-------
form (Appendix A.7) provided by EPA Headquarters. Codes listed on the form
vail be used to describe the Data Assessment Summary.
STANDARD OPERATING PROCEDURE Page 2 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Revision: 11
2.1.6 Data Review Log; it is recommended that each data reviewer should maintain a log of the
reviews completed to include: a. date of start of case review
b. date of completion of case review
c. site
d. case number
e. contract laboratory
f. number of samples
g. matrix
h. hours worked
i. reviewer's initials
2.1.7 Telephone Record Log - the data reviewer should enter the bare facts of
inquiry, before initiating any phone conversation with CIP laboratory.
After the case review has been completed, mail white copy of Telephone
Record Log to the laboratory and pink copy to SMO. File yellow copy in
the Telephone Record Lag folder, and attach a xerox copy of the Telephone
Record Log to the completed Data Assessment Narrative (Appendix A.2).
2.1.8.1 Upon completion of review, the following are to be forwarded to the Regional
Sample Control Center (RSCC) located in the Surveillance and Monitoring Branch:
a. data package
b. completed data assessment checklist (Appendix A. 1, original)
c. SMD Contract Compliance Screening (CCS)
d. Data Summary Sheet (Appendix A.5) along with completed Data Assessment
Narrative (Appendix A.2)
e. Record of Communication (copy)
f. CLP Reanalysis Request/Approval Record (original + 3 copies)
g. Appendix A.7 (original).
2.1.8.2 Forward 2 copies of completed Data Assessment Narrative (Appendix A.2)
along with 2. copies of the Inorganic Data Assessment Form (Appendix A.7) and
Telephone Record Log , if any,: one each for appropriate Regional TPO,
and the other one to EPA EMSL office in Las Vegas. The addresses of TPOs and EPA office
in Las Vegas are given in Appendix A-4.
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STANDARD OPERATING
Title: Evaluation of Metals Data for the
Contract laboratory Program
PROCEDURE
3 Of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
2.1.9 Piled Paperwork - Upon completion of review, the following are to be filed
within MMB files:
a. Two copies of completed Data Assessment Narrative
Appendix A.7.
b. Telephone Record Log (copy)
c. SMD Report (copy Appendix A-3)
d. CLP Reanalysis Request/Approval Record
(Appendix A. 2) each carrying
(copy)
3.0
— ^^^^^^^^^^^^^^™^^™^»«
Each data package is checked by a Regional Sample Control Coordinator (RSSC) for
completeness. A data package is assumed to be complete when all the deliverables
required under the contract are present. If a data package is incomplete, the RSSC
would call the laboratory for missing document(s). If the laboratory does not resj
within a week, SMD and MMB coordinator of Region II will be notified.
4.
- All values determined to be unacceptable on the Inorganic Analysis Data
Sheet (Form I) must be lined over with a red pencil. As soon as any review criteria causes
data to be rejected, that data can be eliminated from any further review or consideration.
L^- In order that reviews be consistent among reviewers, ace
criteria as stated in Appendix A.I (pages 4-25) should be used. Additional guida
be found in the National Inorganic Functional Guidelines of October 1, 1989.
can
problems, both
even if CCS is not pr«=*:
be used by the reviewer.
- This is intended to aid reviewer in locating any
ted and uncorrected. However, the validation should be carried out
it. Resubmittals received from laboratory in response to CCS must
- Data reviewers must note all items of contract
••^•^•^••^^^•••^•••^•^H^^^^^^MM^aA^B^^ABWi^^fv — ^—-- ^—• • • •• —' — mmf^f^f «*^b^b. ^^«^«*^^ ^^^ ^^wV 1.\JL!_TJ%.TJ~\T A BMU A—^^MUU^^L^UGU Jv^7
within Data Assessment Narrative.If holding tirnps and sample storage times have not been
exceeded, TPO may request reanalysis if items of non-compliance are critical to data
assessment. Requests are to be made on "CLP Re-Analysis Request/Approval Record".
8.0 Record of 'v—™j"ation - Provided by the Regional Sample Control Center (RSCC) to
indicate which data packages have been received and are ready to be reviewed.
9.
'*•«"*« Ti t*rv
- The
reviewer will follow the standard practice.
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STANDARD OPERATING PROCEDURE Page 4 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES m N/A~
A.I.I Contract rv»npi-iqpee screening Report (CCS) - Present? [ ]
ACTION; If no, contact RSCC.
A. 1.2 Record of OnmnTni-cation (from RSCC) — Present?
ACTION; If no, request from RSCC.
A.I.3 Trip Report - Present and complete?
ACTION: If no, contact RSCC for trip report.
A.I.4 «ampi«> Traffic Report - Present? [ ]
Legible?
ACTION: If no, request from Regional Sample Control
Center (RSCC).
A.I.5 Cover Page - Present?
Is cover page properly filled in and signed by the lab
manager or the manager's designee? [ ]
ACTION; If no, prepare Telephone Record Log, and
contact laboratory.
Do numbers of samples correspond to numbers on Record
of Communication?
Do sample numbers on cover page agree with sample
numbers on:
(a) Traffic Report Sheet?
(b) Form I's?
ACTION; If no for any of the above, contact RSCC for
clarification.
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1- -e:
STANDARD OPERATING PROCEDURE
Evaluation of Metals Data for the
Contract laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Page 5 of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
A.1.6
A.I.6.1
A.I.6.2
pnrm J
TSf
Yes
Are all the Form I thrombi Form IX labeled with:
laboratory name?
Case/SAS number?
EPA sample No.?
SDG No.?
Contract No.?
Correct units?
Ifetrix?
AL'l'lON: If no for any of the above, note under
Contract Problenv/Non-Conpliance section
of the "Data Assessment Narrative".
Do any oomputation/transcription errors exceed 10% of
reported values on Forms I-IX for:
(NOTE: check all forms against raw data. )
(a) all analytes analyzed by ICP?
(b) all analytes analyzed by GEAA?
(c) all analytes analyzed by AA Flame?
(d) Mercury?
(e) Cyanide?
ACTIOM: If yes, prepare Telephone log, contact
laboratory for corrected data and
correct errors with red pencil and initial.
[ 3
[ ]
[ ]
[ ]
NO N/A
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STANDARD OPERATING PROCEDURE
Page 6 of 35
Title: Evaluation of Metals Data for the
Contract laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Date: Sept. 1991
Number: HW-2
Revision: 11
A.1.7 Raw Data
A. 1.7.1 Digestion Log* for flame AA/ICP (Form XIII) pit
nt?
Digestion Log for furnace AA Form XIII present?
Distillation Log for mercury Form XIII present?
Distillation Log for cyanides Form XIII present?
Are pH values (pH<2 for all metals, pH>12 for cyanide)
present?
*Weights, dilutions and volumes used to obtain values.
Percent solids calculation present for soils/sediments?
Are preparation dates present on sample preparation
logs/bench sheets?
A. 1.7.2 Measurement read out record present? ICP
Flame AA
Furnace AA
Mercury
Cyanides
A. 1.7.3 Are all raw data to support all sample analyses and
QC operations present?
Legible?
Properly Labeled?
ACTICBT: if no for any of the above questions
in sections A.I.7.1 through A.I.7.3,
write Telephone Record Log and contact
laboratory for resubmittals.
[ ]
[ ]
[ ]
C ]
[ ]
t _ ] _ _
aS
if pH
-------
STANDARD OPERATING PROCEDURE Page 7 of 35
Evaluation of Metals for the Contract Date: Sept. 1991
laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Gcrapliance (Total Review)
Bftid-iTvy TimoQ - (aqueous and soil samples )
(Examine sample traffic reports and digestion/distillation logs.)
Mercury analysis (28 days) ....... exceeded? _ [ _ ]
Cyanide distillation (14 days) ..... exceeded? _ [ _ ]
Other Metals analysis (6 months) .... exceeded? _ [ _ ]
MOIE: Prepare a list of all samples and analytes
for which holding timps have been exceeded. Specify
the number of days from date of collection to the date
of preparation (from raw data) . Attach to checklist.
ACTION; If yes, reject (red-line) values less than
Instrument Detection Limit (IDL) and flag
as estimated (J) the values above IDL even
though sample (s) was preserved properly.
Is pH of aqueous samples for:
Metals Analysis >2
Cyanides Analysis <12
Action; if yes, flag the associated metals and cyanides
as estimated.
p-inal
Are all Form I's present and complete? [ _ ] _
ACTION; if no, prepare telephone record log and contact
laboratory for submittal.
Are correct units (ug/1 for waters and rag/kg for soils)
indicated on Form I's? [ ]
Are soil sample results for each parameter corrected for
percent solids?
Are EPA sample # s and corresponding laboratory sample
ID # s the same as on the Cover Page, Form I's and
in the raw data?
Are all "less than IDL" values properly ""flM with "U"? [ _ ]
-------
Was a brief physical description of sample
STANDARD OPERATING PROCEDURE
Title: Evaluation of Metals Data for the
Contract laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
given on Form I's? [ ]
8 of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
Were the correct concentration qualifiers used with
final data?
ACTION; If no for any of the above, prepare Telephone
Record leg, and contact laboratory for corrected
data.
Were any samples diluted beyond the requirements of
contract?
If yes, were dilutions noted on Form I's?
; If no, note under Qarrtrart-Pcoblem/Non-Compliance
of the"Data Assessment Narrative".
YES
m N/A
\. t.Q
A. 1.10.1 Is record of at least 2 point calibration
present for ICP analysis?
Is record of 5 point calibration present for
Hg analysis?
