final quality assurance project plan · mpi malcolm pirnie, inc. nist national institute of...

FINAL QUALITY ASSURANCE PROJECT PLAN

NON-PUBLIC PROPERTIES

NEWHALL STREET NEIGHBORHOOD HAMDEN, CONNECTICUT

Prepared for:

Olin Corporation Cleveland, Tennessee

Prepared by:

MACTEC Engineering and Consulting, Inc. 511 Congress St.

Portland, ME 04101

August 2009

Revision 0

FINAL

QUALITY ASSURANCE PROJECT PLAN

NON-PUBLIC PROPERTIES NEWHALL STREET NEIGHBORHOOD

HAMDEN, CONNECTICUT

Revision 0

Prepared for:

Olin Corporation Cleveland, Tennessee

Prepared by:

MACTEC Engineering and Consulting, Inc. 511 Congress St.

Portland, ME 04101

August 2009

MACTEC Project No.: 6107-09-0004

MACTEC Electronic Signature MACTEC Electronic Signature

Nelson Walter, P.E. Rod Pendleton, P.G. Project Manager Principal Scientist

DOCUMENT CERTIFICATION I have personally examined and am familiar with the information submitted in this document and all attachments thereto, and I certify, based on reasonable investigation, including my inquiry of those individuals responsible for obtaining the information, that the submitted information is true, accurate and complete to the best of my knowledge and belief. I understand that any false statement made in the submitted information is punishable as a criminal offense under §53a-157b of the Connecticut General Statutes and any other applicable law. Nelson Walter, Project Manager _______________________________________________ MACTEC Engineering and Consulting, Inc.

drpendletonRectangle

Quality Assurance Project Plan August 2009 Non-Public Properties, Newhall Street Neighborhood Site-Hamden, Connecticut

i

TABLE OF CONTENTS LIST OF FIGURES ........................................................................................................................ iii LIST OF TABLES .......................................................................................................................... iii LIST OF ACRONYMS AND ABBREVIATIONS ...................................................................... iv 1.0 INTRODUCTION ........................................................................................................... 1-1

1.1 PROJECT/TASK DESCRIPTION ....................................................................... 1-1 1.2 DATA QUALITY OBJECTIVES ........................................................................ 1-2

2.0 DATA GENERATION AND ACQUISITION .............................................................. 2-1

2.1 SAMPLING METHODS ..................................................................................... 2-1 2.1.1 On-Site XRF Screening Analytical Methodology .................................... 2-2 2.1.2 Off-Site Soil Sampling Methodology ....................................................... 2-2 2.1.3 Collection of Fill Samples for Waste Characterization Analyses ............. 2-2 2.1.4 Decontamination of Sampling Equipment ................................................ 2-3

2.2 SAMPLE HANDLING AND CUSTODY ........................................................... 2-3 2.2.1 Field Custody Procedures ......................................................................... 2-3 2.2.2 Laboratory Custody Procedures ............................................................... 2-6

2.3 QUALITY CONTROL ......................................................................................... 2-6 2.3.1 Analytical Methods .................................................................................. 2-6 2.3.2 XRF Analysis and Quality Control ........................................................... 2-7 2.3.3 XRF and Off-Site Laboratory Correlation Analysis ................................. 2-8 2.3.4 Off-Site Sample Quality Control Procedures ........................................... 2-9

2.4 INSTRUMENT/EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE ............................................................................................... 2-11 2.4.1 Field Equipment ..................................................................................... 2-11 2.4.2 Laboratory Equipment ............................................................................ 2-11

2.5 INSTRUMENT/EQUIPMENT CALIBRATION AND FREQUENCY ............ 2-11 2.5.1 Field Equipment Calibration Check Procedures .................................... 2-11 2.5.2 Laboratory Calibration Procedures ........................................................ 2-12

2.6 DOCUMENTATION ......................................................................................... 2-12 3.0 ASSESSMENT AND OVERSIGHT .............................................................................. 3-1

3.1 ASSESSMENTS AND RESPONSE ACTIONS .................................................. 3-1 3.1.1 Field Assessments and Response Action ................................................. 3-1 3.1.2 Laboratory Assessments and Response Action ....................................... 3-1

3.2 REPORTS ............................................................................................................. 3-2 3.2.1 Laboratory ............................................................................................... 3-2 3.2.2 Field Activities ......................................................................................... 3-3

4.0 DATA VALIDATION AND REPORTING .................................................................. 4-1 5.0 REFERENCES ................................................................................................................ 5-1 FIGURES TABLES

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TABLE OF CONTENTS - CONTINUED APPENDICES

APPENDIX A - STANDARD OPERATING PROCEDURES - SOIL SAMPLING AND EQUIPMENT DECONTAMINATION

APPENDIX B - STANDARD OPERATING PROCEDURE - ELEMENTAL ANALYSIS

USING THE INNOV-X SYSTEMS FIELD X-RAY FLUORESCENCE ANALYZER (XRF)


iii

LIST OF FIGURES

Figure No. Title

1-1 Site Location Map

LIST OF TABLES

Table No. Title 2-1 Analyses for Determination of Hazardous Characteristics

2-2 Required Containers, Preservation Techniques, and Holding Times



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LIST OF ACRONYMS AND ABBREVIATIONS

CTDEP Connecticut Department of Environmental Protection DQO Data Quality Objective HASP Health and Safety Plan ICP Inductively Coupled Plasma LCS Laboratory Control Samples MACTEC MACTEC Engineering and Consulting, Inc. MDLs Method Detection Limits mg/kg milligram per kilogram MPI Malcolm Pirnie, Inc. NIST National Institute of Standards and Technology NPP Non-Public Properties Olin Olin Corporation PAH Polycyclic Aromatic Hydrocarbon PID Photoionization Detector QA Quality Assurance QAPP Quality Assurance Project Plan QC Quality Control r2 correlation coefficient RCP Reasonable Confidence Protocol RLs Reporting Limits RSR Remediation Standard Regulation SAP Sampling and Analysis Plan SDG sample delivery group Site Non-Public Properties Study Area, Hamden, Connecticut TCLP Toxicity Characteristic Leaching Procedure UCL Upper Confidence Limit USEPA United States Environmental Protection Agency XRF X-Ray Fluorescence


1-1

1.0 INTRODUCTION

This Quality Assurance Project Plan (QAPP) has been prepared for the remediation of the Non-

Public Properties (NPP) study area in Hamden, Connecticut (Figure 1-1). As part of the

remediation process, soil/fill samples will be collected for on-site and off-site analyses to confirm

the limits of the excavation of fill material within the NPP Consent Order Boundary of the Newhall

Street Residential Area, as documented in the Excavation Confirmation Approach for Fill Materials

(MACTEC, 2007), and the Final Design/Generic RAP (MACTEC, 2009a). In addition, some

analytical characterization of the fill may be required to determine hazardous characteristics to

evaluate disposal options.

The principal elements of the proposed sampling and analysis associated with the project are

summarized in the Sampling and Analysis Plan (SAP) (MACTEC, 2009b). This QAPP describes

the quality assurance, quality control, and other technical activities that will be

implemented to ensure that the results of the sampling to be performed will meet project

requirements. MACTEC is responsible for ensuring that the QAPP is followed on-site.

The QAPP is organized into the following sections:

Section 2.0 Data Generation and Acquisition

Section 3.0 Assessment and Oversight

Section 4.0 Data Validation and Usability

Section 5.0 References

Significant portions of this QAPP are based on the Malcolm-Pirnie, Inc. QAPP (MPI, 2004), which

was approved for use in the Supplemental Investigation by the Connecticut Department of

Environmental Protection (CTDEP) to evaluate limits of fill within the NPP.

