted when necessary by the addition of an acid or base. The reactors were monitored routinely for the operational parameters of pH, dissolved oxygen, temperature, mixing speed and mixing watts (all monitored daily), and ammonia nitrogen, nitrate, nitrogen, and orthophosphate (monitored twice a week).

400600 Technical Evaluation Laboratory Treatability Study-CarroU and Dubies Superfund Site-Final Report inpr/1644-150/101094 3:58 5-2

AIR SUPPLY (Oj SUPPLY OPTION A)

REGULATOR

y

FLOW METER

HUMIDIFIER

(OBSERVATION PORT)

O ACID/CAUSTIC ADDITION FOR pH CONTROL

o SUPPLEMENTAL NUTRIENT ADDITON (N.P)

30% HjOj ADDITION (O, SUPPLY OPTION B)

SL

MIXER

E^

o o m

VALVED SAMPLE PORT

O o (Ji o

HEAVY DUTY GLASS REACTOR (7 GALLON CAPACITY)

'/"/«!'

CARROLL AND DUBIES DEER PARK. NEW YORK

3-1644-888 I N . * t . l H « M . «MlV( l i IK . K«f«1y • * "CWC « . . ta MM to rM>

. . i M i to M m . <««« i u n n t t . • * fri. uii.«r«lw)dnf Utol I i . lto( lo k-

to Mr M M M U . II IhtM M l k. • • n c i ^ . . tar w f ^ ^ M Miar Hun • fMcWCr M f i n l t o . In . A U . . y ICTCC 4 . . . t on i r l f "

ft^n 'tn-tm.,

FIGURE 5 - 1 SCHEMATIC OF BENCH-SCALE

SLURRY REACTOR

Prior to mixing the soil and water into a slurry, triplicate initial soil samples were collected and analyzed for pH, total organic carbon (TOC), VOCs and SVOCs by GC/MS, and BTEX by GC. A single sample was analyzed for total microbial count and volatile (toluene) degraders. Immediately after 15 minutes of initial mixing, a sample of the slurry was removed from the reactor and the solid and liquid phases were separated by centrifiigation. Centriftigation was done to ensure, as much as possible, that detected site constiments-of-concem are soluble and not associated with any suspended material. Only the aqueous phase was submitted for analysis. After this initial sampling, the solid phase of each reactor was sampled on Days 1,3,7, and 14 of operation and analyzed for BTEX. Solid phase samples collected on Day 7 were also analyzed for VCXIs and SVOCs. Solid phase samples for microbial counts (total heterotrophs and toluene degraders) were collected on Day 1 and Day 7. At the conclusion of each smdy (Day 21), each reactor was disassembled and the liquid and solid phases of the final slurry were centrifuged, separated, and analyzed. Final solid phase samples were analyzed in triplicate for the same parameters as the mitial solid phase samples, excluding TOC. Initial and final solid phase samples were analyzed in triplicate to provide a database for statistically comparing initial and final concentrations in the lagoon material. Initial and final aqueous samples were analyzed for pH, suspended solids, BTEX (GC), VOCs (GC/MS), SVOCs (GC/MS), ammonia nitrogen, nitrate nitrogen, and ortho-phosphate. Table 5-2 summarizes all solid and aqueous samples collected from the slurry reactors.

5.2 Results

This section presents the results from the bench-scale slurry reactor smdies conducted on materials from Lagoon 3 and Lagoon 7. A summary of the analytical results from solid and aqueous samples collected during the smdies is presented in Appendix D. As discussed above, both the solid and aqueous phase samples were collected and analyzed from each slurry reactor. The results for Lagoon 3 materials and Lagoon 7 materials are discussed separately below.

Lagoon 3 Slurry Reactor

The solid phase evaluation of the Lagoon 3 material utilized BTEX analysis (using GC analysis), for the tracking of treatment progress. VOCs (using GC/MS analysis), and SVOCs (using GC/MS analysis) results were used to determine the response of all the measured organics to the treatment process. Results of final solids analyses for SVOCs were not available for this

400602 Technical Evaluation Laboratoiy Treatability Study-Carroll and Dubies Superfund Site-Final Report mpr/1644-150/101094 3:58 5-4

TABLE 5-2

SLURRY REACTOR STUDY

ANALYTICAL SAMPLING SCHEDULE

PARAMETER

(Soil)

pH

TOC

BTEX (GC)

Volatiles (GC/MS)

Semivolatiles (GC/MS)

Microbial Coimts 1 (Total, toluene deg.)

1 (Water)

pH

1TSS/VSS/FSS

| B T E X ( G C )

VolatUes (GC/MS)

Semivolatiles (GC/MS)

NHj-N

1NO3-N

10-PO4-P

INITIAL'" DAYl

3

3

3

3

3

1

-

-

1

-

-

1

Initial

NUMBER OF SAMPLES

DAY 3 DAY 7 DAY 14

-

-

1

-

-

-

1

-

-

1

1

1

1

-

-

1

-

-

-

Final

DAY 21 (Final)

3

-

3

3

3

1

.

'

1

• 1

"' These initial characterization results were also used as initial samples for the vapor extraction testing.

400603

Technical Evaluation Laboratory Treatability Study-Carroll aixl Dubies Superfiind Site-Final Report nvr/1644-150/101094 3:58 5-5

report and will be provided as an addendum when they are complete. However, all available SVOC data is presented in Appendix D.

Table 5-3 presents a summary of the initial and final (after 21 days of slurry treatment) solids concentrations for all VOCs and SVOCs detected. Initial and final solid concentrations presented represent the average of triplicate samples. A less than sign in front of a value indicates that all three samples analyzed for that parameter were below detection limits. For all analytes that were below detection limits, the reported sample detection limit was used in computing the average concentration. If only one or two samples were below detection limits, the average concentration was calculated using the detection limits for those samples, but a less than symbol was not placed in front of the value. Based upon the initial san^ile results, four compounds were determined to be primary volatile constiments-of-interest for the treatability smdy of Lagoon 3 material. These compounds were benzene, toluene, total xylenes, and tetrachloroethene.

Table 5-3 also shows the percent removal of each compound based on the average initial and final solids concentrations. As shown in the table, good removal of each parameter was obtained. All VOCs measured by GC/MS were reduced to concentrations below detection limits except for acetone and 2-butanone. These two compounds are considered common laboratory artifacts and results from the final solids analyses were flagged by the laboratory because of acetone and 2-butanone contamination in the method blank associated with these samples (Appendix D). BTEX concentrations measured by GC were also reduced to near or below detection limits. Solid phase concentrations of total BTEX were reduced from 51,267 (ig/Kg to 27.6 /ig/Kg. Figure 5-2 graphically shows the reduction of solid phase concentrations of benzene, toluene, xylenes, and total BTEX over time as measured by GC analysis. Concentrations of all parameters decreased rapidly at the beginning of the smdy and continued to decrease until the conclusion of the smdy on Day 21 except for a large spike in the total xylenes concentration on Day 14.

Laboratory reports indicate that quantification and identification of total xylenes in this sample is considered an ananomaly due to hydrocarbon interference. The high concentration of xylenes reported on Day 14 is also reflected in the graph for the total BTEX concentration, which shows a sharp spike because of the xylenes result. With the exception of this data point, the BTEX compounds show a definite, consistent reduction in concentrations throughout the slurry reactor smdy.

. 400604

Technical Evaluation Laboratory Treatability Study-CarroU and Dubies Superfiind Site-Final Repon nipr/1644-150/101094 3:58 5-6

FIGURE 5-2 BTEX (GQ CONCENTRATIONS IN SOLID PHASE

LAGOON 3 SLURRY

BENZENE CONCENTRATION VS TIME TOLUENE CONCENTRATION VS TIME 30^000

29.000

ao^goo

u,oao

1 10.000 -

3,000 >•

0

0

T IUpie*eaU95% J . Oonfideace Intervali

^ "

r KlZl-.

30,000

40,000

30,000

30,000

10.000

I RepreMata95% Confidcaee Intervali

10 25 (d*j>)

10 15 Tinw(dqn)

20

TOTAL XYLENES CONCENTRATION VS TIME 30,000

I Rqiteaeats 95% Confidence Intervals

TOTAL BTEX CONCENTRATION VS TIME 100,000

ettjaota

40,000

2 30,000

I Repreaenu9S% Confidence Interval*

( t i ty)

Note: Initial and final values represent averages of triplicate samples;

all other values are from single samples.

V. 400605

Technical Evaluation Laboratory Treatability Smdy-CarroU and Dubies Superfiind Site-Final Report mpr/1644-150/101094 3:58 5-8

Figure 5-3 graphically shows the reduction of solid phase concentrations of benzene, toluei^, total xylenes, and tetrachloroethene over tune as measured by GC/MS. The data indicates that all parameters had been reduced to concentrations that were below detection limits by Day 7 of slurry operation, except for tetrachloroethene. All four parameters were below detection limits in the final soil samples.

Table 5-4 presents the initial and final aqueous phase concentrations from the Lagoon 3 slurry reactor. Only analytes detected in either Lagoon 3 or Lagoon 7 materials are listed in this table. Final results for the aqueous phase SVOC results were not yet available and will be included in an addendum to this report. The table shows there was considerable removal of volatile compoimds from the aqueous phase. BTEX compounds measured by GC were reduced from an initial concentration of total BTEX of 3,570 ngfL to a final aqueous concentration of 105 jug/L. Benzene was reduced from 2,200 /xg/L to below detection limits (<1.0 /ng/L). Concentrations of all VOCs measured by GC/MS were below detection limits in the final aqueous sample, although sample detection limits were slightly increased. The laboratory reported that the increased sample detection limits were due to the presence of tentatively identified compounds (TICs), Initial sample results indicated some suspended solids in the aqueous phase (197 mg/L total suspended solids (TSS), mostly associated with the volatile suspended solids (VSS) present (159 mg/L VSS). The final sample indicated a significant decrease in suspended solids concentrations (6.0 mg/L VSS and 12.0 mg/LTSS. All results indicate that there was significant removal of volatiles from the aqueous phase during this smdy. This reduction can be attributed to biodegradation and volatilization of the constiments-of-interest.

Figure 5-4 graphically presents the Lagoon 3 microbial counts measured in the solid phase during the smdy. The numbers of total microbes and volatile degraders are shown. Initially, the number of microbes in the material was low at 10,0(X) cfti/g (colony forming units/gram) for total microbes and 1,000 cfii/g for volatile degraders. As shown, the number of total microbes generally mcreased during the smdy, except for a slight decline at Day 7. The number of total microbes at the end of the smdy (Day 21) was 18,400,(X)0,000 cfii/g. The number of volatile degraders increased until Day 7, then declined back to origmal levels by Day 21. These results indicate that the indigenous bacteria became acclimated fairly rapidly (within the first few days) and conditions were maintained in the reactor to sustain the microbial population throughout the smdy. The decline in the number of volatile degraders was probably due to the fact that nearly all of the non-halogenated volatile organic compounds present were removed by Day 7 and there was no other food source present for these bacteria. This would be consistent with the data

400606

Technical Evaluation Laboratory Treatability S&idy-CarroU and Dubies Superfiind Site-Final Repon ' inpr/1644-150/101094 3:58 5-9

FIGURE 5-3 VOLATILE ORGANICS (GC/MS) CONCENTRATIONS

IN SOLID PHASE - LAGOON 3 SLURRY

BENZENE CONCENTRATION VS TIME TOLUENE CONCENTRATION VS TIME

TOTAL XYLENES CONCENTRATION VS TIME 3,000

I Repreients 95% Confidence Intervals

T E T R A C H L O R O E T H E N E CONCENTRATION VS TIME i4,cao

12,000

10,000

i 1,000 -

«,000

4,000

2,000

I Ri^jreaeoU 95% Confidence Intervali

Note: Initial and final values represent averages of triplicate san^les;

all ottier values are from single samples. 40060.7

Technical Evaluation Laboratoiy Treatability Study-Carroll and Dubies Stqierfiuid Site-Final Report inpr/1644-150/101094 3:58 5-10

TABLE 5-4

BVmAL AND FINAL AQUEOUS SAMPLES FROM LAGOON 3 SLURRY

SAMPLE ID

DATE SAMPLED

INITIAL

08/23/94

Q

Conventloiial Parameter?

pH, S.U.

