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103331

Bench Scale Treatability Study for the Electrokinetic Remediation of Soil from the Mercury Refining Site, Colonic, New York

Quality Assurance Program Plan

Prepared for: U.S. Environmental Protection Agency

290 Broadway New York, New York 10007-1866

Prepared by: R. Mark Bricka and Brad Hensarling

PO Box 3536 Mississippi State, MS 39762

Revised: 01 September 2005 Final Revision 5.0

305392

Bench Scale Treatability Study for the Electrokinetic Remediation of Soil from the Mercury Refining Site, Colonie, New York

The attached Quality Assurance Program Plan (QAPP) for the Bench Scale Treatability Study for the Electrokinetic Remediation of Soil from the Mercury Refining Site, Colonie, New York is hereby recommended for approval.

Signature / Date ^ R. Mark Bricka Senior Research Environmental Engineer Dave C. Swalm School of

Chemical Engineering Mississippi State University

W^y^ |\1VW^ \ \ \ L \ \ ^ C Signature / Date Thomas Taccone Remediation Project Manager US Environmental Protection Agency, Region 2

New York, NY

% ^ iM-SOJ^ Signajjire / Date Brad Hensarling Chemical Engineer Dave C. Swalm School of


'So$ Signature / Date WiUiamSy Quality Assurance Officer US Environmental Protection Agency, Region 2 Edison, NJ

MLM^^f^f!fA lO-S'-oS /Signature / Date Rafst61 Hemandez Internal Quality Assurance Manager Dave C. Swalm School of


Signature / Date John Hill External Quality Assurance Manager Dynamac Corp. Ada, OK

305393

Tab le of C o n t e n t s

1.0 Project Management ;. 7 1.1 Project/Task Organization 7 1.2 Problem Definition/Background 8 1.3 Project/Tasks Description ; 8 1.4 Quality Objectives and Criteria for Measurement Data 10

1.4.1 Representativeness : ^ 10 1.4.2 Completeness 10 1.4.3 Comparability 11 1.4.4 Accuracy ; : H 1.4.5 Precision 12 1.4.6 Sensitivity ......;... 12

1.5 Special Training Requirements /Certification 12 1.6 Documentation andRecords 13 1.7 Data Archival and Sample Disposal 13

2.0 Measurernent/Data Acquisition 20 2.1 Sampling Process Design (Experimental.Design) 20 2.2 Sampling Methods Requirements : 20 2.3 Sample Handling and Custody Requirements ; 21 2.4 Analytical Method Requirements.... 21 2.5 Quality Control Requirements 22

2.5.1 Types of QC Samples Produced 22 2.5.2 Data Quality Indicators 24

2.5.2.1 Mean (X). . . . . . 24 2.5.2.2 Variance (o^) 24 2.5.2.3 Standard Deviation (o) 25 2.5.2.4 Relative Percent Difference (RPD) 25 2.5.2.5 Percent Recovery 25

' 2.5.2.6 Percent Error... , ;. 25 2.5.2.7 Relative Standard Deviation (RSD):....... 26 2.5.2.8 Least Squares Analysis 26 2.5.2.9 Correlation Coefficient (r) 27 2.5.2.10 Coefficient of Determmation (r^) 27 2.5.2.11 Student's t-Test \ 27 2.5.2.12 Analysis of Variance (ANOVA) 27

2.5.3 Data Validation 28 2.6 Instrument/Equipment Testing, Inspection, and Maintenance Requirements 29 2.7 Instrument Calibration andFrequency 29

2.7.1 Microwave Digestion :... 29 2.7.2 Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) 30 2.7.3 Hydrogen Ion Concentration (pH) 31 2.7.4 Quality Control Checks 31

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2.8 Inspection/Acceptance Requirements for Supplies and Consumables 31 2.9 Data Acquisition Requirement (Non-direct Measurements) 32 2.10 Data Management 32

2.10.1 Documentation, DataReduction and Reporting 32 2.10.2 DataReduction andReporting 32 2.10.3 Selection of Analytical/Testing Methods 33 2.10.4 Analytical Methodology Descriptions 33

2.10.4.1 Toxicity Characteristic Leaching Procedure (TCLP) ..33 2.10.4.2 Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES)... 34

2.10.5 Geotechnical Characterization 34 2.10.5.1 Bulk Density and Soil Compaction. 34 2.10.5.2 Test Method for Particle-Size Analysis of Soils (EM 1110-2-1906 App. V-21) 36 2.10.5.3 Falling Head Permeability (EM 1110-2-1906 App. Vn-13) 36

3.0 Assessment/Oversight , 38 3.1 Assessments and Response Actions........ 38 3.2 Reports to Management ...; 38 3.3 Data VaUdation and Usability , 39

3.3.1 Data Review, Validation and Verification Requirements 39 3.3.2 Validation and Verification Methods 39 3.3.3 Reconcihation with User Requirements :. 40

4.0 References .'.'. 43

305395

Distribution List

1. Mr. Thomas Taccone USEPA Region 2 290 Broadway, 20* Floor New York, NY 10007-1866

2. William Sy USEPA Facilities Raritan Depot 2890 Woodbridge Avenue Mail Code: 2\5MS2\5 Edison, NJ 08837-3679

3. Dr. Frank Tsang Site Manager CDM Federal Programs Corp: 125 Maiden Lane, 5* Floor New York, NY 10038

4. Dr. Daniel F. Pope, Ph.D. Dynamac Corporation 3601 Oakridge Boulevard Ada OK 74820

5. Dr. Mark Bricka Dave C. Swalm School of Engineering PO Box 3536 Mississippi State, MS 39762

6. Dr. Rafael Hemandez Dave C. Swalm School of Engineering PO Box 9595 Mississippi State, MS 39762

7. Mr. Brad Hensarling Dave C. Swalm School of Engineering PO Box 3536 Mississippi State, MS 39762

8. Mr., Chris Fetters Fetters Consulting 18463 White Oak Dr. Prairieville, LA 70769

3 0 5 3 9 6

Distribution List . (continued)

9. Mr. Prashanth Buchireddy Dave C. Swalm School of Engineering PO Box 3536 Mississippi State, MS 39762

10. Mr. Anirudha Marwaha Dave C. Swalm School of Engineering PO Box 3536 Mississippi State, MS 39762

11. Ms. Amy Hall Dave C. Swalm School of Engineering PO Box 3536 Mississippi State, MS 39762

12. Ms. Heather Thomas Dave C. Swalm School of Engineering PO Box 3536 Mississippi State, MS 39762

13. Mr. John Hill Dynamac Corporation 3601 Oakridge Dr. Ada, O K 74820

14. Mr. Rick King Dynamac Corporation 3601 Oakridge Dr. Ada, OK 74820

3 0 5 3 9 7

Bench Scale Treatability Study for the Electrokinetic Remediation of Soil from the Mercury Refming Site, Colonie, New York

Quality Assurance Program Plan Project Management

1.0 Project Management

1.1 Project/Task Organization

A project organization chart for this treatability study (TS) is presented as Figure 1. Mr. Thomas

Taccone at the U.S. Environmental Protection Agency (USEPA) serves as the Remediation

Project Manager (RPM) and has overall project responsibility for this study. The USEPA prime

contractor having oversight and execution responsibilities for the remediation of the Mercury

Refining Company (MERECO) Property Site is CDM Federal Programs Corporation. Dr. Frank

Tsang is the CDM project coordinator for this effort. The Electrokinetic (EK) treatability study

is a subtask of the overall remediation effort and the remainder of the project organization

discussion is limited to this treatability study.

To accomplish this bench scale treatability study the USEPA Region 2 tasked the USEPA Robert

S. Kerr Environmental Research Center (USEPA Kerr Center) to implement a task order contract

to complete the TS. Mr. David Burden is the Contracting Officer's Technical Representative

(COTR) for this portion of the TS. Currently, the Dynamac Corporation has an active task order

agreement with the USEPA Kerr Center to execute the TS task. Dr. Kelly Hurt and Mr. Wayne

Kellogg have the shared responsibility of overseeing the TS. As part of Dynamac's effort, they

will serve as the Quality Assurance Manager (QAM), external to the data generation unit. The

person to serve in the capacity of the external QAM is Mr. John Hill of Dynamac.

Dr. Mark Bricka will supervise the team that will be directly responsible for the data generation^

Dr. Bricka will serve as the senior research environmental engineer and have overall project

responsibility and management; hence he is responsible for overall fiscal and technical

performance of the project on a day-to-day basis. Dr. Bricka will be assisted by an internal

QAM (Dr. Rafael Hemandez), who will conduct monthly quality assessment / quality control

(QA/QC) audits. Mr. Brad Hensarling will serve as a research scientist under Dr. Bricka's 7

3 0 5 3 9 8

supervision. Mr. Hensarling's efforts will be supported by Mr. Christopher Fetters (an outside

contractor) and Mr. Prashanth Buchireddy, both having extensive experience in EK testing and

evaluation. Mr. Anirudha Marwaha will have oversight responsibility for any analytical analysis-

conducted as part of this study. Project activities will be supported by at least two technicians,

Ms. Amy Hall and Ms. Valerie Hemandez.