1.1 PROJECT/TASK DESCRIPTION

The principal elements of the proposed sampling and analysis associated with the project are

summarized in the SAP (MACTEC, 2009b), and include the following:



1-2

e X-Ray aterial to be

• Confirmatory sampling for off-site laboratory analysis of lead in soil/fill; and

l samples for hazardous characteristics.

ata quality will be assured through compliance with the analytical, field, and project management

h

or less yses in the

SAP (MACTEC, 2009a); and

ntrations with a flag ("J" for organics, "B" for

The RLs are values that the method may achieve under ideal conditions; actual limits

tly and accurately quantified in a specific sample due to matrix interference

• Screening of soil/fill samples for total lead in the field using portablFluorescence (XRF) devices to confirm visual delineation of fill mexcavated during remediation;

• Off-site laboratory analysis of fil

1.2 DATA QUALITY OBJECTIVES

D

procedures set forth in this QAPP.

T e principal quantitative data quality objectives (DQOs) requiring quality assurance are:

• determine the presence or absence of lead at detection limits that are equal to or less than the 400 milligrams per kilograms (mg/kg) numeric criteria specified for XRF analyses in the SAP (MACTEC, 2009a);

• determine the presence or absence of lead at detection limits that are equal to than the 400 mg/kg numeric criteria specified for off-site confirmatory anal

• determine the potential hazardous characteristics of excavated fill material.

The quantitative analytical DQOs will be determined by the method detection limits (MDLs) and

reporting limits (RLs) to be specified by the analytical laboratory selected for the remediation

project. MDLs and RLs are highly dependent upon the sample matrix and concentrations of target

constituents present. The MDL is a statistically derived value, representing the theoretical

minimum level at which a particular analyte can be detected. MDL studies are performed annually

by the laboratory. The RL (also referred to as the PQL, CRQL or CRDL) is a detection limit that

the laboratory is confident can be accurately achieved consistently over time. Because laboratory

instruments are usually capable of detecting compounds at concentrations less than the RL, the

laboratory convention is to report these conce

inorganics).

may vary by sample due to matrix interference.

If any applicable criterion for a substance in soil is less than the concentration for such substance

that can be consisten



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effects, the Remediation Standard Regulations (RSRs) allow for use of approved alternative

analytical methods.

CTDEP Reasonable Confidence Protocols (RCPs) (CTDEP, 2007) will be adhered to by the

CTDPH-approved analytical laboratory selected to perform the analyses. The RCPs are analytical

procedures that include enhanced laboratory quality assurance and quality control (QA/QC)

criteria. The RCPs state that for samples collected on or after September 1, 2007, the CT DEP

expects that all analytical data used to support investigation and remediation projects be generated

using the RCPs (or methodologies that contain a level of quality control and documentation at least

equivalent to the RCPs). The RCPs were developed to provide guidelines for the type of QA/QC

documentation that will be expected for analytical laboratory data used by environmental

professionals. Other components of this guidance include a laboratory QA/QC certification form

to indicate if the data meets the guidelines for Reasonable Confidence. When Reasonable

Confidence is achieved for a particular data set, the environmental professional will have

Reasonable Confidence that the laboratory has followed the RCPs and has described non-

conformances, if any, and the environmental professional has adequate information to make

judgments regarding data quality.


2-1

2.0 DATA GENERATION AND ACQUISITION

Fill excavation within the boundaries of the NPP will be confirmed by observation, portable XRF

techniques, and off-site laboratory analysis. In addition, some analytical characterization of the fill

may be required to determine hazardous characteristics to evaluate disposal options. The following

subsections describe how these methods will be applied.

2.1 SAMPLING METHODS

Details of the sampling of soil/fill as part of the remedial action are presented in the SAP

(MACTEC, 2009b). In general, sampling procedures and collection techniques follow the standard

operating procedures presented in Appendix A to assure consistent collection and reliable data

generation. Appendix B provides the standard operating procedure for lead analysis using the

Innov-X systems field x-ray fluorescence analyzer (XRF).

This section describes the approaches necessary for collecting representative samples. Field

sampling activities include soil/fill sampling. Operating guidelines for the field activities that

require further detail than presented here are provided in Appendices A and B. Field staff will

refer to the SAP (MACTEC, 2009b) and standard operating procedures when conducting field

sampling activities. Field staff will be required to adhere to the health and safety protocols

provided in the Health and Safety Plan (Olin, 2009a). Personnel with appropriate up-to-date health

and safety training certifications per Occupational Health and Safety requirements will comprise

the field team. Prior to field activities, all on-site personnel will be instructed on site-specific

health and safety protocols. Field logbooks will be maintained to document all activities performed

in the field. General information to be recorded each day include time of each activity performed,

weather conditions, and other pertinent observations. The referenced procedures contained in the

SAP (MACTEC, 2009b) and Appendices A and B will be used to guide or direct field personnel in

decision making and collection practices. Actual procedures will be determined in the field and

may follow one or more of the referenced procedures or be modified in response to field

conditions. The type of and rationale for any modifications to procedures will be recorded in a

field logbook.



2-2

2.1.1 On-Site XRF Screening Analytical Methodology

Confirmation sampling of fill excavation within the boundaries of the Consent Order is presented

in the SAP (MACTEC, 2009b). Appendix B provides the Standard Operating Procedure for

elemental analysis using the Innov-X systems alpha-4000 field XRF. Fill removal will be

confirmed by a combination of visual observations performed by an environmental

professional/technician specifically trained in visually identifying fill, and field analysis using

portable XRF techniques to analyze samples for lead. Once observed fill material has been

excavated, portable XRF techniques will be utilized to screen the soil left in place for lead, the

primary constituent of concern. Correlation between XRF and laboratory results will be

established during the initial excavation activities at the beginning of the Project so that samples

can be evaluated in real time. A memorandum regarding the correlation of XRF data with

laboratory analytical data will be submitted to CTDEP for review and comment. Calibration of

XRF equipment will be documented in a field log book.

Soil samples will be analyzed on-site for lead by the United States of Environmental Protection

(USEPA) Method 6200 using the Innov-X alpha-4000 XRF instrument,. The procedures used to

prepare samples and conduct the XRF analyses are described in Appendix B.

2.1.2 Off-Site Soil Sampling Methodology

Collection of soil/fill samples for off-site analysis of lead will be conducted in accordance with the

SAP (MACTEC, 2009b) and procedures defined in Appendix A. Off-site laboratory confirmation

analyses for lead (USEPA Method 6010B) will be conducted at a frequency of one laboratory

analysis for every 20 XRF samples (5%). This frequency is based on the “Standard Operating

Procedure for Elemental Analysis Using the X-Met 920 Field X-Ray Fluorescence Analyzer”

published by USEPA Region 1 in October 1996 (USEPA, 1996a).

2.1.3 Collection of Fill Samples for Waste Characterization Analyses

To evaluate disposal options, the hazardous characteristics of excavated fill may require analytical

testing. The analytical methods required for determination of hazardous characteristics are



2-3

resented in Table 2-1. Samples will be collected either in-situ from excavations or from fill

a

ield equipment will be decontaminated according to procedures provided in Appendix A to

miz ple media.

n a manner that maintains the original form and chemical

omposition. Table 2-2 details the sample preservation measures necessary for the various sample

e involves the custody of samples in the laboratory. Laboratory

ustody starts with the receipt of samples and continues through sample storage, analysis, data

The foll maintaining the field custody of samples:

ion

Shipping Records

p

materi l stockpiles as grab samples.

2.1.4 Decontamination of Sampling Equipment

F

mini e the potential for cross-contamination of sam

2.2 SAMPLE HANDLING AND CUSTODY

All samples will be handled i

c

matrices and analytical methods.

Sample custody procedures will be applied to the project in two stages. The first stage involves the

custody of samples in the field. Sample labeling, chain-of-custody forms, packaging, and shipping

procedures for the project are designed to maintain that proper integrity and custody of the samples

in the field. The second stag

c

reporting, and data archiving.