MTOOM: If no for any of the above, write in the
Contract Prcblem/Non-Compliance section of
the "Data Assessment Narrative".
A. 1.10.2 Is record of 4 point calibration present for:
Flame AA?
Furnace AA?
Cyanides?
MOTE: i. if less than 4 standards are measured in absorbance
mode, then the remaining standards in concentration
mode must be run immediately after calibration and
be within +10% of true value.
2. For all AA (except Hg) and Cyanide analyses, one
calibration standard is at CRDL level. If not,
write in the Q>ntract-Problem/Non-Ccnpliance section
t ]
C ]
-------
of the "Data Assessment Narrative".
STANDARD OPERATING PROCEDURE Page 9 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: ll
Compliance (Total Review)
m N/A"
ACTION; Flag aggpcd.at'-fd data as estimated if standards
are not within +10% of true values. Do not flag
the data as estimated in linear range indicated by
good recovery of standard(s).
A. 1.10.3 Is correlation coefficient* less than 0.995 for:
Mercury Analysis?
Cyanide Analysis?
Atomic Absorption Analysis?
ACTION; If yes, flag the associated data as estimated.
A.I. 11 ppT^n H JL (Initial
A.I. ll.l Present and complete for every metal and cyanide?
Present and complete for AA and TCP when both are
used for the samp analyte?
ACTION; If no for any of the above, prepare Telephone
Record Log and contact laboratory.
A. 1.11. 2 Circle on each Form II A all percent recoveries that
are outside the contract windows. Are all calibration
standards (initial and continuing) within control
limits:
Metals- 90-110R%?
Hg - 80-120R%? [ _ ]
Cyanides- 85-115R%? [ _ ]
* .<5 reviewer will calculate correlation coefficient.
-------
STANDARD OPERATING PROCEDURE Page 10 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NO N/A"
ACTION: Flag as estimated (J) all positive data (not
flagged with a "U") analyzed between a
calibration standard with %R between 75-89%
(65-79% for Hg; 70-84% for CN) or 111-125%
(121-135% for Kg; 116-130% for CN) recovery and
nearest good calibration standard. Qualify results
CRDL) analyzed (CRI)
for each ICP run?
(Note: CRI for AL,Ba,Ca,Fe,Mg,Na,or K is not required.)
ACTION; If no for any of the above, flag as estimated
all data falling within the affected ranges.
The affected ranges are:
AA Analysis - **True Value + CRDL
ICP Analysis - **True Value + 2CRDL
CN Analysis - **True Value + 0.5 x True Value.
**True value of CRA, CRI or mid-range standard. Substitute IDL for CRDL when IDL > CRDL.
ite tiie concentration of the missing mid-range standard from the calibration range.
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STANDARD OPERATING PROCEDURE
Page 11 of 35
L—..e: Evaluation of Metals Data for the
Contract Laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Date: Sept. 1991
Number: HW-2
Revision: 11
A.I. 12.2
\.1.13
&..1.13.1
Was CRI analyzed after ICV/ICB and before the final
CCV/CCB, and twice every eight hours of ICP run?
ACTION; If no, write in Contract Problem/Non-Conplia
Section of the "Data Assessment Narrative".
YES NO
N/A
A. 1.12.3 Circle on each Form TIB all the
nt recoveries that
are outside the acceptance windows.
Are CRA and CRI standards within control limits:
Metals 80 - 120%R?
Is mid-range standard within control limits:
Cyanide 80 - 120%R?
ACTION: Flag as estimated all sample results within
the affected ranges if the recovery of the
standard is between 50-79%; flag only positive
data if the recovery is between 121-150%; reject
(red line) all data if the recovery is less
than 50%; reject only positive data if the
cy is greater than 150%. Qualify 50% of
Note:
the samples on either side of CRI standard outside
the control limits.
Flag or reject the final results only when sample
raw data are within the affected ranges and the CROL
standards are outside the acceptance windows.
c ]
Bonn, t TT fInitial and GantiMiiner Calibration
Present and complete?
For both AA and ICP when both are used for the
same analyte?
Was an initial calibration blank analyzed?
Was a continuing calibration blank analyzed after
every 10 samples or every 2 hours (whichever is more
frequent)?
ACTION; If no, prepare Telephone Record Log, contact
laboratory and write in the Contract-Problems/
Non-Compliance section of the "Data Assessment Narrative".
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STANDARD OPERATING PROCEDURE Page 12 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NON/A"
A. 1.13.2 Circle on each Form HI all calibration blank values
that are above CRDL (or 2 x IDL when IDL > CRDL).
Are all calibration blanks (when IDKCRDL) less than or
equal to the Contract Required Detection Limits (CRDLs)? [ ]
Are all calibration blanks less than two
Instrument Detection Limit (when IDLX3SDL)?
ACTION: If no for any of the above, flag as estimated
(J) positive sample results when raw sample
value is less than or equal to calibration
blank value analyzed between calibration blank
with value over CRDL (or 2xIDL) and nearest good
calibration blank.
Flag five samples on either side of the
calibration blank outside the control limits.
.1-4 IORM HI
(Note: The preparation blank for mercury is the same
as the calibration blank.)
A. 1.14.1 Was one prep, blank analyzed for: each 20 samples? [ ]
each batch?
each matrix type?
both AA and ICP when both are used for
the samp analyte? [ ]
ACTION; If no for any of the above, flag as
estimated (J) all the associated positive
data <10 x IDLs for which prep, blank
was not analyzed.
NOTE; if only one blank was analyzed for more
than 20 samples, then first 20 samples analyzed
do not have to be flagged as estimated (J).
A.I. 14.2 Is concentration of prep, blank value greater
than the CRDL when IDL is less than or equal to CRDL? [ ]
If yes, is the concentration of the sample with
the least concentrated analyte less than 10 tijpeg
the prep.blank? [ ]
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T- -e:
STANDARD OPERATING PROCEDURE
Evaluation of Metals Data for the
Contract laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Rage 13 of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
ACTION; If yes, reject (red-line) all associated
data greater than CRDL concentration but
less than ten times the prep, blank value.
A.I. 14.3 Is concentration of prep, blank value (Form HI) less
than two times IDL, when IDL is greater than CRDL?
ACTION: If no, reject (red-line) all positive sample
results when sample raw data are less than 10
times the prep, blank value.
YES
NO N/A
A.I.14.4
A. 1.15
A 15.1
IS
fixation of prep, blank below the negative CRDL?
ACTION: If yes, reject (red-line) all associated sample
results less than lOxCRDL.
Present and complete?
(MOTE: Not required for furnace AA, flame AA, mercury,
cyanide and Ca, Mg, K and Na.)
Was ICS analyzed at beginning and end of run
(or at least twice every 8 hours)?
ACTION; If no, flag as estimated (J) all the samples for
which AL, Ca, Fe, or Mg is higher than in ICS.
Circle all values on each Form IV that are more
than + 20% of true or established mean value. Are all
Interference Check Sample results inside the control
limits (± 20%)?
If no, is concentration of Al, Ca, Fe, or Mg lower
than the respective concentration in ICS?
ACTION: If no, flag as estimated (J) those positive
results for which ICS recovery is between 121-150%;
flag all sample results as estimated if ICS
recovery falls within 50-79%; reject (red-line)
those sample results for which ICS recovery is less
than 50%; if ICS recovery is above 150%, reject
positive results only (not nagged with a IfU").
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STANDARD OPERATING PROCEDURE
14 Of 35
— .e: Evaluation of Metals Data for the
Contract laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Date: Sept. 1991
Number: HW-2
Revision: 11
A. 1.16
N/A
( Note: Not required for Ca, Mj, K, and Na (both matrices), Alf and Fe
(soil only.)
A. 1.16.1 Present and complete for: each 20 samples?
each matrix type?
each cone, range (i.e. low, med., high)?
For both AA and ICP when both are used for the
same analyte?
ACTION; If no for any of the above, flag as
estimated (J) all the positive data less
than four tiinps the spiking levels specified
in SOW for which spiked sample was not analyzed.
NOTE; If one spiked sample was analyzed for more
than 20 samples, then first 20 samples
analyzed do not have to be flagged as
estimate (J).
A. 1.16.2 Was field blank used for spiked sample?
ACTION; If yes, nag all positive data less than
4 x spike added as estimated (J) for which
field blank was used as spiked sample.
A. 1.16.3 Circle on each Form VA all spike recoveries that
are outside control limits (75% to 125%).
Are all recoveries within control limits?
If no, is sample concentration greater than or
to four times spike concentration?
[ ]
ACTION; If yes, disregard spike recoveries for analytes
whose concentrations are greater than or equal
to four t.imes spike added. If no, circle those
analytes on Form V for which sample concentration
is less than four times the spike concentration.
[ _ ] _ _
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STANDARD OPERATING PROCEDURE Page 15 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW—2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YJS NO N/A
Are results outside the control limits (75-125%)
flagged with "N" on Form I's and Form VA? [ ]
aCTIOM: If no, write in the Contract - Problem/Non -
Compliance section of "Data Assessment Narrative".
A.I.16.4 Aaueous
Are any spite recoveries:
(a) less than 30%?
(b) between 30-74%?
(c) between 126-150%?
(d) greater than 150%?
aCTION; If less than 30%, reject all associated aqueous
data; if between 30-74%, flag all associated
aqueous data as estimated (J); if between
126-150%, flag as estimated (J) ail asgociat'od
aqueous data not flagged with a "IP1; if
greater than 150%, reject (red-line) all
associated aqueous data not flagged with a "U1'.
Are any spite recoveries:
(a) less than 10%?