1.2 Problem Definition/Background

As explained in detail in the Treatability Study Work Plan (TSWP) for the Mercury Refining

Site - Colonie, New York (Bricka 2005), this study will focus on determining the ability of EK

technologies to remove Hg from soil collected from the MERECO Property site located in

Colonie, NY. Site history, location, and description are provided in the TSWP.

1.3 Project/Tasks Description

This effort will focus primarily on the transport of elemental mercury (Hg) and Hg complexes

from soil under the application of direct current (DC) fields. Soil will be collected by a separate

contractor and provided to Mississippi State University (MSU) as part of this TS. Once the soil

is received, it will be homogenized and characterized for the parameters listed in Table 1. After

the soil is characterized, batch testing will be performed on the contaminated soil to determine

the most effective pH range and chelator concentration for Hg solubilization as described in

section 2.4 of the TSWP. In addition the samples will be analysed for Hg, As and Mn according

to USEPA method 601 OB as described in the TSWP and this QAPP.

After the batch testing is complete and the optimal conditions are identified for the MERECO

property site soil, EK testing will commence. As described in the TSWP section 2.5, EK testing

will involve running duplicate cells for 4 sets of experiments as shown below:

a) Unamended soils b) Soils amended with Hg extract 1 and cathode buffering c) Soils amended with Hg extract 2 and cathode buffering d) Soils amended with Hg extract 3 and cathode buffering

Experimental runs of each set of tests are to be terminated after 75 days of EK processing. To

speed the experimental process 4 cells will be ran simultaneously. During this processing,

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samples will be collected from the anode and cathode half cells as well as the three sampling

ports, as described in detail in the TSWP. These samples will be collected once daily until the

rate of treatment is determined. If the treatment rate is found to be slow, sampling frequency

will be adjusted accordingly. At the termination of EK processing, the soil will be removed from

the cell and divided into at least four sections. Soils samples will be collected, extracted, and/or

digested and analyzed for Hg as Usted in Table 1.

It is anticipated that the laboratory portion of this study will be completed ten months after

receipt of the soil samples. Data analysis and report preparation are expected to take an

additional two months as discussed in section 2.7 of the TSWP.

Prior to the initiation of any laboratory analysis of liquid or soil samples, the MSU laboratory

will conduct analysis of the contaminants of concem using the methods specified in the TSWP

and this QAPP. Both liquid and soil Standard Reference Material (SRMs) will be the subject of

this set of analysis. Seven SRM liquid and soil sample will be utilized for performance

evaluation (Table 2). All samples analyzed as part of this performance evaluation - pre

analytical testing phase, must meet the QC data established for the SRMs.

The data generated, as part of this study will be recorded on official log sheets and laboratory

notebooks dedicated to this TS. The TS's Principal Investigator (PI - Dr. Mark Bricka) will

conduct weekly reviews of the log sheets and laboratory notebooks. The results of the monthly

internal QA/QC audits will be discussed with the EK team members and any corrective action

will be reported to the extemal Quality Assurance Manager (QAM) and RPM. The TS report

will detail the effectiveness of EK treatment and the data quality associated with the study. The

TS report must be approved by the USEPA-RPM prior to study completion and termination.

305400

1.4 Quality Objectives and Criteria for Measurement Data

1.4.1 Representativeness Representativeness is the degree to which data accurately and precisely represents the true value

of a characteristic of a population, parameter variations at a sampling point, a process condition,

or an environmental condition intended to be characterized. The representativeness of the data is

addressed primarily in the experimental design through the selection of appropriate samples and

analytical procedures. It will also be ensured by the proper collection, handling, storage and

analysis of samples within the specified holding times so that the material analyzed reflects the

material collected as much as possible.

Sample representativeness will be maintained in the laboratory through appropriate sample

handling and storage techniques, as well as, thorough sample vessel cleaning procedures. Such

procedures will minimize contamination and protect sample integrity. Documentation associated

with laboratory analyses will include sample receipt and log-in records, sample preparation

records, sample processing logs, analytical instrument printouts, and equipment calibration logs.

Examples of these logs are provided in Appendix A. Details of laboratory documentation will be

included in the analytical written records. Initially, data will be recorded either (1) electronically

onto computer storage media from laboratory systems or (2) manually into laboratory notebooks

or on established data forms. Laboratory notes will be written in ink! Corrections to hand-

entered data will be initialed, dated, and justified. Completed forms, laboratory notebooks, and

other forms of hand-entered data will be signed and dated by the individual entering the data. It

will be the responsibility of the internal QAM and PI to ensure that data entries and hand

calculations are verified. Laboratory records of sample preparation will be maintained in sample

batch books.

1.4.2 Completeness

Completeness is a measure of the amount of valid data expressed as a percentage obtained from a

measurement system compared to the amount that is expected to be obtained under normal

conditions. The completeness of the study will be evaluated by reconciling the chain-of-custody

(COC) forms for the sample intended to be prepared as described in the TSWP with the list of

samples actually analyzed. Samples that have the proper integrity will be analyzed for target

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parameters and those samples affected by sampling handling and that cannot be analyzed will be

documented on the COC forms and in the laboratory notebooks. If any samples are missing, the

PI will evaluate the effect of the missing data on the TS objectives and take any appropriate

corrective action as necessary. The project data quality objective (DQO) is to obtain a 90%

completeness as calculated as follows:

Percent Completeness = ' . -

(Samples Analyzed / Samples produced as documented on the COC From) x 100

1.4.3 Comparability

Comparability is the measure of the confidence of one data set compared to another.

Comparability is addressed through the use of established laboratory methods (e.g.,

U.S. Environmental Protection Agency; U.S. Army Corps of Engineers; American Society for

Testing and Materials; American Public Health Association). Deviations from written protocols

or established laboratory methods will be documented and described in the TS report.

1.4.4 Accuracy Accuracy is the agreement between an observed value and an accepted value. Analytical

accuracy will be evaluated based on known standards. In addition, accuracy will also be

determined by evaluating recovery of target analytes from the analysis of available standard

reference materials (SRM) or fortified soil. Matrix spike (MS) sample will also be used to

determine the accuracy of the laboratory analysis by determining the percent recoveries in the

MS samples. Accuracy will be determined by measuring the percent error (PE) between the

measure value and the accepted reference or true value. The DQO for these MS samples are

provided in Table 2.

The quality control samples, their frequency, and acceptance criteria are listed in Table 2. Any

corrective actions taken will be documented. Generally this will consist of reanalysis of samples

not meeting the DQOs. Any acceptance of out-of-range QC results will be justified in writing

and approved by the PI. There are no established criteria for acceptance of out-of-range QC.

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The PI will review the cause of any out-of^range QC data and evaluate data acceptability for

supporting the evaluation of objectives on a case-by-case basis. Any QC deviations and

corrective actions will be summarized in the case narrative supplied with each batch of analytical

data in the QA final report.

1.4.5 Precision

Precision is defined as the degree of reproducibility among individual measurements of the same

property obtained under similar conditions. The measure of analytical precision will be

determined through the analysis of method and analytical duplicates as well as laboratory-

prepared Matrix Spike Duplicate (MSD) samples. Analytical precision for laboratory analyses

will be determined by measuring the relative percent difference (RPD) between the

concentrations of duplicate samples with the RPD between duplicate analyses serving as a

measure of precision. The goals for RPD for method, analytical and MSD samples are listed in

Table 2.

1.4.6 Sensitivity

Sensitivity is the capability of the methodology or instrumentation to discriminate among

measurement responses for quantitative differences of a parameter of interest. Method detection

limits (MDLs), defined by the EPA in 40 CFR 136, Appendix B, Definition and Procedure for

Determination of the Method Detection Limit, (CRF 2003) will be determined for the target

analytes of interest for this project. For practical purposes, the use of practical quantitation limits

(PQL) will be reported where the PQL is five times the MDL. In addition to reporting the MDL

and PQL, the range of standards used to calibrate the analytical insttument will also be reported.

1.5 Special Training Requirements/Certification

Dr. Mark Bricka and Mr. Anirudha Marwaha attended training and were certified by

PerkinElmer Global Customer Training Department as having completed the Optima Instrument

Series with Inductively Coupled Plasma (ICP) WinLab 32 Software training course. This will be

the primary analytical tool used for Hg analysis as part of this TS. Dr. Bricka is also a 40 hr

Certified OSHA HazWOper and Mr. Marwaha is a 24 hr Certified OSHA HazWOper both as

described by 29 CFR 1910 (CFR 2003). Mr. Hensarling is scheduled for HazWOper ttaining in

FY 05. No other special training or certification has been identified as part of this TS. 12

- 305403

1.6 Documentation and Records

As part of this study, weekly project meetings will be conducted to examine the study progress

and coordination. Dr. Bricka (the project PI) will be responsible for scheduling and conducting

these meetings. During these project meetings, any changes made to the Quality Assurance

Program Plan (QAPP) will be discussed, and up on approval by the EPA project manager the

QAPP will be revised. Any approved revision will be incorporated in to the QAPP and revised

copies of the QAPP will be distributed to each team members. In addition, team members' log

sheets and data books will be reviewed for completeness to ensure that the proper protocols are

maintained.