2.2.1 Field Custody Procedures

owing elements are important for

Sample Identificat

Sample Labels

Custody Records

Packaging Procedures



2-4

mbered sequentially.

In orde field sample number for every sample collected is unique; a 12-

haracter sample identification system will be used. An example of a field sample number is as

N436NH-SON0102

The following bullet items present information to be used when assigning sample identifications

n-site and off-site analyses):

igit 1 Will be the designation for the Block in which the sample is collected (i.e., A,C, E,

Digits 2,3,4 number of the prope

Digits 5,6

eet

t ue

HS – Harris Street SM – Saint Mary Street

reet SS – Shepard Street

MR – Mill Rock Road WA – Winchester Avenue

MS – Morse Street WD - Wadsworth

Samples will be identified using a unique alphanumeric identifier correlated to the block system

described in the Work Plan (Olin, 2009b). The sample identification numbering system is

described below.

To maintain consistency and comparability of sample location identification throughout the course

of the program, samples will be labeled by sample type and exploration location. New locations

will be nu

r to ensure that each

c

follows:

(o

D

F, H, J, K, L, M, N, P, Q, R, or S)

Will be the address rty

Will be the two-digit street name identifier, as defined below:

AS – Augur Street NH – Newhall Street

BS – Butler Street NS – North Sheffield Str

BT – Bryden Terrace PL – Prospect Lane

ES – Edwards Street RS – Remington Street

GS – Goodrich Stree SA – Shelton Aven

MA – Marlboro St




Digit 7

igits 8,9 Will be a double letter designation to indicate what type of sample has been

the different types of samples and letter

igit 10 Will be used to designate whether the sample is a normal sample “N”, a duplicate

e sample “M”, or a matrix

spike duplicate sample “2”

Digits 11,12

f sampling interval).

2-5

For example, N436NH-SON0102, would correspond to Block N, 436 Newhall Street, soil/fill

sample collected from a depth of 2 feet below ground surface

Sample labels will be affixed to each sample bottle prior to the field activities. An entry will be

made for each sample on the custody record. The custody record will include sampler names and

signatures, station numbers, date, time, type of sample, location, and analysis requested. After

samples are carefully collected, sample bottles will be tightly sealed and the outside wiped clean

before being placed inside plastic bags. The sample bags will be carefully packed in ice in coolers

to maintain that the samples' integrity during shipment. Each cooler will be securely taped and

prepared for shipping. The chain-of-custody forms will be placed in a separate plastic bag and

accompany the shipment. The identity of samples in each cooler will be maintained in the field log

book. When picked up by the carrier, the "Relinquished by" and "Received by" sections of each

form will be signed and dated. Samples will be transported to the laboratory under custody either

by an overnight delivery service or by laboratory personnel, who will assume custody of the

Will be a hyphen

D

collected. The following list shows

designation that will be used.

SO soil/fill sample

LQ liquid sample

D

sample “D”, a rinse blank sample “R”, a matrix spik

Will be used to indicate the exploration identification

Digits 13,14 Will be used to indicate the depth in feet below ground surface (e.g., 00 to 99) at

which the sample was obtained (signifies top o


2-6

mples upon receipt. One copy of the custody record will remain with the field team while the

ples. Samples will be stored under appropriate

onditions at the laboratory prior to analysis. Once analyzed, any remaining sample will be

h their facility. Sample custody is maintained from sample

ceipt to delivery of the data package to archiving of sample data and extracts. The samples are

us personnel assigned to analyze the samples. A complete

escription of the custody procedures is included in the USEPA Contract Laboratory Program

cal laboratory will be required to meet the quality standards of the methods

sed. Sample holding times are provided in Table 2-2. Analytical methods, detection limits, and

cedures are outlined in this section. The laboratory will follow

ternal quality control procedures in accordance with SW-846 and in compliance with CTDEP

ethods

necticut Department of

ealth. Off-site laboratory confirmation analyses will be conducted for lead using USEPA Method

sa

remaining copies will accompany the sam

c

retained for further analysis or stored in the laboratory refrigerator for at least 90 days.

2.2.2 Laboratory Custody Procedures

Unless otherwise specified by the field team, the analytical laboratory will employ USEPA custody

protocols to track the samples throug

re

relinquished and received by the vario

d

Statement of Work (USEPA, 2005).

2.3 QUALITY CONTROL

Data quality will be maintained through compliance with the analytical, field, and project

management procedures set forth in this QAPP. The purpose of this section is to detail the

analytical quality assurance program dictated by the DQOs defined in Section 1.2. All data

generated by the analyti

u

analytical quality control pro

in

RCPs (CTDEP, 2007).

2.3.1 Analytical M

Soil/fill samples will be analyzed on-site for lead by USEPA Method 6200 using the Innov-X XRF

instrument. The procedures used to conduct the XRF analyses are described in the SAP

(MACTEC, 2009b).

Samples sent to off-site will be analyzed by a laboratory certified by Con

H



2-7

ation of hazardous characteristics are specified in

able 2-1. The MDLs and RLs for each parameter will be specified in an addendum to the QAPP

de the following QC measures: instrument

andardization resolution check standard, initial and continuing calibration check standards,

tandardization Resolution Check Standard:

6010B. The analytical methods for determin

T

once the analytical laboratory for the remediation work has been procured.

2.3.2 XRF Analysis and Quality Control

Daily operation of the XRF instrument will inclu

st

method blanks, and field duplicate samples. Also refer to the Standard Operating Procedure for the

XRF Analyzer provided in Appendix B, which includes corrective actions recommended by the

instrument manufacturer and USEPA Method 6200.

S The XRF instrument operating condition will be

ment is powered up

om the off mode. The standard will check x-ray tube and detector performance.

checked during the instrument start up procedure, with a manufacturer provided standardization

resolution check standard. This standard will be analyzed each time the instru

fr

Initial and Continuing Calibration Checks: Calibration check standards will be analyzed at the

beginning of each day to verify instrument sensitivity and factory calibration.

The QC acceptance criteria (percent difference from the known concentration) for the initial and

ontinuing calibration checks is 20%. National Institute of Standards and Technology (NIST)

lanks:

c

Standard 2711 will be used to perform the initial and continuing calibration checks. The NIST

Standard 2711 is comprised of multiple target elements but was assessed for lead (lead

concentration = 1,162 mg/kg), the site analyte of concern.

B Blanks will be analyzed to verify the presence or absence of contamination during sample

s.

preparation and instrument analysis. The blank for the program will consist of a clean silicon

dioxide (sand) sample purchased from a supply vendor. The blank will be analyzed at the

beginning of each analytical day after the initial calibration check standard




ield Duplicates:

2-8

F The project goal for collection of field duplicates for XRF analysis is five

ercent difference goal of less than

0 percent for soil analysis by XRF has been established for the project.

icate result will be

alculated for both the XRF and 6010B methods.

at will be performed to determine how well the XRF data

orrelates with off-site lab data (USEPA Method 6010B).

percent for the confirmatory soil removal program. A relative p

5

The relative percent difference between the field sample result and field dupl

c

2.3.3 XRF and Off-Site Laboratory Correlation Analysis

This section presents statistical analysis th

c

Statistical Analysis: The on-site XRF and off-site data results will be compared and analyzed for

correlation and accuracy. Also refer to the Standard Operating Procedure for the XRF Analyzer

provided in Appendix B, which includes corrective actions recommended by the instrument

manufacturer and USEPA Method 6200.