(b) between 10-74%? [ ]
(c) between 126-200%?
(d) greater than 200%?
aCTION: If less than 10%, reject all associated data; if
between 10-74%, flag all associated data as estimated;
if between 126-200%, flag as estimated all associated
data was not flagged with a "U"; if greater than 200%,
reject all associated data not flagged with a "U*1.
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STANDARD OPERATING PROCEDURE
Page 16 of 35
Title: Evaluation of Metals Data for the
CuitLia^L Laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Date: Sept. 1991
Number: HW-2
Revision: 11
YES
A. 1.17
A. 1.17.1
Utarm VT Ta>>
Present and complete for: each 20 samples?
each matrix type?
each concentration range (i.e. low, ned. , high)?
both AA and ICP when both are used for the
analyte?
ACTION; If no for any the above, flag as estimated
(J) all the data >GRDL* for which duplicate
sample was not analyzed.
Note; 1. If one duplicate sample was analyzed for
more than 20 samples, then first 20 samples do not
have to be flagged as estimated.
2. If percent solids for soil sample and its duplicate
differ by more than 1%, prepare a Form VI for each
duplicate pair, report concentrations in ug/L
on wet weight basis and calculate RPD or Difference
for each analyte.
A. 1.17.2 Was field blank used for duplicate analysis?
ACTION: If yes, flag all data >CRDL* as estimated
(J) for which field blank was used as duplicate.
A.I.17.3 Are all values within control limits (RPD 20% or
difference < 4CRDL)?
If no, are all results outside the control limits
flagged with an * on Form I's and VI?
ACTION; If no, write in the Contract - Problems/Non-
Compliance section of "Data Assessment Narrative".
: 1. RPD is not calculable for an analyte of the
sample - duplicate pair when both values are
less than IDL.
NO N/A
[ 1
Substitute IDL for CRDL when IDL > CRDL.
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STANDARD OPERATING PROCEDURE Page 17 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
NO N/A
2. If lab duplicate result is rejectable due
to coefficient of correlation of MSA,
analytical spike recovery, or duplicate
injections criteria, do not apply precision
criteria.
circle on each Form VI all values that are:
RPD > 50%, or
Difference > CRDL*
Is any RPD greater than 50% where sample and duplicate
are both greater than or equal to 5 times *CRDL?
Is any dlfferenee** between sample and duplicate greater
than *CRDL where sample and/or duplicate is less than
5 tvi-mes *CRDL?
If yes, flag the associated data as estimated.
Circle on each Form VI all values that are:
RPD > 100%, or
Difference > 2 x CRDL*
Is any RPD (where sample and duplicate are both
greater than or equal to 5 tunes *CRDL) :
> 100%?
Is any **dif ference between sample and duplicate
(where sample and/or duplicate is less than 5x*CRDL) :
> 2x*CRDL?
* Substitute IDL for CRDL when IDL > CRDL.
** Use absolute values of sample and duplicate to calculate
the difference.
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STANDARD OPERATING PROCEDURE Page 18 of 35
Evaluation of Metals Data for the Date: Sept. 1991
Ccnti'dcL laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
A. 1.18.2
1*
ACTION: If yes, flag the associated data as estimated.
A. 1.18 Field Duplicates
A. 1.18.1 Were field duplicates analyzed? [ _ ] _
ACTION; If yes, prepare a Form VI for each aqueous field
duplicate pair. Prepare a Form VI for each soil
duplicate pair, if percent solids for sample and
its duplicate differ by more than 1%; report
itrations of soils in ug/1 on wet weight
basis and calculate RPDs or Difference for each
analyte.
VOTE: l. Do not calculate RPD when both values are
less than IDL.
2. Flag all associated data only for field
duplicate pair.
Circle all values on self prepared Form VI for
field duplicates that are:
RPD > 50%, or
Difference > CRDL*
Is any RPD greater than 50% where sample and duplicate
are both greater than or equal to 5 times *CRDL?
Is any **difference between sample and duplicate greater
than *CRDL where sample and/or duplicate is less than
5 times *CRDL? [ ]
ACTION; If yes, flag the associated data as estimated.
* Substitute IDL for CRDL when IDL > CRDL.
** Use absolute values of sample and duplicate to calculate the difference.
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STANDARD OPERATING PROCEDURE
Title: Evaluation of Metals Data for the
Contract Laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Page 19 of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
YES
NO
N/A
Circle all values on self prepared Form VI for
field duplicates that are:
RPD >100%, or
Difference > 2 x CRDL*
Is any RPD (where sample and duplicate are both
greater than 5 times *CRDL) :
Is any **difference between sample and duplicate
(where sample and/or duplicate is less than 5x *CRDL ) :
>2x *CRDL?
If yes, flag the associated data as estimated.
(Note: I£S - not
required for aqueous Hg and cyanide analyses.)
Was one LCS prepared and analyzed for:
every 20 water samples?
every 20 solid samples?
both AA and ICP when both are used for the same
analyte? [ j
ACTION; If no for any of the above, prepare Telephone
Record Log and contact laboratory for submittal
of results of LCS. Flag as estimated (J) all
the data for which LCS was not analyzed.
NOTE; If only one LCS was analyzed for more than 20
samples, then first 20 samples close to LCS
do not have to be flagged as estimated.
* Substitute IDL for CRDL when IDL > CRDL.
-------
** Use absolute values of sample and duplicate to calculate the difference.
STANDARD OPERATING PROCEDURE
Title: Evaluation of Metals Data for the
Contract laboratory Program
Appendix A.I: Data Assessment - Contract
Compliance (Total Review)
Rage 20 of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
A. 1.19. 2
A. 1.19. 3
NQ N/A
Circle on each Form VII the I£S percent recoveries
outside control limits (80 - 120%) except for aqueous
Ag and Sb.
Is any LCS recovery: less than 50%?
between 50% and 79%?
between 121% and 150%?
greater than 150%?
Less than 50%, reject (red-line) all data;
between 50% and 79%, flag all associated data
as estimated (J) ; between 121% and 150%, flag
all positive (not flagged with a "U") results
as estimated; greater than 150%, reject all
positive results.
1. If "Pound" value of LCS is re j actable due to duplicate
injections or anaiyHrai spite recovery criteria,
regardless of ICS recovery, flag the associated data
as estimated (J) .
2. If IDL of an analyte is «j«O. to or greater than
true value of ICS, disregard the "Action" below even
though ICS is out of control limits.
Is I£S "Found" value higher than the control
limits on Form VII?
ACTION: if yes, qualify all associated positive data
as ~ •'
-------
STANDARD OPERATING PROCEDURE Page 21 of 35
TJ— ue: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
VRS NO N/A
Is I£S "Found" value lower than the Control
limits on Form VII? _
ACTION; if y^ qualify all associated data as
A.. 1.20 prvrm TTT (ICP CQT-ial Dilut —
VOTE: Serial dilution analysis is required only
for initial concentrations equal to or
greater than 10 x IDL.
A. 1.20.1 Was Serial Dilution analysis performed for:
each 20 samples? [ _ ]
each matrix type? [ _ ]
each concentration range (i.e. low, med.)? [ _ ]
aCTK»: If no for any of the above, flag as estimated
all the positive data > lOxIDLs or > CRDL when
lOxIDL < CRDL for which Serial Dilution Analysis
was not performed.
\. 1.20.2 Was field blank(s) used for Serial Dilution Analysis? _
ACTEM; If yes, flag all associated data > 10 x IDL
as estimated (J) . If lOxIDL < CRDL, flag all
data > CRDL.
^.1.20.3 Are results outside control limit flagged with an "E"
on Form I's and Form IX when initial concentration on
Form IX is equal to 50 times IDL or greater. [ _ ]
-------
STANDARD OPERATING PROCEDURE Page 22 of 35
Tj^e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NO N/A
ACnOK: If no, write in the Gantxact-Problem/Non-
Conplianoe section of the "Data Assessment
Narrative".
A.I.20.4 Circle on each Form IX all percent difference
that are outside control limits for initial
concentrations equal to or greater than 10 x IDLs only.
Are any % difference values:
> 10%? [ ]
> 100%?
ACTION; Flag as estimated (J) all the associated sample
data > lOxTDTfi (or > CRDL when lOxIDL > CRDL)
for which percent difference is greater than 10%
but less than 100%. Reject (red-line) all the
associated sample results equal to or greater
than lOxIDLs (or > CRDL when lOxIDL < CRDL) for
which PD is greater than or equal to 100%.
Note; Flag or reject on Form I's only the sample results
whose associated raw data are > lOxIDL (or >. CRDL
when lOxIDIx CRDL)
A. 1.21
A. 1.21.1 Are duplicate injections present in furnace raw data
(except during full Method of Standard Addition) for
each sample analyzed by GEAA? [ ]
ACTION; If no, reject the data on Form I's for which
duplicate injections were not performed.
A. 1.21.2 Do the duplicate injection readings agree within 20%
Relative Standard Deviation (RSD) or Coefficient of
Variation (CV) for concentration greater than CRDL? [ ]
Was a dilution analyzed for sample with post digestion
spike recovery less than 40%? [ ]
ACTICM: If no for any of the above, flag all the
associated data as estimated (J).
-------
STANDARD OPERATING PROCEDURE Page 23 Of 35
Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.I: Data Assessment - Contract Revision: 11
* Compliance (Total Review)
YES NO N/A
A. 1.21. 3 Is *analytical spike recovery less than 10% or
greater than 150% for any result? _ [ _ ] _
If yes, reject (red-line) the affected data if
recovery is <10%; reject data not flagged with
"U" if spike recovery is >150%.