Fixed Suspended SoUds (mg/L)

Volatile Suspended SoUds (mg/L)

Total Suspended SoUds (mt/L)

7.3

38.0

159.0

197.0

Nutrients (inf^>

Nitrate NitroRcn

Orthophosphate

28.3

0.15

0.64

FINAL

09/13/94

Q

7.7

6.0

6.0

12.0

< 0.10

0.096

11.30

Benzene

Ethylbenzene

Toluene

Xylenes, total

Volatile Oniantcs(n

Acetone

Benzene

Chloromethane

1.2-DichIoroethene. total

Ethylbenzene

Methylene chloride

Styrcne

1,1 J[.2-Tetrichloroethane

Tetrachloroethene

Toluene

Xylenes, total

2.200

150

1.100

120

3.570

< I.O

22.0

37,0

45.0

1 105.01

lU

< 2.500

2.300

< 500

240

< <

250

500

200

180

< 250

970

520

J

J

J

< < < < < < < < < < <

5,000

500

1,000

500

500

1,000

500

500

500

500

500

Benzoic acid

2-ChIoronaphthalene

Di-n-butyl (dithabte

Diethyl phthalate

Isophorone

Naphthalene

Phenol

3-MethvlpheBol/4-methvtehenol

< <

5.900

UOO

350

< < < < <

UOO

1.200

1.200

UOO

L200

J

(2)

(2)

(2)

(2)

<2)

(2)

(2)

ffi

Notes: (DCompounds that are less than a detectioa limit aie summed at one times the detection limit (2)AnaIytical results not yet available from laboratoiy. J: Compound detected below quantitatioa limit Value repoited is estimated.

Q: Qualifier Column.

400608

Technical Evaluation Laboratory Treatability Smdy-CarroU and Dubies Superfimd Site-Final Repon mpr/1644-150/101094 5:22 5-11

o g

l i Ul

I

I

I

I

S

FIGURE 5-4 MICROBIAL COUNTS VS TIME

LAGOON 3 SLURRY l.OOE+ll

l.OOE+10

^ l.OOE+09

y , l.OOE+08

•I g l.OOE+07

l.OOE+06 d

>> l.OOE+05 s o

W l.OOE+04 i : - /

LOOE+03

O o o

LOOE+02

10 15 Time (days)

presented in Figures 5-2 and 5-3, which show that nearly all of the BTEX compounds and tetrachloroethene, the primary constiments-of-interest, were removed from the solid phase by Day 7 of the slurry operation. The number of total microbes continued to grow because there were other sources of organic carbon present in the material that the microbes could metabolize.

Lagoon 7 Slurry Reactor

The solid phase evaluation of Lagoon 7 material was primarily directed at BTEX (using GC analysis), VOCs (using GC/MS analysis), and SVOCs (using GC/MS analysis). Results of final solids analyses for SVOCs were not available for this report and will be provided as an addendum when they are complete. However, all available SVOC data is presented in Appendix D.

Table 5-5 presents a summary of the initial and final (after 21 days of slurry treatment) solids concentrations for all volatile and semivolatile compounds detected. Initial and final solids concentrations presented represent the average of triplicate samples. A less than sign in front of a value indicates that all three samples analyzed for that parameter were below detection limits. For all analytes that were below detection limits, the reported sample detection limit was used in computing the average concentration. If only one or two samples were below detection limits, the average concentration was calculated using the detection limits for those samples, but a less than symbol was not placed in front of the value.

Based on the initial sample results, four compounds were determined to be primary volatile constiments-of-interest for treatability testing in Lagoon 7. These compounds were benzene, toluene, total xylenes, and tetrachloroethene. In addition to these primary constiments-of-interest, there were concentrations of several other volatile compounds detected in the initial solid phase samples, including methylene chloride (203,333 /ig/Kg) and trichloroethene (143,333 ixg/Kg).

Table 5-5 also shows the percent removal of each compound based on the average initial and final solids concentrations. Benzene and ethylbenzene were not detected by GC analysis of the initial samples. However, toluene and xylenes, showed considerable removal from the solid phase. Tohiene concentration was reduced from 4,566,667 /ig/Kg initially to 60,333 /ig/Kg (98.7 percent removal) and concentrations of total xylenes were reduced from 316,667 /ig/Kg to 38,667 /tg/Kg (87.8 percent removal). Total BTEX concentration in the solid phase was reduced by 98.1 percent overall, from 5,443,333 /ig/Kg to 103,667 /ig/Kg. Figure 5-5 graphically shows the

400610 Technical Evaluation Laboratory Treatability Study-CarroU and Dubies Superfund Site-Final Report nvr/1644-150/101094 3:58 5-13

TABLE 5 - 5

LAGOON 7 SLURRY REACTOR SOLID PHASE ANALYTICAL RESULTS FOR DETECTED COMPOUNDS

SAMPLE ID DATE SAMPLED

Initial^ ^ 08/22/94

FinaH*> 09/13/94

Conventional Parameters I Total SoUds, % pH, s.u. TOC, mg/Kg

40J 5.0

103,767

56.7 7.5

NA •-: -:o.::V::::::.BTEX,(Me/ke) 1

Benzene Ethylbenzene Toluene Xylenes, total Totol BTEX^^>

< 280,000 < 280,000

4,566,667 316,667

5,443.333

< 2333 < 2333

60333 38,667

103.667 Volatile OrKanic Compounds (fig/ks) 1

Acetone Benzene Carbon disulfide Ethylbenzene Methviene chloride Tetrachloroethene Toluene Trichloroethene Xylenes, total

< 1,566,667 150,000

< 156,667 < 156,667

203.333 1,533333 4,133333

143.333 330,000

Semi-Volatile Organic Compounds (M.g/kR Bis(2-ethyihexyl)phthalate 2 - Chloronaphthale ne Di-n-butyl phthalate Naphthalene

< 215,000 157,667

3366,667 < 65,667

24333 < 8,433

6,267 5,700

< 17,000 52,000 57333

< 8.433 41,.333

) ( ) (i) (3) (3)

Microbial Counts (CFU/g)^'*^ Total Microbes Volatile Degraders

9,000 UOO

680,000,000 1,000

Percent Removal, %

, •

99.2 99.2 98.7 87.8 98.1

98.4 94.4 96.0 96.4 91.6 96.6 98.6 94.1 87J

Notes:

Microbial counts are recorded on a wet weight basis, all other parameters are recorded on a dry weight basis.

(')Results are the average of triplicate samples.

(^Compounds that are less than a detection limit are summed at one times the detection limit.

(^)Analytical results not yet available from laboratory.

(^'Results are from analysis of single samples.

NA - Not Analyzed

< - indicates all samples were below detection limits for this parameter.

400611

Technical Evaltuttion Laboratoiy TieatabiliQ' Study-CarroU and Dubies Superfiind Site-Final Report nvr/1644-150/101094 5:22 5-14

FIGURE 5-5 BTEX (GC) CONCENTRATIONS IN SOLID PHASE

LAGOON 7 SLURRY

BENZENE CONCENTRATION VS TTME

300,000

-T RcptewDU 95% JL Coofideoce Intervals

^ k u\ f V-^

TOLUENE CONCENTRATION VS TIME i4.aao.aao

13.000,000

10,000,000

8,000,000

6,000,000

4,000,000

2,000,000

-I Repreaeots 95% Coofidence Intervals

10 IS

X lme( (b j« )

20

TOTAL XYLENES CONCENTRATION VS TIME

3^000,000

2^<nn^nnn

i 1,300^000

IJOMJDOO

SOOtjOOO

— I Repreaeots 95% Confidence Intervals

TOTAL BTEX CONCENTRATION VS TIME 16,000,000

14,000,000

i2,ooa,aw

10,000.000

1,000,000

6,000,000

I jftfflyopff

I Kfip(eieab95% Confidence Intervals

(d«}i)


all other values are from single samples. J n 0 ^ 1 9

Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Siqwrfiiiid Site-Final Report mpr/1644-150/101094 3:58 5-15

http://i4.aao.aao

reduction of solid phase concentrations of benzene, toluene, xylenes, and total BTEX over time as measured by GC analysis. The GC results for BTEX have an erratic pattem, showing a decrease in concentrations initially, then increasing again. The graph of the total xylenes concentrations also shows a large spike in the Day 14 sample, as previously discussed for the Lagoon 3 slurry sample from Day 14. This data point is qualified due to hydrocarbon interference. The increased xylenes concentration from Day 14 is again reflected in the graph for total BTEX.

As shown in Table 5-5 and Figure 5-6, VOCs measured by GC/MS showed significant reduction of concentrations in the solid phase. Removal of volatiles measured by GC/MS ranged from 87.5% removal for total xylenes to 98.6% removal for toluene. Figure 5-6 graphically shows the reduction of solid phase concentrations of benzene, toluene, total xylenes, and tetrachloroethene over time as measured by GC/MS. The data indicates that all parameters showed consistent reduction in concentrations throughout the entire study. The rate of removal for each parameter was slightly greater during the first seven days of the study, then tapered off between Day 7 and Day 21 of operation. All four parameters showed greater than 85% removal from the solid phase.

V Table 5-6 presents the initial and final aqueous phase concentrations from the Lagoon 7

slurry reactor. Only analytes detected in either Lagoon 3 or Lagoon 7 materials are listed in this table. Final results for the aqueous phase SVOC results were not yet available and will be included in an addendum to this report. The table shows there was considerable removal of volatile compounds from the aqueous phase. BTEX compounds measured by GC were reduced from an initial concentration of total BTEX of 46,2(X) fig/L to a final aqueous concentration of 740 /ig/L. Benzene was reduced from 3,4(X) g/L to below detection limits (<25.0 /xg/L) and toluene was reduced from 37,0(X) fig/L to 550 ngfL. Concentrations of all VOCs measured by GC/MS were below detection limits in the final aqueous sample except for acetone and 2-butanone, which are common laboratory artifacts. As with Lagoon 3 materials, sample detection limits were increased due to the presence of TICs. Initial sample results showed high suspended solids concentrations in the aqueous phase (1,450 mg/L TSS). Again, similar to Lagoon 3 material, the TSS was mostly associated with the volatile suspended solids present (1,1180 mg/L VSS). The final sample showed a significant decrease in suspended solids concentrations (3.0 mg/L VSS and 5.0 mg/L TSS). All results indicate there was a significant removal of volatiles from the aqueous phase during this stody. This reduction can be attributed to biodegradation and volatilization of the constituents-of-interest.

400613 Technical Evaluation Laboratory Treatability Study<:arroU and Dubies Superfund Site-Final Report inpr/1644-150/101094 3:58 5-16

E[GURE5-6 VOLATILE ORGANICS (GC/MS) CONCENTRATIONS

IN SOLID PHASE - LAGOON 7 SLURRY

BENZENE CONCENTRATION VS TIME atNMMO

TOLUENE CONCENTRATION VS TIME 1,000.000

tJOOOJOOO

10 15

1bae(day i )

2.000,000

y T Reprefeota 95% X Oonfideace Intervals

" "

l\ 10 15 TtaM(dqn)

ao 25

TOTAL XYLENES CONCENTRATION VS TIME

I-

J T R^n-eaents 95% J . Confidence Intervals

:v

.X -\ ^ _ _

TETRACHLOROETHENE CONCENTRATION VS TIME 3,000,000

2.500,000

2.000,000

1,500,000

1,000,000

500,000

T Rqire*eoU95% X Confidence Intervals

X" ^ \ ^

10 15

>(day»)

25 10 U


all other values are from single samples.

35

400614

Technical Evaluation Laboratory Treatability Smdy-CarroU and Dubies Superftuid Site-Final Report nvr/1644-150/101094 3:58 5-18

Figure 5-7 graphically presents the Lagoon 7 microbial coimts measured in the solid phase during the study. Initially, the number of microbes in the material was low at 9,000 cfii/g for total microbes and 1,200 cfu/g for volatile degraders. As shown, the number of total microbes increased steadily during the study, although populations were less than those obtained for Lagoon 3 material. The number of total microbes at the end of the study (Day 21) was 680,000,000 cfu/g. The number of volatile degraders increased until Day 7, then declined back to original levels by Day 21. These results indicate that the indigenous bacteria became acclimated fairly rapidly (within the first few days) and conditions were maintained in the reactor to sustain the microbial population throughout the study. As in the Lagoon 3 material, the decline m the number of volatile degraders was probably due to the non-halogenated volatile organic compounds present being removed by Day 7 and there was no other food source present for these bacteria. This would be consistent with the GC/MS data presented in Figures 5-5 and 5-6, which show that most of the BTEX compounds and tetrachloroethene were removed from the solid phase by Day 7 of the slurry operation. The number of total microbes continued to grow because there were other sources of organic carbon present in the material that the microbes could metabolize.