As part of this study, two reports will be prepared. The first will present the technical details of

the study including background, materials and methods, results and interpretation, and

conclusions. The second report will focus on data quality. This report will include calibration

log sheets, EK processing run log sheets, raw analytical files (electtonic) that will include the

order the samples were performed, analytical quality control (spikes, duplicates, blanks, and

calibration), as well as the analysis of standard reference material, method spikes, and method

blanks. Any deviation from the QAPP will be documented in this report, as well as any

corrective actions taken. The outcome of this report will be an assessment detailing the overall

data quality.

1.7 Data Archival and Sample Disposal

All archived liquid sample will be stored at 4°C until the sample analysis is verified or the

sample expires. Once the liquid samples exceeds their holding time, they will be disposed

appropriately. Soil sample will be stored at 4°C until completion of the TS and the final report is

approved by EPA project manager. After the report is approved the samples will be disposed.

All hazardous wastes generated by this project will be disposed turned over to the MSU

hazardous waste disposal team and disposed according to the RCRA regulations.

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All electronic data generated, as part of this study will be transferred to CDs. Lab books, paper

copies of the data as well as the CD will be stored in record holding for a period of 10 years after

the study completion.

14 , . .. „ . . 305405

USEPA Project Sponsor USEPA Region 2 - Remediation Project Manager

Mr. Thomas Taccone

EPA Prime Contractor - Site Remediation CDM Federal Programs Corp.

Dr. Frank Tsang

COTR - Task Order Contract USEPA Robert S. Kerr Environmental Reserach Center

Dr. David Burden

Task Order Contractor and Project Oversite Dynamac Corp.

Dr. Kelly Hurt Mr. Wayne Kellogg

Techno logyTTea tab i l i t yS tudy^ ' v i " ' • ^Evaluat ion o f E lec t rok ine t i c ,Remediatio,n;

- A t the M E R E C O ' P r o p e r t y S t i e * ' . _'

Extemal Quality Assurance Manager Dynamac Corp.

Mr. Jonh Hill

Principal Investigator and Project Manager Dr. R. Mark Bricka

Senior Research Environmental Engineer MSU

Internal Quality Assurance Manager Dr. Rafael Hernandez

Chemical Engineer MSU

Research Scientist Mr. Brad Hensarling Chemical Engineer

MSU

Extemal Technical Support Mr. Christopher Fetters

Fetters Consult ing Enviomnental Engineer

Analytical Support Mr. Anirudha Marwaha


Internal Technical Support Mr. Prashanth Buchireddy


Laboratory Technical Suport Ms. Amy Hall

Ms. Valerie Hernandez MSU

Figure 1. Project Organization Chart

15

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TABLE 1. TREATABILITY STUDY SAMPLESG

ON

Sample Media

Soil

Pore Water

Batch Testing . L/S

Extractant Screening

Treated Soil

Number of

Samples > 100

40

8

Approx. 3000

15

75

96

8

Sample Location(s)

Baseline homogenization ..

Baseline sample of the untreated soil

Baseline sample of the untreated soil

EK cathode, anode, & pore water sampling ports.

Shake test

Shake test

EK treated soil contained in Cell

EK treated soil contained in Cell

Sampling Procedure Scooping

Scooping as.cell Packed

Scooping as cell Packed

Sample withdrawal

Filtration & Collection

Filtration & Collection Sample removal and dividing

Sample' removal & homogenization _

Field Measurements

NA

- NA

NA

NA

. NA

NA

NA

NA .

Sample Analysis EPA SW-846, Method

3 051/601 OB (total Hg, As, Mn) Moisture (Bricka 1992)

EPA SW-846, Method 3051/601 OB (total Hg, As, Mn)

EPA SW-846, Methods 1311/6010 (TCLP for Hg& As)

EPA Method 9045C (pH)

EPA SW-846, Method 3051/6010B (total Hg, As, Mn, CI, I)

Hach 8350 ( E D T A ) EMI 1110-2-1906 App VII-13

(Permeability) ASTMD-698-91 modified (Bulking)

EMI 110-2-1906 App V21 (Particle size distribution)

EPA9081(CEC) EPA SW-846, Method 601 OB

(total Hg, As, Mn, CI, and I) Hach 8350 (EDTA)

EPA SW-846, Method 601 OB (total Hg, As, Mn,Cl, and I)

Hach 8350 (EDTA)

EPA SW-846, Method 601 OB (total Hg, As, Mn, CI, and I)

Hach 8350 (EDTA) EPA SW-846, Method

3051/601 OB (total Hg, As, Mn, CI, and I)

Hach 8350 (EDTA) EPA SW-846, Methods

1311/6010B (TCLP for Hg & As)

EMI 1110-2-1906 App VII-13 (Permeability)

ASTMD 698-91 modified (Bulking)

EMI 110.2-1906 App V21 (Particle size distribution)

Performing Laboratory

MSU

MSU

MSU

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TABLE 2. TABLE OF DATA QUALITY OBJECTIVES FOR TREATABILITY STUDY

w o m 1 ^ o 00

Variable Completeness Comparability Acciu-acy Precision

Sensitity

Method Quality Control

Analytical Quality Control [Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES)]

' ' ^ E - Percent error '

QC Sample Type or Measurement Procedure

WA'-'' Use of standard or published method Analytical Check Standards and SRM Analytical, Method, and MSD duplicate samples Calibration Standards, PQL and MDL

Analytical Chemistry Method Duplicate y Method Blanks

Method Matrix Spike^ ' Method Matrix Spike Duplicate*- ' SRM ' ,,

Liquid** - Hg, As, Mn Soir - Hg, As, Mn

Analytical Blank Analytical Check Standard Analytical Internal Standard Analytical Duplicate Sample Analytical Matrix Spike"- -* Analytical Matrix Spike Duplicate* -' Analytical Calibration (Target Compounds) •"SRM - Standard reference material

Frequency of Use 1 per phase of study Each test See below See below

See below

1 per batch of test prep 1 per 15 samples

1 per day or matrix 1 per day or matrix

1 per 50 samples 1 per EK set of soil analysis or 1 per 30 samples 1 per 15 samples 1 per 15 samples each sample 1 per 15 samples 1 per 15 samples 1 per 15 samples Daily or each new matrix

Data Quality Objective >90% 100% See below See below

See below

N/A, <MDL or <5% of Regulatory limit or <5% of the measured cone. Recovery 50% -150% RPD ^ <35% Within certified parameters (+/- 25% for warning and

+/-30% for action)

<MDL PE ' <25% PE <25% RPD <20% Recovery 75 - 125% RPD <20% r2(3> > 0.995

' ^ Typical Matrix Spike Conc.= 1 mg/I ^ •*RPD - Relative percent difference

Coefficient of determination (3)j.2 ^%/A - Not applicable * N/A-Not Applicable

^^ Typical Matrix Dup.Spike Cone. Img/l

17

TABLE 2. TABLE OF DATA QUALITY OBJECTIVES FOR TREATABILITY STUDY (CONTINUED)

o en

o

* SOIL SRM SUGGESTED CONCENTRATIONS - in mg/kg

Sample A Sample B Sample C

As

35 70 175

Hg

20 40

100

Mn

5 ' • 10

2 5 .; • •

** LIQUID SRM SUGGESTED CONCENTRATIONS - in ugA

Sample A Sample B Sample C Sample D

As

175 350 700 875

Hg

100 : 200

400 500

Mn

25 50 100 125

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TABLE 3. RECOMMEND SAMPLE HANDLING MEHTOD AND HOLDING TIMES

Sample Type

1. Phase I - Homogenization a. Homogenized Soil b. Soil Sub Samples c. Liquid Samples

2. Phase II - Characterization a. Soil Samples b. pH c. Moisture

d. CEC - Solid - Liquid

e. TCLP -Solid - Liquid

f. Particle Size g. Permeabihty h. Bulk Density

i. Total Metals -Sohd - Liquid

3. Phase m - Batch Testing a. Solids b. Liquids

4. Phase IV - EK Testing a. Solids . b. Liquids

Container Type

5-gal Plastic Pail Plastic Bags HDPE Bottles

Plastic Bags HDPE Bottles Aluminum Pans

Plastic Bags HDPE Bottles

Plastic Bags HDPE Bottles Plastic Bags Plastic Bags Brass Molds




Preservation Method

4°C 4°C pH <2,4°C

4°C pH<2,4°C N/A

4°C p H < 2 , 4 T

4°C pH <2 ,4''C 4°C 4°C N/A

4°C pH <2 , 4°C

4 ^ pH <2 , 4 ^

4 ° C • '•

pH<2,4°C

Holding Times (Days)

N/A N/A H g - 2 8 , O A - 1 8 0

N/A H g - 2 8 , OA-180 N/A - Must be Analyzed ASAP

N/A . H g - 2 8 , OA-180

N/A H g - 2 8 , O A - 1 8 0 N/A N/A N/A - Must be Analyzed ASAP

N/A H g - 2 8 , OA-180

N/A H g - 2 8 , OA-180

N/A H g - 2 8 , OA-180

N/A = not applicable OA = Other analytes ASAP = As soon as possible

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2.0 Measurement/Data Acquisition

2.1 Sampling Process Design (Experimental Design)

Specific details of the experimental design are outlined in the TSWP. For this TS, a total of over

3000 samples are anticipated to be collected and analyzed according to the methods listed in

Table 1. Samples will be analyzed in the laboratory at the Chemical Engineering Department of

MSU. Samples identified in this table are considered critical to the study.

