RECRA ENVIRONMENTAL, INC. GRAND PATRON

HELPINGTO BRING THE WORLD TO BUFFALO

Chemical and Environmental Analysis Services

THE ERIE COUNTY/EPA WRITE PROGRAM

QUALITY ASSURANCE PROJECT PLAN

ULTRASONIC CLEANING USING A HEATED INORGANIC CLEANING FLUID

PREPARED FOR:

Ue8m ENVIRONMENTAL PROTECTION AGENCY Office of Research and Development

Risk Reduction ~ngineering Laboratory 26 West Martin Luther King Drive

Cincinnati, Ohio 45268

Project Officer: Paul Randall

PREPARED BY:

RECRA ENVIRONMENTAL, INC. Audubon Business Centre

10 Hazelwood Drive Amherst, New York 14228-2298

RE1 Project No. 0C2448

October, 1991

Audubon Business Centre 10 Hazelwood Driv,e Amherst, New York 14228-2298 l (716) 691-2600 . FAX (716) 691-3011

TABLE OF CONTENTS

PAGE

1.0 Project Description ............................. 1

2.0 Analytical Data Quality Assurance Objectives .... 9

3.0 Site Selection and Sampling Procedures.......... 12

4.0 Analytical Procedures and Calibration........... 18

5.0 Data Reduction, Validation & Reporting .......... 20

6.0 Internal Quality Control Checks................. 24

7.0 Performance and Systems Audits.................. 30

8.0 Calculation of Data Quality Indicators.......... 32

9.0 Corrective Action............................... 36

........... 10.0 ~uality Control Reports to Management 38

11.0 - References...................................... 39

QA Plan Distribution List:

Mr. Paul Randall, Project Officer, RREL Mr. Guy Simes, Quality Assurance Officer, RREL Mr. Paul Kranz, P.E., Project Manager, Erie County Dr. Michael E. Ryan, Director, NYS Center for Hazardous Waste Management Ms. Theresa D. Schaab, Project Manager, Recra Environmental, Inc.

Mr. Robert K. Wyeth, Executive Vice President/QA Officer , Recra Environmental, Inc. Mr. Thomas F. stan.czyk, Senior Vice President/Project Principal, Recra Environmental, Inc. Ms. Deborah J. Kinecki, Vice President, Recra Environmental, Inc.

LIBT OF TABLES

Table 1 - Containers, Preservation and Holding Times

LIBT OF FIGURES

Figure 1 - QA Project Plan Organization Chart Figure 2 - Project Schedule Figure 3 - Chain-of-Custody Record Figure 4 - Schematic of Conax's Ultrasonic Cleaning System

Figure 5 - Analytical Report Writing Figure 6 - QA/QC Process

APPENDICES

Appendix A - Sample Bottle Cleaning Protocol Appendix B - Recra Environmental, Inc. Audit Form Appendix C - Analytical Methods 9070 and 9060

1.0 PROJECT DESCRIPTION

The Erie County/EPA WRITE Program Assistance I.D. No.

CR-816762-01-0 was established May 4 , 1990 to implement and

evaluate a minimum of five innovative waste minimization

technologies over a three-year span. As part of that program,

this Quality Assurance Project Plan (QAPjP) has been prepared for

the project entitled: IrUltrasonic Cleaning Using a Heated

Inorganic Cleaning Fluidw.

The implementation of the technology will be completed at

the facilities of Conax Buffalo Corporation (Conax). The study,

evaluation and preparation of the final report will be a joint

effort by Erie County Department of Environment and Planning,

Division of Environmental Compliance Services (ECS), Recra

Environmental, Inc. (RECRA), and the New York State Center for

Hazardous Waste Management (NYSCHWM).

The intent of this project is to determine, for ultrasonic

cleaning, the economic benefits and associated waste volume and

hazards reduction in comparison to freon vapor degreasing of

various stainless steel components. In addition, the impact to

production and product quality will be documented. Conax and

Chautauqua Metal Finishing Supply (CMFS) , manufacturer of the ultrasonic cleaning technology purchased by Conax will

participate in the waste reduction evaluation. Project results

will be tabulated in a final report to be submitted to the EPA

for distribution in the promotion of the implementation of this

waste minimization technology.

1.1 Project Purvose and Objectives

It is the intent of this WRITE Program evaluation to

comparatively analyze the economic advantages of employing an

ultrasonic cleaning system for reducing both the use and

generation of hazardous waste materials associated with

conventional chlorofluorocarbon (CFC) freon usage. The freon

vapor degreasing unit previously employed at the metal shop vapor

degreasing operation will be used for a comparison.

The objectives of the Miraclean aqueous ultrasonic cleaning

system waste reduction evaluation as an alternative to vapor

degreasing using CFCrs are as follows:

o to determine the economics associated with cleaning oil

and dirt from stainless steel components using Conaxrs

ultrasonic cleaning system employing an inorganic

cleaning fluid

o to evaluate the characteristics of any hazardous

materials from Conaxrs ultrasonic cleaning system

o to evaluate the treatment performance of Conaxrs aqueous

ultrasonic cleaning system in phase separating the

surface contamination removed from the stainless steel

components

1.2 Project Orsanization and Res~onsibilitv D N A B V

The Erie County EPA WRITE Program is a cooperative agreement

between the U.S. EPA and the Erie County Department of

Environmental Compliance Services. The organizational structure

for the project is shown in Figure 1. The Project Manager for

the WRITE Program in Erie County is Paul B. Kranz, P.E. His

responsibilities include interfacing with the EPA Project Officer

and coordination of efforts between ECS, Recra Environmental and

the NYS Center for Hazardous Waste Management. In addition, Mr.

Kranz will take a lead role in the economic evaluations of the

waste minimization technologies.

Michael Raab, Deputy Commissioner for the Erie County

Department of Environment and Planning and head of the Environ-

mental Compliance Division, will participate in the program as an

interface with the Industrial Advisory Board. Mr. Raab will also

serve in an advisory capacity with respect to technology

solicitation, selection and evaluation.

Thomas R. Hersey, Assistant Environmental Quality Engineer,

will be involved in the selection, evaluation and implementation

of candidate technologies, and act as a principal contact for

businesses participating with the Erie County/EPA WRITE Program.

The project team members from the New York State Center for

Hazardous Waste Management include Dr. Ralph Rumer, Executive

Director for the Center and Dr. Michael E. Ryan. Dr. Ryan, who

will be the principal project participant from the Center, is the

Director for the Center's Business-Industry Affiliates Program.

He will assist in identifying needs and acquiring potential

technologies for waste minimization for evaluation through the

development of a Roundtable on Source Reduction of Hazardous

Wastes for small to medium-size businesses.

Figure 1

U.S. Environmental Protection A ency

Project ~ f i c e r Paul Randall -

Project Coordinator Thomas Hersey

Technical Advisor Michael Raab

Erie Co./EPA Write Program Project Manager

Paul B. Kranz, P.E.

Conax Facilities Engineer

Joe Frysz

Pro'ect Quality ~ontro/ and Assurance

R. Wyeth

NYSCHWM Technical Assessment

Michael Ryan

Recra Environmental, Inc. Technology Evaluation

Theresa Schaab

Erie County Assistant Engineer Mary Sonntag

Project Principal T.F. Stanczyk

The Erie County/EPA WRITE Program will receive additional

support from Recra Environmental, Inc. for the selection of

candidate technologies through their Environmental Business

Incubator and for the required analytical expertise utilizing

their U.S. EPA CLP laboratories. Theresa D. Schaab is Recra's

Proj ect Manager and Thomas F. Stanczyk, Senior Vice President, will act as the Project Principal. Project Quality Control and

Assurance regarding sample collection and analysis will be

performed by Robert K. Wyeth, Executive Vice President and QA/QC

Officer for Recra Environmental, relative to sampling and

analytical services. Recra Environmental will be responsible for

collection and analysis of any environmental samples obtained

under this project. Deborah J. Kinecki, Vice President, is

responsible for Recra's New York laboratory operations and Brian Fischer, Manager of Field Services, will oversee sampling

activities.

The following descriptions are the quality assurance/quality

control (QA/QC) responsibilities of the individuals involved with

any sampling and analysis performed for the project:

o Recra Project Manaser: The Recra Project Manager is

responsible for:

- Coordinating all project activities, including QA/QC, sampling procedures and schedules, data interpretation

and reporting with Erie County.

- Ensuring that the required analytical instruments, materials and personnel are available.

- Conducting site visits, developing project protocol and QA/QC plan and implementing such with the

assistance of the project personnel.

- Ensuring that documentation on all samples taken is complete and correct and transmitted with the samples

to the analytical laboratory.

- Analyzing and interpreting the analytical results received, verifying the results, and comparing and discussing these results with EPA project officers.