5.3 Conclusions

The results of these slurry reactor studies indicate that lagoon materials evaluated initially contained relatively high concentrations of VOCs, especially Lagoon 7 material. Slurry reactor treatment removed most of the VOC contamination from both Lagoon 7 and Lagoon 3 material. Final data on the concentrations of SVOCs was not available to be included in this report. A discussion of the removal of SVOCs from lagoon materials will be presented in an addendum to this report. Concentrations of total BTEX as measured by GC were reduced by greater than 98% in the solid phase in both slurry tests. All VOCs measured by GC/MS showed removal rates of approximately 90% or more. Concentrations of volatile organics in the aqueous phases of both reactors were also significantly reduced.

Initially, there were low nimibers of indigenous bacteria present in both materials. As shown by the mineralization and OUR data, presence of high concentrations of certain volatile chlorinated hydrocarbons inhibited biological activity. As the concentrations of the biotoxic chlorinated compounds decreased due to physical transfer, favorable conditions were developed for microbial growth and biodegradation could begin to take place.

400.615 Technical Evaluation Laboratory Treatability Smdy-Carroll and Dubies Superfiind Site-Final Report mpr/1644-150/101094 3:58 5-19

il U H ^

I I I

I

ra

-S g

I.OOE+IO

l.OOE+09

l.OOE-l-08

l.OOE+07

gj l.OOE+06 J

tx; l.OOE+05 J

& o

g l.OOE+04

l.OOE+03

l.OOE+02

FIGURE 5-7 MICROBIAL COUNTS VS TIME

LAGOON 7 SLURRY

Total Microbes Volatile Degraders 'li .-.. . --.?**»--,•.,„

O o CO

0 i I

10 15 Time (days)

20 25

cn

6.0 PROJECT CONCLUSIONS/RECOMMENDATIONS

The following section reviews the conclusions of the individual studies, provides a discussion of the combined results, and based on the combined results presents recommendations for fiirther actions at the site.

6.1 Conclusions

The results of these tests indicate that altemative technologies are effective in reducing die concentrations of volatile organics in the material from the Carroll and Dubies site. Semivolatile data and interpretation of that data will be provided as an addendum to this report. The successful completion of the screening level evaluation (Figure 1-1) provides a proof of concept for the technologies.

The specific findings of each treatability test are provided in the following sections.

6.1.1 Vapor Extraction Conclusions

The vapor extraction colunm studies reached the following conclusions:

• Based on vacuum propagation, organic vapor measurements, and analytical data, air flow was readily achieved through a column of unamended material from Lagoon 3. Air flow was limited through a column of unamended material from Lagoon 7.

• It was demonstrated that the application of vacuum to the lagoon materials did result in significant drying. Vacuum dewatering of the Lagoon 7 material appears to be feasible based on geotechnical analysis and the treatability testing; however, field testing is recommended.

• Significant reductions in VOC concentrations were achieved in unamended Lagoon 3 material (74% to 98%). Lagoon 3 material had much greater removal than unamended Lagoon 7 material, indicating a higher amenability to in-situ treatment. Lagoon 7 material had significant removal of all VOCs (greater than 99%) with the addition of amendments, indicating an amenability to ex-situ treatment.

400617 Technical Evahiation Laboratory Treatability Study-CarroU and Dubies Superfimd Site-Final Report nipr/1644-150/101094 4:24 6-1

• Ex-sito testing indicates that the amoimt of material required to achieve air flow is limited (15% by weight). The amended materials from both lagoons were permeable to air and elevated organic vapor readings were achieved under a low vacuum.

• The combined data indicates that Lagoon 3-type material is highly amenable to in-situ vapor extraction treatment for organics. Lagoon 7-type material is marginally amenable to in-sim treatment, but could be effectively treated in an ex-situ configuration with the addition of amendments.

6.1.2 Mineralization Condusions

The mineralization and oxygen uptake rate testing concluded:

• Significant inhibitory factors are present in the imtreated Lagoon 3 materials and to a greater extent in Lagoon 7 material.

• Treating the materials for seven days in the slurry reactors removed the observed inhibition, suggesting that volatile chlorinated compounds were the source of the inhibition.

After the initial treatment period, high levels of benzene mineralization and oxygen uptake were maintained in the materials, indicating that biodegradation was occurring.

6.1.3 Slurry Reactor Conclusions

The slurry reactor study reached the following conclusions:

• The slurry reactors achieved a 90% plus reduction in total VOCs over the test period. A 98% plus reduction was achieved for non-halogenated VOCs.

• Microbial counts confirm the mineralization smdies which indicated an initial biotoxicity. Following an initial treatment period biological activity increased to significant levels.

• The reduction in concentrations is likely to occur due to physical transfer as well as biodegradation. The fuU scale reactor would be designed to take advantage of both actions through capture and treatment of off-gas and the addition of an acclimated microbial seed in the second phase of treatment.

400618 Technical Evaluation Laboratoiy Treatability Sudy-CarroU and Dubies Superftuid Site-Final Report nq)r/1644-150/101094 4:24 6-2

/ 6.2 Discussion

The results of the individual studies demonstrate that the material is potentially amenable to treatment using the altemative technologies. The most direct treatment tested, vapor extraction, relies on the physical transfer of constiments to the vapor phase so that they can be removed by an air stream for treatment. This physical transfer is controlled primarily by the ability of the constiment to transfer to the vapor phase, and the physical characteristics of the material. The majority of the constiments are readily transferred to the vapor phase based on their Henry's Law constants.

The movement of air through the material is controlled by air permeability of the material. When competing fluids are held within the matrix, these fluids (organic separate phase liquids, and water) restrict the ability of air to pass through the matrix. As the matrix dries (moismre decreases), air permeability will increase. The material dries due to the influence of the vacuum through the material. To begin the drying process, an initial vacuum, known as the air-entry vacuum, is required. As the material dries it evenmally reaches a point where a nearly exponential increase in vacuum is required to remove additional water. The lagoon materials, due to their origin as a mix of waste streams, have permeability and water holding characteristics that are significantly different than a soil. For example, in Lagoon 3 material an air flow was easily achieved and the material readily dried imder the test conditions. Lagoon 7 material, which based on grain size analysis should have a relatively high intrinsic permeability, held the competing fluids tightly in the matrix. These fluids significantly reduced air flow through the column. The high matric suction also restricts the physical transfer of the constiments to the vapor phase.

The slurry reactor smdy demonstrated that the technology was effective at reducing concentrations of VOCs. When the results of the slurry smdy are combined with the mineralization smdy it is apparent that the treatment occurs in two phases. In the initial phase biological activity is low; however, constiment concentrations decrease rapidly. In the second phase VOC concentrations continue to decrease and biological activity increases. With the data collected the inhibiting factor caimot be identified, but it can be inferred that one or more of the volatile chlorinated compounds is the factor. This inference is based on the removal mechanisms present in the initial phase (physical transfer, low biological) and that non-halogenated compounds were generally below biotoxic levels.

400619t

Technical Evaluation Laboratory Treatability Suidy-CarroU and Dubies Superfiind Site-Final Report nipr/1644-150/101094 4:24 6-3

It should be noted that while chlorinated compounds are considered, in general, to be biotoxic, research indicates that many do imdergo active aerobic biodegradation. Biodegradation of chlorinated compounds has been demonstrated on both an in-sim and ex-sim basis [Wackett, et. al., 1989; Oldenhuis, et. al., 1989; Garland, et. al., 1990; Roberts, et. al., 1989]. As noted in the microbial counts, BTEX-specific degraders decreased while the total population continued to increase. It is possible that degradation of chlorinated compounds was occurring and fiimre smdies will quantify the actual degradation process.

In microbial systems, a variety of compounds may function as electron acceptors in oxidation reactions under different redox conditions, including oxygen, nitrate, sulfate, and carbon dioxide. The associated metabolic processes are known respectively as aerobic metabolism, denitrification, sulfate reduction, and methanogenesis. The prevailing redox condition and metabolic process may in mm affect the transformation pathway. Substimtion reactions are mediated using a variety of specialized enzyme systems. These enzymatic systems may have either evolved specifically for catalyzing the decomposition of toxic compounds or be normally produced for other metabolic ftmctions and catalyze dehalogenation reactions. Reduction reactions in microbial systems normally involve the replacement of halogen substiments by hydrogen (hydrogenolysis) under anaerobic conditions. Methanogens employ nickel containing enzymes or co-factors such as F-430 to carry out reduction reactions. Bacterial oxidations are presumed to occur via epoxidation, but in general these pathways are poorly understood. Dehydrohalogenation reactions have not yet been observed for microbial systems. A summary of halogenated compounds which been observed to undergo some degree of biotransformation is provided in Table 6-1 [Vogel, 1987].

Table 6-2 lists chlorinated hydrocarbons that are known to be biodegradable under aerobic conditions and for which pure cultures have been isolated [Leisinger, 1983; Motosugi and Soda, 1983, Janssen, et. al., 1985]. Although these data illustrate the potential of microorganisms to degrade chlorinated organics, the compounds listed only represent a fraction of the total xenobiotics that have been identified in surface water or groimdwater. So far, no unequivocal positive evidence for biodegradation has been obtained for trihalomethanes, carbon tetrachloride, 1,1,1-trichloroethane, or 1,2-dichloropropane.

Pure culmre smdies with bacteria that degrade chlorinated organics have enabled the establishment of several mechanisms of chloride release from organic substrates. Halogenated compounds must be dehalogenated before they enter the central metabolic routes that lead ta^ fj c O A

Technical Evaluation Laboratoiy Treatability Study-Carroll and Dubies Superfiind Site-Final Report mpr/1644-150/101094 4:24 6-4

TABLE 6-1

BIOTRANSFORMATION OF HALOGENATED ALIPHATIC COMPOUNDS BY

MICROORGANISMS COMPOVNP PRODUCTS SYSTEM

Methanes Chloromethane Dichloromethane

Trichloromethane

Tetrachloromethane

Bromethane

Ethanes 1,1 -Dichloroethane 1,2-Dichloroethaiie

1,1, l-Trichloroethane

1,1,2,2-Tetrachloroethane

Hexachloroethane Bromoethane 1,2-Dibromomethane

Ethenes Chloroethene

Dichloroethene

Trichloroethene

Tetrachloroethene

Formaldehyde Carbon Dioxide Carbon Dioxide Carbon Dioxide Carbon Dioxide Formaldehyde Carbon Dioxide Carbon Dioxide Dichloromethane Carbon Dioxide Chloroform Carbon Dioxide Chloroform Formaldehyde

Chloroethane Carbon Dioxide Chloroethanol Carbon Dioxide 1,1-Dichloroethane

Not identified 1,1,2-Trichloroethane

Tetrachloroethane

Ethene Ethene Carbon Dioxide

Carbon Dioxide Carbon Dioxide Chloroethene Chloroethene Carbon Dioxide Dichloroethene Dichloroethene Dichloroethene Carbon Dioxide Carbon Dioxide Trichloroethene

E 0/M 0/P 0/M 0/P E AM/m 0/S A/M A/M/m A/M/m

A/S E/mo

A/M/m 0/P/p 0/P/x A/M/m A/S A/M/m A/M A/M/m A/M/m AM 0/M/s 0/P/x 0/S AM/mJi 0/S

A/M/m 0/P/mb AM/m A/S, A/M

A/M/m A/S A/M 0/P 0/S A/M/m AM

400621 Technical Evaluation Laboratoiy Treatability Study-CarroU and Dubies Superfimd Site-Final Repon mpr/1644-lS0/101094 4:24 6-5

TABLE 6-1 (Continued)

BIOTRANSFORMATION OF HALOGENATED ALIPHATIC COMPOUNDS BY

MICROORGANISMS

COMPQVNP EROmiClS SXSIEM

Propanes

1-Chloropropane — 0/P/x 1,2-Dichloropropane - 0/P/x l/2-Dibromo-3-chIoropropane Propanol 0/A

Note: A comma separates different experimental systems that result in similar products. Slashes separate information regarding each experiment. O = aerobic; A = anaerobic, which often is methanogenic (m), but often is not explicitly stated; M = mixed culture; P = pure culture; S = soil or aquifer used as biological seed; E = enzyme derived from microorganism; m = methanogenic culture; x = Xanthobacter: mo = monooxygenase; mb = Mycobacterium: p = Pseudomonas

400622 Technical Evaluation Laboratory Treatability Soidy-Carroll and Dubies Superfiind Site-Final Report nipr/1644-150/101094 4:24 6-6

TABLE 6-2

CHLORINATED SOLVENTS THAT CAN BE DEGRADED BY PURE BACTERIAL CULTURES

CcMnpounds ' • , ' • " ' ' \\

Dichloromethane 2-Chloroethanol Methylchloride, ethylchloride,

propylchloride, butylchloride, 1,2-dichloroethane, 1,3-dichloropropane, allylchloride

Chlorobenzene

Hyphomicrobium, Pseudonumas Pseudorttonas Xanthobaaer

unidentified baaerium

Stucki et. al., 1981 SOicld etal . , 1981 Janssen et.al., 1985 Keuning et.al., 1985

Reinelce and Knackmuss, 1984

V

400623

Technical Evahiation Laboratory Treatability Study-Carroll and Dubies Superfiind Site-Final Report mpr/1644-150/101094 4:24 6-7

carbon dioxide or cell mass. Thus, dechlorination reactions play a crucial role in detoxification

and metabolism of halogenated compounds. A summary of dehalogenation mechanisms that have

been demonstrated to be operative in aerobic bacteria is given in Table 6-3.