Correlation: Correlation indicates the strength and direction of a linear relationship between two

ariables. A linear correlation plot of on-site XRF results versus off-site laboratory (USEPA

, a best fit linear regression equation (y = mx + b, where m is the slope of the

ne and b is the intercept), and the correlation coefficient (r2) to illustrate the relationship between

the on-site XRF and off-site results. A good correlation will be represented by an r2 value greater

than 0.9 5.

v

Method 6010B) results will be constructed for lead. A plot of the data will include points for on-

site XRF/off-site data

li

and an m value between 0.75 and 1.2


2-9

ables\4.2_Work_Plans\Construction Work Plans\Final_Submittal_CTDEP_19Aug2009\Quality Assurance Project Plan\Quality Assurance Project Plan Final_Rev0_19Aug2009.doc

lation coefficient

x = independent variable (ICP data)

s = sample standard deviations

The correlation coefficient is determined from the following calculation from the linear regression

analysis of the data:

where:

r2 (the correlation of determination) = the square of the corre

y = dependent variable (XRF data)

n = sample size

i = each variable up to the nth variable

Accuracy: Accuracy is a measure of how close the experimental results are to the “true” or

accepted value. For the purposes of the remediation portion of the program, the off-site laboratory

reported results will be considered the accepted value, and the on-site XRF results will be

considered the experimental value. The relative percent difference (RPD) values between the off-

te laboratory result and the on-site XRF result will be calculated as a measure of accuracy. si

Following the Region I Inorganic Data Validation Functional Guidelines (USEPA, 2008), Section

X Field Duplicates, an RPD of 50% will be considered acceptable.

100 ) ( 5.0

) ( xLabinAmountXRFinAmount

LabinAmountXRFinAmountRPD+

−=

2.3.4 Off-Site Sample Quality Control Procedures

2.3.4.1 Field Quality Control Samples

Field Rinsate Blanks: Field rinsate blanks will be included with the environmental samples at a

rate of one per sample shipment whenever sampling equipment is decontaminated in the field.

Rinsate blanks using laboratory generated analyte-free water will be analyzed to determine if cross

contamination of samples is a problem at the site. Field blank data will be evaluated by

omparison to the trip blanks and laboratory blanks to determine if a problem related to sampling

exists.

c

P:\Projects\Olin Hamden Newhall St\4.0_Deliver


2-10

Trip Blanks: One trip blank will be analyzed per sample shipment for volatile organic analysis.

rip blanks will contain laboratory generated analyte-free water and will be used to determine if T

volatile cross-contamination occurred during sample shipment and/or handling. Trip blank data

will be compared to the rinsate and laboratory blanks to determine if a problem exists.

Field Duplicates: One soil sample per 20 and one groundwater or surface water sample per

sampling event will be collected and split into duplicates. The two samples will be submitted to

the laboratory as blind duplicates. Sample results will be compared to one another to determine the

recision of the sampling technique employed. Because duplicate soil samples are difficult to p

obtain (i.e., sample heterogeneity), there will not be a cut-off criteria for the results. Water samples

will be judged based on 30 percent relative percent difference between the sample and the duplicate

results (USEPA, 1996b).

2.3.4.2 Laboratory Quality Control Samples

Method Blanks: Laboratory method blanks will be run at a rate of one per every 12 hours of

quipment run time; one at the start of the day and one the midway point of the analytical

ntal sample.

e

sequence. Organic method blanks must contain less than five times the RLs for common

laboratory solvents such as methylene chloride, acetone, and toluene, and less than the RL of any

other target compound. Inorganic blanks must contain less than one-tenth the concentration of a

compound detected in a corresponding environme

Matrix Spikes/Matrix Spike Duplicates: Field personnel will select one sample for matrix spiking

per every 20 samples collected. In addition, the laboratory will select one environmental sample

per 20 samples of the sample delivery group (SDG) for matrix spiking for each sample matrix.

Matrix spike compounds representing each analytical fraction (volatiles, semi-volatiles,

pesticides/PCBs, and metals) will be added to the samples in known concentrations. Percent

recoveries and relative percent differences between the duplicate results will be used to determine

accuracy, precision, and the effect of the sample matrix on the overall analytical results.

Laboratory Control Samples: Laboratory Control Samples (LCS) will be run for each method used

per batch of samples. An LCS is blank laboratory DI water spiked with compounds being analyzed



2-11

pa ol

easure of method and instrument performance.

urrogate Recovery:

by a rticular method. Percent recoveries of each compound are used as a quality ' contr

m

S Surrogates are compounds not expected to be in the sample, which are spiked

terest. Surrogates must be within the recovery limits established by the specified

nalytical methods. If surrogate recoveries exceed analytical method criteria, the laboratory must

trix effects and report results in the case narrative.

use

chnicians. SOPs for preventative maintenance include details on equipment log records, routine

ce schedules, problem identification

rocedures, and failure analysis protocols are provided with the preventative maintenance protocols

into samples or blanks at known concentrations. Surrogate analytes are used as indicators of the

method's ability to recover the actual analytes of interest. Surrogates are used to demonstrate

correct sample preparation and the absence of matrix effects impacting the recovery of the actual

analytes of in

a

re-analyze the sample to evaluate ma

2.4 INSTRUMENT/EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE

2.4.1 Field Equipment

Preventative maintenance of field equipment is performed routinely before each sampling event;

more extensive maintenance is performed based on hours of use. The Project Manager, project

task leads and general equipment custodians will oversee and implement maintenance programs as

applicable.

2.4.2 Laboratory Equipment

Make and model numbers for laboratory instrumentation will be provided by the laboratory for

preventative maintenance, and will be issued as an addendum to this QAPP following selection of

the analytical laboratory. Some laboratories rely on local service representatives of the appropriate

manufacturers for preventative maintenance. Day-to-day maintenance is conducted by in-ho

te

maintenance, and troubleshooting. Equipment maintenan

p

in the laboratory's SOP manual.



2-12

.5 INSTRUMENT/EQUIPMENT CALIBRATION AND FREQUENCY

alibration procedures for field and laboratory instrumentation used during the project are

instrument calibration procedures will be issued as

n addendum to this QAPP following procurement of the analytical laboratory. The portable XRF

.5.1 Field Equipment Calibration Check Procedures

calibrated prior to the start of the fieldwork and thereafter at

frequency specified by the manufacturer. Check standards will be analyzed daily to verify the

ell as the signature of the calibrating technician will be entered into the instrument's log book and

2

C

discussed in this section. Analytical laboratory

a

units are the only field instruments requiring calibration to be employed during field activities.

2

Each field instrument will be initially

a

initial calibration. Dates and times of calibration, serial numbers, and calibration techniques as

w

field log book.

Portable XRF Instrument: The XRF instrument will be calibrated as specified in Section 2.3.2.

2.5.2 Laboratory Calibration Procedures

All laboratories will employ appropriate methods for calibration of all instruments used for sample

analysis.

Frequency: All instruments employed by the laboratory will be calibrated at the frequency

escribed in the analytical methods.

rocedures:

d

P The calibration procedures for the laboratory are derived from the analytical methods.

ples. The QA/QC report

cludes a level 2 data validation summary plus inductively coupled plasma (ICP) interference

Originals of chain-of-custody records will be forwarded with the samples to the analytical

laboratory. The analytical laboratory will electronically report laboratory results to Olin’s

consultant within 14 days of receipt of samples. The format will include all data fields necessary

for smooth incorporation into the project database. The laboratory will also submit printed

analytical results and QA/QC reports within 21 days of receipt of sam

in




nd map references), description of the sample

reservation, sample identification number, analyses requested, and the name of the laboratory to

on-site. The sampling

analytical reports, and copies of chain-of-custody and

art of the project records.

pling survey leader to record pertinent

formation and observations. The sampling team will record all physical measurements, field

vation of odors, changes in the sample,

quipment problems, weather conditions, or any other observations could prove helpful. The

oversight lead will review logbooks, field sheets, calibration records, and chain-of-custody records

prior to their inclusion in the project notebook or electronic database. The field team will maintain

a project field notebook. The notebook will include all information necessary to properly conduct

the fieldwork. At a minimum this will include:

1.) the project work plan with any changes, additions, deletions, etc.;

2.) sample identification numbers;

3.) copies of past field sampling sheets;

4.) all field instrument calibration records; and

5.) the project Health and Safety Plan (HASP).