- Preparing and submitting the final report (and other reports as required) to the Erie County Project Manager and EPA Project Officer.

o Recra Analytical Laboratories: The responsibilities of

the analytical laboratories include:

- Verification that all required analytical instruments are functioning properly and are calibrated in

accordance with approved EPA methods.

- Assisting in the design of the project analytical plan and providing advice as to the most appropriate

sampling equipment, containers, etc., to use for field

sampling .

- Implementation of the analytical plan ensuring that all quality control measures are executed as written.

- Reviewing samples and results for questionable data and determining if repeated samples or analyses are

advisable.

- Preparing spikes, duplicates and blanks in accordance with this QAPjP and providing these for analysis along

with the field samples.

o Qualitv Assurance Officers: The EPA RREL Quality

Assurance Officer, Guy Simes and Recra Quality Assurance

Officer, Robert K. Wyeth will advise and assist the

project team and Recra staff in all aspects of QA/QC and

will:

- Assist in developing the QA portion of the project, including the numbers and types of blanks to be run

and frequency of standards, duplicates and spikes.

- Provide information to the project team concerning sample handling, preservation and transportation

procedures.

- Provide QC check samples to the project team, if required, and review all QC data generated.

- Assist in reviewing data for questionable results, making recommendations on the adequacy of results

obtained and verifying that calculations have been

made properly and that no systematic errors occur in

the data.

1.2.1 Industrial Particivant

The industrial participant for the evaluation of the

ultrasonic cleaning technology is Conax Buffalo Corporation, a

medium-sized business located at 2300 Walden Avenue in Buffalo,

New York. Conax is engaged in the design and manufacture of

highly engineered stainless steel components.

1.3 Samvlinq, Laboratory Analysis and Revortinq Bchedule

Sampling, laboratory analysis and data reporting will be

performed under the Technical Evaluation task identified in the

project schedule (Figure 2).

Figure 2 PROJECT TITLE: RECRA ENVIRONMENTAL, INC.

PAGE 1 OF 1 Erie County Conaz QAPjP PROJECT SCHEDULE

DATE October 4.1991

TASK NO. TASK DESCRIPTION

YEAR 1991-1992 MONTHS

I LZ.

JUNE JULY AUG. SEPT. OCT. NOV. DEC. JAN. FEB. MARCH APRIL MAY JUNE JULY I I I I I I I I I I

i 5ii

Project Selection

Rojcct Work Plan Submittal & Approval

Project QAPjP Submittal & Approval

Rojcct Start

Technical & Economic Evaluation

Baft F i Report

Intanal & EPA Review Rcpm

Fml Report Complaion md Submittal

- i

! m :

i i

I i - i

i i :

2.0 ANALYTICAL DATA OUALITY ASSURANCE OBJECTIVES

Analytical methods used for analysis of the ultrasonic

cleaning systemfs wastes follow EPA SW-846 Test Methods for

Evaluating Solid Waste, Physical/Chemical Methods 3rd Edition.

All 3rd Edition SW-846 data will be compliant with method-defined

criteria as well as Chapter 1 and Section 8.0 (of each method)

requirements.

Data quality objectives with regard to Recrafs environmental

testing services are described in terms of accuracy, precision,

completeness, representativeness and comparability. Definitions

of these terms which express data quality are as follows:

o Precision - a measure of mutual agreement among individual measurements of the same property, usually

under prescribed similar conditions. Precision is

expressed in terms of standard deviation. Various

measures of precision exist depending upon the

"prescribed similar conditionsu.

For purposes of this QAPjP, relative percent difference (as

a comparative measure of standard deviation) will be used as a

measure of precision.

o Accuracy - the degree of agreement of a measurement (or an average of measurements of the same property), X,

with an accepted reference or true value, T, usually

expressed as the difference between the two values, X-T,

or the difference as a percentage of the reference or

true value, 100 (X-T)/T, and sometimes expressed as a

ratio, X/T. Accuracy is a measure of the bias in a

system.

For purpose of this QAPjP, the determination will be made as

percent ( % ) recovery of known constituent additions (spikes).

The QA objectives for precision and accuracy, as well as

method detection limits will be consistent with the criteria

specified in the following analytical methods:

- Method 9070 - Oil t Grease - Method 9060 - Total Organic Carbon (TOC)

o Com~leteness - a measure of the amount of valid data obtained from a measurement system compared to the

amount that was expected to be obtained under correct

normal conditions.

Completeness is anticipated to be 80% for this project and

represents the minimum percentage of data which must meet the

accuracy and precision criteria. If not all data meets the

established criteria but any percentage of data greater than or

equal to the completeness criteria, the data for the critical

segment will be deemed to have met the quality assurance

objective of the study.

o Representativeness - expresses the degree to which data accurately and precisely represent a characteristic of a

population, parameter variations at a sampling point, a

process condition, or an environmental condition.

Samples will be collected using SW-846 procedures and

equipment where applicable, to ensure representative samples are

obtained for analysis. Sample collection procedures are defined

in Section 3.0 relating sampling points and sample matrices. Any deviations from the sampling procedures which may affect

representativeness of the samples will be documented and

subsequently reported.

o Com~arabilitv - expresses the confidence with which one data set can be compared to another.

I

3.0 BITE BELECTION AND BAMPLING PROCEDURES

All wastes generated ,from the Ultrasonic Cleaning System are

anticipated to be non-hazardous materials, based on the MSDSs for

the coolant and cutting oils used for machining, and on the MSDS

for the silicate cleaner. However, in order to evaluate the

performance of the cleaning system in phase separation of the

contaminants removed from the stainless steel components, various

samples will be collected for analysis.

The sampling and analysis program will be conducted on

1) the non-hazardous waste concentrate, and 2) wastewater from

the rinse tank. The analyses will include two parameters; oil

and grease, and TOC (Total Organic Carbon). These two parameters

were selected as indicators of potential soluble pollutants.

The Ultrasonic Cleaning System employed at Conax is depicted

in Figure 3. Sampling procedures will be conducted as follows:

a. ULTRASONIC CLEANING TANK: waste concentrate

Within the cleaning tank, a sodium metasilicate cleaning

agent (Metex TS-40-A, MacDermid, Inc.) is utilized at roughly 8%

concentration to enhance the ultrasonic cleaning effectiveness.

A MacDermid Alkaline Test Kit, which measures concentration in

ounces of solution per gallon of water, will be utilized by Conax

personnel to indicate the bath concentration during production.

Concentrated cleaning agent and make-up water will be added to

the tank, as necessary, to maintain this desired bath

concentration. Based on the suppliers' recommendation, when the

amount of concentrated cleaning agent required for maintaining

the system is equivalent to the amount originally added to the

system, the bath is considered waste, and will be changed. When

the cleaning tank bath is changed, the entire tank contents (200

gallons) will be pumped via a portable vacuum pump into four (4)

55-gallon drums. A composite liquid sample will be obtained from

FIGURE 3

CONAX'S MIRACLEAN SYSTEM SCHEMATIC

HOT RINSE COUNTERELOW RENSE ULTRASONIC CLEAN 180°F AMB AMB 150 - 180'~

WATER TO ORA l N

the four drums using an open tube sampler (theif). This sampler

is basically a hollow glass tube which is about four to five feet

in length. It generally has an inside diameter of 1/411 to 1/2",

depending on the viscosity of the liquid to be sampled.

Procedures for Use:

1. Insert the sampler into the material to be sampled to

the depth desired.

2. Place gloved thumb securely over open end of tube and

carefully'withdraw the sampler.

3. Transfer sample into laboratory-cleaned sample bottles

and follow procedures for preservation and transport.

Two (2) 1-liter glass jars will be completely filled for the

samples collected.

b. OVERFLOW RINSE TANK: rinsewater

The counterflow rinse (CFR) tanks utilized in the ultrasonic

cleaning system operate on a flow through basis. Water at room

temperature, is introduced into the second CFR tank and overflows

into the first CFR tank at a rate of three (3) gallons per

minute. The overflow from this tank is directed to the sewer

discharge lines.

The rinse water will be sampled at the discharge point of

the first CFR tank for analysis. This liquid sample will be

obtained using an open tube sampler, as described above. Two (2)

1-liter jars will be completely filled for the samples collected.

Sample bottles will be purchased new from Eagle Picher and

have been cleaned according to the protocols identified in

Appendix B. The samples collected will be preserved in

accordance with U.S. EPA protocols before any critical

measurements. The containers, preservation and holding times

prior to instrumental analysis are summarized in Table 1.