Further enzyme evolution, in nature or in the laboratory, will possibly produce new enzymes that do have the ability to aerobically degrade more compoimds. Dehalogenases that split off chlorine from a secondary carbon atom (as in 2-chloropropionic acid) from a double or triple substimted carbon atom (2,2-dichloropropionic acid and trichloroacetic acid) have already been described. Thus, there is no reason to exclude the possibility of hydrolytic dehalogenation of compounds like 1,2-dichloropropane and 1,1,1-trichloroethane.

As indicated in the vapor extraction smdies, the compounds readily volatilized. While past smdies have indicated that volatilization from the covered slurry reactor is a minor transfer mechanism, spot measurements of organic vapor that were taken for health and safety purposes indicate that organic vapor concentrations of 150 ppm were released from the reactor. This indicates that the physical transfer is also an active mechanism in the removal of VOCs from the lagoon material.

V Detailed treatability smdies would provide a quantification of the actual mechanisms occurring during reactor treatment. This quantification would be necessary as part of the design of tbe fiiU scale unit to insure that if volatilization occurs, the off-gases are captured and properly treated. The detailed smdy would also identify the requirements for optimization of biological growth.

6.3 Recommendations

There are two basic approaches available for evaluating the altematives for treatment of

the source material at the Carroll and Dubies site. These approaches are:

• Conduct in-sim pilot scale vapor extraction testing on Lagoon 3 and lagoons with similar physical characteristics. The test would be conducted using standard vacuum extraction. On Lagoon 7 and similar lagoons, initiate pilot scale vacuum dewatering/vapor extraction testing and ex-sim testing following the addition of an amendment to increase permeability.

400624

Technical Evaluation Laboratory Treatability Snidy-Carroll and Dubies Superfiind Site-Final Report nipr/1644-150/101094 4:24 6-8

TABLE 6-3

DEHALOGENATION MECHANISMS OF HALOGENATED XENOBIOTICS IN AEROBIC BACTERIA

1. Nucleophilic substimtion by dichloromethane dehalogenase (glutathione-S-transferase).

Reaction: CHjClj -I- GSH - GS-CHjCl -I- HCl GS-CH2CI -I- H2O - GS-CH2OH + HCl GS-CHjOH - GSH + HCHO

Substrates: CHjClj, CHzBrCl, CHzBi.CHjIj

Organisms: Hyphomicrobium, Pseudomonas (Stucki et al; 1981; Leisinger, 1983)

2. Hydrolytic dehalogenation of carboxylic acids (haloalkanoic acid dehalogenase).

Reaction: CH^Cl-COOH + H O - CHjOH-COOH + HCl

Substrates: dichloroacetate, trichloroacetate, bromoacetate, dibromoacetate, fluoracetate, chloroacetate, iodoacetate, 2-chloropropionate, 2,2-dichloropropionate, 2-bromopropionate, 2-chlorobutyrate, 2-bromobutyrate

Organisms: Pseudomonas, Moraxella (Motosugi and Soda, 1982)

3. Hydrolytic dehalogenation of haloaikanes (haloalkane dehalogenase).

Reaction: CH2CI-CH2CI 4- H O - CHjOH-CHjCl -I- HCl

Substrates: some n-haloalkanes

Organisms: Xanthobacter autotrophicus (Keuning et al., 1985)

4. Hydrolytic dehalogenation of aromatics (4-chlorobenzoate dehalogenase).

Reaction: 4-chlorobenzoate -I- HjO - 4-hydroxybenzoate -f HCl

Substrates: 4-chlorobenzoate, 4-fluorobenzoate, 4-bromobenzoate

Organism: Arthrobacter

5. Oxidative dehalogenation of aliphatics ((haloalkane hydroxylase).

Reaction: CH2CHCH2)7-CH2C1 -J- O -f NADPHj -CHO-(CHj)7-CH2Cl -I- H2O -I- NADP + HCL

Substrates: 1,9-dichlorononane, 1,6-dichlorohexane, l,S-dichloropentane, 1-bromoheptane, 1-iodoheptane, 1-chloroheptane

Organism: Pseudomonas

400S25

Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Siqierftind Site-Final Report nq)r/1644-150/101094 4:30 6-9

TABLE 6-3 (Continued)

DEHALOGENATION MECHANISMS OF HALOGENATED XENOBIOTICS IN AEROBIC BACTERIA

Oxidative dehalogenation of aromatics by monooxygenase (4-chlorobenzoate-4-hydroxylase).

Reactitm:

Substrates:

Organism:

4-chlorobenzoate -I- O2 + NADPH2 - 4-hydroxybenzoate -I- HCl -I-NADP -I-H2O

4-chlorobenzoate, 3-chlorobenzoate

Pseudomonas

Oxidative ddialogenation of aromatics by dioxygenase (2-fluorobenzoate-dioxygenase). NADH2 NAD

Reaction: 2-fluorobenzoate -I- O2 - catechol + HF

Substrates: 2-fIuorobenzoate, 4-chlorophenylacetate

Organisms: Pseudomonas B13, Pseudomonas CBS3

Anti-elimination after cycloisomerization of ring-fission products (non-enzymatic after cycloisomerase action).

Reaction: 2-dilorohydrox}rmuconic acid -4-carboxymethyl- A -butenolide + HCl

Substrates: halomuconic acids derived from 3-chlorobenzoate, 4-chlorobenzoate, 4-fluorobenzoate, chlorobenzene, 3-chlorophenol, 3,5-dichlorocatechol, 4-fluorohpenylacetic acid, 3,5-dichIorobenzoate, 2,4-dichIorohpenoxyactetic acid

Organisms: Pseudomonas, Alcaligenes (Motosugi and Soda, 1983)

Reductive dechlorination after ring-fission (chloromaleoylacetate reductase, chlorosuccinate reductase).

Reaction: chloromaleoylacetate -I- NADH2 - 3-oxoadipate + NAD -I- HCl

Substrates: ring-cleavage products from 3,S-dichlorocatechol

Organism: Pseudomonas

400626

Technical Evaluation Laboratory Treatability Study-Carroll and Dubies Superfund Site-Final Report nq)r/1644-lS0/101094 4:33 6-10

V-

7.0 REFERENCES

ASTM, 1993 Method D698, 3810, and 8000. 1993 Annual Book of ASTM Standards. Section

4 (Construction), Volume 04.08. Published by ASTM.

Blasland, Bouck, and Lee, 1994. Source Area Feasibility Study, Carroll and Dubies Site, Port Jervis, NY.

Clark, F., 1985. "Agar-Plate Method for Total Microbial Count." In: Methods of Soil

Analysis. Volume 2. pp. 1460-65, American Society of Agronomy, Madison, WI.

Garland, S.B., A.V. Palumbo, G.W. Strandberg, T.L. Donaldson, L.L. Farr, W. Eng, CD. Little, 1990, "The use of methanogenic bacteria for the treatment of groimdwater contaminated widi trichloroethene at the U.S. Department of Energy Kansas City Plant," Oak Ridge National Laboratory, Report No. ORNL/TM-11084.

Janssen, D.B., Scheper, A., Dijkhuizen, L. and Witholt, B., 1985. Degradation of halogenateed aliphatic conqwunds by Xanthobacter autotrophicus GJIO. Appl. Environ. Microbial. 49: 673-677.

Keuning, S., Janssen, D.B. and Witholt, B., 1985. Purification and characterization of hydrolytic

haloalkane dehalogenase from Xanthobacter autotrophicus GJIO. J. Bacterial., in press.

Leisinger, T., 1983. Microorganisms and xenobiotic compoimds. Experiential 39: 1183-1191.

Motosugi, K. and Soda, K., 1983. Microbial degradation of synthetic organochlorine compounds. Experiential 39: 1214-1220.

Oldenhuis, R., R. Vink, D.B. Jannsen, and B. Witholt. 1989. "Degradation of chlorinated aliphatic hydrocarbons by methylosinus trichosporium 0B3b expressing soluble methane monoxygenase," Applied Environmental Microbiology, 55(ll):2819-2826.

Reineke, W. and Knackmuss, H.J. 1984. Microbial metabolism of haloaromatics: isolation and properties of a chlorobenzene degrading bacterium. Appl. Environ. Microbial. 47: 395-402.

400627 Technical Evaluation Laboratoiy Treatability Study-Carroll and Dubies Superfimd Site-Final Report. nipr/1644-150/101094 3:28 7-1

RETEC, 1994a. Technical Memorandum: Altemative Remedial Technology Evaluation, Carroll and Dubies, July 15, 1994.

RETEC, 1994b. Vapor Extraction and Bioslurry Treatability Investigation Worlq)lan, Carroll and Dubies Site; July 25, 1994.

Roberts, P., L. Semprini, G. Hopkins, and P. McCarty. 1989. " Biostimulation of methanotrophic bacteria to transform halogenated alkenes for aquifer restoration," Proceedings Conference of Petroleum Hydrocarbons and Organic Chemicals in Groundwater, NWWA, Houston TX.

Shiaris, M. and J. Cooney, 1983. "Replica Plate Method for Estimating Phenanthrene-Utilizing and Phenanthrene-Cometabolizing Microorganisms." Applied Environmental Microbiology. Vol. 45 (2), pp. 706-710.

Smcki, G., Brunner, W., Staub, D. and Leisinger, T., 1981. Microbial degradation of chlorinated Cl and C2 hydrocarbons. In: T. Leisinger, A.M. Cook, R. Hutte and J.

V, Nuesch(Editors), Microbial Degradation of Xenobiotics and Recalcitrant Compounds. Academic

Press, London, pp. 131-137.

Vogel, T.M., Criddle, C.S., McCarty, P.L. Transformations of Halogenated Aliphatic Compounds. Environmental Science and Technology, Vol. 21, No. 8, pp. 722-736 (1987).

Wackett, L.P., G.A. Bnisseau, S.R. Householder, and R.S. Hanson, 1989. "Survey of microbial oxyhenases: Trichloroethylene degradation by propane-oxidizing bacteria," Applied Environmental Microbiology, 55(ll):2960-2964.

400628

Technical Evaluation Laboratory TreatabOi^ Study-CarroU and Dubies Superfiind Site-Final Report mpr/1644-150/101094 3:28 7-2

(

APPENDIX A

Grain Size and Bulk Density Data

400629

Sample ID: Lagoon 3 - Initial

Client Client Project

Project No. Boring No. Depth (ft) Sample No.

Visual Description

QUANTERRA '

C-4H23001 94262 NA NA GDI

GRAY SLUDGE

UNIT WEIGHT

Tested By KBL Date Checked By * ^ ^ Date

Wt. of Mold Igm) Mold Volunne (cc)

09-15-94 q-Z.\~A'J

4785 644.5

Wet Density

Wt. Mold & WS (gm) Wt. Mold (gm) Wt. WS (gm) Mold Volume (cc)

6057 4785 1272 645

Wet Density (gm/cc) Wet Density (pcf)

1.97

123.2

Tare Number Wt. Tare & WS (gm) Wt. Tare & DS (gm) Wt. Water (gm) Wt. Tare (gm) Wt. DS (gm)

1072 1354.8 1222.4

132.4 106.81

1115.59

Water Content (%) Dry Density (pcf)

11.9 110.1

400630

Client QUANTERRA Client Project C-4H230001 Project No. 94262 uses Classification snn

Boring No. NA Depth(ft) NA Sample No. 004 USDA Classification NA

Soil Description BROWN SILTY SAND WITH GRAVEL

uses USDA

SIEVE ANALYSS GRAVEL SAND

GRAVEL

HYDROMETER SILT AND CLAY FRACTION

SAND SILT CUY

C/5

"2-

5 • •

S3

to

10 10 10 PARTICLE

1 10 DIAMETER IN

10 MM

10 1 0


WASH SIEVE ANALYSIS

^

Client Client Project Project No. Boring No. Depth(ft.) Sample No. Soil Description

Wt. of Total Sampleldry) Wt. of -H #200 Sample Wt. of -#200 Sample

Sieve

12" 6" 3" 2"

1 1/2" 1"

3/4" 1/2" 3/8" #4

#10 #20 #40 #60

#140 #200 Pan

Water Content Tare No. Wgt. Tare + WS. Wgt. Tare + DS. Wgt. Tare Wgt. Of Water Wgt. Of DS.