2.2 Sampling Methods Requirements

Aqueous and soil samples will be collected during the TS as described in the TSWP (sections

2.2, 2.3, 2.4.1, 2.5.4.3, and 2.5.4.4) and shown in Table 1. Liquid samples will be colleted by

either pipetting or gravity flow. Liquids will be stored in capped HPDE sample containers. Soil

samples will be collected using aplastic scoop or spatula and stored in plastic bags or HPDE

botties. Samples will have unique sample identification as illustrated in the attached log sheets

(Appendix A) and each sample will be labeled with this sample identification, the project name,

the date the sample was generated, and the technician responsible for its generation.

Due to the high levels of Hg found in the soil and the fact that complete treatment is determined

to be 31 mg/kg of Hg (CDM 2003) the Hg concentrations are expected to be well above any

residuals found in new (never before used) containers. Thus, for this TS, new unwashed

containers will be used for sample collection.

Aqueous samples collected will be tested for pH, filtered and/or centrifuged, and analyzed for Hg

as described in Table 1. Soil samples will either be subjected to total digestion SW846 Method

3051 (USEPA 1998) or the TCLP extraction SW846 method 1311 (USEPA 1998) as listed in

Table 1. Sample holding times for Hg as listed in SW846 is 28 days, thus Hg samples will be

analyzed prior to 28 days. Other contaminants of concem and analytes will be analyzed prior to

the 180 day holding period as specified in Table 3.

The primary source of waste materials will be those residues and wastes resulting from the

laboratory studies. Examples of the types of wastes generated include reagents, expended

20 •' 305411

standard solutions, and soils used in the treatability studies. The wastes generated during any

laboratory activity will be disposed of through the appropriately licensed and permitted MSU

hazardous waste disposal office. Wastes will be incorporated into the MSU waste streams

without special requirements because none of the wastes generated during this study are

anticipated to require special handling, except for their hazardous characteristic.

2.3 Sample Handling and Custody Requirements

MSU's procedures for sample tracking and custody will be followed. In brief, custody will be

relinquished to a Laboratory Technician (LT). Upon receipt, a LT will examine the samples,

verify that the sample-specific information is correct and that the recorded custody form agrees

with the sample's label, verify that the samples' integrity are uncompromised, log the samples

into the MSU sample log forms, and sign the custody forms. Unique laboratory IDs will be

assigned to each sample as shown in the log sheets (Appendix A). Any discrepancies between

sample labels will be documented on the custody forms and the PI will be notified immediately.

Any samples released to outside laboratories for analysis will be accompanied by sample transfer

documentation.

All soil and liquid will be generated or colleted as needed for this TS. Samples will be collected

in the containers as shown in Table 3. Preservation and holding times for each matrix are also

provided in Table 3.

2.4 Analytical Method Requirements

TS sampling and analysis will be conducted to evaluate the mobility of Hg under the influence of

an electric field. In this study, the soil will be characterized to establish the baseline properties

of the soil and then the soil will be treated using EK. During soil characterization, both physical

and chemical properties of the soil will be determined. In addition, batch studies will be

conducted to identify effective Hg extractants, their effective concentration, and pH ranges. EK

cells will be run in an unamended and amended (addition of Hg chelating agents) mode. Pore

water samples will be collected during an EK run, and treated Hg contaminated soil will be

21 305412

subjected to a variety of chemical and physical tests. The samples to be collected along with the

number of samples to be collected and the specific analyses to be performed are summarized in

Table 1.

Prior to treatment, the untreated soil will be analyzed to establish baseline conditions. A sample

of the soil will be analyzed for total Hg, TCLP-Hg, and the physical characteristics of .

permeability, bulking, and particle size distribution.

During EK treatment, pore water samples will be collected to assist in determining the rate of Hg

removal from the soil. Currentiy, it is recommended that these samples should be collected

daily. The pore water sampling interval will be modified as treatability data becomes available,

if it is determined that the time required for treatment is greater than originally anticipated, daily

sampling will be increased to sampling once every two days. If after one week of sampling ever

other day, the movement of Hg is still slow, sampling will be increased to once every three days

or twice weekly. The sampling interval will not be increased beyond twice weekly. Pore water

samples will be analyzed for pH, and Hg. Soil samples after EK treatment will be analyzed for

Hg and As, TCLP- Hg and As, permeability, particle size distribution, and bulk density as listed

in Table 1.

2.5 Quality Control Requirements

2.5.1 Types of QC Samples Produced The types of samples that will be utilized during the treatability study include various authentic

samples and laboratory quality control (QC) samples. The QC samples to be used include -

blanks, splits, composites, duplicates, and spikes (fortified with an analyte or surrogate of

interest). The general use of these sample types is discussed below.

Analytical blank samples will be used to zero the analytical instruments and to detect analytical

problems during analysis. An analytical blank is a "clean" sample, which generally consists of

the reagent used to prepare the samples (sample matrix) and contains very little or no measurable

quantity of the analyte of interest. Typically, analytical blanks are composed of deionized water,

deionized water and reagent acids, or uncontaminated soils.

22 , 305413

A split sample is a sample that is divided into two or more portions. Each split will be

transferred to separate containers and then analyzed. Split samples are used to measure

analytical precision. Often, the sample preparation process or the method of analysis for one

analyte is destructive or modifies the sample with respect to a different analyte. Sample splits

will then be used to conduct different analyses on the same representative sample. Additionally,

a split sample may be handled as a blind sample for analysis by a third party to verify laboratory

accuracy.

Method duplicate samples are differentiated from split samples in that duplicate samples are

obtained when two samples are taken from the same site (or test), at the same time, using the

same method, and independently analyzed in the same manner. These types of samples represent

the same experimental conditions. Duplicates can be used to detect variability in treatment,

testing, and analysis.

Analytical matrix spike (MS) samples are environmental samples to which known concentrations

of analytes are added. The spiked samples are then processed through the analytical procedure,

and percent recovery of the spike is calculated. Recovery of the matrix spike analytes is used to

monitor for unusual matrix effects or gross sample processing errors.

Analytical matrix spike duplicate (MSD) samples are a second aliquot of a MS. MS samples are

carried throughout the analytical process as a separate sample. MSD samples are used to

document the precision and bias of the analytical method.

These QC samples will be used throughout the treatabihty study. The following control samples

will be collected:

Method Duplicate (one per day per matrix type) Method Blanks (one per 15 samples or batch) Method MS (one per day or matrix type) Method MSD (one per day or matrix fype) Analytical Laboratory Blanks (one per 15 samples) Analytical Check Standards (one per 15 samples)

23 305414

• Analytical Intemal Standards (each analytical sample) • Analytical Duplicate (one per 15 samples) • Analytical MS (one per 15 samples) • Analytical MSD (one per 15 samples).

2.5.2 Data Quality Indicators Well-accepted and commonly used indicators of data quality will be used to describe the results

obtained from laboratory analysis. These indicators include descriptive statistics, measures of

precision and interpretive tests as discussed below.

General descriptive statistics that will be used in data analysis include the calculation of the

Mean {X), Variance (o^), and Standard Deviation (o). The precision of analyses will be

determined by calculating the Relative Percent Difference (RPD) and Relative Standard

Deviation (RSD) of quality control samples included for analysis. Calibrations and correlation in

the results will be analyzed using Least Squares Analysis, with measures of the "goodness of fit"

determined through the calculation of the Correlation Coefficient (r) and/or the Coefficient of

Determination (r^). Interpretive tests such as the Students ^test and Analysis of Variance

(ANOVA) will be used to evaluate the differences between treatments. General equations as

well as the methods used for calculation of these indicators, are discussed below in brief

2.5.2.1 Mean(X)

The arithmetic mean {X), commonly called the average, is a measure of the "central tendency"

of the specified variable. Generally, the mean is reported with its confidence intervals. The

mean is calculated by summing the individual observations (X,) and dividing by the number of

observations («) in the sample (equation 2.1).

^ = - S ^ , (2.1)

2.5.2.2 Variance (a^)

The variance (o ) is a measure of the confidence interval for the mean in a population. The

confidence interval provides a range of values around the mean where the "true" mean is located

with a level of certainty. Variance will be calculated as shown (equation 2.2):

2" 305415

=^l(^ ' -^) ' (2.2)

2.5.2.3 Standard Deviation (a) The standard deviation (o) is a commonly used measure of the confidence interval or variation.

The standard deviation of a population of observations is computed as shown (equation 2.3):

Ji%? /=i (2.3)

2.5.2.4 Relative Percent Difference (RPD) The relative percent difference {RPD) is a measure of the precision of two replicate samples.

RPD is calculated as follows (equation 2.4):

RPD = \x,-x,^

xlOO (2.4)

where: X\ is the measured value for replicate 1 andX2 is the measured value for replicate sample 2.