Parameter

Method 9070

Oil & Grease

Table 1

CONTAINERS, PRESERVATION & HOLDING TIMES

Container Preservation Holdina Time

Glass Cool, 4Oc 28 Days

PH <2t/H2S04

Method 9060 Glass, Amber Cool, 4Oc

Total Organic Teflon-lined pH <2,/HC1

Carbon cap or plastic

28 Days

Product Quality Standards for parts cleanliness set by Conax

will be maintained throughout the waste reduction evalution.

These standards are qualitative, not quantitative, and thus

cannot be measured analytically. This WRITE Program evaluation

will therefore depend on Conax personnel for their qualitative

measurement of product cleanliness, as follows:

o Products which have been cleaned using either the freon

vapor degreasing unit or aqueous ultrasonic cleaning

system are visually inspected in the Quality

Department's Final Inspection Area.

o Cleaned parts may contain no visual residues or white

powder in order to pass inspection. They must be

completely dry.

o Parts which do not pass final quality inspection must be

returned to the finishing department and be re-cleaned.

3.1 Chain-of-Custodv Procedures

A Chain-of-Custody Form (Figure 4) will be maintained for

all analytical samples and will accompany the samples from

collection to delivery to the laboratory. At a minimum, the

Chain-of-Custody manifest will include the following:

Site name

Sample I.D. number

Sample type (e.g. water, soil, or sludge)

Date and time of collection

Parameters for which analyses are requested

Signature of sample collection personnel

Signature of persons involved in the chain-of-custody

Condition of samples upon arrival at laboratory

To assure proper identification and sample control in the

laboratory, all analytical samples will be labeled in a clear and

consistent manner. Waterproof sample labels will be fixed to each

sample container and marked with a unique label identification

number in indelible ink. All sample containers or containers of

any style will be sealed with chain-of-custody tape. Care will

be exercised to minimize potential for sample cross-contamination

subsequent to collection and limit the possibility of breakage.

Custody of the samples is defined as actual physical

possession, in view after physical possession, or locked and/or

sealed in a tamper resistant container after physical possession.

At the time of custody transfer, the individual relinquishing the

samples shall observe as the transferee inspects the samples for

integrity and number, and dates and signs the chain-of-custody

manifest. A signed copy of the manifest will be returned to

Recra project personnel once the samples are delivered to'the

laboratory. It is anticipated that all sample analysis will be

performed by Recra Environmental, Inc. at the analytical

laboratories in Tonawanda, New York.

RECRA ENVIRONMENTAL, INC.

The sample tracking process begins once a sample or set of

samples is received and an analytical service request form (ASRF)

is completed by the Sample Controller. Then the original ASRF is

transferred to the Sample Controller and the samples are logged

into the sample inventory log. The original ASRF is stapled to

any Chain of Custody forms or paper work that accompanied the

samples. At this point several copies of the original ASRF are

made and distributed to the following areas as appropriate:

- Laboratory Operations Manager - Customer Service

Representative

- Inorganic Manager - Organic Manager - GC/MS Supervisor - GC Supervisor - Metals Supervisor

- Laboratory Director - Analytical Program Manager - Waste Laboratory Supervisor - Sample Controller - Accounting - Project Manager (s) - Field Services Manager - Central File

The original ASRF, sign-off form and accompanying paperwork

is placed in the job folder located in the Laboratory Operations

Manager s Off ice. Regularly scheduled meetings are held between

the Laboratory Operation's Manager, Area Supervisors, Analytical

Program Manager and the Customer Service Representative. The

Laboratory Operations Manager sets priorities and defines

completion schedules to the supervisors when conflicts occur

while the Customer Service Representative provides any input and

special requests from the client. Individual analysts review and

initial results of their work and submit these to the Department

Supervisor/Manager for review. Individual department managers

provide raw data to the Analytical Project Managers for

calculation and subsequent review. Completion dates for tasks

are entered into the laboratory computer on a daily basis.

4.0 ANALYTICAL PROCEDURES AND CALIBRATION

The analytical procedures proposed for use in this project are from the:

3rd Edition SW-846, Test Methods for Evaluating Solid

Wastes; Laboratory Manual, Physical/Chemical Methods;

September 1986:

Determination of organic analytes:

o Method 9060 Total Organic Carbon

o Method 9070 Total Recoverable Oil and Grease

(Gravimetric, Separatory Funnel Extraction)

Total Orqanic Carbon Method 9060

Organic carbon is measured using a carbonaceous analyzer.

This instrument converts the organic carbon in a sample to carbon

dioxide (COZ) by either catalytic combustion or wet chemical

oxidation. The C02 formed is then either measured directly by an

infrared detector or converted to methane (CH4) and measured by a

flame ionizer detector. The amount of C02 or CH4 in a sample is

directly proportional to the concentration of carbonaceous

material in the sample.

Carbonaceous analyzers are capable of measuring all forms of

carbon in a sample. However, because of various properties of

carbon-containing compounds in liquid samples, the manner of

preliminary sample treatment as well as the instrument settings

will determine which forms of carbon are actually measured.

Carbonate and bicarbonate are inorganic forms of carbon and

must be separated from the total organic carbon value. Depending

on the instrument manufacturer s instructions, this separation

can be accomplished by either a simple mathematical subtraction,

or by removing the carbonate and bicarbonate by converting them

to C02 with degassing prior to analysis. Recra will utilize the

latter separation technique.

Total Recoverable oil and Grease Method 9070

To analyze for total recoverable oil and grease, the sample

is acidified to a low pH (2) and serially extracted with

fluorocarbon-113 in a separatory funnel. The solvent is

evaporated from the extract and the residue is weighed.

Calibration procedures and frequencies are specified within

the cited methodologies. All other equipment will be calibrated

daily consistent with use. Balances, ovens and other equipment

are also monitored daily, consistent with requirements of

maintaining Recrafs laboratory certification with New York State

Department of Health, Department of Environmental Conservation,

and other such state and federal agencies.

5 . 0 DATA REDUCTION, VALIDATION AND REPORTING

All analytical results generated by Recra's laboratories are

reviewed for accuracy, precision and completeness, as well as

compliance with other specific contract or method requirements.

The analyst has prime responsibility and accountability for

the correctness and completion of his/her data. Each laboratory

analyst has responsibility for QA/QC functions at their level and

within their assigned tasks. The reduction of data, its

validation and the ultimate reporting of results is aided greatly

by automated data management systems throughout the laboratories.

Figure 5 illustrates schematically, the automatic organic and

inorganic data routines and generalizes the Report Writing

activities. More specifically, the QA/QC function is

schematically provided in Figure 6. Initial review by the

analyst is completed in relation to compliance with methodology

and acceptability of precision and accuracy results. Review at

the supervisor/manager level includes these above elements plus

data acceptability relative to trends in precision and accuracy,

verification of calibration, compilation and comparison of

findings within each department (i.e., metals data collectively

as opposed to on an elemental basis). It is at this level of

operations, that the "piecesw of the report are initially

collected for submission by department heads to the analytical

report writing department. Tertiary review occurs at the

Laboratory administration level with input as required from the

Corporate or facility QA officer.

Figure 5

ANALYTICAL REPORT WRITING

Final Product u

F i g u r e 6

QA/QC PROCESS

WATER r

QUALITY GC METALS G C M DATA DATA DATA DATA

I

( ANALYST REnEw 1 RE-*NbLYSIS I REQUIRED

SUPERVISOR1 MANAGER

I HARDCOPY I

, T 1

OR I DlSKE'ITE I TO CLIENT

ANALYTIAL PROJECT

MANAGER .

+,. COPY

REPORT PREPARATION

Generally, for any and all measurement systems at Recra, the

following chronological steps are adhered to at one or more

levels of the review process:

sample receipt;

sample logging, inventory, chain-of-custody;

sample splitting and preservation (if and/or required);

sample storage;

sample preparation (extraction and/or digestion);

sample analysis (standard, QC and samples);

data calculation;

data reporting (internal);

data review/QC logging;

re-analysis (if and when required) and assessment;

report preparation;

report review/final QC review;

report issuance/central file maintenance;

sample archival and/or disposal.

The specific means by which each group processes this data

is in general agreement with the above steps but is more

specifically outlined below.

6.0 INTERNAL OUALITY CONTROL CHECKS

As previously described, steps are taken by Recra to ensure

the quality of analytical results. Measures such as proper

sampling techniques; appropriately cleaned sample bottles (or

purchased as "certified cleanw); proper sample identification and

logging; applicable sample preservation; storage and analysis;

and use of controlled materials, standards reagents or solvents

all contribute to maintenance of overall laboratory control.

The quality control program in effect at Recra Environmental

Laboratories is based principally upon recommendations contained

in the EPA Handbook for Analytical Oualitv Control in Water and

Wastewater Laboratories (March 1979), 600/4-79-019.

Internal quality control checks will consist of several

methods including blanks, replicates and spike samples.