% Water

Sieve Opening

(mm)

300.00 150.00 75.00 50.00 37.50 25.00 19.00 12.50 9.50 4.75 2.00 0.85

0.425 0.250 0.106 0.075

"

QUANTERRA C-4H230001 • 94262 NA NA 004

Tested By Checked By

KBL Date ^ ^ Date

BROWN SILTY SAND WITH GRAVEL

Wt. of Soil Retained

(qm.)

0.00 0.00 0.00 0.00 0.00 0.00 0.00

13.51 12.49 73.90 84.34 50.41 25.83 12.60 11.36 2.51

101.19

1087 892.80 494.30 106.16 398.50 388.14

102.7

388.14gm. 286.95 gm. 101 .19gm.

Percent Retained

0.0 0.0 0.0 0.0 0.0 0.0 0.0 3.5 3.2

19.0 21.7 13.0 6.7 3.2 2.9 0.6

26.1

Accumulated Percent Retained

0.0 0.0 0.0 0.0 0.0 0.0 0.0 3.5 6.7

25.7 47.5 60.5 67.1 70.4 73.3 73.9

100.0

09-15-94 •7-2'-' ' ' /

Percent Finer

100.0 100.0 100.0 100.0 100.0 100.0 100.0

96.5 93.3 74.3 52.5 39.5 32.9 29.6 26.7 26.1

400632


Client Client Project Project No.

Boring No. Depth (ft) Sample No.

Visual Description

QUANTERRA

C-4H23001 94262 NA NA 004

GRAY SLUDGE

UNIT WEIGHT

Tested By KBL Date Checked By ' ^ ' ^ Date

Wt. of Mold (gm) Mold Volume (cc)

09-15-94

4785 740.3

Wet Density

Wt. Mold & WS (gm) Wt. Mold (gm) Wt. WS (gm) Mold Volume (cc)

5592 4785 807 740

V;-

Wet Density (gm/cc) Wet Density (pcf)

1.09 68.0

Tare Number Wt. Tare & WS (gm) Wt. Tare & DS (gm) Wt. Water (gm) Wt. Tare (gm) Wt. DS (gm)

1087 892.8 494.3

398.5 106.16 388.14

Water Content {%) Dry Density (pcf)

102.7 33.6

400633

APPENDIX B

Plots of Daily Photoionization Readings

400634

Column 3A-5 Interval Photoionization Readings for August 30, 1994 (186 minutes) j

4.5

E

c o .CO

8 c o o

2.5

0 30 60

A: represents 6 minute interval ||

90 120 Time (minutes)

150

30 Minute Averages I

180 210

r

Column 3A-6 Interval Photoionization Readings for August 31,1994 (514 minutes)!

CO

en

240 270 300 Time (minutes)

540

A: represents 4 minute interval | 30 Minute Averages

Column 3A-7 Interval Photoionization Readings for September 1,1994 (383 minutes)!

3.5

2.5

E o. o.

o 1 8 1-5 C o O

0.5

o CD a CO -si

0 30 60 90 120 150 180 210 240 Time (minutes)

270 300 330 360 390 420


A: represents 23 minute interval

Coiunnn 3A-9 Interval Photoionization Readings for September 2,1994 (460 minutes) |

E S 3 h c g 2

• . *

c o 2 o o.

1 -

I l l l l J L l i l l l l

60 120 180 240 300 Time (minutes)

360 420 480 540

O CD

CO CO

A: represents 10 minute intervaijj

30 Minute Averages

Column 3A-12 Interval Photoionization Readings for September 4, 1994 (114 minutes))

o o en CO CD

.-, 5 E Q. a. c o

c 0) u c o

20 30 40 50 60 70 80 Time (minutes)

90 100 110 120 130

30 l\Alnute Averages i

/ f

Column 3A-15 Interval Photoionization Readings for September 6,1994 (503 minutes) |

o o en

2.5

E S 2 c o

1 8 c o O

1.5

0.5 -L -L

0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 Time (minutes)

30 Minute Averages

A: represents 23 minute interval |

Column 7A-7 Interval Photoionization Readings for September 1,1994 (543 minutes))

E Q. a. c o

35

30

25

1 20

8 o O 15

10

1 ^ o o en

60 120 180 240 300 360 Time (minutes)

420 480 540 600

30 Minute Averages

A: represents 3 minute interval \

Column 7A-5 Interval Photoionization Readings for August 30,1994 (197 minutes) |

E CL Q . C

o to

o c o o

O O cn

^ ^ ro

30 60 90 120 Time (minutes)


A: represents 17 minute interval)

Column 7A"6 Interval Photoionization Readings for August 31,1994 (521 minutes)}

26

24

22

I 20 a. tz o •g 18

8 § 16 o

14

12

10 0

o o

60 120 180 240 300 360 Time (minutes)

420 480 540 600


^ ^ 1

A: represents 11 minute interval!

50

45

40

35

E" 30 Q.

a.

I 25 « o

8 20

15

10

o o

Column 3B-5 Interval Photoionization Readings for September 8,1994 (107 minutes)

_L 30 60

Time (minutes) 90 120

30 Minute Averages

Column 3B-7 Interval Photoionization Readings for September 9, 1994 (375 minutes) [

o o <:»

25

20

Q. Q.

C o

4 . ^

(0 i _

• <

c 8 c o O

15

10

0 30 60 90 120 150 180 210 240 270

Time (minutes) 300 330 360 390 420


A: represents 15 minute intervali

o o

Column 7B-10 Interval Photoionization Readings for September 12, 1994 (460 minutes)

30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 Time (minutes)


A: represents 10 minute inten^al|

tP3k o o o

Column 7B-11 Interval Photoionization Readings for September 13, 1994 (446 minutes) [

33

31

E Q. a. c o •g 29 ••-» c 8 C o O

27

25 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480

Time (minutes)


Column 7B-12 Interval Photoionization Readings for September 14,1994 (478 minutes))

CD CD

CO

25

20

E Q.

S 15 c o

I 10 o O

30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 Time (minutes)


CD O 05

16

1

14

B 12

1 1 10 o

8

a

|Column 7B-13 Interval Photoionization Readings for September 15,1994 (492 minutes;

1

A ^ " ^ ^ • ^ • ^ • ^ ^ - ^ ^

^ 1 A 1 1 1 1 1 1 1 1 L l U 1

J

0 60 120 180 240 300 360 420 480 540 | Time (minutes)


|A: represents 12 minute intervali

CD CD (Ji CJl

o

16

14

| 1 2 3

Con

cent

ratio

n

00

o

6

A

Column 7B-14 Interval Photoionization Readings for September 16, 1994 (438 minutes]

- T

- \

: ^ - ^ ^ ^ ^ . ^ . ^ ^ ^ ^ ^ ^

l l l l l i l l l i l l l l !

J

0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 Time (minutes)


|A: represents 18 minute inten/all

APPENDIX C

t ^ SOPs

400651

STANDARD METHOD FOR MEASURING "C-SUBSTRATE MINERALIZATION

Date: V W f ^

Date: 2 - . ^ - ^ 3

1.0 SCOPE AND APPLICATIONS

This test method desciil}es a procedure for measuiing the production of ^ C labeled caibon dioxide from radiolabded compounds. Carbon dioxide produced through microbial respiration of "C labeled substrate is evidence of the complete degradation (mineralization) of a portion of the target compound. Commonly used target substrates are those which can be used as the sole carbon source by several genera of microorganisms therefore rendering the compound biodegradable. The use of non-volatile substrate simplifies expeiim^ital protocol and subsequoit interpretation of analytical results, however the use of volatile substrates is possible using modified apparatus.

The radioactive target compound is generally universally ring labeled or otherwise strategically labeled so that release of a molecule of zadiolabdled carbon dioxide requires significant compound degradation. Since a portion of the labeled carbon substrate (roughly half) is used for cdlular growth and is incorporated into microbial biomass, the amount respired as *^C-labded caibon dioxide is a minimum estimate of the fraction of the total compound which has been mineralized.

Expedmental data and results are generally expressed as percentage of added *C substrate recovered as *^02 as a function of incubation time, with the environmental sample of test organisms.

2.0 SIGNIHCANCE AND USES

This assay is used to verify the presence of microorganisms capable of mineralizing a compound of interest in an environmental sample or in a microbial culture which may be seeded for use in a treatment system requiring substrate biodegradation. This method may also be used to compare mineralization rates in different environmmtal samples or to assess the effects of different expoimental amendments (l.e., nutrients) on the substrate-mineralizing capacity of the

"^ 400652

SOP #543 3/30/92 Paget of 5

Experimoital results obtained using this method indicate only the potential for indigenous microbial populations to mineralize contaminants of interest, and should not be used to infer the rates of biodegradation in a culture or sample in situ.

3.0 MATERIALS

Incubation Vessels. The radiotracer assay may be conducted in 2S0-mL sidearm biometer flasks or 160-mL glass serum bottles fitted with screw-cap Tefion-lined caps. The caps of bottle vessels are modified to allow trapping of evolved caibon dioxide in sodium hydroxide. A polypropylene cup is inserted into tiie cap to contain the sodium hydroxide trapping solution, and the insotion is sealed on the inner and outer sides with silicon glue. Sidearm flasks are used as received from the manufiicturer.

Sodium Hydroxide Trapping Solution. Reagent-grade sodium hydroxide is weighed into a known volume of deionized water. The solution is then boiled to drive off any caibon dioxide and is stored in a sealed bottle for later use.

^^C-Labeled Test Substrate. Compounds being utilized for radiotracer studies should be labeled dther uniformly, or on a caibon position which wHl require either ring cleavage or substantial degradation for the release of radiolabeled carbon dioxide. Prior to utilization in a degradation study, the radiochemical purity of the test compound should be evaluated by thin-layer chromatography. Approximatdy 4S-S0 nCi of radiolabeled substrate should be added to environmental samples for measuremoit of the biodegradative potential of the indigenous microbial community.

Scintillation Cocktail. 10-15 ml Ultima Gold scintillation flour (Packard Instruments, Downers Grove, IL) is added to scintillation vials containing samples in preparation for scintillation spectrometry.

Liquid Scintillation Counter. A Beckman LS 5000TD ^eckman Instrumoits, Fullerton, CA) is used to determine '^COj respired.

Scintillation Vials. 20-ml polyethylene plastic vials with foil-lined polypropylene cs^s (Fisher Scientific, Pittsburgh, PA) are used to contain samples for liquid scintillation counting.

4.0 PROCEDURES

If soil microbial activity is to be determined, soil must first be air-dried and sieved ( < 2 mm) to provide a veiy fine particle size, homogenous starting material. The moisture content of the treatment soil and pH should also be determined.

Additionally, nutrient content of the matrix should be analyzed for ammonium-nitrogen (NH4-N), phosphorus (P) and nitrate-nitrogen (NC|,-N). Organic content of the treatment soil

SOP #543 3/30/92 Page 2 of 5

400653

v~

should be determined by total volatile solids (TVS) or total volatile solids (TVS) or total organic (TOQ treatment Results of the initial soil characterization enable determination of the amount of nutrients required to achieve optimal conditions in the soil.

The oivironmental matrix and/or microbial culture to be assayed is added to triplicate incubation vessels. Moisture, pH and nutrient levels are adjusted to levels determined as optimal by initial soil characterization.

The radiolabeled substrate is added at 45-50 nCi per reactor. Mixing may be accomplished with a sterile spatula or by gentie shaking of bottie contents.

A small volume of sodium hydroxide solution (1.5 molar solution in deionized water) is added to the biometer sidearm or bottie trapping cup. Incubation vessels are then tightiy capped and incubated appropriately.

At predetermined time intervals during incubation, the base trapping solution is withdrawn fiom biometer sidearms or polypropylene cups and transferred to 20 ml scintillation vials containing Ultima Gold fiuor. Samples are radioassayed by liquid scintillation counting. Es^erimental counts per minute are corrected by subtraction of bacl^ound counts obtained from sterile control matrix botties to accurately represent mineralization due to biological processes.