2.5.2.5 Percent Recovery The percent recovery (PR) the quantity of an added analyte measured in a sample of known concentration calculated as a percentage. PR is calculated as follows (equation 2.5)

Pi? = Cone, of MS - pre spike sample cone

Cone, of the spike added to the MS xlOO (2.5)

2.5.2.6 Percent Error The percent error (PE) is the difference between the true value and the measured value expressed as a percentage. PE is calculated as follows (equitation 2.6)

PE = X - T

T xlOO (2.6)

where: X is the measure value, and T is the accepted reference or true value of the sample.

25 3 0 5 4 1 6

2.5.2.7 Relative Standard Deviation (RSD) The relative standard deviation {RSD) is a measure of the precision of three or more replicate

samples. The RSD is calculated as follows (equation 2.7):

f ^ ^ cr RSD = X xlOO (2.7)

\ X J where:

Ox is the sample standard deviation for the replicate measurements, and {X)'\s the sample mean for the replicate samples.

2.5.2.8 Least Squares Analysis

Data generated for the purpose of instrumental calibration will be subjected to least squares

analysis, commonly called regression analysis or linear regression. The least squares analysis

allows a curve to be fitted to the XT coordinate data. In the least squares distance-weighted

smoothing procedure, the influence of individual points decreases with the horizontal distance

from the respective points. Least squares analysis will be conducted with the aid of hand

calculators and/or spreadsheet application programs (e.g., Microsoft EXCEL®). In general, the

output for the least squares analysis will use the general form of the equation presented in

equation 2.8.

DR = mC + b (2.8)

where:

DR is the detector response (e.g. absorbance, area counts, peak height or width), m is the slope of the line obtained fi^om the least squares regression analysis (equation 2.9), C is the concentiation of the calibration solution, and b is the intercept of the line obtained from the least squares regression analysis (equation 2.10).

m = S^

b = ^ m ^ ^ ^

(2.9)

(2.10)

26 305417

where:

i=i V '=1 y

A 2 ,

,'=1 y and '=' ^'=' ^

2.5.2.9 Correlation Coefficient (r)

The correlation coefficient (r) represents the linear relationship between two variables. The

correlation coefficient for a regression analysis will be calculated with the aid of hand calculators

or spreadsheet application programs (e.g. Microsoft EXCEL®).

r = •

^ =^ yy (2,11)

where:

Sxx and Sxy are defined above, and:

f n . \ ^

2.5.2.10 Coefficient of Determination ( r )

The square of the correlation coefficient is the coefficient of determination (r^) and represents the

proportion of common variation in the two variables (i.e., the "strength" or "magnitude" of the

relationship). The coefficient of determination for a regression analysis will be calculated with

the aid of hand calculators or spreadsheet application programs (e.g., Microsoft EXCEL®).

2.5.2.11 Student's t-Test

The /-tests are based on the "/"-probability, which is similar to a nortnal population but

dependent on the sample size taken. Some of the more common uses of the /-test include

hypothesis testing and the comparison of the means of sample populations. The /-test analysis

will be calculated with the aid of statistical software packages (e.g. SigmaStat, SAS, Jandel

Scientific) or spreadsheet application programs (e.g., Microsoft EXCEL®).

2.5.2.12 Analysis of Variance (ANOVA) The ANOVA test wdll allow the investigators to evaluate the effectiveness of two or more

treatments for more than two populations. The ANOVA is easily calculated with the aid of

27 305418

statistical software packages (e.g. SAS, SigmaStat, Jandel**Scientific) or spreadsheet application

programs (e.g., Microsoft EXCEL®).

2.5.3 Data Validation

A series of reviews by technical personnel wdll be implemented to ensure that the data generated

for this treatability study meets the data quality indicators. The first step in this process will be a

review of the all utilized QA/QC procedures and data by the extemal QAM shortly after project

initiation. As the project proceeds as series of intemal QA/QC reviews will be also conducted.

These reviews will include the following:

• Data and related project records will be reviewed by laboratory personnel at the end of each work week to ensure that sample collection and analytical activities are completely and adequately documented.

• The PI will be responsible for reviewing analytical results and supporting documentation. The results of QC sample analyses wdll be compared to pre-established criteria as a measure of data acceptability.

• Calculations performed manually will be checked for accuracy. Calculations performed by software will be checked at a frequency sufficient to verify their accuracy.

• Data entered into spreedsheets will be either manually verified for accuracy or entered in duplicate followed by a comparison program to identify any discrepancies.

• Bi-weekly reviews of all QA/QC procedures and collected data will be conduced by the internal QAM. Any shortfalls Jn the QA/QC procedures identified by the intemal QAM will be corrected immediately.

Data that do not meet the data quality indicators will be identified and brought to the attention of

the PI. The PI will determine the appropriate action; for example, the data may not be reported

or may be reported with qualifiers. The implications of such actions, if taken will be discussed

in the final report.

Once the data has been approved by the intemal QAM the data will be summated bi-weekly for

extemal review. In addition, upon request data will be submitted to the extemal QAM for

review. After project completion all data will be validated by the extemal QAM ensure that the

DQO have been met, that instrument calibration and maintenance requirements have been met,

and that the data are complete, accurate, and traceable.

28 305419

2.6 Instrument/Equipment Testing, Inspection, and Maintenance Requirements

Equipment and instmments used as part of the TS will be calibrated to ensure proper operation.

When available the equipment manufacture's standard operation procedures for calibration will

be followed. When instruments do not meet the calibration requirements, maintenance will be

conducted and recalibration will be performed to ensure calibration requirements are met. For

the equipment that does not have a calibration method or where calibration is not possible, these

instruments will be inspected prior to use to ensure such equipment is operating within the

equipment manufacturer's specifications. When operating problems are identified, action will be

taken to correct such issues, or the equipment will be replaced. Table 4 presents a listing of

equipment proposed to be use for this TS.

2.7 Instrument Calibration and Frequency

Most of the equipment requiring calibration for this test focuses on the analytical needs. The ICP

will be calibrated daily or prior to the analysis of a different sample mafrix. Balances and pH

meters will be calibrated daily and checked using known standards periodically throughout the

day. Calibration and check standards will be recorded on calibration log sheets.

Some analytical methods (e.g., sieve analysis for particle size distribution) are rather simple and

require only (American Standard Testing Materials) ASTM or NIST traceable equipment. The

analytical balance used (Mettler Toledo Model Ag204) to weigh samples to 0.001 gram will be

calibrated daily. Other methods require more sophisticated calibration procedures. Calibration

procedures for the analytical methods are documented below.

2.7.1 Microwave Digestion

Samples collected for analysis of Hg concenttation include soils and aqueous samples. These

samples will be extracted using microwave assisted acid digestion prior to analysis by

inductively coupled plasma (ICP). These methods are described briefly below and in detail in

the referenced method.

29 3 0 5 4 2 0

Soil samples will be digested following procedures detailed in EPA SW-8476, Method 3051

(USEPA 1998) using an Anton Paar Multiwave Microwave Digestion Unit. Although there are

no specific calibration procedures associated with the Anton Paar, any quality conttol data

associated with the digestion process are maintained and available for reference or inspection for

a period not less than three years frorn project completion. Method duplicate samples will be

processed on a routine basis. A method duplicate sample will be processed with every other

analytical batch or every 15 samples, whichever is the lesser number. A method duplicate

sample will be prepared for each matrix type (i.e., soil, or water). In addition SRM soil samples

will be provided by EPA conttact laboratory program (CLP) and analyzed by MSU. One SRM

soil sample will be analyzed for each 30 soil samples analyzed. Results of the SRM analysis

will be scored EPA's CLP .

2.7.2 Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) Sample digestates will be analyzed for total metals according to EPA SW-846, Method 6010B,

Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled

Plasma-Atomic Emission Spectrometry. Samples analyzed for total metals will be reported on a

dry-weight basis.

.A three-point (minimum) calibration (r > 0.995) will be performed just prior to analysis of

authentic samples. Duplicate measurements will be conducted for each sample and a mid level

check standard will be analyzed after every ten authentic samples to ensure that the ICP-AES

system remains in calibration over the course of sample analysis. If the detector response for the

mid-level standard is not within 25% (PE<25%) of the average initial calibration detector

response, the initial calibration must be repeated. If a linear regression calibration method is

used then the mid-level standard will be quantified like a sample and the determined

concentration should be within 25% (PE <25%) of the "true" standard concentration.

If the PE is greater than the acceptable criteria, remedial maintenance will be performed on the

instrument, a new initial calibration will be performed, and the affected batch of samples will be

•^° 305421

reanalyzed at the discretion of the analyst and PI. Any deviations from calibration or data

objectives will be documented in the project files.

2.7.3 Hydrogen Ion Concentration (pH) The hydrogen ion concentration will be determined using an electronic pH Meter (Orion ATT

370 series pH meter or equivalent) equipped with a reference electtode and temperature

compensation. The reference electrode will be a silver-silver chloride or other reference

electrode of constant potential.

Prior to acquiring data with the Orion pH meter, the instrument/electrode system must be

calibrated at a minimum of two points bracketing the expected pH of the samples. The

calibration of the pH meter may be accomplished using commercially available pH buffer

solutions that are approximately three pH units or more apart. For example, two buffer solutions

having pH values of 4 and 10 may be used to calibrate the pH meter system for samples that

have pH values of approximately 5 to 8. Repeat adjustments on successive portions of the two

buffer solutions until readings are within 0.1 pH units of the buffer solution value.