An analyst must always be aware of the potential problems

associated with contamination of glassware, reagents, solvents,

etc. The method used to monitor possible contamination problems

is the analysis of blanks. There are generally five (5) types of

blanks that are routinely analyzed.

o Method Blanks

The method blank which consists of analyzing deionized

water in exactly the same fashion as a sample. This

type of blank points out problems, such as contaminated

glassware and reagents. A method blank is performed

with each set of analyses in the laboratory regardless

of the number of samples in the set.

o Reagent/Solvent Blanks

A second type of blank is a reagent/solvent blank which

is utilized to check the purity of the new batches or

lots of reagents or solvents. This type of blank is performed as necessary.

o Trip Blanks

The primary purpose of this type of blank is to detect

possible sources of contamination of samples in the

field during collection, transportation to, or while in

storage in the laboratory. A trip blank consists of a

set of sample bottles filled at the laboratory with

laboratory demonstrated analyte-free water. Trip blanks

will be handled, transported and analyzed in the same

manner as samples acquired that day, except that the

sample containers are not opened in the field. Rather,

they just travel with the sample collector. Trip blanks

will accompany samples at a rate of one per sampling

event when volatile organics are being analyzed.

o Holding Blanks

The primary purpose of this blank is similar to that of

a trip blank but is specific to identifying the source

of cross-contamination, should such contamination be

found to exist. That is, cross-contamination developed

as a result of storage at the laboratory or unrelated to

field activities or transport of samples to the

laboratory.

o Field Blanks

The primary purpose of this type of blank is to provide

an additional check on possible sources of contamination

beyond that which is intended for trip blanks. A field

blank is used to indicate potential contamination from

ambient air and from sampling instruments used to

collect and transfer samples from point of collection

into sample containers. Since no reusable sampling

equipment (disposable theifs) will be used, no field

blanks are proposed.

Other QC Samples include:

o Replicates

Collection of field replicate samples will provide for

the evaluation of the sampling procedures8 performance

by comparing analytical results of two samples from the

same location. Replicate samples will be included for

each matrix at a minimum rate of 10 percent (10%).

o Matrix Spikes/Matrix Spike Duplicates

As specified in 3rd Edition SW-846 Chapter 1, and in the

individual 3rd Edition Analytical Methods, a minimum of

5% matrix spikes and 5% matrix spike duplicates of

samples analyzed will be prepared by spiking with known

amounts of the compounds being analyzed or method

surrogates. The amount of compound recovered from the

samples compared to the amount added is expressed as

percent recovery.

6.1 Standard Reference Materials (SRM1s)

Standard Reference Materials (SRM1s) are used for all

applicable analysis. Sources of SRMfs include the US

Environmental Protection Agency, commercially available material

from EPA and/or laboratory produced solutions (spiked blanks,

project specific compounds). SRM1s are processed and analyzed on

a frequency of one (1) per set of samples, regardless.of the

number of samples in a set.

6.1.1 Standard Solutions

Stock and working standard solutions and separate spiking

solutions are prepared from materials supplied by the USEPA

repository or purchased from commercially available sources.

Standard curves are generated and/or verified daily for all

organic procedures as opposed to simply verifying "working

standard curvew. Standard curves are produced once per working

shift/day and/or are verified by re-analysis of mid-range

standards at least every tenth sample. Standard curves are also

reviewed for consistency to help identify problems that could be

associated with the applicable instruments and/or the standard

solutions.

6.2 Laboratory Reaqent Ouality

The quality of reagents used in conducting analytical

determinations is continuously monitored by the laboratory staff.

All standards and reagents are prepared with chemicals that meet

the American Chemical Society "Analytical Reagent Gradew

standards. Special reagents are utilized for procedures which

require purity beyond reagent grade. For example, nitric acid

which is specially prepared to be low in trace metals is utilized

as a preservation reag-ent and for metals digestion.

All reagent solutions are labeled as to their content, date

prepared, and the analyst's initials. In addition to analyzing

method blanks to check for reagent contamination, the reagents

are continuously observed for signs of degradation, such as

precipitation, change in color, or mold formation.' Unstable J

reagents, such as various titrants, are standardizeB each day I.

they are used. vr~ .&, - .L

4: f- C

6.3 Laboratory Water I 1

.'-

The laboratory water used for making reagents and rinsing of

glassware is constantly monitored by an in-line meter to meet and exceed the electrical conductivity requirements of TYPE I water

described in the EPA Quality Control Handbook, March 1979.

6.4 Bolvents -- - L .

All laboratory solvents utilized for sample extr~dtions are

minimally pesticide grade. Solvents are checked for ~ ? i t y on a

continuing basis for compounds which may interfere5%ith the 4- ,+ specific analysis being performed. L. .-, 1

6 . 5 Gases < l.- k

Gases used for chromatographic procedures are hig*'pu~i!y or 1

ultra high purity and equipped with in-line s~rubbers?~td"2'emove -%:

trace constituents. These scrubbers take the fordkf oxygen

traps, molecular sieves, and moisture traps. Each is dseful for

specific applications in gas chromatography.' Various

combinations of the above scrubbers are employed depending8'%n the ... , .,

L . particular instrument requirements.

6.6 Laboratory Glassware

Whenever possible, disposable glassware is employed to

reduce the possibility of cross-contamination of samples. Glassware used for metals analyses is cleaned as follows:

1. Glassware is rinsed with a 1:l nitric acid-water mixture

2. Thorough rinsing with tap water

3 . Final rinsing is accomplished with copious quantities of

deionized water

Glassware for extractable organics is cleaned according to

the following procedure:

1. Rinsed with last solvent used

2. Rinsed with reagent grade acetone

3. Tap water rinsed

4. Detergent washed

5. Tap water rinsed

6. Nitric acid rinsed (25% v/v)

7. Deionized water rinsed

8. Rinsed with reagent grade acetone

9. Rinsed with pesticide grade hexane

Internal quality control checks include analysis of blanks

used to validate successful glassware cleaning activities . The

frequency of this activity is monthly or more frequent if

required by methodology or contract.

7.0 PERFORMANCE AND SYSTEMS AUDITS

By NEIC definition, an audit is a systematic check to

determine the quality of operation of some function of activity.

Audits are further defined as being of two basic types;

performance and system audits.

A performance audit is one in which quantitative or

qualitative data is independently obtained for comparison with

routinely obtained data from a measurement system. Performance

audits are completed at Recra Environmental, Inc. via a number of

mechanisms including the New York State Department of Health

Laboratory Certification Program as well as the analysis of EPA

check samples and EPA's quality assurance check sample program.

The New York State Department of Health (NYSDOH) samples are

analyzed for all drinking water parameters on a semi-annual

basis. Recra Environmental, Inc, is currently certified by the

NYSDOH for the determination of metals and metaloids in potable

water, the wet chemical examination of potable water and the

determination of volatile organic halogens in potable water.

Also the commercially available check samples and/or the EPA

check samples are processed through the laboratory each month per

department. The routine use of all available applicable SRMJs

also provides for a more or less continuous performance audit.

Systems audits, as opposed to performance audits, are

strictly qualitative and consist of an on-site review of a

laboratory's quality assurance system and physical facilities for

calibration and measurement. System audits are routinely

performed (approximately once per year) by the New York State

Department of Conservation (NYSDEC), DOH and EPA as element of

our participation in their certification programs. The New York

State Department of Environmental Conservation has also audited

our facility on numerous occasions relative to our analytical

services contracts and our New York State Superfund contract.

The New York State Depar,tment of Environmental Conservation

personnel are also anticipated as being the initiators of

additional audits as a part of their management of the Superfund

program. Additionally, detailed internal audits are performed on

a semi-annual basis by the Corporate Quality Assurance Officer.

On an annual basis, or as required by contracts held by Recra,

system audits of subcontractor laboratories are performed by the

Corporate Quality Assurance Officer in order to assure quality

data from the subcontractors whose data is ultimately reported

with results obtained by the Recra laboratories. Health and

Safety audits are also performed by the Corporation's Internal

Environmental Health and Safety Officer. A copy of the Recra

Environmental, Inc. audit form is attached as Appendix B.

Internal, as well as subcontractor audit results, are

maintained in a permanent file. The findings of these audits are submitted to the Laboratory Director or the subcontractor

laboratory. Necessary corrective action based upon these audits

are responded to in writing and are also maintained in a

permanent file.

8.0 CALCULATION OF DATA OUALITY INDICATORB

Most routine QA procedures are based on the particular

methodology being used for the specific analyses. These

procedures include determination/maintenance of standard response

and linearity, instrument tuning, internal standard responses,

surrogate recoveries in blanks and samples, spike recoveries and

replicate precision. Many of the QA criteria are method based

and decisions as to corrective action in the form of re-analysis

are made by the analyst. Surrogate, internal standard and spike

recoveries are routinely plotted on control charts so that more

subtle trends in data quality can also be monitored and

appropriate and timely corrective action taken.