The percentage of added ^ C substrate (q)m) recovered as * C02 is then calculated at each sampling. In order to optimize growth and the biodegradative capability of aerobic microbial conununities, it may be necessary to flush the headspace of test botties with air or oxygen following each sampling. Incubation periods required for *C substrate mineralization studies vary between environmental matrices and microbial cultures. However, our expeneacc indicates that bacterial mineralization is generally initiated within 24 to 72 hours and differences between samples or treatments may be apparent after a 5-7 day incubation.

At completion of the incubation, respired carbon tn^ped in the soil or water matrix may t>e rdeased and quantitated by acidifying the bottie contents to a pH below 3.0 (generally 0.2 ml at 6N HCl is sufficient). Tlie * C02 released is collected in the base traps containing 0.3 ml of 1.5 molar sodium hydroxide.

5.0 QUALITY ASSURANCE AND CONTROL

AH standard lab and sampling procedures are followed to ensure that accurate and reliable data are obtained. Lab procedures ensure that the liquid scintillation counter is calibrated using sealed internal standards and that badcground fluor radiation levels are determined daily.

Sampling methods are performed in accordance with stated objectives and in a manner which is representative of test conditions established for the study. Sample design and data interpretation are in accordance with statistical methodologies to ensure definitive conclusions of the experiment

3/30/92 4 0 0 6 5 4 Page 3 of 5

Work areas used for radiolabeling studies are monitored by wipe test to ensure that the areas are not contaminated.

6.0 RESPONSIBHITIES

The project engines/scientist is responsible for the lab, sampling procedures, sampling design and operating parameters for each «q)a imai t The project engineer is also in charge of the final report, files and notebooks of the project.

The project manager is expected to coordinate scheduling and specific objectives of each assay.

The laboratory technician is responsible for the ^cecution of the test As required by the State of Washington, radioisotope usage must be under the supervision of the radiation safety officer. Standard lab procedures are followed to ensure safety, accuracy and precision. He/she is also expected to record the methods, observations and deviation in protocol of each test in the dedicated notebook for that specific project.

7.0 HEALTH AND SAFETY

A comprdiensive health and safety program has been developed and is maintained at RETEC's laboratory facilities. All analytic^ chemistry and treatability work is conducted in accordance with the Corporate Chemical Hygiene Plan and the Health and Safety Program.

All technical and support staff receive regular training and instruction in safe work practices and in procedures for dealing with accidents involving test substances. All laboratory operations are approved by the laboratory manager prior to implementation. Select carcinogens, reproductive toxins and substances having a high degree of acute toxicity are used only in posted, "Designated Areas".

Formal laboratory inspections are conducted on a quarteriy basis to ensure compliance with existing laboratory policies and government regulations. Worlq>lace air samples and wipe samples are omducted for determination of the amount and nature of airi>ome and/or surface contamination, and for use in the evaluation and maintenance of appropriate laboratory conditions, ^ r sampling is accomplished using the NiOSH grab sampling method with Drager colorimetzic tube apparatus. Results of air monitoring are posted as required by the OSHA Lab Standard (29CFR 1910.1450).

Material Safety Data Sheets (MSDS) for aU chemicals in the laboratory are maintained in tiuee ring binders. AU laboratory en^loyees are trained in accessing and proper inteipretati(»i of MSDS files. The MSDS documents are readily available to employees and are located just adjacent to the laboratory, in the Eealth and Safety Officers possession. This area is accessible to all employees, at all times, la addition to the MSDS files, a number of other

3/30/92 4006|55Page4of5

technical references whidi provide information pertaining to proper hazardous chemical handling procedures, proper diqx>sal i«actices of chemicals in laboratories and various mcyclopedias of chemicals, drugs and biologicals are available.

All personnd involved in use of hazardous agents obtain yearly medical taminations and surveillance and are provided with proper protective equipment necessary for the safe performance of their jc^s. Personal protective equipment includes, but is not limited to, safety glasses with side shields, gloves, a clean lab coat and/or apron and a respirator. A standard operating procedure for tiie selection, care and proper use of respirators is available and is based on tiie OSHA Respiratory Protection Standard ^ 9 CFR 1910.134). Work practices are designed using proper engineering controls (fume hoods) so that an employee's exposure to hazardous chemicals in the laboratory is minimized.

400656

SOP #543 3/30/92 Pages of 5

Tdi\T SOP NO.: 701 REVISION NO.: 1 LAST REV. DATE: 0907/94 BY:RLW-F»GH

STANDARD OPERATING PROCEDURE

V-

BIOLOGICAL SLURRY REACTOR TESTING

.„. -ILJJ-44^ fitjpproyed

Approved By: ^<rVC-^ / iUi

Date: ^ L l / ^ J ^

Date: J-J j - ' rV

400657

SOP NO. 701 REVSION NO: 1 LAST REV. DATE: 9/27/94 BY: RLW-PGH PAGE: 1/8

STANDARD OPERATING PROCEDURES

Biological Slurry Reactor Testing

1.0. PURPOSE AND APPLICABILITY

This Standard Operating Procedure (SOP) describes the operation of a bench-scale biological siury reactor. A biological slurry reactor is a suspended growth biological reactor used to assess the biodegradability of chemicals in contaminated soils or sludges. A slurry reactor consists of a vessel in which a soil/water or a sludge/water mixture is continually stirred to keep the solids in suspension. The constant mixing of the reactor vessel maximizes the liquid/solid contacting and maintains an optimum environment for the microbial populations necessary for biodegradation. The proper reactor environment requires the maintenance of proper nutrient levels, sufficient electron acceptors, temperature and pH. A slurry reactor can be operated under aerobic or anaerobic conditions in a batch or a semi-continuous feed mode. Supplemental

y_ chemicals may also be added to provide an organic-carbon supplement for the bacteria and/or to enhance the solubility of the soil contaminants in the aqueous solution.

The objective of biological sluny reactor testing is to detemnine the technical feasibility of biodegrading soil/sludge material containing organics in a suspended growth reactor maintained under optimum environmental conditions for biological activity. This SOP provides a very reliable and relatively quick means (4-6 weeks) for the assessment of soil/sludge treatment. The test results are not directly applicable to land treatment or composting processes in terms of rate data but do provide an indication as to the maximum extent of contaminant reductions that are achievable in any process configuration. In terms of full-scale slurry reactor treatment, test results are directly applicable. Procedures for determining to what extent these observed reductions are due to volatilization are discussed in SOP No. 721 (Air Monitoring for Biological Slurry Reactors).

This SOP specifically provides the responsibilities, supporting materials, methods and procedures, quality assurance/quality control, health and safety, and documentation considerations associated with slurry reactor testing.

2.0 RESPONSIBILITIES

The project manager is responsible for determining what specific site soils should be evaluated regarding slurry reactor testing.

/^n assigned project engineer/scientist is responsible for seeing that the wori( is executed in the proper manner. He is also responsible for writing the "VJork Request Sheet" (WRS) for the wori< to be done. Once

^ completed, the WRS has to be reviewed and signed by the project manager or his designee before work

" '" 400658

r^^iT SOP NO. 701 REVSION NO: 1 LAST REV. DATE: 9/27/94 BY: RLW-PGH PAGE: 2/8

(

The approved WRS is then earned out by either the project engineer/scientist or an assigned technician. If a technician performs the wori<, then the project engineer/scientist must supervise the wori<. Whoever does the testing is responsible for executing the wori< in accordance with good sound laboratory practices as detailed in this SOP. This person is also responsible for recording the specific procedures used and results obtained on standard RETEC laboratory sheets which are then placed in a project laboratory file. Such information could also be stored in a dedicated lab notebook specifically assigned to the project.

3.0. SUPPORTING MATERIALS

The following special materials and equipment are needed (in addition to standard laboratory equipment) to set up and operate a slurry reactor.

1. Reactor Vessel-(4-10 L) stainless steel or glass or with top cover and sampling ports.

2. Mechanical stin-er & impeller. 3. Air stone and oxygen supply (set up with air filter and humidifier) or,

alternatively a 30 percent solution of hydrogen peroxide, for aerobic reactor. 4. Inert gas (nitrogen) for anaerobic reactor. 5. Supplemental nutrient source (nitrogen, phosphoms). 6. Other amendments (biological seed culture, surfectants, solvent,

supplemental organics, etc.). 7. pH meter, D.O. meter, drying oven, balance 8. Nutrient test kits (N,P) 9. Air monitoring equipment (if required, see SOP No. 721) 10. Dupont Sorvall RC-5B refrigerated and variable superspeed centrifuge - spins 6 full 380 ml

cylinders at approximately 12,500 rpm or 16,004 RCF at maximum setting.

4.0 METHODS AND PROCEDURES

4.1 REACTOR SET-UP

A Combine solid-liquid mixture in a reactor that is capable of thorough mixing. Use a buffer solution (distilled water with 200 mg/L NaHCO,) as the liquid portion of the slurry. NOTE: The specific composition of the slurry mixture is dependent on the objectives of the study. Usually a 10 to 20% solids weight is used unless toxicity or material suspension problems are anticipated.

B. Mix slurry with a mechanical mixer to maintain the solids in suspension. The reactor configuration and mixer type will dictate the mixer speed and impeller position needed for proper mixing.

400659

SOP NO. 701 REVSION NO: 1 LAST REV. DATE: 9/27/94 BY: RLW-PGH PAGE: 3/8

(IMS

Aerate the slurry using an air stone and oxygen source to maintain an adequate amount of dissolved oxygen (D.O.). Alternatively, an aqueous stock solution of 30 percent hydrogen peroxide may be used to provide D.O. The peroxide is pumped into the reactor periodically using an automatic timer. The amount of peroxide added tot he reactor is optimized to maintain a sufficient D.O. level. If operating anaerobically, use bottled nitrogen gas to keep the D.O. levels low. The air stone should be securely attached to the reactor.

Once mixing, add the nutrients as indicated below:

15-25 mg/L ammonia nitrogen (as (NHJjSOJ 15-25 mg/L phosphorus (as H3PO4)

• nitrate (as NaNOj) as required for the anaerobic reactor

V^

E. Adjust the pH of the aerobic and anaerobic sluny to levels between 7-7.5 and 7-8, respectively, using 5% -10% solutions of H2SO4 or NaOH.

F. Add any chemicals needed to enhance the contaminant solubilities such as surfactants, solvents, polymers, biological seed sources, or supplemental organics.

4.2 OPERATION AND MAINTENANCE

A. Initially Check:

B. Dailv Check:

C. Weeklv Check:

pH dissolved oxygen slurry volume air flow % solids suspended in slurry temperature mixing speed and horsepower (if applicable) Nitrogen, Phosphorus

pH slun7 volume air flow temperature

dissolved oxygen DO uptake nutrient levels % solids suspended in sluny

400660

Ts^lT SOP NO. 701

( REVSION NO: 1 ( LAST REV. DATE: 9/27/94

BY: RLW-PGH PAGE: 4/8

D H - pH is recorded using a standard pH meter. EPA Method 150.1 is followed.

Dissolved Oxvoen - This is determined using a dissolved oxygen meter. A standard BOD bottle is used to hold the slurry during testing. The ideal dissolved oxygen readings should be >3 mg/L and <0.5 mg/L for an aerobic and anaerobic slurry reactor, respectively.

Volume - The initial volume is marked and maintained with buffer solution (distilled water with 200 mg/L NaHCOa) to compensate for evaporation. When sampling, a new volume is reconJed to take into account the volume loss due to sampling. This will then serve as the new initial volume for the next time interval.

Air Source - The air stone is checked to ensure there is no clogging of the pores. The air flow is also to be checked (usually 1-3 L/min).

% Solids Suspended in Slurry - This is done initially and throughout the study to ensure that an adequate amount of soil remains in suspension.

Nutrients - This is monitored using HACH test kits for ammonia nitrogen, nitrate nitrogen and phosphorus as orthophosphate.

*AII information and data are recorded on data sheets as shown in Attachment 1.