2.7.4 Quality Control Checks

The qualify conttol checks incorporated in the analysis of samples include such qualify control

samples as blanks, reagent blanks, duplicate samples, matrix spike, and matrix spike duplicate

samples. These quality conttol checks are summarized in Table 2.. The EPA Methods prescribe

the specific quality control measures to be used and the frequency of those qualify control

samples for the analytical methods to be used. Descriptive statistics such as the mean, variance,

and standard deviation will be used to describe and evaluate the results of sample analysis.

Analytical precision will be evaluated using the concenttations of duplicate samples and/or

MS/MSD to calculate the RPD between replicate analyses.

2.8 Inspection/Acceptance Requirements for Supplies and Consumables

The PI will approve any consumables utilized for this study. Each purchase order for

consumables will be reviewed and approved prior to purchase. Consumables utilized for this TS

must meet the specifications as listed in the standard method or standard operational procedures

31 3 0 5 4 2 2

normally utilized in the laboratory. The PI, prior to use, must approve any consumable item not

specified in the cited methods. Such items include sample bottles, chemical reagents, EK cells

and parts, reagent water, deionized water, ICP supplies, ICP standards, and soil storage

containers.

2.9 Data Acquisition Requirement (Non-direct Measurements)

This TS is not anticipated to utiUze any non-direct measurements.

2.10 Data Management

2.10.1 Documentation, Data Reduction and Reporting

Documentation associated with laboratory analyses will include sample receipt and log-in

records, sample processing logs, sample preparation records, analytical instrument printouts, and

equipment logs. Initially, data will be recorded either (1) electronically onto computer storage

media from laboratory systems or (2) manually into laboratory notebooks or onto established

data forms and the laboratory will be written in ink. Corrections to hand-entered data will be

initialed, dated, and justified. Completed forms, laboratory notebooks, or other forms of hand-

entered data will be signed and dated by the individual entering the data. It will be the

responsibility of the PI to ensure that data entries and hand calculations are verified. In addition

to these documentation procedures, sample logs associated with laboratory custody and ttacking

will be maintained in project files.

2.10.2 Data Reduction and Reporting

ICP data will be acquired and reduced on a Perkin Elmer WinLab 32 dedicated Laboratory

Automation System. Data files will be transferred electronically to a PC so that the data can be

incorporated into an electronic file for final quantification and tabular results presentation. EPA

has requested that the raw data files be supplied to the extemal QAM (Dynamac) and the EPA

QAM (Dr. William Si) bi-monthly (every two weeks) as data are generated. In addition to raw

data reports data reduction and reporting will include the following:

• MDLs will be applied on a sample specific basis and qualified. Once the MDLs are established for each mattix PQL will be determined.

32 i 305423

• Concentrations of the target compounds will be presented on dry weight basis. Analytes that were not detected will be reported as "less than the established PQL."

• Samples may be blank corrected at the discretion of the PI. If data are blank corrected, both the original and the blank corrected data will be reported. If data are blank corrected a justification will be provided.

• Amounts expected and recovered, and percent recoveries, and RPD for MS and MSD samples will be reported. Comparisons between the MS and the MSD samples will be reported as ELPD.

• Results of replicate analyses will be reported.

• Results of analyses of SRMs, certified values, and the PE between the results and the certified values will be reported.

• Results of all QA/QC measurements, an overall assessment of sample qualify, and the raw sample files will be provided to the extemal QAM for review. This information will also be supplied to EPA upon request.

2.10.3 Selection of Analytical/Testing Methods

The analytical methods relevant to the evaluation of the primary performance criteria have been

selected from appropriate methods published by the USEPA; U.S. Army Corps of Engineers; and

ASTM. These methods will be followed as closely as possible to ensure comparability of the

results of the study. However, any deviations from the selected methods will be documented and

recorded in the project records. The PI will document what impact, if any, that these deviations

have on the quality of the data or interpretation of the results of the study.

2.10.4 Analytical Methodology Descriptions

Leaching procedures are available to evaluate the potential for a metal to migrate. These

procedures require that the soil be combined with an appropriate extraction fluid and tumbled for

18 hours in a rotary agitator. The resulting liquid is then filtered, digested with acid, and

analyzed for target metals by ICP-AES.

2.10.4.1 Toxicity Characteristic Leaching Procedure (TCLP)

The TCLP is designed to evaluate the mobility of both organic and inorganic analytes present in

liquid, solid, and multi-phase wastes. For this study, we will focus only on metal extraction and

analysis. Any solid waste capable of leaching one or more of the identified constituents (EPA

SW-846, Method 1311) (USPEA 1998) in concenttations greater than the regulated level is

33 305424

regarded as hazardous waste. The TCLP defines the toxicity of a waste by measuring the

potential for toxic constituents to leach and contaminate ground water at levels of environmental

or human health concem. In conducting the TCLP, consideration is given to the relative percent

solids content of the waste material tested and the exttaction fluid is selected as a function of the

alkalinity of the solid phase of the waste. The extraction fluids selected are made from glacial

acetic acid (CH3COOH), water and, if necessaty, a sodium hydroxide (NaOH) solution. Two

exttaction fluids are prescribed, the first having a pH of approximately 4.95 and the second

having a pH of approximately 2.88. If an analysis of the TCLP extract indicates that a regulated

compound is present at concentrations above the regulatoty level for that compound, the waste is

hazardous. The regulatory hazardous leachate level for Hg is 0.2 mg/L. In this study, the target

cleanup level is a TCLP extract of <0.2 mg/1.

2.10.4.2 Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES)

The technique of ICP-AES (EPA SW-846, Method 601 OB) will allow the investigators to

accurately determine the concentration of ttace elements in solution. The method is applicable to

the elements listed in Table 5 along with their recommend wavelength and estimated insttument

detection limit. Sample matrices including TCLP and soils may require digestion prior to

analysis.

2.10.5 Geotechnical Characterization The soils will be characterized for their fundamental geotechnical properties; bulk density,

particle size distribution, and permeability. Each test is described in the following subsections.

2.10.5.1 Bulk Density and Soil Compaction

The bulk density of treated and untreated soils will be evaluated by faculty and staff from MSU

following procedures modified from ASTM D 698-91. Modifications to the compaction

requirement and mold size have been made to the method. ASTM D 698-91 calls for a

compactive effort of 12,400 ft-lbf/ft'' to be applied by a compaction hammer to a soil sample.

This is the compaction effort delivered in the standard Proctor test. The molds used in

ASTM D 698-91 require a large volume of sample and produce a large volume of waste. To

minimize the amount of material used, ASTM C 109-93 molds are to be used for this study.

34 305425

This test involves the use of two 2 x 2 x 2 - inch ASTM C 109-93 molds. The base plate from

one of the molds is removed and the two molds are stacked on top of each other and secured to

the base plate. The reason for this is that the bottom molds can be filled to a point that is above

the 2-inch level and be compacted. Any excess soil can be trimmed to the desired 2-inch level.

This ensures that the cube is filled with material that has been subjected to a known compactive

effort.

In addition to using the stacked molds, modifications to the compaction hammer were necessary.

These modifications ensured that the compaction hammer would fit the mold and deliver the

required compactive effort. The hammer was modified by attaching a l . 9 x 1 . 0 x 5 - inch brass

head to the end of a conventional ASTM D 698-91 compaction hammer.

The procedure for making the samples consists first of assembling the stacked molds. These

molds consist of a gang of three 2 x 2 x 2 - inch cube samples. For the compaction of the first

lift, soil is placed in each cube until it is filled 3/4 full. The soil is then compacted by positioning

the hammer on one side of the mold, raising the weight as far as possible and releasing it (this is

referred to as one blow of compaction hammer). The hammer is then rotated 90° so that the

hammer is perpendicular to the first blow and a second blow is delivered by raising and dropping

the weight again. This is performed five times for the first lift as illusttated,below, ,

XI ^: 7

A

T\ ^

Positioning of the hammer for first compaction lift.

The second lift is prepared by compacting another lift as described above. Soil is added to

ensure that the height of the completed cubes is greater than 2 inches. This lift is compacted as

illustrated below wdiich ensures equal blows on all sides of the completed cube.

Positioning for hammer for second compaction lift.

35 305426

z A

N ^

After compaction is complete, the top mold is removed. When prepared correctiy there should

be a small amount of excess soil over the lip of the bottom mold. This is trimmed off ensuring

that the 2 x 2 x 2 - inch cube is completely filled. Samples are then exttuded from the molds and

if done properly, this process should produce three compacted soil cubes measuring exactly 2" x

2" X 2". These cubes are then ttansferred to pre-weighing boats and the weight of each

compacted cube is recorded. The density of the compacted cube is determined using equation

2.7.

BulkDensity = SM SV

(2.7)

where: SM = mass of the sample determined from the test. SV = volume of the sample (8 in^).