As a part of Recra Environmental, Inc.'s routine quality

assurance/qual ity control program, the following information is

generated:

o Precision

Precision will be determined by the analysis of

replicate samples, and if three (3) or more values are

determined, will be expressed as the standard deviation, s,

which is determined by the following equation:

where s = standard deviation

x = individual measurement result

N~ = number of measurements

Relative standard deviation may also be reported. If

so, it will be calculated as follows:

S RSD = 100 - x

where RSD = relative standard deviation, expressed in

percent

S = standard deviation

X = arithmetic mean of replicate measurement

If only two values are determined, precision will be

estimated by calculation of relative percent difference

(relative range) by the following equation:

(Dl - Dp) 100 RPD =

+ D2)'2

where RPD = relative percent difference

Dl = the larger of the two observed values

D2 = the smaller of the two observed values

o Accuracy

Accuracy will be estimated from the analysis of QC

samples whose true values are known, surrogate spike

recoveries, or matrix spike recoveries. Accuracy will be

expressed as percentage recovery. The formulas to calculate

these values are:

For QC samples:

measured value Percent wcovery = 100 ( true )

For surrogate spikes:

measured value Percent recovery = 100 ( spiked 1

For matrix spikes:

Ci - C, Percent recovery = 100 t

Where Co = value of unspiked aliquot

Ci = value of spike aliquot

Ct = value for spike added

o Completeness

Completeness will be reported as the percentage of all

measurements made whose results are judged to be valid. The

following formula will be used to estimate completeness:

Where C = percent completeness

V = number of measurements judged valid

T = total number of measurements

o Method Detection Limit (MDL)

This approach for determining MDL and method

quantitation limit (MQL) is taken from Chapter 1 of SW-846

(3rd Ed. ) .

The detection and quantification limits of analytes will

be evaluated by determining the noise level for each

analyte. If analyte is present, the noise level adjacent in

retention time to the analyte peak may be used. The method

of standard additions will then be used to determine the

calibration curve for the extracted sample in which the

analyte was not detected. The slope of the calibration

curve, m, should be used to calculate MDL and MQL by using

the following:

m = slope of calibration line

SB = standard deviation of the average noise level

MDL (MQL) = KSB/m

For K = 3; MDL = method detection limit

For K = 5; MQL = method quantitation limit

The methods given in SW-846 (3rd Ed.) provide MDLts and

practical quantitation limits (PQLs) for the waste matrices.

CORRECTIVE ACTION

If a particular analysis is deemed "out of controlw

corrective action must be taken to ensure data quality. An

analyst that obtains a value that fails to meet the method

criteria for accuracy or precision will notify the supervisor of

the applicable analytical section.

The following presents a number of corrective actions which

may be employed, depending upon the particular situations.

a. Calculations are re-checked.

b. Sample handling; digestion, concentration, and/or

extraction logs are checked for discrepancies in sample

handling.

c. Analyte concentration is reviewed to determine if it has

severely influenced the reliability of the precision or

recovery calculations.

d. Instrument and method performance is verified by

inspecting data on standard reference materials

processed in the same data set.

e. Quality control data on the other samples in the data

set, including surrogate recovery, internal standards,

etc. are reviewed to determine if the problem is method

related or sample related.

f. If original sample is available, the sample is assessed

for homogeneity.

g. If sample is unavailable and no explanation for poor

quality control results can be determined, the client

is notified and additional sample is obtained. If

additional sample is unavailable, the results are

issued with a qualification as to their accuracy.

The coordinator of each analytical section is responsible

for initiating corrective action when necessary. The Laboratory

Operation's Vice President, Ms. Deborah J. Kinecki, is

responsible for approving the appropriate corrective action.

1 0 . 0 DUALITY ASSURANCE REPORTS TO m A G E M E N T

Critically important to the successful implementation of the

QA Plan is the reporting system which provides the means by which

the program can be reviewed, problems identified and programmatic

changes made to remediate or improve the plan. Quality Assurance

reports to management take a number of forms as follows:

o Audit reports, internal and external audits with responses

o Performance evaluation sample results; internal and

external sources

o Daily QA/QC exception reports; corrective actions

o QA charts (trend analyses)

QA/QC exceptions reports are presented to laboratory

management personnel so that performance criteria can be

monitored on a daily basis for all analysis from each analytical

department. The trend/QA charts are also distributed at least

monthly and reviewed by various levels of laboratory management as well as the QA Officer.

In the project summary report, a separate QA section will

summarize the data quality information obtained during the tests.

Reports presenting analytical data will also summarize any

quality assurance data generated during the reporting period.

The quality assurance section of the final report will include:

o A data quality statement for precision

o A data quality statement for accuracy

o A discussion of QA objectives that were met and not met

o If QA objectives were not met, a discussion of the

impact to the project for not having met them

11.0 REFERENCE8

1. U.S. Environmental Protection Agency Manual, "Chemical

Analysis of Water and Wastesff, EPA-600/4/79-020 Revised

March 1983.

2. U.S. Environmental Protection Agency "Guidelines

Establishing Test Procedures for the Analysis of Pollutants

Under the Clean Water Actft, 40 CFR Part 136, October 1984.

3. U.S. Environmental Protection Agency "Pesticide Residue

Analysis in Water", EPA-430/1-76-015, November 1976.

4. U.S. Environmental Protection Agency "Test Methods for

Evaluating Solid Waste - Physical/Chemical Methodsw, SW-846, 3rd Edition, September 1986.

5. U . S . Environmental Protect ion Agency ##Interim Methods for the Sampling and Analysis of Priority Pollutants in Sediment

and Fish TissueH, EPA-600/4-81-055, August 1977, Revised

October 1980.

6. U. S . Environmental Protection Agency Itchemistry Laboratory Manual for Bottom Sediments and Elutriate TestingN, PB-294

596, March 1979.

7. U.S. Environmental Protection Agency ttExtraction and

Analysis of Priority Pollutants in Sediment and Soilu, PPS-

10/83 Analytical Support Branch USEPA, Athens, Georgia.

APPENDIX A

SAMPLE BOTTLE CLEANING PROTOCOL

LEVEL I1 CERTIFICATION

Eagle-Picher Level I1 bottles have been washed in conjunction with the procedures set by the EPA for quality-controlled sample containers.

WASH PROCEDURE B (Glass Bottles)

1. Vials, septa and caps washed in laboratory-grade, non-phosphate detergent.

2. Rinsed three times with distilled water.

3. Rinsed three times with ASTM-Type 1 organic-free water.

4. Oven-dried for one hour.

Verified by: A @

LEVEL I1 CERTIFICATION

Eagle-Picher Level I1 bottles have been washed in conjunction with the procedures set by the EPA for quality-controlled sample containers.

WASH PROCEDURE C (Plastic Bottles)

1. Bottles, liners and caps washed in laboratory-grade, non-phosphate detergent.

2. Rinsed three times with distilled water.

3. Rinsed with with 1:l nitric acid.

4. Rinsed three times with ASTM-Type 1 organic-free water.

4. Air-dried.

Verified by: ~ ~ ~ ! & ! @

, APPENDIX B

RECRA ENVIRONMENTAL, INC. AUDIT FORM

Page 1 o f 11

RECRA ENVIRONMENTAL. INC . LABORATORY AUDIT

Laboratory:

Type o f Eva lua t ion :

Evaluator ; Date:

Personnel Contacted .

A u d i t Sumury C r n t s and O b s e r v a t i o n s ~

T i t l e -

p a g e 2 o f 11

RECRA E ~ V IRONMENTAL, INC. LABORATORY AUDIT

I. ORGANIZATION AND PERSONNEL

ITEM R A T I N G ( C i r c l e One)

Laboratory Manager ( i n d i v i d u a l responsible f o r 0 1 2 3 4 o v e r a l l t echn i ca l e f f o r t .

Do personnel have the appropr ia te educational 0 1 2 3 4 background?

Do personnel have the appropr la te l e v e l and 0 1 2 3 4 type o f exper ience?

I s the l abo ra to r y adequately s ta f f ed t o meet 0 1 2 3 4 comnltments i n a t i m e l y manner?

RAT 1% TOTAL ;

C o m n t s and Observat ions;

I . F A C I L I T I E S AND EQUIP1CNT

I l 'EM RATING ( C i r c l e One\

Does the l a b o r a t o r y have a source o f distilled/ 0 1 2 3 4 d m 1 nera l i zed water?

Is the conduc t i v i t y . o f d i s t l l led/demlneral i z e d 0 1 2 3 4 water rou tl ne l y checked and recorded?