D. Sampling and Analysis

The sampling schedule is set forth by the project manager at the initiation of the project. This sampling schedule could include air monitoring (SOP No. 721), slurry samples, initial and final soil/sludge samples, aqueous phase samples, and/or solid phase samples. These samples could then be analyzed for a number of chemical parameters. The type of analyses depends upon the initial material contaminants and final treatment criteria. Generally, a slurry reactor sampling schedule would include the following:

Initial soil/sludge samples prior to loading reactor (replicates) initial aqueous phase samples (after 15 minutes of mixing)

• initial soil/sludge samples (after 15 minutes of mixing) weekly soil/sludge samples final aqueous phase samples final (treated) soil/sludge samples (replicates)

* air monitoring (if necessary, ^roughout study)

Aqueous phase and soil/sludge samples are obtained by cenbifuging a slurry sample into its' respective solid and water phase. In order to obtain a more clear centrate, a pre-detenmined amount of CaClj (typically <2000 mg/L) can be added to each centrifuge tube and mixed for approximately 15 to 30 minutes

400661

T^\T SOP NO. 701 REVSION NO: 1 LAST REV. DATE: 9/27/94 BY: RLW-PGH PAGE: 5/8

prior to 30 minutes of centrifuging at 12,500 rpm. CaClj should not be added if any portion of the slurry is to be returned to the reactor. After centrifuging, centrates from all tubes are to be combined and submitted for respective chemical parameter analyses. The same compositing is to be performed for the soils. It should be noted that if total dissolved solids (TDS) is to be oin on an aqueous phase sample it may be inaccurate if CaClj was added for tiie centrifuge step.

5.0. QUALITY ASSURANCE/QUALITY CONTROL

All standard lab and sampling procedures are followed to ensure tinat accurate and reliable data are generated. Lab procedures ensure the equipment is cleaned and adequate for the objectives of the study to minimize ambiguous results. Sampling methods are done in accordance with stated objectives and in a manner which is representative of test conditions established for tiie study. Sample design and data interpretation are in accordance with statistical methodologies to ensure definitive conclusions of the experiment.

All wori< perfonned on a reactor or test is recorded in tiie laboratory files for future reference. Chain-of-custody sheets accompany all samples entering and exiting tiie lab. A copy of tiie chain-of-custody is also kept on file until completion of tiie study.

6.0. HEALTH AND SAFETY

All standard health and safety procedures are to be followed while performing this wori< in tiie laboratory (in particular wearing safety glasses). Additional precautions include wearing gloves and working under a hood (to the extent possible). All slurry reactors should be operated under a hood. As in all laboratory programs, a meeting will be held with tiie health and safety officer prior to its initiation to address all healtii and safety issues related to a particular sample.

7.0 DOCUMENTATION

Proper documentation for this SOP includes:

1. An approved Woric Request Sheet, 2. A completed Sluny Reactor Start-up sheet (Table 1), 3. A completed Slurry Reactor Weekly Data sheet (Table2), 4. A description of the site where samples were obtained, and 5. The respective sheets or designated project notebook

where all otiier observations and notes were recorded.

All documentation will be retained in tiie laboratory project file during testing and in tiie office cenb^l files once the overall project is completed.

400662

TSiiT SOP NO. 701 REVSION NO: 1 LAST REV. DATE: 9/27/94 BY: RLW-PGH PAGE: 6/8

8.0 REFERENCES

"Mettiods for Chemical Analysis of Water and Wastes." EPA-60014-79-020, U.S. EPA, Cincinnati. Ohio (1979).

• «

H -

mmn

": l? SOP NO. 701 REVSION NO: 1 LAST REV. DATE: 9/27/94 BY: RLW-PGH PAGE: 7/8

TABLE 1

SLURRY REACTOR START-UP SHEET

PROJECT NAME: BY: _

PROJECT NO. DATE:

REACTOR LD. NO.

REACTOR LOADING

BUFFER SOL N VOLUME -WATER WEIGHT -SOIL a SOILWETWr.-SOU.DRYWT(C*D)-TOTAL WT. (B+D) -» SOLIDS ^BF'IOOT -

I .

« SOUDS

%

. •f /LNUfCOj

c d. c I P h. a(mAL.\ND ADJUSTED pH ( S L U R R Y ) - _ _ _ _ _ — L pH ADJUSTMENT - ml»N»OH » , «l H^SO. % j . hrUTRIENTS - WTOALNHrN -

INmALO.ro^ -mrriAL NO r^ -NTIROOEN ADDED -PHOSPHATE ADDED - _ _ _ _ _ ^ _

k, VOLUME OF SLURRY USED FOR INTIIAL CHARACTERIZATION_______ • ! CENTRATE L REMAININO VOLL-ME L a . ADDmOWAL BUFFER SOL-N ADDED t- mtA-SMCOj u. M U m . STARTING VOLUME (l.*ttC\ m L & SEED ADDED - a l

n . TNTTIAL CHARACTERIZATION (List Parameters)

a. nnriAL son. -

bk SEPARATED SOIL (after U aia. ia lUny) -

& SEPARATED CENTRATE (aOcr U aia. ia •!"««») - _ _ _ _ _ _ _ ^ _ _ ^ _ ^ _ _ « _ _ _ _ ^ , ^ ^ _ _ ^ « _ _

• « d. SLURRY

tCIES:

llfHi

71^ IT SOP NO. 701 REVSION NO: 1 LAST REV. DATE: 9/27/94 BY: RLW-PGH PAGE: 8/8

TABLE 2

R*T«C SLURRY REACTOR WEEKLY DATA SHEET

mojecTN«ie_ PROjeCTNO.: l«ACTQnNO.i

DAY

DATE

READINGS

AlrarN, fiam.Vihn

MxingSp*«ti«ni

Mxfig W i t t i

MXftQnOW, flpfll

StarthaVotfiMil

Cantata VokmAddad I

ButhrSernAddMKavp

DaeaitaUsMMaa

ConBUMVoljMkl CanaiMDrySai

TESTS (SLURRY)

pHlMi

TOTQiTtttnh C

CondjelMy.isrhoa/em

%SoidaSuasandid

0. O..ino/I

0.0.\](tat»

TESTS (CENTRATB

O-Pq. aaP. moA

^»i,•NaaKalO/l

NOs.awrt

Mmlnig/I

ADOmONS

NiOHO \ , m

MjSO, e xam

M^SQ ( Va*i

M,K5.( l a *

NiNCS.911

WatgaancmTHMW

SolS«clMT#aR

HON

Air San«iM Tdian

TUB WED THU

•

FM

. >«

SAT SUN

40fKs

STANDARD OPERATING PROCEDURES OXYGEN UPTAKE RATES OF LIQUID/SOLID REACTORS

Date: . / ^ ^ 2 - /9lf/

^^^^M^T^ Date: / ' ^ Z ^ / ^ ^ y

1.0 SCOPE AND APPLICATIONS

This standard operating procedure (SOP) describes the method for determining the o^gen uptake rate of subsamples from liquid/solid reactors using a dissolved oxygen (DO) meter. TTiis test is usehil for monitoring biological activity and providing rapid information on system performance, upsets and effects of amendments.

Because test conditions are not necessarily identical to operating conditions, the measured value may not be identical to the actual oxygen consumption rate.

2.0 SIGNIFICANCE AND USE

The oxygen uptake rate of slurry samples are monitored at intervals to assess the level of biological activity during a liquid/solid bioreactor treatment scheme. This measurement represents an inexpensive approach to assessing the biological response to proposed treatment scenarios. It is also used as an indication of nutrient limitations and possible toxicity of the contaminated waste.

3,0 MATERIALS

dissolved o?Q gen meter and probe (YSI model SIB); 50 ml BOD bottle; magnetic stir plate; magnetic stir bar; and wash bottle-

wmn Revision: 1 SOP #502 01/18/91 Page 1 of 3

4.0 PROCEDURE

1. Cah'brate the meter following the manufacture's instructions.

2. Fill a 50-mI BOD bottle, containing a clean magnetic stir bar, with sample up to the neck of the bottle.

3. Place the DO probe in the mouth of the bottle making sure there are no air bubbles under the probe.

4. The sample should be stirred constantly during DO measurements with a magnetic stir plate.

5. Record DO measurements from the meter at one minute intervals. If the sample is very active, readings should be taken at smaller intervals. Take readings over a 6-10 minute period, if possible, and longer if uptake is slow. The goal is to measure a linear rate of DO loss for at least 2 mg/1.

6. Record the Oxygen Uptake Rate as mg/l/min, by determining the slope of DO readings to time. Use the linear portion of the relationship to determine the rate. DO values below 2 mg/I should not be used for calculating uptake rates.

5.0 HEALTH AND SAFETY

A comprehensive health and safety program has been developed and is maintained at ReTeC's laboratory facilities. All analytical chemistry and treatability work is conducted in accordance with the Corporate Chemical Hygiene Plan and the Health and Safety Program-

All technical and support staff receive regular training and instruction in safe work practices and in procedures for dealing with accidents involving test substances. All laboratoiy operations are approved by the laboratory manager prior to implementation. Select carcinogens, reproductive toxins and substances having a high degree of acute toxicity are used only in posted, "Designated Areas".

Formal laboratoiy inspections are conducted on a quarterly basis to ensure compliance with existing laboratory policies and government regulations. Workplace air samples and wipe samples are conducted for determination of the amount and nature of airborne and/or surface contamination, and for use in the evaluation and maintenance of appropriate laboratory conditions. Air sampling is accomplished using the NiOSH grab sampling method with Drager colorimetric tube apparatus. Results of air monitoring are posted as required by the OSHA Lab Standard (29CFR 1910.1450).

Revision: 1 SOP #502 01/1$/91 Page 2 of 3

Material Safety Data Sheets (MSDS) for all chemicals in the laboratoiy are maintained in three ring binders. All laboratory employees are trained in accessing and proper interpretation of MSDS files. The N^DS documents are readfly available to employees and are located just adjacent to the laboratoiy, in the Health and Safety OfBcers possession. This area is accessible to all employees, at all times. In addition to the MSDS files, a number of other technical references which provide information pertaining to proper hazardous chemical handling procedures, proper disposal practices of chemicals in laboratories and various encyclopedias of chemicals, drugs and biologicals are available.

All personnel involved in use of hazardous agents obtain yearty medical examinations and surveillance and are provided with proper protective equipment necessary for the safe performance of their jobs. Personal protective equipment includes, but is not limited to, safety glasses with side shields, gloves, a clean lab coat and/or apron and a respirator. A standard operating procedure for the selection, care and proper use of respirators is available and is based on the OSHA Respiratory Protection Standard (29 CFR 1910.134). Work practices are designed using proper engineering controls (fume hoods) so that an employee's exposure to hazardous chemicals in the laboratoiy is minimized.

40IIS8 Revision: 1 SOP #507 4 01/18/91 Pag#3of3 >'.>

APPENDIX D

Sununary of Analytical Results - Solid and Aqueous Samples

a

wm . f 7 . >

LAGOON 3 SLURRY REACTOR SOLID PHASE ANALYTICAL RESULTS

1 SAMPLE ID IDATESAMPIED

1 Initial A 06/22/94

Q Initial B

08/22/94 Q Initial C

a&rmi Q Dayl

08/24A)4 Q Day3

08/26/94 0

1 Convedt ibna lKin ia ie len

Tolal Solids, %

pH,s.u.

1 TOC, mc/Ks « — , « « . . — K ^

1 74.0

5.9 13.400

70.9

5.2 46.000

70.4

5.3 .50.600

75.7

NA NA

67.4

NA NA

:•• :• • • , • . . , . . .:..••• :: 'BTEXraeA.^ .... • • ' • ' , ; II

Benzene

Ethylbenzene

1 Toluene Xylenes, total

1 ToUl BTEXC)

14,000

8,600

27,000

8,500

58.100

9,400

< 3,500

18,000

< 3..50O

34.400

2ft000 < 3,600

34,000

3.700

61.300

3,600

< 3,300

9,600

< 3J0O

19.800

< <

3,700

3,700

6,200 < 3.700

17.300 1 Volatile Oreanic Compounds fjic/kcV 1

Acetone

Benzene

2-Butanone

Ethylbenzene

Tetrachloroethene

1 Toluene

1 Xylenes, total

< 34,000

22,000

< 34,000

< 3,400

8,900

41,000

2.200 J

< 35,000

24.000

< 3.5,000

< 3,500

10,000

45,000

< 3.-500

< 36,000

28,000

< <

36,000

3,600

11,000

47,000

2.100 J

NA NA NA NA NA NA NA


Scmi -Vola t i l eOraan ic Compounds C/ix/kKV 1 Bis(2-ethylhexvl)phthalate

2-Chloronaphthalene

1 Di-n-butyl phthalate

Naphthalene ^ ^ ^ « « « i

< 89,000

< 89,000

loaooo < 89.000

< 47.000

< 47,000

96,000

< 47.000

< <

94.000

94,000

130,000 < 94,000

NA NA NA NA

NA NA NA NA

(•. , ^ ••••• •• •"•••-• ••:.,.: :••••.:.:.;••••• Microbial Counts rCFUAtV: •.••.;• •': II

1 Total Microbes

1 Volatile Degraders

10,000

1.000

NA NA

NA NA

3O,70a00O

28.000

NA NA

1

Notes:


('^Compounds that are less than a detection limit are summed at one times the detection limit.