2.10.5.2 Test Method for Particle-Size Analysis of Soils (EM 1110-2-1906 App. V-21)

Soil samples will be prepared by thorough air-dtying followed by sieving through standard

sieves as detailed in EM 1110-2-1906, App. V-1. After the soils have been prepared and sieved,

the particle size distribution of the soil will be determined following the hydrometer method of

particle-size analysis (EM 1110-2-1906, App. V-8). The hydrometer method is a method widely

used to quantitatively determine the disttibution of particle sizes in soils. The distribution of

particle sizes larger than 75 pm (retained on a No. 200 sieve) is determined by sieving, while the

distribution of particle sizes smaller than 75 pm (typically the size class ranging from

approximately 0.77 to 0.001 mm) is determined by the hydrometer method. One of the principal

utilities of the hydrometer method involves obtaining the clay percentage of a soil or sediment.

The hydrometer method is based on the relationship between the velocity of falling spheres in a

fluid, the diameter of the sphere, the specific weight of the sphere and of the fluid, and the

viscosity of the fluid. The test will be performed to assist in soil characterization.

2.10.5.3 Falling Head Permeability (EM 1110-2-1906 App. VII-13) The coefficient of permeability is a constant of proportionality defining the ease with which a

fluid passes through a porous medium. Permeability will be determined following procedures

36 305427

detailed in EM 1110-2-1906 App. VII-13. This method provides for the determination of the

coefficient of permeability. The procedure establishes representative values of the coefficient of

permeability for soils having a permeability of less than l.OE-04 cm/sec. This test will be used to

assist in soil characterization.

37 305428

3.0 Assessment/Oversight

3.1 Assessments and Response Actions

As discussed earlier, intemal QA/QC audits will be conducted as part of the TS. These intemal

audits will be conducted by Dr. Rafael Hemandez with oversight provided by Dr. Mark Bricka.

If any deviation from the QAPP or issues with data quality are identified, the appropriate

corrective action will be recommended. Generally such corrective actions will involve the

recalibration of effected equipment or the re-analysis of analytical samples not meeting the

DQO. If the corrective actions do not resolve the data quality issues one month after

implementation, the TS will be suspended pending review by the Extemal Quality Assurance

Manager and the USEPA RPM - Mr. Tomas Taccone. Samples missing or absent will be

discussed the USEPA RPM as these are discovered. Any corrective action as a result of these

discussion will be implemented.

3.2 Reports to Management

As discussed earlier, the results of the monthly intemal QA/QC audits will be discussed with the

team and any corrective action will be reported to the extemal quality assurance manager and

RPM. The TS report will detail the effectiveness of EK treatment and the data quality associated

with the study. The TS report must be approved by the USEPA RPM prior to study completion

and termination.

\ . .

The TS report will be accompanied by a data quality (DQ) report . This report will include

calibration log sheets, EK processing run log sheets, raw analytical files (electtonically) that will

include the order the samples were performed, analytical quality control (spikes, duplicates,

blanks, calibration), as well as the analysis of standard reference material, method MS, method

MSD, and method blanks. Any deviation from the QAPP will be documented in this report as

well as any corrective actions. The outcome of this report will be a statement detailing the

overall data quality. All TS and DQ reports will be provided to the USEPA RPM officer at study

completion.

•

3g 305429

3.3 Data Vahdation and Usability

3.3.1 Data Review, Validation and Verification Requirements Intemal QA audits for the TS will be the responsibility of the Intemal Quality Assurance

Manager and the PI. These QA audits will be conducted according to specifications detailed in

the procedures and methods cited in this document. Intemal QA audits will include the

monitoring of facilities, equipment, personnel ttaining, procedures, record keeping, and data

processing and reporting for conformance to this QAPP. The audits will include inspections of

data collection activities, statistical audits of reported data, and reviews of technical reports.

The extemal QA audit will be conducted at the conclusion of the data collection phase of this TS.

Any discrepancies between what was performed and the procedures detailed in this QAPP will

be identified and documented. Discrepancies will be reconciled by re-analyzing sample,

repeating test and preparing new samples, or if either of these reconciliation modes are not

possible, the QA discrepancy will simply be documented.

3.3.2 Validation and Verification Methods Periodically, the TS team will identify the need for corrective action during the course of their

work or through QA audits. Each individual performing laboratoty or data processing activities ,

will be responsible for notifying the appropriate supervisory personnel of circumstances that

could affect data quality or integrity.

Technical problems in the laboratory, such as sample loss, improper instrument calibration, or

out-of-compliance QC results, will be first addressed by the laboratoty staff and managers.

Significant technical issues will be brought to the attention of the PI. Issues that affect the cost,

schedule, or performance of the project will be reported to the RPM. Subsequentiy, the RPM

will be responsible for evaluating the overall impact of these issues on the project and

implementing the necessaty'corrective actions.'

Deficieincies identified through QA audits will be brought to the attention of the PI.

Implementing corrective actions will be the responsibility of the PI.

39 3 0 5 4 3 0

The data will be validated and verified through the use of a double review and checking

procedure. This will consist of having the PI independently check any calculations and data

provided by the Research Scientist and research team. Any discrepancies will be discussed and

resolved through these discussions. Only verified data will be reported in the TS report.

3.3.3 Reconciliation with User Requirements Evety attempt will be made to meet the DQO outiined in this QAPP. Where DQO are not met

these will be discussed with the USEPA RPM and action will be taken as directed.

40 305431

TABLE 4. EQUIPMENT TO BE UTILIZED FOR THIS TREATABILITY STUDY

1 Equipment Description

1 Analytical Balance

1 Top Loading Balance

1 pH Meter 1 Parr Digestion Unit

Mechanical Pipettes Volumetric Glass Ware ICP

Permeability

1 Caliper 1 Sieves 1 Hydrometers 1 EK Power Supplies

EK pH Controllers

1 Oven for Moisture 1 Analysis

Make and Model or Type

Mettler Toledo AG-204

Denver Insttuments TL-8102D

Oakton pH-310 Anton Parr Multiwave

Eppendorf (various volumes) Class A (Various Volumes) Optima 4300 DV

Humboldt HM-3891

Flower Max -Cal Gelson - Various Sizes ERTCO - Soil Hydrometer Agilent E-3612A

Etatton 56025

Precision economy oven Model 31026

Inspection Frequency Daily

Daily

Daily Daily

Daily Daily Daily

Daily

Daily Daily Daily Daily

Daily

Daily

Maintenance

Manufacture Specification Manufacture Specification N/A Manufacture Specification N/A N/A Manufacture Specification Manufacture Specification N/A N/A N/A Manufacture Specification Manufacture Specification N/A

Calibration Frequency Weekty

Weekly

Daily N/A

Weekly N/A See Section 1.4 & 2.5 N/A

N/A • N/A N/A N/A-

Weekly

Weekly

N/A = Not available

41 305432

TABLE 5. RECOMMENDED WAVELENGTHS AND ESTIMATED INSTRUMENTAL DETECTION LIMITS

Target Analyte

Aluminum Antimony Arsenic Barium Beryllium Boron Cadmium Calcium Chromium Cobalt Copper Iron Lead Lithium Magnesium Manganese Mercury . Molybdenum Nickel Phosphorus Potassium Selenium Silica (SiO) Silver Sodium Sttontium Thalhum Tin Titanium Vanadium Zinc

Wavelength (nm)"

308.215 206.833 193.696 455.403 313.042

249.678x2 226.502 317.933 267.716 228.616 324.754 259.940 220.353 670.784 279.079 257.610

194.227x2 202.030

231.604x2 213.618 766.491 196.026 251.611 328.068 588.995 407.771 190.864

189.980x2 334.941 292.402

213.856x2

Estimated IDL (jae/L)"

30 21 35

0.87 0.18 3.8 2.3 6.7 4.7 4.7 3.6 4.1 28 2.8 20

0.93 17 5.3 10 51 C

50 17 4.7 19

0.28 27 17 5.0 5.0 1.2

"The wavelengths listed (wdiere x2 indicates second order) are recommended because of their sensitivity and overall acceptance. Other wavelengths may be substituted (e.g., in the case of an interference) if they can provide the needed sensitivity and are tteated with the same corrective techniques for spectral interference. In time, other elements may be added as more information becomes available and as required.

''The estimated instrumental detection limits shown are provided as a guide for instmmental detection limits. The actual method detection limits are sample dependent and may vaty as the sample matrix varies.

"Highly dependent on operating conditions and plasma position.

42 305433

4.0 References

Bricka, R Mark, "Treatability Sttidy Work Plan (TSWP) for the Mercuty Refining Site -Colonie, New York," Version 2.1, 28 Januaty 2005, Prepared for the US Environmental Protection Agency, New York, NY.

USEPA. 1998. "Test Methods for Evaluation of Solid Waste: Physical/Chemical Methods," SW-846, 5* ed.. Office of Solid Waste and Emergency Response, Washington, DC.

CFR. 2003. "Code of Federal Regulations, Protection of the Environment,' 40CFR, Part 261, Govemment Printing Office, Washing, DC.

43 3 0 5 4 3 4

5.0 APPENDIX A

EXAMPLE LOG SHEET

305435

44

M i s l K i p p i State University ^ ^ , Environmental Technology L a b

Pro j ec t : Hg Soil Remediation Site: Colonie, New York

Date of Field Sample Collection Date Received by MSU:

Sheet of

Chain of Custody - Laboratory Bulk Sample Tracking Form

Sample Date:

Receipt Time:

Lab ID Sample Received By:

Sample Reconciled with Field COC Form

Location Where Stored

Sample Sealed Y/N

Remarks

No.