Are exhaust hoods p rov ided t o a1 l o w e f f f c i e n t 0 1 2 3 4 worlt wi t h v o l a t i l e ma te r i a l s?

Page 3 o f 11

RECRA ENVIRONMENTAL, INC . . LABORATORY AUDIT

I I. F A C I L I T I E S AND EQUIPMENT (con t inued)

I s the l abo ra to r y ~ i n t a i n t d i n a c lean and organized manner?

Are contaminat i .on-free work areas p rov ided f o r the hand1 f ng o f t o x i c m a t e r i a l s?

Are the t o x i c chemical hand l ing areas e i t h e r a s t a i n l e s s s tee l bench o r an impervious ma te r i a l covered w i t h absorbent m a t e r i a l ?

Are adequate fac i 1 i t i e s prov ided f o r separate s torage o f sampl es, e x t r a c t s , and standards, i n c l u d i n g c o l d s torage?

I s the temperature of t he c o l d s torage u n l t s recorded d a i l y I n 1 ogbooks?

Are chemical waste d isposa l p o l ic ies/procedures adequate?

Can the 1 aboratory document t h a t t r a c e - f ree water i s a v a i l a b l e f o r p repa ra t i on o f standards and b l anks?

Do adequate procedures e x l s t f o r d lsposa l of waste 1 i q u l d ?

I s the l abo ra to r y secure?

RATING TOTAL ;

R A T I N G ( C i r c l e Onel

C m n t s and bbsewa t l ons ;

Page 4 o f 11

RECRA ENVIRONMENTAL, INC. LABORATORY AUDIT

11. FACILITIES AND EQUIPMNf (con t inued)

0 . Equipment

ITEM

Are manufacturer 's opera t ing manuals r e a d l l y a v a i l a b l e t o the opera to r?

Is the re a c a l l b r a t i o n p ro toco l a v a i l a b l e t o tne opera t o r ?

Are c a l i b r a t i o n r e s u l t s k e p t i n a permanent record?

I s a permanent se rv i ce record m f n t a f n e d I n a logbook?

I s a1 1 necessary major i n s t r u m n t a t i o n ava i l ab le?

I s i n s t r u m n t a t i o n adequate t o hand1 e work1 oad?

RAT ING TOTAL ;

R A T I N G ( C i r c l e 9ner

0 1 2 3 4

C m n t s and O b s e r v r t l o n s ~

Page 5 o f i l

RECRA ENV IRONMENTAL, INC . LABOR AT ORY AUO I T

111. DOCUMENTATION

A. Documents t ion/Track i n 3

ITEM

I s a sample custodian designated?

Are the sample cus tod ian 's procedures and responsibi 1 i t i e s documented?

Recording a l l p e r t i n e n t in format ion i n sample check-in logbook; i , e . ;

o Condit ion o f custody seal

o cond i t i on o f samples received

o conta iners received

o sanple identification and v e r i f i c a t i o n of sample tag in format ion against custody records

o d i screpanc i t s noted

o custodian dates and sfgns logbook when e n t r i e s are conpleted

Generates labora tory ch in -o f - cus tody fo r each case number and asslgns 1.0. numer?

Are w r i t t e n Standard Oper r t l n Procedures ( SOP) S developed f o r r e c e l p t o f srmp es? If yes, m e r e are the SOP documnted ( 1 aboratory, manual, w r i t t e n l n s t t u c t l o n s , e t c ? )

Are qua1 f ty rssur rnce procedures documented and ava i l ab le to the r n r l y s t s ? If yes, where are these d o c u r n w ?

Are w r i t t e n S t r n d r r d Oper r t lng Procedures ( SOP) developed f o r cocnpillng and m i n t a i n i n g sanrple document f i 1 es?

Are the magnetic tapes stored I n a secure area? Back-up tape capabf 1 I t l e s ?

RATING ( C i r c l e One)

0 1 2 3 4

fb RATING TOTAL:

Page 6 o f 11

RECRA ENVIRONMENTAL, INC . LABORATORY AUD I T

1 . DOCUMENTATION (cont inued)

B. Documn t a t i on/Notebook s

ITEM

IS a ptfmanently bound notebook w i t h p repr in ted consecut ively nunbered pages being used?

I s the type of work c l e a r l y d isp layed on the notebook?

I s the notebook m i n t a i n e d i n a l e g i b l e manner?

Are e n t r i e s no t i ng anomalies r o u t i n e l y recorded?

Has the ana lys t avoided obl f t e r a t f ng en t r i es?

Has the supervisor o f the i nd fv idua l mainta in ing the notebook persona l ly examf n ta and reviewed the notebook p t t i o d i c a l l y , and signed h i s / h t r name therein, together w i t h the date and appropr fate conments as t o whether o r no t the notebook i s being maintained i n an appropr iate manner?

Are proper nunbering/I.D. codes assigned t o case f i l e t o p rov ide documnt accountabi l i t y ?

I s con f i den t i a l i t y of data understood and maintained?

RATING ( C i r c l e n n e )

0 1 2 3 4

RATING TOTAL ; -- -- --

Com#nts and bbsewat lons ;

Page 7 o f 11

RECRA EN.V IRONMENTAL, INC . LAEORATORY AUO I T

I V . A N A L Y T I C A L METHODOLOGY

I T E M R A T I N G ( C i r c l e One)

Are the requ i red methods used?

A re w r i t t e n a n a l y t i c a l procedures p r o v i ded t o the analyst?

Are reagent grade o r h igher p u r i t y chemicals used t o prepare standards?

Are f resh a n a l y t i c a l standards prepared a t a frequency cons i s ten t w i t h good QA?

I s a Standards prepara t ion and t rack ing logbook maintained?

00 the ana lys ts record bench data i n a neat and accurate manner?

I s the appropriate ins t rumtn ta t f on used I n accordance w i t h the requ i red pro toco l ( s I ?

RATIMG TOTAL;

Comnnts and O b s e r v r t l o n s ~

RECRA ENVIRONMENTAL, INC. LABORATORY AUDIT

Page 8 o f 11

V . OUAL I T Y CONTROL MANUAL CHECKLIST

ITEM RATING ( C i r c l e One)

Does the l a b o r a t o r y ma in ta ln a Qua1 1 ty Cont ro l 0 1 2 3 4 Manual ?

Does the manual address the impor tan t elements 0 1 2 3 4 o f a QC program?

Are QJC respons ib i 1 i t f e s and r e p o r t i n g re1 a t l o n - 0 1 2 3 4 ships c l e a r l y def lned?

Have standard curves been adequately documnted? 0 1 2 3 4

Are 1 abora t o r y standards t raceab l e? 0 1 2 3 4

Are qua1 l t y c o n t r o l c h a r t s ma ln t r l ned f o r each 0 1 2 3 4 . r o u t l n e ana l ys i s?

Do s u p t r v l sory personnel rev iew the d r t a and 0 1 2 3 4 QC resu l t s?

Are c o r r e c t i v e a c t i o n procedures I n p lace? 0 1 2 3 4

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - - - - - - - - - - - - - - - - - - - RAT I NG TOTAL ;

C o m n t s and Observat ions;

RECRA ENVIRONMENTAL, INC. LABORATORY AUDIT

V I . DATA HANDLING CHECKLIST

ITEM

Are data c a l c u l a t i o n s checked by a second person?

P a g e 9 - o f 11.

R A T I Y G ( C i r c l e One)

Are data c a l c u i a t i o n s documented? 0 1 2 3 4

Do records i n d i c a t e C o r r t c t i v e a c t i o n t h a t has 0 1 2 3 4 been taken on r e j e c t e d data?

Are l i m f t s of. d e t e c t i o n determined and repo r t ed p rope r l y?

Are qua1 4 t y c o n t r o l da ta (e.g., s tandard curve, r e s u l t s o f dup l f c r t f o n and sp lkes 1 access ib le f o r a l l a n a l y t f c a l r e s u l t s ? -

RAT I NG TOTAL :

C m n t s and Obsewr t f ons ;

Page 10 o f 11

RECRA f NV IRONMENTAL, 1NC . LABORATORY AUDIT

V I I . SAMPLE BOTTLE PREPARATION AND INITIATION OF C H A I N OF CUSTODY

ITEM

B o t t l e s a re cleaned and prepared/preserved i n accordance wd t h spec i f f c methods and p a r a m te r s?

re the b o t t l e p repa ra t i on I t ' t e t hod /p rO~ tdu t t~ w r i t t e n ?

B o t t l e s p repa ra t i on processf ng area, system?

Batch t e s t i n g and c e r t i f i c a t f o n o f con ta iners?

Overa l l c o n d i t i o n and types of con ta ine rs used?