KXffi: Reject or flag the data only when the affected
sample (s) was not subsequently analyzed by Method
of Standard Addition.
* Post digestion spike is not required on the pre-digestion spiked sample.
\.1.22 po'nn vui (Method of st"a>Ti^aT^l ^iM-ition Results)
^.1.22.1 Present? [ _ ] _
If no, is any Form I result coded with "S" or a "+"? _ [ _ ] _
*craCN; If yes, write request on Telephone Record log
and contact laboratory for submittal of form VUI.
^.1.22.2 Is coefficient of correlation for MSA less than 0.990 for
any sample? r -j
If yes, reject (red-line) affected data.
. 22. 3 Was *MSA required for any sample but not performed?
Is coefficient of correlation for MSA less than 0.995?
Are MSA calculations outside the linear range of the
calibration curve generated at the beginning of the
analytical run?
9CTHW: If yes for any of the above, flag all
the associated data as astiimatgcl (J) .
L.I. 22. 4 Was proper quantitation procedure followed correctly
as outlined in the SOW on page E-23? [ _ ] _ _
ACTOOM; if no, note exception under Contract Problem/
Non-Campliance section of the "Data Assessment
Narrative", and prepare a separate list.
-------
STANDARD OPERATING PROCEDURE Page 24 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW-2
Appendix A.1: Data Assessment - Contract Revision: 11
Compliance (Total Review)
HIm K/A
A. 1.23 Dissolved/Total or inorganic/Total
A. 1.23.1 Were any analyses performed for dissolved as well as
total analytes on the sane sample (s). [ ]
Were any analyses performed for inorganic as well as total
(organic + inorganic) analytes on the samp sample(s)?
* MSA is not required on LCS and prep, blank.
VOTE: l. If yes, prepare a list comparing differences
between all dissolved (or inorganic) and
total analytes. Compute the differences as
a percent of the total analyte only when
dissolved concentration is greater than CRDL
as well as total concentration.
2. Apply the following questions only if in-
organic (or dissolved ) results are (i) above
CRDL, and (ii) greater than total constituents.
3. At least one preparation blank, ICS, and DCS
should be analyzed in each analytical run.
A. 1.23.2 Is the concentration of any dissolved (or inorganic)
analyte greater than its total concentration by
more than 10%?
A. 1.23.3 Is the concentration of any dissolved (or inorganic)
analyte greater than its total concentration by
more than 50%?
ACTKM: if more than 10%, flag both dissolved (or
inorganic) and total values as estimated (J);
if more than 50%, reject (red-line) the data
for both- values.
A. 1.24 p*vrm I (Field piMTrl -
A.I.24.1 Circle all field blank values on Data Summary Sheet
that are greater than CRDL, (or 2 x IDL when IDL > CRDL).
Is field blank concentration less than CRDL
(or 2 x IDL when IDL > CRDL) for all parameters
of associated aqueous and soil samples? [ ]
-------
Title: Evaluation of Metals Data for the
Contract Laboratory Program
Appendix A.I: Data Assessment - Contr
Compliance (Total Review)
Date: Sept. 1991
Number: HW-2
Revision: 11
YES NO
N/A
If no, was field blank value already rejected due to
other QC criteria?
If no, reject (except field blank results)
all associated positive sample data less
than or equal to five t.iTnps the field blank
value. Reject on Farm I's the soil sample
results that when converted to ug/L on wet
basis are less than or equal to five
the field blank value.
[ 3
A.I.25
A 25.1
Form X. XI. *TT (Verificati*
Is verification report present for:
Instrument. Detection Limits (quarterly)?
ICP Interelement Correction Factors (annually)?
ICP T.inpar Ranges (quarterly)?
ACTIGM: If no, contact TFO of the lab.
A.I.25.2
required for Cyanide.)
LtsJL - (Note: IDL is not
A.I.25.2.1 Are IDLs present for:
all the analytes?
all the instruments used?
For both AA and ICP when both are used for the same
analyte?
If no for any of the above, prepare
Telephone Record I/-»j and contact
laboratory.
C ]
-------
SIRNDAKD OPERATING PROCEDURE Page 26 of 35
Title: Evaluation of MetalsJteta for the Date: Sept. 1991
GiiLtawL Laboratory Program Number: HW-2
Appendix A.1: Data Assessment - Contract Revision: 11
Compliance (Total Review)
YES NO N/A
A.I.25.2.2 Is H3L greater than CRDL for any analyte? f" 1 ~~^
If yes, is the concentration on Form I of the sample
analyzes on the instrument whose TEL exceeds CRDL,
greater than 5 x CRDL.
Action : if no, flag as estimated all values less
than five t"imps IDL of the instrument whose
IDL exceeds CRDL.
A. 1.25.3.1 Was any sample result higher than high linear range
of ICP. ^
Was any sample result higher than the highest
calibration standard for nan-ICP parameters?
If yes for any of the above, was the
sample diluted to obtain the result on Form I?
acnx»: If no, flag the result reported on Form I
as estimated (J).
A.1.26
A.I.26.1 Is soil content in sediment(s) less than 50%?
ACTION; If yes, qualify as estimated all delta
not previously rejected or flagged due
to other QC criteria.
-------
STANDARD OPERATING PROCEDURE Page 27 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.2: Data Assessment Narrative Revision: 11
Case*
SDG#
Contractor
Site
Lab
Reviewer
Matrix: Soil
Water
Other
A.2.1 The case description and exceptions, if any, are noted below with reason(s)
for rejection or qualification as estimated value (s) J.
-------
STANDARD OPERATING PROCEDURE Page 28 of 35
Evaluation of Metals Data for the Date: Sept. 1991
Contract Laboratory Program Number: HW^
Appendix A. 2: Data Assessment Narrative Revision: 11
\.2.1 (continuation)
-------
STANDARD OPERATING PROCEDURE Page 29 Of 35
1—..e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A. 2: Data Assessment Narrative Revision: 11
A.2.1 (continuation)
-------
STANDARD OPERATING PROCEDURE
— .e: Evaluation of Metals Data for the
Contract laboratory Program
Appendix A. 2: Data Assessment Narrative
Page 30 of 35
Date: Sept. 1991
Number: HW-2
Revision: 11
A. 2.2 Omrtxac±-Prt±?lem/TJon-Oopplianoe
MMB Reviewer:
Signature
Contractor Reviewer:
Signature
Verified by:
STANDARD OPERATING PROCEDURE
_^tle: Evaluation of Metals Data for the
Date:
Date:
Date:
Page 31 of 35
Date: Sept. 1991
-------
Contract laboratory Program Number: HW-2
Appendix A. 3: Contract Non-Compliance Revision: 11
(SMD Report)
" CONTRACT NCN-CCMPLIANCE
(SMD
Regional Review of Uncontrolled Hazardous Haste
Site Contract Laboratory Data Package
CASE NO.
The hardcopied (laboratory name) ___
Inorganic data package received at Region II has been reviewed and the quality assurance and
performance data summarized. The data reviewed included:
SMD .Sample No.:
Cone. & Matrix:
Contract No. WA87-K025.K026.KD27fSCW7871 requires that specific analytical work be done and
that associated reports be provided by the contractor to the Regions, ZMSL-LV, and SMD. The
general criteria used to determine the performance were based on an examination of:
- Data Completeness - Duplicate Analysis Results
- Matrix Spike Results - Blank Analysis Results
- Calibration Standards Results - MSA Results
** ' of non-compliance with the above contract are described below.
Comments:
Reviewer's Initial Date
-------
STANDARD OPERATING PROCEDURE Page 32 of 35
— e: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW—2
Appendix A. 4: Mailing List for Data Reviewers Revision: 11
-------
STANDARD OPERATING PROCEDURE Page 33 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix'A.5: Summary of Inorganics Revision: 11
Quality Control Data
-------
STANDARD OPERATING PROCEDURE Page 34 of 35
Evaluation of Metals Data for the Date: Sept. 1991
Contract.laboratory Program Number: HW^
Appendix A.6: CLP Data Assessment Revision: 11
Summary' Form (Inorganics)
-------
STANDARD OPERATING PROCEDURE Page 35 of 35
Title: Evaluation of Metals Data for the Date: Sept. 1991
Contract laboratory Program Number: HW-2
Appendix A.7: CLP Data Assessment Checklist Revision: 11
Inorganic Analysis
INORGANIC REGIONAL DATA ASSESSMENT Region
CASE NO. SITE
NO. OF SAMPLES/
IABQRATORY MATRIX
SDGI _ Rfc.VJl.WER (IF NOT BSD).
SOW# REVIEWER'S NAME
DPO: ACTION FYI COMPLETION DATE
DATA ASSESSMENT SUMMARY
ICP AA Hg CYANIDE
1. HOLDING TIMES
2. CALIBRATIONS
3. BLANKS
4. ICS
5. ICS
•S DUPLICATE ANALYSIS
MATRIX SPIKE
8. MSA
9. SERIAL DILUTION
10. SAMPLE VERIFICATION
11. OTHER QC
12. OVERALL ASSESSMENT
O = Data has no problems/or qualified due to minor problems.
M = Data qualified due to major problems.
Z = Data unacceptable.
X = Problems, but do not affect data.