San

Date:

iplelD: (

New ID

CNHg/LabID

Division of Sample for Lab Use Intended Purpose

for Sample

/ Homoeenized / Untr

Storage Container

Type

3ated / Intended 1

New Location

Jse /Number

New Location

Site Prepared

Signature of

Custodian

Notes

i.e. = A bulk sample for Digestion and ICP from the hot spot area, first sample: CNHg-HS-U-BK- AICP-1 Note: all samples will be untreated for this log sheet

U)

o

OJ Ol

ID Explanation : Intended Use:

-Analysis = A -pH = pH -Moisture = M -DigestionyiCP = ICP -CEC = CEC -TCLP = TCLP .• -Particle Size - PS

-Bulk Density -BD . -Permeability-PERM

Bulk Samples:

-Batch Test-BT • -EKTesfEK

45

Mississippi State University g ^ Environmental Technology Lab

Project: Hg Soil Remediation Site: Colonie, New York

Technician:

Sheet of

Batch Testing

Sample Type:

Base Sample Description/ID:

Date: Time: S t a r t ! Finish:

Amendment: L/S ratio: pH:

00 o Ul

• J

No. Sample ID

Admend. Cone. mg/1

Wt. Raw Soil

Vol. of Solution

Wt. of Raw Soil + Water

Wt. of Admend.

Total Wt.

Final pH

Date Sub. for

Analysis

Comments

Sample ID: CNHg / Sample Type/Batch/Amendment/Concentration/No. i.e: A Sample from the hot spot for batch testing with NaCL at 0. IM, number 1 = CNHg-H-B-NaCl-0.1-1

46

^ ^ Mississippi State University P " Environmental Technology Lab


Tracking Form)

Admendment: Replicate: A / B

Data Log Sheet Electrokinetic's Cell SampUng

Sample Type: Base Sample Description/ID:

Sheet of

(Taken from the Bulk Sample

Cell#

Technician:

w o in

00

No:

1

Date: Sample ID Sample Collection Location

Preserved in Cooler

Y/N

Signature Date Analyzed

Comments:

*ie, anode,cathode,portl,port2,port3 Sample ID: CNHg/EK/Cell/Sample Locatio / No.

ie: A sample collected from port 2 of the EK cell 2 first sample = CNHg-EK-2- p2 - 1

47

Ik * Mississippi State University

Environmental Technology Lab

Data Log Sheet Electrokinetic's Cell Operation


Tracking Form)

Sample Type; Base Sample Description/ID:

Sheet of

(Taken from the Bulk Sample

Amendment: Replicate: A / B

Technician:

Time Period:

Cell#

No. Date: Run Day

CeU Voltage

(V)

Cell Current

(mA)

P o r t l Current

(mA)

P o r t l Current

(mA)

Port 3 Current

(mA)

Anode Overflow

(ml)

Cathode Overflow

(ml)

Sample CoUected

Y/N

Cum. Anode

Overflow (ml)

Cum. Cath.

Overflow (ml)

Acid Vol. (ml)

Amount Acid

Consumed (ml)

Notes: This EK Cell operation log sheet corresponds to the, EK cell sampling log sheet

I 48 s e ^ s o c

Mississippi State University Environmental Technology Lab

Sheet

Digestions/Analysis

of



(Taken from the Bulk Sample Tracking Form)

No. Date: Time Technical

\

Sample ID

Rep. W t o f Sample

Digested

(g)

Dilution Volume

(ml)

Date Analyzed

Moisture Content

%

Liquid Cone.

DryWt Soil

Cone. mg/Kg

Comments

CO

o en

o

Note: one method blank for each set of digestions Sample ID: CNHg/Sample Type/Digestion/Treated or Untreated/Source ID/Rephcate No..

i.e.: A hot spot sample from the EK cell 2, replicate 2 digestion sample = CNHg- H-D-T-(CNHg-EL-2)-R2

49

1 Mississippi State University ip Environmental Technology Lab

Sheet of


Date: . Time:

pH/Acid Neutralization

S ample Type: • Base Sample Description/ID:


Technician:

Rep. No.

Sample ID

•

Sample Mass (g)

Diluted Volume (ml)

Amount O.IN HCL added (ml)

Time Tumbled

Initial pH

Final pH

Amount of Base Added (ml)

Parts CaCo3 Equivalent/million parts of soil

; Sample ID: CNHg / Sample Type/AN / Treat or Untreated / Source ID / Rephcate No. ; i.e: A hot spot sample from the EK cell 2, Acid Neutralization replicate 1 = CNHg-H-AN-T-(CNHg-EK-2)-Rl

w o m

H

50

\ Mississippi State University ' ^ Environmental Technology Lab

Sheet of


Date: Time: Technician:

Permeability



Method (falling head or constant head) Cross section area for container:

U) o Ul

to

Rep. No.

Sample ID Sample Mass

Sample length (cm)

, Initial height

reading (ml)

Final height reading

(ml)

Start time

Finish time Comments

Sample ID: CNHg / Sample Type /PERM / Treat or Untreated / Source ID / Replicate No. i.e: A hot spot sample from the EK cell 2, Permeability replicate 1 = CNHg-H-PERM-T-(CNHg-EK-2)-Rl

51

11 Mississippi State University Environmental Technology Lab

Sheet of

Cation Exchange Capacity



Date: Time: Technician:

Col. #

1 2 3 MB

Sample ID Sample Mass (g)

Volume Extraction fluid (ml)

Comments

to o

Co

Sample ED: CNHg / Sample Type / CEC / Treated or Untreated/ Source ID / Replicate No,. i.e.: A hot spot sample from the EK cell 2, replicate 2 CEC sample = CNHg- H-CEC-T-(CNHg-EL-2)-R2

52

Mississippi State University Environmental Technology L a b

Sheet of

TCLP


Technician: Time:

Sample Type: ^ Base Sample Description/ID:

Date: (Taken from the Bulk Sample Tracking Form)

Pre Test / Extraction Fluid Determination Replicate

# 1 2 3

Sample ID PH

SampIe/HjO

PH of Sample + H2O +HCL

Extraction Fluid Choice

Comments

P H of Extract ion Fluid: Extraction Fluid Lot Date / I D :

Rep.

1 ' 2 3

MB

Sample ID Sample Mass

(g)

Final pH

Preserved Sample

Vol. (ml)

Date Sample

Analyzed

Cone, of Extractant

mg/1

Comments

Motor Speed: (RPM) Time Extraction Start: Time Extraction End:

CO Sample ID; CNHg / Sample Type/TCLP / Treat or Untreated / Source ID / Replicate No. S i.e: A hot spot sample from the EK cell 2, TCLP replicate 1 = CNHg-H-TCLP-T-(CNHg-EK-2)-kl

53

^ L Mississippi State University " "'"t Environmental Technology Lab

Sheet of

Moisture Analysis

Project: Hg Remediation Site : Colonie, New York


Technician: Date: Time:

Star t : Finish:

Replicate Sample ID Wt. of Container (g)

Wt.Of Sample + Container

(S)

Wt. of Diy Sample + Container

(g)

% Moisture Comments

Sample ID: CNHg/ Moisture / Treat or Untreated /Source ID / Replicate No. i.e: A sample from the EK cell 2, Moisture replicate 2 = CNHg-M-T-(CNHg-EK-2)-R2

Sf-f-SOC

54

Misissippi State University Environmental Technology Lab

Sheet of

Bulk Density

Project: Hg Soil Remediation

Site: Colonie, New York Sample Type: -

Base Sample Description/ID:

Technician: Date: Time

CO

o Ul

Replicate Sample ID

Moisture Content

%

Dimensions (inches)

Length Width Height

Weight

(g)

Comments:

Sample ID: CNHg/Bulk Density-BD/Treat or Untreated / Source ID / Replicate/No. i.e: A sample from the EK cell 2 replicate 1, and 4 of 5 replicates for bulk density - CNHg-BD-T-(CNHg-EK-2)-R4

55

^ Mississippi State University 1 ^ Environmental Technology Lab

Sheet of

Particle Size Analysis


Date: Time; Technician:

Sample ID:

Sample Type: • Base Sample Description/ID:

Replicate No. :_


Total Amount of Soil Used (g)

( -

Sieve Size •

12.5mm sieve • 9.0 mm sieve

4.5mm sieve •' 2.0mm sieve : 1.0 mm sieve , 500um sieve

250 um sieve 125 um sieve lOSum sieve 75 um sieve Pass 75 um

Particle Size

Retained (g)

--

Hydrometer Test

Total Amount of

Soil(g)

fc * " ' 1

* 1 • * *

Sampling Time (min)

4 15 30 60 120 240 1440

Temp "C Hydrometer Reading

Sample ID: CNHg / Sample Type /PS / Treat or Untreated / Source ID / Replicate No. , I.e: A hot spot sample from the EK cell 2, Particle Size rephcate 1 = CNHg-H-PS-T-(CNHg-EK-2)-Rl

z.tf'Soe 56

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