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
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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
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
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
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
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 .
C
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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O u a o ~ u o l i c s t c a n a l y s i s P
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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