The analytical laboratory(ies) performing analyses for the project will be required to conform to the

RCPs (CTDEP, 2007) requirements for report deliverables.

check standard for metals and Laboratory Control Standard for all other parameters. The data and

QA/QC reports will be validated for conformance with method requirements and data quality

objectives as described in Section 1.2. The field and laboratory data will be archived in the project

database.

2.6 DOCUMENTATION

A permanently bound field notebook indicating the time, date, and location of sample collection if

applicable (including a written description a

p

which any off-site analytical samples were sent shall be maintained

notebook and associated maps, laboratory

analysis request forms will be maintained as p

A project field logbook will be maintained by the sam

in

analyses, and any pertinent observations in the project field logbook. Auxiliary data often proves

very useful in the interpretation of the results; thus the obser

e


3-1

3.0 ASSESSMENT AND OVERSIGHT

3.1 ASSESSMENTS AND RESPONSE ACTIONS

Field and laboratory performance and laboratory system assessments will be used to monitor

project activities to ensure compliance with QA objectives and procedures. Olin’s consultant may

perform laboratory quality assessments if a problem is encountered. The following sections

summarize the proposed field and laboratory assessments to be conducted during the project.

3.1.1 Field Assessments and Response Action

At the discretion of the project manager, internal assessments of field operations may be performed

during the project. Field assessments will monitor sample holding times, preservation techniques,

field quality control, equipment calibration, and soil/fill sampling. If the field assessments yield

results that do not satisfy the QA objectives of the project, the project manager will initiate

corrective actions. These actions may range from adding solvent washes to the decontamination to

changing the sampling strategy to obtaining representative samples. The project manager has the

ability to stop all work if audit results warrant such action.

3.1.2 Laboratory Assessments and Response Action

Performance Assessments: The laboratory will perform internal QC sample runs on an

independent basis. Samples will be run once per calendar quarter and will be analyzed as single

blind samples. Results of internal QC performance audits will be available upon request from the

laboratory. Performance evaluation samples will be submitted to the appropriate analyst by the

internal QC staff and will be analyzed as single blind samples. Results will be evaluated for

compliance with the project QA objectives by the QC staff. Samples will be analyzed by the

laboratory as part of their internal QC program.

System Audits: System audits will be performed on a regular basis by the laboratory's QA staff. In

addition, the project auditor may perform system audits as needed during the course of the project.

Response Action: Corrective actions will be implemented if unsatisfactory performance and/or

system assessment results are recorded. Corrective action may also be implemented if the results




3-2

Corrective actions, data assessment results, and validation results will be documented in a manner

consistent with USEPA protocols and the RCPs. Data assessment checklists will be generated for

of data assessment or internal QC checks warrant such action. The following is an outline of

protocols for corrective action to be used during the project. Non-conformances discovered during

formal assessments, laboratory data validation, or data assessment will be addressed by taking

corrective action. Such action(s) are initiated by the laboratory QA manager who is responsible for

filing a non-compliance report to lab management. Quality control charts are used to monitor day

to day variations in precision and accuracy. Means and standard deviations are determined for

historical data generated by the lab. This enables the use of statistical analysis in evaluating lab

data and determining the need for corrective action. Short-term corrective actions are initiated as a

result of malfunctioning equipment or improper used of analytical methodologies. Long-term

actions are initiated through the QA officer who assigns personnel to the investigation of the

problem. A series of evaluations then follows to assure the action is necessary and the results are

complete.

3.2 REPORTS

3.2.1 Laboratory

The analytical laboratory will validate data prior to submitting the data report/electronic data

deliverable (EDD) to Olin’s consultant. The laboratory will be required to evaluate their ability to

meet the DQOs stated earlier in this document and those presented in the analytical methods.

Outlying data will be flagged in accordance with laboratory SOPs and corrective action will be

taken to rectify any problems.

Non-compliance reports will be filed to laboratory and/or project management whenever an out of

control situation occurs. Reports will include a summary of accuracy and precision data, quality

problems, and the status of corrective actions. Meetings will be held between the laboratory

management and the QA staff to alert the appropriate personnel of problems needing corrective

action. A quality assurance field report is filed based on the findings of the meetings. Appropriate

actions and modifications will be incorporated into the lab's operating procedures as a result of

findings.



any QC problems encountered in the

nalysis and any corrective actions taken by the lab.

.2.2 Field Activities

ifying corrective actions for field activities and describing the schedule and

progress of the actions.

review by the internal QC staff on a per-case basis. The laboratory will submit a case narrative

with each set of sample analyses. The narrative will describe

a

3

Field personnel will be responsible for documenting the results of all field assessments.

Assessment results will be documented in the QA log book to be kept for all field assessments. A

report will be filed ident



4-1

• The final validation report will be reviewed to verify the report summarizes all validation actions for the project data set and identified any data associated with USEPA or CTDEP

4.0 DATA VALIDATION AND REPORTING

The laboratory will be required to evaluate their ability to meet the QA objectives stated earlier in

this document and those presented in the analytical methods. Corrective action will take place to

rectify any problems.

The lead analyses will be completed using USEPA SW-846 Method 6010B (USEPA, 1996a) in

compliance with CTDEP RCPs (CTDEP, 2007). Analytical results for lead generated at the off-

site laboratory will be validated using USEPA Region I validation guidelines (USEPA, 1996b;

USEPA, 1989). The data validation will include both Tier II and Tier III procedures. Tier III

validation will be conducted on ten percent of the samples to provide a definitive verification of the

analytical data obtained at the off-site laboratory. Tier II validation will be completed for all

remaining samples analyzed at the off-site laboratory. During the data validation process,

validation checks specified in the USEPA guidelines will be completed using QC goals specified in

the RCP guidelines when applicable. Results will be qualified in accordance with the validation

guidelines if necessary. Edits will be made to preliminary results based on the validation actions to

generate a final data set. Data quality interpretations, qualifications, and professional judgments

will be summarized in data validation reports presented in the characterization report.

Olin’s consultant quality assurance lead will provide a senior review of all validation reports and

data qualifications leading to the production of the final data presented in project reports. Data

quality assessment and usability shall be conducted per guidance provided in Laboratory Quality

Assurance and Quality Control, Data Quality Assessment and Data Usability Evaluation (CTDEP,

2009). During the QA review the following examinations will be completed:

• Validation procedures used during validation will be compared to procedures scoped for the project to verify that the correct guidelines, QC criteria, and levels of validation were completed;

• Data qualification actions will be reviewed for all data delivery groups to verify that the correct qualifiers are applied and actions meet specifications of the referenced validation guidelines;

• Professional judgment decisions described in validation reports will be reviewed to provide a final review of judgment decisions;



idation, outlying data will be flagged in accordance with USEPA Region I

aboratory Data Validation Functional Guidelines (USEPA, 1989 and USEPA, 1996b). Data

qualifie

er than the associated

J -

N - reported analyte is uncertain. The N qualifier is also used reported as tentatively identified

compounds (TICs); and

ation sampling will be included in

the construction completion reports for individual properties. Summary tables and figures

presenting the analytical data will be provided for each report.

RCP measurements that are not met. Data usability statements will be developed based on the data validation and incorporated into the project report.

As a result of val

L

rs include:

U - The target compound was not detected at concentrations greatquantitation limit;

The reported concentration is considered an estimated value;

The identification of the to identify non-targeted compounds that are

R - Result is rejected and considered unusable.

The evaluation of the data obtained during excavation confirm


5-1

5.0 REFERENCES

CTDEP, 2007. Laboratory Quality Assurance and Quality Control Guidance - Reasonable

Confidence Protocols, State of Connecticut Department Of Environmental Protection. June 12, 2007.