NA - Not Analyzed

B - Analyte found in blank.

J - Compound detected at a concentration below detection limits, value reported is an estimated value.

* - Quantification and identirication of compound may be considered suspect due to hydrocarbon interference.

LAGOON 3 SLURRY REACTOR SOLID PHASE ANALYnOU. RESULTS

1 SAMPLE ID I D A T B SAMPLED

1 Day7 1 08/301^4

Q Day 14

09/06/94

Q Day21A

09/13/94

Q Day21B

09/13 )4 Q Day 21C

1 09/13/94 YQ\

1 C o n v e n t i o n a l P a r a m e t e r *

1 Tolal Solids, %

p H , s.u.

T O C m s / K R

71.7 NA NA

NA

NA

62.3 7.3

NA

63.1 7.3

NA

62.5 7.3

NA r '•••'y •'•••"' • • .••. .•-:^V- • • B T E X r a « A B ^ V.::., . , , • .,..;

1 Benzene

Ethylbenzene

1 Toluene

1 Xylenes, lotal

ToUlBTnxC)

< <

170 170 490 670

1.500

< 490 14,000

< 490 40.000

54.980

•

•

5.6 < 3.2

XI 4.5

20.4 •

3.3 < 3.2

6.5 13.0

26.0

< 3.2 9.2

11.0 13.0

36.4

* • •

1 Volatile Oreanic Compounds fuK/kK^ 1

Acetone

Benzene

2-Butanone

Ethylbenzene

Tetrachloroethene

1 Toluene

Xylenes, total i — ^ — . - J

< < < <

8,700 870

8,700 870 530

< <

870 870

J


330 < 80 < 800 < 80 < 80 < 80 < 80

BJ 2,900 < 79

97 < 79 < 79 < 79 < 79

B

J

1,600 < 80 < 800 < 80 < 80 < 80 < 80

B

1 Semi-Volat i le Orxanic Compounds liK/kK> II

1 Bis(2-elhylhejiyl)phthalate ^ ^ ^ ^ ^ ^ H

2-Chloronaphthalene

1 Di-n-butyl phthalate

Naphthalene ^ ^ ^ ^

19,000 < 18,000

68,000 < 18.000

NA NA NA NA

Microbial Counts rCFUAtV 1

1 Tolal Microbes

1 Volatile Degraders 1

2.5,000,000 500.000

NA NA

18,400,000,000 1,600

NA NA

NA NA

^ 9 .

S

Notes: Microbial counts are recorded on a wet weight basis, all other parameters are recorded on a dry weight basis. (''Compounds that are less than a detection limit are summed at one times the detection limit. NA - Not Analyzed B - Analyte found in blank. J - Compound detected at a concentration below detection limits, value reported is an estimated value. * - Quantification and identification of compound may be considered suspect due to hydrocarbon interference.

INITIAL AND FINAL AQUEOUS SAMPLES FROM LAGOON 3 SLURRY

SAMPLE ID

DATE SAMPLED

INFITAL

08/23/94

Cdnventibnal Parameters

pH,s.u.

Fixed Suspended Solids (mg/L)

Volatile Suspended Solids (mg/L)

Total Suspended Solids (mg/L)

Q FINAL

09/13/94

73

38.0

159.0

197.0

Q

1 7.7

6.0

6.0

12.0

'"•: :V:::'v:--'isS/;::;4:::;:S::;S (mg/V y .-fiv- f i:::.-.:.

Ammonia Nitrogen

Nitrate Nitrogen

Orthophosphate

28J

0.15

0.64

< 0.10

0.096

1130

B T E X ( M R / L ) ••.. •

Benzene

Ethylbenzene

Toluene

Xylenes, total

Total BTEX<*)

2^00

150

1,100

120

3470

< 1.0

22.0

37.0

45.0

lOS.O

:%: -Q-:<':v-:: -':-: -:M QxtifV)

Acetone

Benzene

Chloromethane

1,2-Dichloroethene, total

Ethylbenzene

Methylene chloride

Styrene

1,1,2,2-Tetiachloroe thane

Tetrachloroethene

Toluene

Xylenes, total

< 2,500

2300

< 500

240

< <

250

500

200

180

< 250

970

520

J

J

J

< <

< <

< < < < < < <

5,000

500

1.000

500

500

1,000

500

500

500

500

500

Semi-Volatilie Organics (/ig/L)

Benzoic acid

2 - Chloronaphthalene

Di-n-butyl phthalate

Diethyl phthalate

Isophorone

Naphthalene

Phenol

3-Methylphenol/4-methylphenol

< <

5,900

UOO

350

< < < < <

UOO

UOO

UOO

1200

UOO

J

(2)

(2)

(2)

(2)

(2)

(2)

(2)

(2)

V

Notes: ^Compounds that are less than a detection limit are summed at one times tbe detection limit. ( 'Analytical results not yet available &om laboratory. J: Compound detected below quantitation limit Value reported is estimated.

49flt?2


1 SAMPLE ID

1 DATESAMPLED

j Total Solids, %

pH, i.U.

Benzene

Elhyibcnzene

Toluene

Xylenes, loul

1 Tolal BTEX<')

Acetone

Benzene

Carbon Disulfide

Ethylbenzene

1 Methylene chk>ride

Tetrachloroethene

1 Toluene

Trichloroelhene

rXvlenes. tolal .^i™..,™.

1 Initial A

1 08/22A>4 [q" Initials

08/2^4 [ Inilial C

08/22/94 Q Davl

08/24/94 ^? Day 3

08/26W4 QI

CoBveaUonii'l araaieteri-^-:;'-:.';:•:;;:;:;;•••,;••.;•• \<.'. \

33.3

.1.0

1 127.000

44.9

5.1

10.5.000

43.3

5.0

79,300

B T E X Y a . / k . V

< 390.000

< 390,000

7,800.000

480.000

9.060.000

< 220,000

< 220.000

3,100,000

240.000

3.780.000

< <

230,000

230.000

2,800,000

230.000

3.490.000

50.3

NA

NA

< <

13,000

13,000

110.000

13.000

149.000

53.7

NA

NA

< 240,000

< 240,000

3,400,000

260,000

4.140,000

Volalile O r u n i c CoBspounds/UKAO 1

< 1,900.000

210,000

< 190.000

< 190.000

280.000

2,100.000

5,400.000

210,000

420,000

J

< 1,400,000

120,000

< 140,000

< 140,000

160.000

1,200,000

3,300,000

110,000

270.000

J

J

J

< 1,400,000

120,000

< <

140.000

140.000

170.000

1,300.000

3,700,000

110,000

300.000

J

J

J

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

II Semi-Volalife OrxanicCoapoBuis f»K/k(t II

1 Bis(2-cthythexyl)phth*Ute

2-Chloronaphthalene

Di-n-bulyl phthalate

1 Naphthalene

Tolal Microbes

1 Volalile Degraders 1

< 400.000

< 400.000

4,600.000

96,000 J

< 1S0,000

39,000

3,200.000

55.000

J

1

< 95.000

34,000

2,300.000

46.000

J

J

NA

NA

NA

NA

NA

NA

NA

NA

n

Microbial Coaalt fCFU/.^ II

9.000

I.J00

NA

NA

NA

NA

12.000

5.000

NA

NA

Notes:

Microbial counts are recorded on a wel weight basis, all other parameters arc recorded on a dry weight basis.

^Compounds that are less than a detection Umil are summed at one-half the detection limit.

NA - Not Analyzed

* - Quantification and idenlilication of compound may be considered suspect due lo hydrocarbon interference.


J - Compound delecled al a concentralion beknw deteclion limits, value reported is an eslimated value.


1 SAMPLE ID 1 DATE SAMPLED

1 Total Solids, %

pH, s.u. 1 TOC. mt/K(

1 Day? 1 08/3W94

Q Day 14 11/11/93

Q Day 21 A U/09/93

Q [ Day 21B 12/05V93

Q Day 21C

I2A)9»3 QI

CoBvealioaal Paraoieleni 1

1 58.8 NA

1 NA NA NA

60.9 7.5

NA

54.0

7.5 NA

•.: , ••:•:•:.BTEX fi.«rtiV-:-: - •

Benzene Ethylbenzene Toluene

Xylenes, total Total BTEX<')

Acetone

Benzene Carbon Disulfide

Ethylbenzene Methylene chk>ride

Tetrachk>roethene

Toluene Trichtoroelhene

1 Bis(2-elhylhexyl)phlhalate

2-Chloronaphthalene Di-n-butyl phthalate Naphthalene 1

1 Tolal Microbes 1

1 Volatile Degraders 1

10,000 12,000

120.000

60.000 202.000

< 52,000 860,000

U00.0fl0 3,300,000

5.712.000

• < 3,300

< 3,300 16,000

12.000 34.600

< 1,900 < 1,900

110,000 79.000

192.800

•

55.1 7.4

NA :-|

< <

1.800

1,800 55,000 25,000

83.600 Volatile Orcanic Componnds fuK/kKl 1

r< 530,000

< 53.000 < 53,000

< 53.000

< 110,000

880,000

1,600,000

36,000 190.000

J

NA

NA NA

NA NA

NA NA

NA NA

30,000

< 10,000

< 10,000

< 10,000

< 21,000

48.000 53.000

< 10,000 38.000

BJ 13,000

< 7,700 4,600

3,800 < 15,000

66,000 66,000

< 7,700 48.000

BJ

J

J

30.000 < 7,600

4.200

3.300 < 15.000

49,000

53,000 < 7,600

38,000

B

J

J

ScBi-Volati ie Orcanic Compouadi fttK/kkV II < 110,000

51,000

< 110,000

74.000

J

1

NA

NA NA

NA

Microbial Counts fCPU/>^ II 350,000

13.000

NA

NA 1 680,000j000

1 l.ooo NA

NA

NA

NA 1

It •4

Notes:


^Compounds thai are less than a detection limit are summed at one-half Ihe detection limit.

NA - Not Analyzed

* - Quantification and identification of compound may be considered suspect due to hydrocarbon interference.


J - Compound delecled at a concentration below detection limits, value reported is an eslimated value.

INITIAL AND FINAL AQUEOUS SAMPLES FROM LAGOON 7 SLURRY

SAMPLEID 1

DATE SAMPLED 1 INITTAL

08/23/94

Q FINAL

09/13/94

Q

Cboventionai Parametera

pH,s.u.

Faed Suspended Solkls (mg/L)

Volatile Suspended SoUds (mg/L)

Tolal Suspended Solids (mg/L)

7.2

263.0

1.180.0

1,450.0

8.0

2.0

3.0

5.0

. Nirtrieiiti '(ing/L) ••• SSiS:--:;: --i

Ammonia Nitrogen

Nitrate Nitrogen

Orthophosphate

46.4

0.47

< 0.10

mm^^VIBX ( M J L )

Benzene

Ethylbenzene

Toluene

Xylenes, total

Totol BTEX<'>

3,400

< 2.500

37,000

3300

464i00

2.60

6.20

25.90

• • • • • ; ; - - : : : : ; X . 5 S ::::,:;,.:•••....] i

<

<

25

25

550

140

740 L , >: :H::- ; *;;:-iJ Votalile Organics (^g/L)-- i :: . ' • •

Acetone

Benzene

2—Butanone

Chloromethane

U-ENchloroethene, total

Ethylbenzene

Methylene chloride

Styrene

1,12,2-Tetrachloroethanc

Tetrachloroethene

Tbiuene

Xylenes, total

38,000

3,100

< 50,000

15,000

<

<

5,000

5,000

15,000

<

<

5,000

5,000

4,900

34,000

< 5.000

J

J

J

89,000

< 4,200

2,400

<

<

<

<

<

<

<

<

<

8300

4,200

4200

8300

4^00

4,200

4,200

4,200

4200

B

J

Semi-TVolatile Organics (/ig/L)

Benzoic acid

2-Chloroiiaphthalene

Di-n-butyl phthalate

Diethyl phthalate

Isophorone

Naphthalene

Hienol

3-Methylphenol/4-nieth)4phencil

830

1,000

47,000

600

2,000

1300

4,900

1,100

J

J

E

J

J

J

J

(2)

(2)

(2)

(2)

(2)

(2)

(2)

(2)

Notes:

('^Compounds that are less than a detection limit are summed at one tiroes the detection limit

(^^Analytkal results not yet available from laboratory. J: Compound detected below quantitatioa Unut Value reported is estimated. B: Analyte detected in blank. E Estimated result Concentration eneeds calibration range.

4Qa67&

report: technology evaluation laboratory treatability

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