ACTION ITEMS:
AREAS OF CONCERN:
NOTABLE PERFORMANCE:
-------
SOP NO. HW-6
Revision #8
CLP ORGANICS DATA REVIEW
AND PRELIMINARY REVIEW
Leon Lazarui, Environmental Scientist
Toxi9 and Hazardous Waste Section
BY:
orge Krras, Chemist
Toxic and* Hazardous Waste Section
BY: -^ nr-r^ ***+
Stelios Gerazounis/ Chemist
Toxic and Hazardous Waste Section
CONCURRED BY:
APPROVED BY:
s Waste Section
Date:
Date:
RoBert Runyon, Chief
Monitoring Management Branch
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
PACKAGE COMPLETENESS AND DELIVERABLES
CASE NUMBER: LAB:
SITE:
1.0 Data Completeness and Deliverables
1.1 Have any missing deliverables been received
and added to the data package? r 1
ACTION: Call lab for explanation/resubmittal of any
missing deliverables. If lab cannot provide
them, note the effect on review of the
package under the "Contract
Problems/Non-Compliance11 section of reviewer
narrative.
1.2 Was SMO CCS checklist included with package? r 1
2.0 Cover Letter SPG Narrative
2.1 Is the Narrative or Cover Letter Present? r 1
2.2 Are Case Number and/or SAS number contained
in the Narrative or Cover letter? X 1
3.0 Data Validation Checklist
The following checklist is divided into three parts.
Part A is filled out if the data package contains any
VOA analyses, Part B for any BNA analyses and Part C
for Pesticide/PCBs.
Does this package contain:
VOA Data?
BNA Data?
Pesticide/PCB data?
Action: Complete corresponding parts of checklist.
- 1 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
PART A! VOA ANALYSES
1-0 Traffic Reports and Laboratory Narrative
1.1 Are the Traffic Report Forms present for
all samples?
ACTION: If no, contact lab for replacement
of missing or illegible copies.
1.2 Do the Traffic Reports or Lab Narrative
indicate any problems with sample receipt,
condition of samples, analytical problems
or special circumstances affecting the
quality of the data?
ACTION: If any sample analyzed as a soil,
other than TCLP, contains 50%-90%
water, all data should be flagged as
estimated (J). If a soil sample
other than TCLP contains more than
90% water, all data should be
qualified as unusable (R).
ACTION: If samples were not iced upon
receipt at the laboratory, flag all
positive results "J" and all Non-
Detects "UJ".
ACTION: If both VOA vials for a sample have
air bubbles or the VOA vial analyzed
had air bubbles, flag all positive
results "J» and all non-detects "R".
-LJ.
J-l
- 2 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
2.0 Holding Times
2.1 Have any VOA technical holding times,
determined from date of collection to date of
analysis, been exceeded? r 1 _
If unpreserved, aqueous samples maintained at 4°C which are to
be analyzed.for aromatic hydrocarbons must be analyzed within
7 days of collection. If preserved with HC1 (pH<2) and stored
at 4°Cf then aqueous samples must be analyzed within 14
days of collection. If uncertain about preservation, contact
sampler to determine whether or not samples were preserved.
The holding time for soils is 10 days.
Table of Holding Time Violations
(See Traffic Report)
Sample Sample Date Date Lab Date
ID Matrix Preserved? Sampled Received Analyzed
ACTION: If technical holding times are exceeded, flag all
positive results as estimated ("J") and sample
quantitation limits as estimated ("UJ"), and document in
the narrative that holding times were exceeded. If
analyses were done more than 14 days beyond holding
time, either on the first analysis or upon re-analysis,
the reviewer must use professional judgement to
determine the reliability of the data and the effects of
additional storage on the sample results. At a minimum,
all results must be qualified "J", but the reviewer may
determine that non-detect data are unusable (R). If
holding times are exceeded by more than 28 days, all non
detect data are unusable (R).
- 3 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YESNON/A
3.0 System Monitoring Compound fSMC) Recovery (Form II)
3.1 Are the VOA SMC Recovery Summaries (Form II) present
for each of the following matrices:
a. Low Water .[ ]_
b. Low Soil I 1
c. Med Soil f ] _
3.2 Are all the VOA samples listed on the appropriate
System Monitoring Compound Recovery Summary for each
of the following matrices:
a. Low Water
b. Low Soil
c. Med Soil
ACTION: Call lab for explanation/
resubmittals. If missing
deliverables are unavailable,
document effect in data assessments.
3.3 Were outliers marked correctly with an
asterisk? _[ ].
ACTION: Circle all outliers in red.
3.4 Was one or more VOA system monitoring
compound recovery outside of contract
specifications for any sample or method
blank?
If yes, were samples re-analyzed? .[ ].
Were method blanks re-analyzed? .[ ].
- 4 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A"
ACTION: If recoveries are > 10% but 1 or
more compounds fail to meet SOW
specifications:
1. All positive results are qualified
as estimated (J).
2. Flag all non-detects as estimated
detection limits ("UJ") where
recovery is less than the lower
acceptance limit.
3. If SMC recoveries are above allowable
levels, do not qualify non-detects.
If any system monitoring compound
recovery is <10% :
1. Flag all positive results as
estimated ("J").
2. Flag all non-detects as unusable
("R").
Professional judgement should be used to qualify
data that only have method blank SMC recoveries out
of specification in both original and re-analyses.
Check the internal standard areas.
3.5 Are there any transcription/calculation
errors between raw data and Form II? r 1
ACTION: If large errors exist, call lab for
explanation/resubmittal, make any
necessary corrections and note
errors in the data assessment.
4.0 Matrix Spikes (Form
4.1 Is the Matrix Spike/Matrix Spike Duplicate
Recovery Form (Form III) present? j; 1
- 5 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
4.2 Were matrix spikes analyzed at the required
frequency for each of the following matrices:
a. Low Water r 1
b. Low Soil .[ 1
c.. Med Soil F 1
ACTION: If any matrix spike data are missing, take
the action specified in 3.2 above.
4.3 How many VOA spike recoveries are outside QC
limits?
Water Soils
out of 10 out of 10
4.4 How many RPD's for matrix spike and matrix spike
duplicate recoveries are outside QC limits?
Water Soils
out of 5 out of 5
ACTION: No action is taken based on MS/MSD
data alone. However, using informed
professional judgement, the MS/MSD
results may be used in conjunction
with other QC criteria to determine
the need for qualification of the
data.
5.0 Blanks (Form IVi
5.1 Is the Method Blank Summary (Form IV)
present? .[ 1
5.2 Frequency of Analysis: for the analysis
of VOA TCL compounds, has a reagent/method
blank been analyzed for each SDG or every
20 samples of similar matrix (low water,
low soil, medium soil), whichever is more
frequent? I 1
- 6 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
5.3 Has a VOA method/instrument blank been
analyzed at least once every twelve hours for
each concentration level and GC/MS system
used?
ACTION:
call
5.4
If any method blank data are missing,
lab for explanation/ resubmittal. if
method blank data are not available,
reject (R) all associated positive data.
However, using professional judgement, the
data reviewer may substitute field blank
or trip blank data for missing method
blank data.
Chromatography: review the blank raw data -
chromatograms (RICs), quant reports or data system
printouts and spectra.
Is the chromatographic performance (baseline
stability) for each instrument acceptable
for VOAs? r 1
ACTION: Use professional judgement to
determine the effect on the data.
6.0 Contamination
NOTE: "Water blanks", "drill blanks", and distilled water
blanks" are validated like any other sample, and are
not used to qualify data. Do not confuse them with
the other QC blanks discussed below.
6.1 Do any method/instrument/reagent blanks have
positive results (TCL and/or TIC) for VOAs?
When applied as described below, the
contaminant concentration in these blanks are
multiplied by the sample dilution factor and
corrected for % moisture when necessary.
6.2 Do any field/trip/rinse blanks have positive
VOA results (TCL and/or TIC)?
ACTION: Prepare a list of the samples associated with
each of the contaminated blanks. (Attach a
separate sheet.)
- 7 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
NOTE: All field blank results associated to a particular
group of samples (may exceed one per case) must be
used to qualify data. Trip blanks are used to
qualify only those samples with which they were
shipped and are not required for non-aqueous
matrices. Blanks may not be qualified because of
contamination in another blank. Field Blanks & Trip
Blanks must be qualified for system monitoring
compound, instrument performance criteria, spectral
or calibration QC problems.
ACTION: Follow the directions in the table below to qualify
TCL results due to contamination. Use the largest
value from all the associated blanks. If any blanks
are grossly contaminated, all associated data should
be qualified as unusable (R).
Sample cone > CRQL
but < lOx blank
value
Sample cone < CRQL
& <10x blank value
Sample cone > CRQL
& >10x blank value
Methylene
Chloride Flag sample result
Acetone with a "U;
Toluene
2-Butanone
Report CRQL &
qualify "U"
No qualification
is needed
Sample cone > CRQL Sample cone < CRQL & Sample cone > CRQL
but < 5x blank is < 5x blank value value & > 5x blank
value
Other
Contam-
inants
Flag sample result
with a "U"
Report CRQL &
qualify "U"
No qualification
is needed
NOTE: Analytes qualified "U" for blank contamination are
still considered as "hits" when qualifying for
calibration criteria.
- 8 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: For TIC compounds, if the concentration in the
sample is less than five times the concentration in
the most contaminated associated blank, flag the
sample data "R" (unusable).
6.3 Are there field/rinse/equipment blanks
associated with every sample?
ACTION: For low level samples, note in data assessment that
there is no associated field/rinse/equipment blank.
Exception: samples taken from a drinking water tap
do not have associated field blanks.
7.0 GC/MS Instrument Performance Cheek fForm V>
7.1 Are the GC/MS Instrument Performance Check
Forms (Form V) present for Bromofluorobenzene
(BFB)?
7.2 Are the enhanced bar graph spectrum and
mass/charge (m/z) listing for the BFB
provided for each twelve hour shift?