Traceabf l i t y o f con ta iners of c l ean ing l o g and records?

Contafner stock adequate t o suppor t the 1 aboratory needs?

Label fng, logg fng and i d e n t f f i c a t i o n o f con ta iners?

Special s torage requf r m n t s ?

Condf t f on and seal i n g o f i c e chests?

- - - - - - - - - - - - -

RATING TOTAL:

RATING ( C i r c l e nne)

0 1 2 3 4

Cocmrnts and O b s e w r t l o n s :

. Page 11 o f 11

RECRA ENVIRONMENTAL, INC . LABORATORY AUD If

V I I I . MAINTENANCE OF SAMPLE SECURITY

ITEM

Samples a r e mainta ined I n a designated, secure, locked area?

Custodian c o n t r o l s access t o samples Index secu r i t y ?

Sample custod ian ensures app rop r i a te cha in -o f - custody form p rope r l y s igned when samples a re accessed?

Custodfan un locks s torage area f o r sample removal o r r e t u r n o f s a w 1 es?

Limf t e d access t o 1 abora t o r y?

Suuri t y system used t o p r o t e c t premises from i n t r u d e r s ?

- - - - - - - - - - - - - - - - - -

RATING TOTAL;

RATING ( C i r c l e Onel

0 1 2 3 4

Cormwnts and Observctfons;

RATING CODE:

4 - E x c e l l e n t 3 - Acceptable 2 - D e f i c i e n t 1 - Unacceptable 0 - Not E v & l ~ r t e e / N o t App l i cab le

APPENDIX C ANALYTICAL METHOD8 9070 AND 9060

METHOD 9060

TOTAL ORGANIC CARBON

1.0 SCOPE AND APPLICATION

1.1 Method 9060 i s used t o determine the concentrat ion of organic carbon in ground water, su r face and s a l f n e waters, and domestic and indus t r i a l wastes. 'Some r e s t r i c t i o n s a r e noted i n Sect ions 2.0 and 3.0.

1.2 Method 9060 i s most appl i c ab l e t o measurement of organic carbon above 1 mg/L.

2.0 SUMMARY OF METHOD

2 . 1 Organic ca.rbon i s measured using a carbonaceous analyze<. This instrument converts the organic carbon in a sample t o carbon dioxide (C02) by e i t h e r c a t a l y t i c combustion o r wet chemical oxidation. The C02 formed i s then e i t h e r measured d i r e c t l y by an in f ra red de t ec to r o r converted t o methane (CH4) and measured by a flame ion iza t ion de t ec to r . The amount of C02 o r CH4 in a sample i s d i r e c t l y proport ional t o t he concentrat ion of carbonaceous materi a1 in the sample.

2 . 2 carbonaceous analyzers a r e capable of measuring a l l forms of carbon in a sample. However, because of various p roper t i es of carbon-contai n i ng compounds in l i qu id samples, the manner of preliminary sample treatment as well as the instrument s e t t i n g s wi l l determine which forms of carbon a re a c tua l l y measured. The forms of carbon t h a t can be measured by Method 9060 a re :

1. Soluble, nonvolati l e organic carbon: e.g. , natural sugars.

2 . .Soluble, v o l a t i l e organic carbon: e.g., me rcq t ans , alkanes, low mol ecul a r weight a1 coho1 s .

3 . Insoluble , p a r t i a l ly v o l a t i l e carbon: e.g., low molecular weight o i l s .

4. Insoluble , p a r t i c u l a t e carbonaceous mater ia ls : e.g., c e l l u lo se f i b e r s .

5. Soluble o r inso lub le carbonaceous mate r ia l s adsorbed o r entrapped on insoluble inorganic suspended matter: e .g , , o i l y mat ter adsorbed on s i l t p a r t i c l e s .

2 . 3 Carbonate and bicarbonate a r e inorganic forms of carbon and must be separated from the t o t a l organic carbon value. Depending on the instrument manufacturer 's i n s t ruc t i ons , t h i s separa t ion can be accompl i shed by e l t h e r a simple mathematical sub t rac t ion , o r by removing the carbonate and bicarbonate by convert ing them to C02 with degassing p r i o r t o ana lys i s .

R e v i s i o n 0 Date September 1986

3.0 INTERFERENCES

3.1. Carbonate and bicarbonate carbon represent an in te r fe rence under the terms of t h i s t e s t and must be removed o r accounted f o r in the f ina l calcula- t i on .

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3.2 This procedure i s app l icab le only t o homogeneous 'samples which can be in jec ted In to the apparatus reproducibly by means of a microl i ter - type syr inge o r p ipe t . The openings of t he syringe o r p ipe t l i m i t t he maximum s i z e of p a r t i c l e w h i c h may be included in t he sample.

3.3 Removal of caibonate and bicarbonate by ac id i f i c a t i on and purging wi th .n i t rogen , o r o the r i n e r t gas , can r e s u l t i n the l o s s of v o l a t i l e organic substances.

4.0 APPARATUS AND MATERIALS

4.1 Apparatus f o r bl endi nq o r homoqeni z i n g sampl es : General l y , a Waring-type blender is s a t i s f a c t o r y .

4.2 Apparatus f o r t o t a l and dissolved orqanic carbon:

.4.2.1 Several companies manufacture analyzers f o r measuri ng carbonaceous material i n l i qu id samples. The most appropr ia te system . should be se lec ted based on considerat ion of the types of samples t o be ( analyzed, the expected concentrat ion range, and the forms of carbon to be measured.

4.2.2 No s p e c i f i c analyzer i s recommended as super ior . I f the technique of chemical oxidat ion i s used, the laboratory must be ce r t a i n t h a t , t h e instrument i s capable of achieving good carbon recoveries i n samples containing p a r t i c u l a t e s .

5.0 REAGENTS

5.1 ASTM Type I1 water (ASTM 01193): Water should be monitored f o r impur i t i e s , and should.be boiled and cooled t o remove C02.

5.2 Potassium hydrogen ph tha la te , . stock so lu t ion , 1,000 mg/L carbon: Dissolve 0.2128 g of potass i um hydrogen phthal a t e (primary standard grade) in Type I1 water and d i l u t e t o 100.0 mL.

NOTE: Sodium oxa la te and a c e t i c acid a r e not recommended as stock - so lu t ions .

5.3 Potassium hvdroqen ph tha la te , standard solut ions: Prepare standard so lu t ions Tram the stock so lu t ion by d i l u t i on with Type 11 water. -

Revision 0 Date Se~tember 1986

5 . 4 Carbonate-bicarbonate, stock solution, 1,000 mg/L carbon: Weigh . 0.3500 g of sodium bicarbonate and 0.4318 g of sodium carbonate and transfer both to the same 100-mL volumetric flask. Dissolve with Type 11 water.

5.5 Carbonate-bicarbonate, standard solution: Prepare a series of standards similar to Step 5.3.

NOTE: This standard is not required by some instruments. - 5.6 Blank solution: Use the same Type I1 water as was used to prepare

the standard solutions.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 All samples must be collected using a sampling plan that addresses the consfderations dis'cussed in Chapter Nine of this manual.

6.2 Sampling and storage of samples in glass bottles is preferable. Sampling and storage in plastic bottles such as conventional polyethylene and cubi tainers is permissible if it is established that the containers do not contribute contaminating organics to the samples.

NOTE: A brief study performed in the €PA Laboratory indicated that Type - I1 water stored in new, 1-qt cubitainers did not show any increase in organic carbon after 2 weeks' exposure.

6.3 Because of the possibility of oxidation or bacterial decomposition of some components of aqueous samples, the time between sample collection and the start of analysis should be minimized. Also, samples should be kept cool (4'C) and protected from sun1 ight and atmospheric oxygen.

6 . 4 In instances where analysis cannot be performed within 2 nr from time of sampling, the sample is acidified (pH ( 2) with HC1 or H2SO4.

7.0 PROCEDURE

7.1 Homogenize the sample in a blender. NOTE: To avoid erroneously high results, inorganic carbon must be -

accounted for. The preferred method is to measure total caroon and inorganic carbon and' to obtain the organic carbon by subtraction. If this is not possible, follow Steps 7.2 and 7.3 prior to analysis; however, volatile organic carbon may be lost.

7.2 Lower the pH of the sample to 2.

7 . 3 Purge the sample with nitrogen for 10 min.

7.4 Fol low instrument manufacturer's instructions for cal i bration, procedure, and calculations.

7.5 For calibration of the instrument, a series of standards should be used that encompasses the expected concentration range of the samples.