CTDEP, 2009. Laboratory Quality Assurance and Quality Control, Data Quality Assessment and

Data Usability Evaluation. May 2009. MACTEC, 2007. Letter report “Excavation Confirmation Approach for Fill Materials, Newhall

Street Neighborhood (SRD-128), Hamden, Connecticut” to Mr. Raymond Frigon, Remediation Division, Bureau of Water Protection and Land Reuse, State of Connecticut Department of Environmental Protection. May 10, 2007.

MACTEC, 2009a. Final Design/Generic Remedial Action Plan, Version 1, Non-Public Properties,

Newhall Street Neighborhood, Hamden, Connecticut, January 2009. MACTEC, 2009b. Sampling and Analysis Plan, Non-Public Properties, Newhall Street

Neighborhood, Hamden, Connecticut, August 2009. MPI, 2004. Supplemental Investigation Quality Assurance Project Plan, Non-public Properties

Study Area, Hamden, Connecticut. May 2004. Olin, 2009a. Health and Safety Plan, Non-Public Properties, Newhall Street Neighborhood Site,

August 2009. Olin, 2009b. Work Plan, Non-Public Properties, Newhall Street Neighborhood Site, August 2009. USEPA, 1989. “Region I, Laboratory Data Validation Functional Guidelines for

Evaluating Inorganic Analyses;” Hazardous Site Evaluation Division; February, 1989.

USEPA, 1996a. Standard Operating Procedure for Elemental Analysis Using the X-Met 920 Field

X-Ray Fluorescence Analyzer. SOP # X-MET 920. United States Environmental Protection Agency, Region 1 - New England. October 1996.

USEPA, 1996b. “Region I, EPA-New England Data Validation Functional Guidelines for

Evaluating Environmental Analyses, Parts I and II,” Quality Assurance Unit Staff; Office of Environmental Measurement and Evaluation; December, 1996.

USEPA, 2005. Contract Laboratory Program Statement of Work. United States Environmental

Protection Agency. November, 2005. USEPA, 2008. Region I Inorganic Data Validation Functional Guidelines. November 2008.




FIGURES

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Site Location Map

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Connecticut1:24,000 scale digital topographic map obtainedfrom Environmental GIS Data for Connecticut -2003 Edition, State of Connecticut Departmentof EnvironmentalProtection.

SITELOCATION

SITELOCATION


TABLES


MATRIX PARAMETER METHODSolid TCLP Metals - RCRA 8 1311/6010C/6020A/7470ASolid TCLP VOCs 1311/8620BSolid TCLP SVOCs 1311/8270DSolid TCLP Herbicides 1311/8151ASolid TCLP Pesticides 1311/8081BSolid PCBs 8082ASolid ETPH CT ETPHSolid Corrosivity/pH 9045DSolid Paint Filter Test 9095ASolid Ignitability 1030Solid Reactive Sulfide SW-846 7.3.4.1Solid Reactive Cyanide SW-846 7.3.3.2

Notes:CT - ConnecticutETPH - extractable total petroleum hydrocarbonsPCBs - polychlorinated biphenylsRCRA - Resource Conservation and Recovery ActSVOCs - semi-volatile organic compoundsSW-846 - Test Methods for Evaluating Solid Waste, USEPA, 1986TCLP - Toxicity Characteristics Leaching ProcedureVOCs - volatile organic compounds

TABLE 2-1ANALYSES FOR DETERMINATION OF HAZARDOUS CHARACTERISTICS

NON-PUBLIC PROPERTIES STUDY AREAHAMDEN, CONNECTICUT

Table 2-1_Haz_Characteristics_Methods

MATRlX PARAMETER CONTAlNER PRESERVATIVE HOLDlNG TIMESoil and Fill ETPH 4 oz. glass Cool to 4°C 14 days

Metals/TCLP Metals* 4 oz. polyethlyene or glass Cool to 4°C 6 months*SVOCs/PAHs 4 oz. glass w/Teflon-lined cap Cool to 4°C 7 days until extraction,

analysis 40 days

PCBs/Pesticides 8 oz. glass w/Teflon-lined cap Cool to 4°C 7 days until extraction, analysis 40 days

VOCs 3-40 mL glass w/Teflon-lined cap + (1) 2 oz. jar for %solids

Cool to 4°C, 1 methanol vial + 2 Na bisulfate

14 days

Notes:* - Mercury holding time is 28 days. Hexavalent and trivalent chromium holding time is 24 hours.°C - degrees CelsiusETPH - extractable total petroleum hydrocarbonsoz. - ouncesPAHS - polynuclear aromatic hydrocarbonsPCBs - polychlorinated biphenylsRCRA - Resource Conservation and Recovery ActSVOCs - semi-volatile organic compoundsTCLP - Toxicity Characteristics Leaching ProcedureVOCs - volatile organic compounds

TABLE 2-2REQUIRED CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES

NON-PUBLIC PROPERTIES STUDY AREAHAMDEN, CONNECTICUT

Table 2-2_Containers-Preservatives-Holding Times


APPENDIX A

STANDARD OPERATING PROCEDURES - SOIL SAMPLING AND EQUIPMENT DECONTAMINATION




APPENDIX B

STANDARD OPERATING PROCEDURE - ELEMENTAL ANALYSIS USING THE INNOV-X SYSTEMS FIELD X-RAY FLUORESCENCE ANALYZER (XRF)

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Table of Contents Section Number and Title 1.0 Scope and Application 2.0 Method Summary 3.0 Definitions 4.0 Health and Safety 5.0 Interferences and Potential Problems 6.0 Personnel Qualifications 7.0 Equipment and Supplies 8.0 Calibration and Operation 9.0 Quality Assurance and Quality Control 10.0 Sample Collection, Preservation and Storage 11.0 Sample Preparation and Analysis 12.0 Documentation and Reporting Results 13.0 Example Calculations 14.0 References

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1.0 Scope and Application

This Standard Operating Procedure (SOP) describes the procedures to be used at the Olin Hamden, Connecticut Site (Site) to analyze soil samples for metals using the INNOV-X Systems portable X-ray Fluorescence (XRF) analyzer. This SOP will be used in conjunction with the INNOV-X Systems XRF Manual. EPA method 6200 will be used to analyze soil and sediment samples using the XRF. A listing of elements and reporting limits of metals analyzed by the XRF is presented in Table 1 of this SOP. The following documents were used to prepare this SOP for elemental analysis at the Olin Hamden, Connecticut Site:

• USEPA Method 6200. Field Portable X-ray Fluorescence Spectrometry For The Determination of Elemental Concentrations in Soil and Sediment. January 1998.

• Region I, EPA-New England. Standard Operating Procedure For Elemental Analysis Using the X-MET 920 Field X-ray Fluorescence Analyzer. USEPA Region I Quality Assurance Unit Staff. October 1996.

• Innov-X Systems, Inc. Metals in Soil Analysis Using Field Portable X-Ray Fluorescence. January 2003.

• Innov-X Systems, Inc. XT-440 MR Analyzer User Manual. Innov-X Systems, Inc. Version 1.1. October 2002.

2.0 Method Summary 2.1 Principles of Operation

XRF is a nondestructive qualitative and quantitative analytical technique used to determine the chemical composition of metals in a sample. In an XRF analysis, primary X-rays emitted from an X-ray tube are utilized to irradiate a sample. The primary X-rays incident on the sample cause the elements present in the sample to emit (that is, fluoresce) their characteristic X-ray line spectra. The elements may be identified by the energies of the wavelengths of their spectral lines. The unit of energy of an X-ray is the kiloelectron volt (keV). The X-ray energy is proportional to the frequency of the X-ray waves and is inversely proportional to the wavelength. Since it is a fluorescent process, the energy of the fluorescent X-rays will always be of lower energy than the primary X-ray energy. In addition to the fluorescent X-rays, there will be a backscattering of the primary X-rays. Energies of the fluorescent and scattered X-rays are converted (within the detector) into a train of electric pulses, the

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amplitudes of which are linearly proportional to the energy. An electronic multichannel analyzer measures the pulse amplitudes which is the basis of qualitative X-ray analysis. The number of counts at a given energy per unit of time is representative of the element concentration in a sample and is the basis for quantitative analysis.