7.3 Has an instrument performance compound been
analyzed for every twelve hours of sample
analysis per instrument?
- 9 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: List date, time, instrument ID, and
sample analysis for which no
associated GC/MS tuning data are
available.
DATE TIME INSTRUMENT SAMPLE NUMBERS
ACTION: If lab cannot provide missing data, reject ("R") all
data generated outside an acceptable twelve hour
calibration interval.
7.4 Have the ion abundances been normalized to
m/z 95? _[ i
ACTION: If mass assignment is in error,
qualify all associated data as
unusable (R).
7.5 Have the ion abundance criteria been met for
each instrument used? _[ i
ACTION: List all data which do not meet ion
abundance criteria (attach a
separate sheet).
ACTION: If ion abundance criteria are not
met, the Region II TPO must
be notified.
7.6 Are there any transcription/calculation errors
between mass lists and Form Vs? (Check at least
two values but if errors are found, check
more.) [ ]
- 10 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
7.7 Have the appropriate number of significant
figures (two) been reported? _[ i
ACTION: If large errors exist, call lab for
explanation/resubmittal, make
necessary corrections and document
effect in data assessments.
7.8 Are the spectra of the mass calibration
compound acceptable?
ACTION: Use professional judgement to
determine whether associated data
should be accepted, qualified, or
rejected.
8.0 Target Compound List fTCL) Analytes
8.1 Are the Organic Analysis Data Sheets (Form I VOA)
present with required header information on each
page, for each of the following:
a. Samples and/or fractions as appropriate _[ 1
b. Matrix spikes and matrix spike
duplicates _[ ]_
c. Blanks
8.2 Are the VOA Reconstructed Ion Chromatograms, the
mass spectra for the identified compounds, and the
data system printouts (Quant Reports) included in
the sample package for each of the following?
a. Samples and/or fractions as appropriate _[ ]. .
b. Matrix spikes and matrix spike
duplicates (Mass spectra not required) _[ 1
c. Blanks
ACTION: If any data are missing, take action
specified in 3.2 above.
- 11 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
8.3 Are the response factors shown in the Quant
Report? _[ i
8.4 Is chromatographic performance acceptable with
respect to:
Baseline stability? _[ i
Resolution?
Peak shape?
Full-scale graph (attenuation)? .[ i
Other:
ACTION: Use professional judgement to
determine the acceptability of the
data.
8.5 Are the lab-generated standard mass spectra
of the identified VOA compounds present for
each sample? _[ ]_
ACTION: If any mass spectra are missing,
take action specified in 3.2 above.
If lab does not generate their own
standard spectra, make note in
"Contract Problems/Non-compliance".
8.6 Is the RRT of each reported compound within
0.06 RRT units of the standard RRT in the
continuing calibration? _[ i
8.7 Are all ions present in the standard mass
spectrum at a relative intensity greater
than 10% also present in the sample mass
spectrum?
- 12 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
8.8 Do sample and standard relative ion
intensities agree within 20%?
ACTION: Use professional judgement to
determine acceptability of data. If
it is determined that incorrect
identifications were made, all such
data should be rejected (R), flagged
"N" (presumptive evidence of the
presence of the compound) or changed
to not detected (U) at the
calculated detection limit. In
order to be positively identified,
the data must comply with the
criteria listed in 8.6, 8.7, and 8.8.
ACTION: When sample carry-over is a
possibility, professional judgement
should be used to determine if
instrument cross-contamination has
affected any positive compound
identification.
9.0 Tentatively Identified Compounds (TIC)
9.1 Are all Tentatively Identified Compound Forms
(Form I Part B) present; and do listed TICs
include scan number or retention time,
estimated concentration and "JN" qualifier? .[ 1
9.2 Are the mass spectra for the tentatively identified
compounds and associated "best match" spectra
included in the sample package for each of the
following:
a. Samples and/or fractions as appropriate r 1
b. Blanks j; ]_
ACTION: If any TIC data are missing, take
action specified in 3.2 above.
ACTION: Add "JN" qualifier if missing.
- 13 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
9.3 Are any TCL compounds (from any fraction)
listed as TIC compounds (example: 1,2-
dimethylbenzene is xylene- a VOA TCL
analyte - and should not be reported as a TIC) ? .[ 1
ACTION: Flag with "R" any TCL compound
listed as a TIC.
9.4 Are all ions present in the reference mass
spectrum with a relative intensity greater
than 10% also present in the sample mass
spectrum? _[ 1
9.5 Do TIC and "best match" standard relative
ion intensities agree within 20%? .£ ].
ACTION: Use professional judgement to
determine acceptability of TIC
identifications. If it is
determined that an incorrect
identification was made, change
identification to "unknown" or to
some less specific identification
(example: "C3 substituted benzene")
as appropriate.
Also, when a compound is not found
in any blank, but is detected in a
sample and is a suspected artifact
of a common laboratory contaminant,
the result should be qualified as
unusable (R). (i.e. Common Lab
Contaminants: CO2 (H/E 44) ,
Siloxanes (M/E 73) Hexane, Aldol
Condensation Products, Solvent
Preservatives, and related by
products - see Functional Guidelines
for more guidance).
- 14 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
10.0 Compound Ouantitation and Reported Detection
Limits
10.1 Are there any transcription/calculation
errors in Form I results? Check at least two
positive values. Verify that the correct
internal standard, quantitation ion, and RRF
were used to calculate Form I result. Were
any errors found?
10.2 Are the CRQLs adjusted to reflect sample
dilutions and, for soils, sample moisture?
.L-l
1-1
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and note errors
under "Conclusions".
ACTION: When a sample is analyzed at more than one
dilution, the lowest CRQLs are used
(unless a QC exceedance dictates the use
of the higher CRQL data from the diluted
sample analysis). Replace concentrations
that exceed the calibration range in the
original analysis by crossing out the "E"
and its associated value on the original
Form I and substituting the data from the
analysis of the diluted sample. Specify
which Form I is to be used, then draw a
red "X" across the entire page of all Form
I's that should not be used, including any
in the summary package.
11.0 Standards Data fGC/MSl
11.1 Are the Reconstructed Ion Chromatograms,
and data system printouts (Quant. Reports)
present for initial and continuing
calibration?
ACTION: If any calibration standard data are
missing, take action specified in
3.2 above.
- 15 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
12.0 GC/MS Initial Calibration (Form VI)
12.1 Are the Initial Calibration Forms (Form VI)
present and complete for the volatile
fraction at concentrations of 10, 20,
50, 100, 200 ug/1? Are there separate
calibrations for low water/med soils
and low soil samples?
ACTION: If any calibration standard forms are missing, take
action specified in 3.2 above.
12.2 Were all low level soil standards, blanks
and samples analyzed by heated purge? _[ 1
ACTION: If low level soil samples were not heated during
purge, qualify positive hits "J" and non-detects "R".
12.3 Are response factors stable for VOA's
over the concentration range of the
calibration (%Relative Standard Deviation
(%RSD) <30.0% )? r 1
ACTION: Circle all outliers in red.
NOTE: Although 11 VOA compounds have a minimum
RRF and no maximum %RSD, the technical
criteria are the same for all analytes.
ACTION: If %RSD > 30.0%, qualify associated positive
results for that analyte "J" and non-detects
using professional judgement. When RSD > 90%,
flag all non-detects for that analyte R (unusable)
NOTE: Analytes previously qualified "U" for blank
contamination are still considered as "hits"
when qualifying for initial calibration
criteria.
12.4 Are the RRFs above 0.05?
Action: Circle all outliers in red.
Action: If any RRF are < 0.05, qualify associated
non-detects (R) and flag associated positive
data as estimated (J).
- 16 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
12.5 Are there any transcription/calculation errors
in the reporting of average response factors
(RRF) or %RSD? (Check at least 2 values, but
if errors are found, check more.) r 1
13.0 GC/MS Continuing Calibration (Form VII)
13.1 Are the Continuing Calibration Forms
(Form VII) present and complete for the
volatile fraction?
13.2 Has a continuing calibration standard
been analyzed for every twelve hours of
sample analysis per instrument?
ACTION: List below all sample analyses that
were not within twelve hours of the
previous continuing calibration
analysis.
J__L
ACTION: If any forms are missing or no continuing
calibration standard has been analyzed within twelve
hours of every sample analysis, call lab for
explanation/resubmittal. If continuing calibration
data are not available, flag all associated sample
data as unusable ("R").
13.3 Do any volatile compounds have a % Difference
(% D) between the initial and continuing
RRF which exceeds the ±25% criteria?
ACTION: Circle all outliers in red.
ACTION: Qualify both positive results and
non-detects for the outlier compound(s)
as estimated. When % D is above 90%, reject
all non-detects for that analyte (R) unusable,
- 17 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
~~~ ~~ YES NO N/A
13.4 Do any volatile compounds have a RRF <0.05? .[ ]_
ACTION: Circle all outliers in red.
ACTION: If the RRF <0.05, qualify associated
non-detects as unusable (R) and "J"
associated positive values.
13.5 Are there any transcription/calculation
errors in the reporting of average response
factors (RRF) or %difference (%D) between
initial and continuing RRFs? (Check at least
two values but if errors are found,
check more.)
ACTION: Circle errors in red.
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and note
errors under "Conclusions".
14.0 Internal Standard (Form VIII)
14.1 Are the internal standard areas (Form VIII)
of every sample and blank within the upper
and lower limits (-50% to + 100%) for each
continuing calibration?
ACTION: List all the outliers below.