Revision 0 Date Seotember 1986

7.6 Quadruplicate analysis is required. Report both the average and the range. ,( '

8.0 QUALITY CONTROL

1 A1 1 qua1 i ty control data should be maintained and available for easy 'reference or inspection.

8.2 Employ a minimum of one blank per sample batch to determine if contamination or any memory effects are occurring.

8.3 Verify calibration with an independently prepared check standard every 15 samples.

8.4 Run one spike duplicate sample for every 10 samples. A duplicate sample is a sample brought through the whole sample preparation and analytical process.

9.0 METHOD PERFORMANCE

9.1 Precision and accuracy data are available in Method 415.1 of Methods for Chemical Analysis of Water and Wastes.

10.0 REFERENCES . (' 1. Annual Book of ASTM Standards, Part 31, "Water," Standard D 2574-79, p. 469 (1976).

2. Standard Methods for the Examination of Water and Wastewater, 14th e d . , p. 532, Method 505 (1975).

Revision 0 Date September 1986

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R e v i s i o n 0 D a t e September 1986

METHOD 9070

TOTAL RECOVERABLE OIL AND GREASE (GRAVIMETRIC, SEPARATORY FUNNEL EXTRACTION)

1.0 SCOPE AND APPLICATION

1.1 'This method measures the fl uorocarbon-113 extractable matter from surface and sal ine waters and industrial, domestic, and aqueous wastes. It ! s applicable to the determination of relatively nonvolatile hydrocarbons, vegetable oils, animal fats, waxes, soaps, greases, and related matter.

1.2 The method is not applicable to measurement of light hydrocarbons that volatil ire at temperatures below 70'C. Petroleum fuels, from gas01 ine through No. 2 fuel oi,ls, are completely .or partially lost in the solvent removal operati on.

1.3 Some crude oils and heavy fuel oils contain a significant percentage of residue-type materials that are not soluble f n fl uorocarbon-113. Accordingly, recoveries of these materials will be low.

1.4 The method covers the range from 5 to 1,000 mg/L of extractable material.

1.5 When determining the level of oil and grease in sludge samples, Method 9071 is to be employed.

2.0 SUMMARY OF METHOD

2.1 The 1-liter sample is acidified to a low pH (2) and serially extracted with f l uorocarbon-113 in a separatory funnel . The solvent i s evaporated from the extract and the residue is weighed.

3.0 INTERFERENCES

3.1 Matrix interferences.wi11 likely be coextracted from the sample. The extent of these interferences will vary from waste to waste, depending on the nature and diversity of the waste being analyzed.

4.0 APPARATUS AND MATERIALS

4.1 Separatory funnel : 2,000-mL, with Teflon stopcock.

4.2 Vacuum pump, or other source o f vacuum.

4.3 - Flask: Boiling, 125-mL (Corning No. 4100 or equivalent).

4.4 Distillinq head: Claisen or equivalent.

Revision 0 Date September 1986

4.5 F i l t e r paoer: Whatman No. 40, 11 cm. ( ' 5.0 REAGENTS

5.1 Hydrochloric a c i d , 1:1: Mix equal volumes of concent ra ted HCl and Type I 1 water .

5.2 Fluorocarbon-113 (l,l,2-trichloro-1,2,2-tri f l uoroethane) : Boi 1 ing p o i n t , 48'C.

5.3 Sodium s u l f a t e : Anhydrous c r y s t a l .

5.4 ASTM Type I1 wa te r (ASTM 01193) : Water should be monitored f o r i m p u r i t i e s .

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 A r e p r e s e n t a t i v e sample should be c o l l e c t e d in a l - l i t e r g l a s s b o t t l e . I f a n a l y s i s i s t o be delayed f o r more than a few hours , t h e sample i s preserved by t h e a d d i t i o n of 5 mL H C 1 (5.1) a t t h e t ime of col l e c t i o n and r e f r i g e r a t e d a t 4'C.

6.2 C o l l e c t a r e p r e s e n t a t i v e sample i n a wide-mouth g l a s s b o t t l e t h a t has been r i n s e d wi th t h e s o l v e n t t o remove any d e t e r g e n t f i l m and a c i d i f y in t h e sample b o t t l e .

6.3 A1 1 samples must have been c o l l e c t e d using a sampling plan t h a t . addresses t h e c o n s i d e r a t i o n s - d i s c u s s e d i n Chapter Nine of t h i s manual.

6 .4 Because l o s s e s of g r e a s e w i l l occur on sampling equipment, t h e c o l l e c t i o n o f a composite sample i s imprac t i ca l . Ind iv idua l p o r t i o n s c o l l e c t e d , a t p r e s c r i b e d t ime i n t e r v a l s must be analyzed s e p a r a t e l y t o o b t a i n t h e average c o n c e n t r a t i o n ove r an extended per iod .

7.0 PROCEDURE

7 .1 Mark t h e sample b o t t l e a t t h e wa te r meniscus f o r l a t e r de te rmina t ion of sample volume. I f t h e sample was n o t . , a c i d i f i e d a t t ime of c o l l e c t i o n , add 5 mL HC1 (5.1) t o t h e sample b o t t l e . A f t e r mixing t h e sample, check t h e pH by touching pH-sens i t ive paper t o t h e cap t o ensure t h a t t h e pH i s 2 o r lower. Add more a c i d i f necessar-y. .

7.2 pour t h e sample i n t o a s e p a r a t o r y funnel .

7.3 Tare a b o i l i n g f l a s k (p re -d r i ed i n an oven a t 103' and s t o r e d in a d e s i c c a t o r ) . Use g loves when hand1 ing f l a s k t o avoid adding f i n g e r p r i n t s . .

Revision 0 Date S e ~ t e m b e r 1986

7.4 Add 30 mL fluorocarbon-113 (5.2) to the sample bottle and rotate the bottle to rinse the sides. Transfer the sol vent into the separatory funnel. Extract by shaking vigorously for 2 rnin. Allow the layers to separate and filter the solvent layer through a funnel containing solvent-moistened filter paper.

NOTE: An emulsion that fails to dissipate can be broken by pouring about 1 g sodium sulfate (5.3) into the filter paper cone and slowly draining the emu1 sion through the ,salt. Additional 1-g portions can be added to the cone as required.

7.5 Repeat Step 7.4 twice more, with additional portions of fresh solvent, combining all solvent in the boiling flask.

7.6 Rinse. the tip of the separatory funnel, the fi 1 ter paper, and then the funnel with a total of 10-20 mL solvent and collect the rinsings in the flask.

7.7 Connect the boiling flask to the distilling head and evaporate the solvent by immersing the lower half of the flask in water at 70.C. Collect the solvent for reuse. A.solvent blank should accompany each set of samples.

7.8 When the temperature in the distilling head reaches 50'C or the flask appears dry, remove the distilling head. To remove solvent vapor, sweep out the flask for 15 sec with air by inserting a glass tube that is connected to a vacuum source. Immediately remove the flask from heat source and wipe the outside to remove excess moisture and fingerprints.

7.9 Cool the boiling flask in a desiccator for 30 min and weigh.

7.10 Calculation:

R - I3 mg/L total oil and grease = - v

R = residue, gross weight of extraction flask minus the tare weight;

8 = blank determination, residue of equivalent volume of extraction solvent, mg: and

V = volume of sample in liters, determined by refilling sample bottle to calibration line and correcting for acid addition, i f necessary.

8.0 QUALITY CONTROL

8.1 All quality control data should be maintained and available for easy reference or inspection.

Revision 0 Date Seotember 1986

8.2 Employ a minimum o f one blank pe r sample ba tch t o determine i f contaminat ion has occurred .

8 .3 Veri f y c a l i b r a t i o n with an independent ly prepared check s tandard every 15 samples. .

8.4 Run one s p i k e d u p l i c a t e sample f o r every I 0 samples i f p o s s i b l e . A d u p l i c a t e sample i s a sample brought through t h e whole sample p repa ra t ion and a n a l y t i c a l p rocess .

9.0 METHOD PERFORMANCE

9.1 The two o i 1 and g r e a s e methods (Methods 9070 and 9071) i n t h i s manual were t e s t e d on sewage by a s i n g l e l abo ra to ry . This method determined t h e o i l and g r e a s e l e v e l i n t h e sewage t o be 12.6 mg/L. When l - l i t e r p o r t i o n s o f t h e sewage were dosed w i t h 14.0 mg of a mixture o f No. 2 fue l o i l and Wesson o i l , t h e recovery was 93%, with a s t anda rd d e v i a t i o n of - +0.9 mg/L.

10.0 REFERENCES

1. 81um, K . A . , and M.J. Taras , "Determination o f Emulsifying Oil in I n d u s t r i a l Wastewater ," JWPCF Research Suppl. , - 40, R404 (1968).

2. S tandard Methods f o r t h e Examination of Water and Wastewater, 14th .ed. , p. 515.

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Revision 0 Date September 1986

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R e v i s i o n 0 Date September ,1986