2.2 Sample Preparation and Analysis Summary

Soil samples will be collected in plastic bags in the field, and screened with the XRF initially as wet weight samples. The soil samples will be homogenized as thoroughly as possible inside the plastic bag, and a minimum of five readings will be taken for total lead only. Results will be recorded in the field logbook. For quantitative analysis of soil; sticks, stones, and other matter that is non-representative of the sample are removed, and the sample is thoroughly homogenized. The sample is dried in an oven at 150oC for 2 to 4 hours and then sieved through a No. 60 mesh sieve. If the sample exhibits a high clay content (clumping), it is ground up using a mortar and pestle prior to sieving. The fraction of the sample that passes the No. 60 sieve is then re-homogenized and transferred into the XRF sample cup. The sample cup is capped with a clear mylar film and the sample identification is clearly labeled prior to analysis. Refer to section 11.0 for a complete discussion of sample preparation. For analysis, the cup is positioned on top of the XRF analyzer and exposed to primary X-rays from the selected radiation source. The sample fluorescent and backscatter X-rays are detected and the results are recorded by the data system. Qualitative determinations of the elements present in the sample are based on the locations of characteristic peaks produced by individual elements in the energy spectra. Quantitative determination of an element present is made by comparing the intensity of a characteristic peak in the sample to a calibration curve of the same peak developed from standards of similar matrix and known concentrations.

3.0 Definitions

• SRM - Standard Reference Material • FPXRF - Field Portable XRF instrument

4.0 Health and Safety

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The INNOV-X XRF analyzer uses an X-ray tube to generate ionizing radiation for sample analysis. During all measurements the sample cup must be positioned on the analyzer so that the sample cup shields the analyst from exposure to radiation. The probe must not be opened except by authorized personnel. Proper training for the safe operation of the instrument and radiation training will be completed by the analyst prior to field operations. Radiation safety information for the INNOV-X XRF can be found in the operator’s manual. Protective shielding should never be removed by the analyst or any personnel other than the manufacturer. The analyst should be aware of the local, state and federal regulations that pertain to the use of radiation-producing equipment. Radiation safety guidelines for the instrument used at the Site are presented in section 3.2 of the INNOV-X Systems Instrument User Manual – Recommended Radiation Safety Training Components. A radiation monitoring program using TLD film badges will not be used at the Site. All reasonable measures, including labeling, operator training, and the concepts of time, distance, and shielding, will be implemented to limit radiation exposure to as low as reasonably achievable (ALARA). 5.0 Interferences and Potential Problems 5.1 Chemical Matrix Interferences An interference occurs when the spectral peak from one element overlaps either partially or completely with the spectral peak of another. If the XRF is calibrated for both elements (CASE 1) i.e. the one causing the interference and the one being interfered with, it is generally capable of correctly handling the interference. In this case, the element being interfered with may be measured with a poorer detection limit or poorer precision, but the analytical results should still be acceptable for field-portable XRF. If the XRF is not calibrated for the element causing the interference (CASE 2), then the XRF may report the presence of elements not in the sample, or greatly elevated concentrations of elements in or not in the sample.

• Example CASE 1: Lead and arsenic. Most XRFs are calibrated for lead and arsenic. Lead interferes with arsenic (although, not vice-versa). The net effect is a higher detection limit for arsenic, and poorer precision. The XRF handles the correction automatically, but the precision is affected. The loss of precision is also reported by the XRF. (Please refer to Innov-X Applications Sheet: In-field Analysis of Lead and Arsenic in Soil Using Portable XRF for more detail).

• Example CASE 2: Bromine in the sample, but XRF is not calibrated for

bromine. Bromine, as a fire retardant, is being seen more and more in soil and other sample types. For this reason, Innov-X analyzers include Br in the calibration data. If Br is not calibrated, but is present in the sample, the

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analyzer will report highly elevated levels of Pb, Hg and As. The levels will depend upon the concentration of Br in the sample.

Interferences between elements can be broadly categorized into a) Z, Z-1, Z+1 interferences, and b) K/L interferences. Interference type “a” occurs when high levels of an element of atomic number Z are present. This can cause elevated levels of elements with atomic number Z-1 or Z+1. Generally, portable XRFs have good correction methods, so this interference only causes problems with very high levels of the element in question. Example: High concentrations of Fe (Z=26) in excess of 10% may cause elevated levels of Mn or Co (Z=25 or Z=27 respectively). The type “b” interference occurs when the L-shell line of one element overlaps with the K-shell spectral line of another element. The most common example is the lead/arsenic interference where the L-alpha line of lead is in nearly the exact same location as the K-alpha line of arsenic. 5.2 Moisture Content Sample moisture content will affect the accuracy of the sample results. The measurement error may be minor when the moisture content is small (5 to 20 %), or it may be significant when measuring the surface of soils that are saturated with water. For quantitative analysis, moisture content will not be an issue because all samples are dried as part of the sample preparation (see Section 2.2). 6.0 Personnel Qualifications Sample analysis will be performed by qualified personnel either experienced in the operation of the XRF analyzer and knowledgeable in X-ray fluorescence, or under the direct supervision of an experienced and knowledgeable individual. The analyst must be thoroughly familiar with this SOP and the Innov-X Systems XRF Reference Manual supplied by the instrument manufacturer. 7.0 Equipment and Supplies 7.1 Innov-X Systems Alpha Series4000 (Alpha-4000) handheld instrument and accessories

• Alpha-4000 instrument • (2) lithium ion batteries. • Batter charger and AC adaptor. • Standardization cap.

7.2 Computer

• Microsoft® Excel program for recording data in spreadsheet format.

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7.3 Supplies

• Ziploc, quart sized plastic bags for sample collection • 2 oz glass soil jars for offsite split samples (QC clean quality) • Oven – for drying sediment and soil samples. • Sieve – No. 60 (250 µm) stainless steel. • Polyethylene XRF sample cups – purchased from SPEX Sample Prep,

LLC. Cat# 3529 (x-ray cell with snap ring, 31mm). • Mylar film for sample containment, 2.5 or 6.0µm thick. • Stainless steel spatulas. • Mortar and pestle (ceramic or glass). • Aluminum drying pans. • Gloves. • Safety glasses. • Portable hood. • Run log book (to record sample analyses). • NIST SRM – For instrument calibration checks (SRM 2709, SRM 2710

and SRM 2711). • Instrument Blank standard provided by Innov-X Systems. • Silicon dioxide (SiO2) 99.995% clean – for method blank analysis.