Sample # Internal Std Area Lower Limit Upper Limit
(Attach additional sheets if necessary*)
- 18 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: 1. If the internal standard area count
is outside the upper or lower limit,
flag with "J" all positive results
quantitated with this internal standard.
2. Non-detects associated with IS area counts
> 100% should not be qualified.
3. If IS area is below the lower limit
(< 50%), qualify all associated non-
detects (U values) "J". if extremely
low area counts are reported, (< 25%)
or if performance exhibits a major
abrupt drop off, flag all associated
non-detects as unusable ("R").
14.2 Are the retention times of the internal
standards within 30 seconds of the
associated calibration standard? _[ i
ACTION: Professional judgement should be
used to qualify data if the
retention times differ by more than
30 seconds.
15.0 Field Duplicates
15.1 Were any field duplicates submitted for
VOA analysis? r i
ACTION: Compare the reported results for
field duplicates and calculate
the relative percent difference.
ACTION: Any gross variation between
duplicate results must be addressed
in the reviewer narrative. However,
if large differences exist,
identification of field duplicates
should be confirmed by contacting
the sampler.
- 19 -
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STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
PART B; SNA ANALYSES
1.0 Traffic Reports and Laboratory Narrative
1.1 Are the Traffic Report Forms present for all
samples? j; ]_
ACTION: If no, contact lab for replacement of
missing or illegible copies.
1.2 Do the Traffic Reports or Lab Narrative
indicate any problems with sample receipt,
condition of samples, analytical problems or
special notations affecting the quality of
the data? [ ]
ACTION: If any sample analyzed as a soil, other
than TCLP, contains 50%-90% water,
all data should be flagged as estimated
("J"). If a soil sample, other than TCLP,
contains more than 90% water, all data
should be qualified as unusable (R) .
ACTION: If samples were not iced upon receipt at
the laboratory, flag all positive results
"J" and all non-detects "UJ".
2.0 Holding Times
2.1 Have any BNA technical holding times,
determined from date of collection to date of
extraction, been exceeded? _[ ]_
Continuous extraction of water samples for
BNA analysis must be started within seven
days of the date of collection. Soil/
sediment samples must be extracted within
7 days of collection. Extracts must be
analyzed within 40 days of the date of
extraction.
- 20 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
Table of Holding Time Violations
(See Traffic Report)
Sample Date Date Lab Date Date
Sample Matrix Sampled Received Extracted Analyzed
ACTION: If technical holding times are exceeded,
flag all positive results as estimated
("J") and sample quantitation limits
as estimated ("UJ"), and document in
the narrative that holding times were
exceeded.
If analyses were done more than 14 days beyond
holding time, either on the first analysis or
upon reanalysis, the reviewer must use
professional judgement to determine the
reliability of the data and the effects of
additional storage on the sample results.
At a minimum, all results should be qualified
11J", but the reviewer may determine that non-detect
data are unusable ("R"). If holding times are exceeded by
more than 28 days, all non detect data are unusable (R) .
3.0 Surrogate Recovery (Form II)
3.1 Are the BNA Surrogate Recovery Summaries
(Form II) present for each of the following
matrices:
a. Low Water _[ ]_
b. Low Soil r 1
c. Med Soil r 1
- 21 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
3.2 Are all the BNA samples listed on the
appropriate Surrogate Recovery Summaries
for each of the following matrices:
a. Low Water j; 1
b. Low Soil r ]
c. Low Soil j; 1
ACTION: Call lab for explanation/resubmittals.
If missing deliverables are unavailable,
document effect in data assessments.
3.3 Were outliers marked correctly with an
asterisk? r 1
ACTION: Circle all outliers in red.
3.4 Were two or more base-neutral OR acid surrogate
recoveries out of specification for any sample
or method blank? .[ 1
If yes, were samples reanalyzed? _[ 1
Were method blanks reanalyzed? j; 1
ACTION: If all BNA surrogate recoveries are
> 10% but two within the base-neutral
or acid fraction do not meet SOW
specifications, for the affected
fraction only (i.e. base-neutral or
acid compounds) ;
1. Flag all positive results as estimated
2. Flag all non-detects as estimated
detection limits ("UJ") when recoveries
are less than the lower acceptance limit.
3 . If recoveries are greater than the upper
acceptance limit, do not qualify non-detects.
- 22 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
~~~~~ YES NO N/A
If any base-neutral or acid surrogate has a
recovery of <10%:
1. Positive results for the fraction with
<10% surrogate recovery are qualified
with "J".
2. Non-detects for that fraction should be
qualified as unusable (R) .
Professional judgement should be used to qualify
data that have method blank surrogate recoveries
out of specification in both original and
reanalyses. Check the internal standard areas.
3.5 Are there any transcription/calculation errors
between raw data and Form II?
ACTION: If large errors exist, call lab for
explanation/resubmittal, make any
necessary corrections and document effect
in data assessments.
4.0 Matrix Spikes (Form III1
4.1 Is the Matrix Spike/Matrix Spike Duplicate
Recovery Form (Form III) present? r 1
4.2 Were matrix spikes analyzed at the required
frequency for each of the following matrices:
a. Low Water
b. Low Soil
c. Med Soil r 1
ACTION: If any matrix spike data are missing,
take the action specified in 3.2 above.
- 23 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
4.3 How many BNA spike recoveries are outside
QC limits?
Water Soils
_ out of 22 _ out of 22
4.4 How many RPD's for matrix spike and matrix
spike duplicate recoveries are outside QC
limits?
Water Soils
_ out of 11 _ out of 11
ACTION: No action is taken on MS/MS D data
alone. However, using informed
professional judgement, the data
reviewer may use the matrix spike and
matrix spike duplicate results in
conjunction with other QC criteria and
determine the need for some
qualification of the data.
5.0 Blanks fForm
5.1 Is the Method Blank Summary (Form IV) present? .[ _ ]_
5.2 Frequency of Analysis:
Has a reagent/method blank analysis been
reported per 20 samples of similar matrix,
or concentration level, and for each extraction
batch? _[ _ I
^^™^^^-
5 . 3 Has a BNA method blank been analyzed for
each GC/MS system used? J _ ]_
(See SOW p. D - 59/SV, Section 8.7)
ACTION: If any method blank data are missing,
call lab for explanation/ resubmittal .
If not available, use professional
judgement to determine if the associated
sample data should be qualified.
- 24 -
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STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
5.4 Chromatography: review the blank raw data -
chromatograms (RICs), quant reports or data
system printouts and spectra.
Is the chromatographic performance (baseline
stability) for each instrument acceptable for
BNAs?
ACTION: Use professional judgement to determine
the effect on the data.
6.0 Contamination
Note: "Water blanks", "drill blanks" and
"distilled water blanks" are validated
like any other sample and are not used
to qualify the data. Do not confuse them
with the other QC blanks discussed below.
6.1 Do any method/instrument/reagent blanks have
positive results (TCL and/or TIC) for BNAs?
When applied as described below, the
contaminant concentration in these blanks are
multiplied by the sample dilution factor and
corrected for % moisture where necessary. _[ ]_
6.2 Do any field/rinse/ blanks have positive
BNA results (TCL and/or TIC)? r 1
ACTION: Prepare a list of the samples associated
with each of the contaminated blanks.
(Attach a separate sheet.)
Note: All field blank results associated to
a particular group of samples (may
exceed one per case) must be used to
qualify data. Blanks may not
be qualified because of contamination
in another blank . Field Blanks must be
qualified for surrogate, spectral, instrument
performance or calibration QC problems.
- 25 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: Follow the directions in the table
below to qualify TCL results due to
contamination. Use the largest value
from all the associated blanks. If
gross contamination exists, all data
in the associated samples should be qualified
as unusable (R).
Sample cone > CRQL Sample cone CRQL
but < lOx blank is< lOx blank value value & >10x blank
Common Phthalate Esters
Flag sample result Report CRQL & No qualification
with a "U"; qualify "U" is needed
Sample cone > CRQL Sample cone < CRQL & Sample cone > CRQL
but < 5x blank is < 5x blank value value & >5 blank value
Other Contaminants
Flag sample result Report CRQL & No qualification
with a "U"; qualify "U" is needed
NOTE: Analytes qualified "U" for blank contamination
are still considered as "hits" when qualifying
for calibration criteria.
ACTION: For TIC compounds, if the
concentration in the sample is less
than five times the concentration in
the most contaminated associated blank,
flag the sample data "R" (unusable).
6.3 Are there field/rinse/equipment blanks
associated with every sample? r 1
ACTION: For low level samples, note in data
assessment that there is no associated
field/rinse/equipment blank. Exception:
samples taken from a drinking water tap
do not have associated field blanks.
- 26 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
7.0 GC/MS Instrument Performance Check
7.1 Are the GC/MS Instrument Performance Check Forms
(Form V) present for Decafluorotriphenylphosphine
(DFTPP)?
7.2 Are the enhanced bar graph spectrum and mass/
charge (m/z) listing for the DFTPP provided for
each twelve hour shift? j; ]_
7.3 Has an instrument performance check solution
been analyzed for every twelve hours of sample
analysis per instrument? j; ]_
ACTION: List date, time, instrument ID, and
sample analyses for which no
associated GC/MS tuning data are
available.
DATE TIME INSTRUMENT SAMPLE NUMBERS
ACTION: If lab cannot provide missing data,
reject ("R") all data generated outside
an acceptable twelve hour calibration
interval.
ACTION: If mass assignment is in error, flag all
associated sample data as unusable (R).
7.4 Have the ion abundances been normalized to m/z
198? r 1
- 27 -
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STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
7.5 Have the ion abundance criteria been met for
each instrument used?