8.0 Calibration and Operation Procedures for calibration and operation of the Alpha4000 instrument are taken from EPA Method 6200 and updated to be specific to the Innov-X analyzer. The XRF instrument will be calibrated at the factory prior to delivery at the Site. The Alpha-4000 instrument will be calibrated by Innov-X Systems Inc. using the Compton Normalization method consisting of the analysis of a single, well characterized standard, such as an SRM. The standard data are normalized to the Compton peak. Operation of the Alpha-4000 instrument at the Site will be performed as described in the Innov-X Systems User Manual Revision B, March 2007. 9.0 Quality Assurance and Quality Control The following section details proper quality assurance is detailed for analysis of sediment and soil samples using the XRF analyzer. All operators will perform QA/QC procedures as described in this SOP. Procedures are listed below: 9.1 Proper Verification of Instrument Operation The following procedures were taken from USEPA Method 6200 and updated to be specific to the Innov-X analyzer. Quality assurance here consists of testing known standards to verify calibration, as well as testing blank standards to

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determine limits of detection and to check for sample cross contamination or instrument contamination. Components of instrument QC: 1. ENERGY CALIBRATION: An energy calibration check sample will be analyzed at the beginning of each day. The Innov-X analyzer performs this automatically; this is the purpose of the standardization check when the analyzer is started. The software does not allow the analyzer to be used if the standardization is not completed. The energy calibration check is performed by placing the snap on metal clip on the front of the analyzer and selecting standardize on the analysis screen. If the energy calibration fails, the analyst will shut down the instrument, replace the battery with a fully charged back up, and restart the instrument. An energy calibration will be performed after restarting the XRF. 2. INSTRUMENT BLANK: An instrument blank will be analyzed at the beginning of each day, and for every 20 environmental samples. The operator should use the silicon dioxide (SiO2) blank provided with the analyzer. The purpose of this test is to verify there is no contamination on the analyzer window or other component that is “seen” by the x-rays. Method 6200 recommends an instrument blank at least once per day, preferably every 20 samples. For either in-situ or prepared-sample testing, the operator should test the SiO2 blank to be sure there are no reported contaminant metals. If target analytes are reported in the instrument blank, all contact surfaces of the instrument will be wiped down with a soft cloth to remove any contamination on the detector window (the instrument blank should also be wiped down to ensure it has not been contaminated, or a different instrument blank may be used, Teflon® or quartz block). If the instrument continues to detect target analytes in the instrument blank, the Kapton® window covering the detector should be replaced. 3. METHOD BLANK: A method blank will be analyzed daily or for every 20 prepared samples. The purpose of the method blank is to verify that cross-contamination is not introduced into samples during the sample preparation process. A method blank will be prepared with each batch of 20 samples (Method 6200 recommends following the sample preparation procedures with clean SiO2 once very 20 prepared samples). If target analytes are detected in the method blank, all sample prep equipment should be thoroughly cleaned and all samples prepped under that blank should be evaluated. An action limit of five times the reported blank concentration will be established. Any sample results greater than the action limit will be accepted. Sample results below the action limit will require re-prepping and re-analyzing the affected samples after the preparation equipment have been thoroughly cleaned. 4. CALIBRATION VERIFICATION: A calibration verification check (NIST SRM check standard) will be analyzed at the beginning of each day, after 20 samples

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have been analyzed, or every 4 hours, whichever is more frequent. A calibration verification standard should be selected with target analyte concentrations less than, at/near, and greater than the project action limit. Each calibration verification standard should be monitored, in turn, throughout the field program, this will provide a check on instrument performance overall. The operator will perform a 2-minute test on a NIST standard. The percent difference (%D) between the FPXRF result for an element and the value of the standard should be 20 or less. If the calibration check is greater than 20% of the standard value, the operator will adjust the calibration factor of the instrument and re-analyze the standard (see instrument manual for re-adjustment of calibration factors). 5. LABORATORY DUPLICATE: A laboratory duplicate sample will be analyzed daily. The laboratory duplicate is prepared and analyzed in duplicate with the original sample. The project control limit for the laboratory duplicate relative percent difference (RPD) between the original sample and lab duplicate sample is 50, when positive results for both samples are ≥ 5 times the quantitation limit. If the laboratory duplicate RPD exceeds the 50, sample preparation techniques (specifically homogenization prior to collection of the raw sample aliquot for drying) will be evaluated and improved, if necessary. 6. PRECISION MEASUREMENTS: The precision of the method is monitored by analyzing samples with target analyte concentrations less than, at or near, and greater than the project action limit. During the beginning phase of the program, after sufficient samples have been collected and analyzed for appropriate selections, one sample from each category will be analyzed in replicate seven times. Statistical analysis of the replicate samples, at each concentration category, will be performed. Statistical analysis includes calculation of the percent relative standard deviation (RSD), the standard deviation (SD), and the mean concentration. For the FPXRF data to be considered precise, the RSD for target analytes should be less than or equal to 20. 10.0 Sample Collection, Preservation and Storage Soil and sediment samples will be collected in press seal plastic bags (Ziploc® or equivalent). Initial homogenization of the sample and removal of non-representative material should take place at the time of sampling. To maintain sample integrity, documentation of all sample locations, dates, times, depth, and associated field sample identification numbers will be recorded in field logbooks at the time of sample collection, On-site sample documentation procedures are presented in the Olin Corporation, Non-Public Properties, Newhall Street Neighborhood, Hamden, Connecticut Site Draft QAPP (August 2009). Samples to be analyzed for lead may be stored at room temperature and have an indefinite shelf life. 11.0 Sample Preparation and Analysis

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11.1 Sample Preparation Soil samples will be collected in plastic bags in the field, and screened with the XRF initially as wet weight samples. The soil samples will be homogenized as thoroughly as possible inside the plastic bag, and a minimum of five readings will be taken for total lead only. Results will be recorded in the field logbook. Field samples are spread out in an aluminum drying pan, clumps are broken up with a stainless steel spatula, and the sample is oven-dried at < 150oC for 2 to 4 hours to remove moisture. After drying, all large organic debris and non-representative material (sticks, twigs, leaves, roots, insects, asphalt, rocks, etc.) are removed and the sample is transferred to a mortar and pestle and ground to a uniform consistency. The dried and ground sample is then sieved through a No. 60 (250 µm) mesh stainless steel sieve. At no time should the material be forced through the sieve. The sieved fraction is collected on a white sheet of paper. Pebbles and organic matter remaining on the sieve should be discarded. The under-sieve fraction of the material constitutes the sample. Fill one XRF sample cup approximately 3/4 full with sample. Cut and tension (wrinkle-free) a piece of mylar film over the top of the cup and seal using the plastic securing ring. Label the sample cups appropriately. The stainless steel sieve and spoons must be wiped clean with a paper towel between sample preparations. 11.2 Sample analysis Analysis of sample, blanks and check standards (SRMs) will be performed using the Innov-X Systems Alpha-4000 instrument and Innov-X Systems Analyzer software. Refer to section 4.0 of the instrument manual for sample analysis using the analyzer software. 11.3 Analysis Sequence

• Install battery in the XRF unit. Battery should remain charging overnight, when the instrument is not in use.

• Install the iPAQ unit on the top of the XRF. Turn on instrument. Allow instrument to warm-up for 1 hour prior to sample analysis.

• Perform the standardization procedure with the standardization clip attached to the front of the analyzer.

• Analyze the initial calibration check using the SRMs provided with the instrument. There are three SRMs (SRM 2709, SRM 2710 and SRM 2711) that will be analyzed. The percent difference (%D) of the calibration check standard must be < ± 20 to continue with analysis. If the %D is greater than 20, the instrument will need to be re-calibrated, per manufactures specifications.

• Analyze the instrument blank (provided with the instrument). There should be no detections greater than the reporting limits.

• Analyze the Method Blank.

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• Analyze 20 samples. • Analyze the Continuing calibration standard (SRM) • Continue analysis of samples, analyzing a continuing calibration sample

after every 20 samples, and a method blank with every batch of 20 samples. A laboratory duplicate sample is analyzed daily.

12.0 Documentation and Reporting Results Sample raw results will be recorded in the field lab log book. The sample raw results will then be evaluated by the field technician for detections above the reporting limit (RL) established for the program (50 mg/kg-dry). Values less than the RL will be reported as “50U”. Analysis results will also be recorded in a Microsoft® Excel spreadsheet for uploading into a database. 13.0 Example Calculations Percent Difference (%D) Known result – Determined result____ X 100 Known result Relative Percent Difference (RPD)

Original result – Duplicate result____ X 100 (Original result + Duplicate result)/2 Standard Deviation (SD) R1 + R2 + R3 + R4 + R5 + R6 + R7

final quality assurance project plan · mpi malcolm pirnie, inc. nist national institute of...

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