ACTION: List all data which do not meet ion
abundance criteria (attach a separate
sheet).
ACTION: If ion abundance criteria are not
met, the Region II TPO must
be notified.
7.6 Are there any transcription/calculation errors
between mass lists and Form Vs? (Check at least
two values but if errors are found, check more.)
7.7 Have the appropriate number of significant
figures (two) been reported? I ]_
ACTION: If large errors exist, call lab for
explanation/resubmittal, make
necessary corrections and document effect
in data assessments.
7.8 Are the spectra of the mass calibration compound
acceptable? J ].
ACTION: Use professional judgement to determine
whether associated data should be
accepted, qualified, or rejected.
8.0 Target Compound List (TCP Analytes
8.1 Are the Organic Analysis Data Sheets (Form I BNA)
present with required header information on each
page, for each of the following:
a. Samples and/or fractions as appropriate .[ ]_
b. Matrix spikes and matrix spike duplicates _[ 1
c. Blanks _[ 1
- 28 -
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STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
8.2 Has GPC cleanup been performed on all soil/
sediment sample extracts? r 1
ACTION: If data suggests that GPC was not
performed, use professional judgement.
Make note in "Contract
Problems/Non-compliance".
8.3 Are the BNA Reconstructed Ion Chromatograms,
the mass spectra for the identified compounds,
and the data system printouts (Quant Reports)
included in the sample package for each of the
following?
a. Samples and/or fractions as appropriate j; 1 _
b. Matrix spikes and matrix spike duplicates
(Mass spectra not required) r 1 __
c. Blanks _[ ]_ _
ACTION: If any data are missing, take action
specified in 3.2 above.
8.4 Are the response factors shown in the Quant
Report? _[ i _
8.5 Is chromatographic performance acceptable with
respect to:
Baseline stability?
Resolution?
Peak shape? _[ ±
Full-scale graph (attenuation)? r 1
Other:
ACTION: Use professional judgement to determine
the acceptability of the data.
- 29 -
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STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
8.6 Are the lab-generated standard mass spectra of
identified BNA compounds present for each
sample?
ACTION: If any mass spectra are missing, take
action specified in 3.2 above. If lab
does not generate their own standard
spectra, make note in "Contract Problems/
Non-compliance". If spectra are missing,
reject all positive data.
8.7 Is the RRT of each reported compound within 0.06
RRT units of the standard RRT in the continuing
calibration?
8.8 Are all ions present in the standard mass
spectrum at a relative intensity greater than
10% also present in the sample mass spectrum?
8.9 Do sample and standard relative ion intensities
agree within 20%?
9.0
ACTION: Use professional judgement to determine
acceptability of data. If it is
determined that incorrect identifications
were made, all such data should be
rejected (R), flagged "N" (Presumptive
evidence of the presence of the compound)
or changed to not detected (U) at
the calculated detection limit. In order
to be positively identified, the data
must comply with the criteria listed in
8.7, 8.8, and 8.9.
ACTION: When sample carry-over is a possibility,
professional judgement should be used to
determine if instrument cross-contamination
has affected any positive compound
identification.
Tentatively Identified Compounds fTIC)
9.1 Are all Tentatively Identified Compound Forms
(Form I, Part B) present; and do listed TICs
include scan number or retention time, estimated
concentration and "JN" qualifier? r 1
- 30 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
9.2 Are the mass spectra for the tentatively
identified compounds and associated "best match"
spectra included in the sample package for each
of the following:
a. Samples and/or fractions as appropriate j; 1
b. Blanks _[ ]_
ACTION: If any TIC data are missing, take
action specified in 3.2 above.
ACTION: Add "JN" qualifier if missing.
9.3 Are any TCL compounds (from any fraction) listed
as TIC compounds (example: l,2-dimethylbenzene is
xylene a VOA TCL - and should not be reported as
a TIC)?
ACTION: Flag with "R" any TCL compound
listed as a TIC.
9.4 Are all ions present in the reference mass
spectrum with a relative intensity greater than
10% also present in the sample mass spectrum? j; 1
9.5 Do TIC and "best match" standard relative ion
intensities agree within 20%? r 1
ACTION: Use professional judgement to
determine acceptability of TIC
identifications. If it is determined
that an incorrect identification
was made, change identification to
"unknown" or to some less specific
identification (example: "C3
substituted benzene") as appropriate.
Also, when a compound is not found in
any blank, but is a suspected artifact
of a common laboratory contaminant, the
result should be qualified as unusable
(R).
- 31 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
10.0 Compound Ouantitation and Reported Detection Limits
10.1 Are there any transcription/calculation errors in
Form I results? Check at least two positive values.
Verify that the correct internal standard/
guantitation ion, and RRF were used to calculate
Form I result. Were any errors found? j; 1
10.2 Are the CRQLs adjusted to reflect sample
dilutions and, for soils, sample moisture? .[ ]_
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and document
effect in data assessments.
ACTION: When a sample is analyzed at more
than one dilution, the lowest CRQLs
are used (unless a QC exceedance
dictates the use of the higher CRQL
data from the diluted sample analysis).
Replace concentrations that exceed the
calibration range in the original
analysis by crossing out the "E" and it's
associated value on the original Form I
and substituting the data from the analysis
of the diluted sample. Specify which Form I
is to be used, then draw a red " X" across
the entire page of all Form I's that should
not be used, including any in the summary
package.
11.0 Standards Data (GO/MS)
11.1 Are the Reconstructed Ion Chromatograms, and
data system printouts (Quant, Reports) present
for initial and continuing calibration? X 1
ACTION: If any calibration standard data
are missing, take action specified
in 3.2 above.
- 32 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
12.0 GC/MS Initial Calibration (Form
12.1 Are the Initial Calibration Forms (Form VI)
present and complete for the BNA fraction? r 1
ACTION: If any calibration standard forms
are missing, take action specified
in 3.2 above.
12.2 Are response factors stable for BNAs over
the concentration range of the calibration?
(% Relative standard deviation (%RSD) < 30.0%) r 1
ACTION: Circle all outliers in red.
NOTE: Although 20 BNA compounds have a minimum
RRF and no maximum %RSD, the technical
criteria are the same for all analytes.
ACTION: If the % RSD is > 30.0%, qualify
positive results for that analyte "J"
and non-detects using professional
judgement. When RSD > 90%, flag all non-
detect results for that analyte R (unusable).
NOTE: Analytes previously qualified "U" due to
blank contamination are still considered
as "hits" when qualifying for calibration
criteria.
12.3 Are all BNA compound RRFs > 0.05? r 1
ACTION: Circle all outliers in red.
ACTION: If any RRF < 0.05
1. "R" all non-detects.
2. "J" all positive results.
12.4 Are there any transcription/calculation errors in
the reporting of average response factors (RRF)
or % RSD? (Check at least two values but if errors
are found, check more.) _[ i
ACTION: Circle Errors in red.
- 33 -
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STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and note
errors in data assessments.
13.0 GC/MS Continuing Calibration rForm VII)
13.1 Are the Continuing Calibration Forms (Form VII)
present and complete for the BNA fraction? r 1
13.2 Has a continuing calibration standard been
analyzed for every twelve hours of sample
analysis per instrument?
ACTION: List below all sample analyses
that were not within twelve hours
of a continuing calibration analysis
for each instrument used.
ACTION: If any forms are missing or no
continuing calibration standard
has been analyzed within twelve
hours of every sample analysis,
call lab for explanation/
resubmittal. If continuing
calibration data are not available,
flag all associated sample data as
unusable ("R").
13.3 Do any semivolatile compounds have a % Difference
(% D) between the initial and continuing RRF
which exceeds the + 25.0% criteria?
ACTION: Circle all outliers in red.
ACTION: Qualify both positive results and
non-detects for the outlier
compound(s) as estimated (J). When %D is
above 90%, reject all non-detects for that
analyte (R) unusable.
- 34 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
13.4 Do any semivolatile compounds have a RRF <0.05? j; ]_
ACTION: Circle all outliers in red.
ACTION: If RRF <0.05, qualify as unusable (R)
associated non-detects and "J" associated
positive values.
13.5 Are there any transcription/calculation errors
in the reporting of average response factors
(RRF) or % difference (%D) between initial and
continuing RRFs? (Check at least two values
but if errors are found, check more). _[ i
ACTION: Circle errors in red.
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and document
effect in data assessments.
14.0 Internal Standards (Form VIII1
14.1 Are the internal standard areas (Form VIII) of
every sample and blank within the upper and
lower limits (-50% to + 100%) for each continuing
calibration? j ]_
ACTION: List all the outliers below.
Sample # Internal Std Area Lower Limit Upper Limit
(Attach additional sheets if necessary.)
ACTION: 1. If the internal standard area count
is outside the upper or lower limit,
flag with "J" all positive results
and non-detects (U values) quantitated
with this internal standard.
- 35 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YESNON/A
2. Non-detects associated with IS areas
> 100% should not be qualified.
3. If the IS area is below the lower limit
(<50%), qualify all associated non-detects
(U-values) "J". If extremely low area counts
are reported (<25%) or if performance
exhibits a major abrupt drop off, flag all
associated non-detects as unusable (R).
14.2 Are the retention times of the internal standards
within 30 seconds of the associated calibration
standard?
ACTION: Professional judgement should be
used to qualify data if the
retention times differ by more than
30 seconds.
15.0 Field Duplicates
15.1 Were any field duplicates submitted for BNA
analysis? _[ ]_
ACTION: Compare the reported results for
field duplicates and calculate
the relative percent difference.
ACTION: Any gross variation between field
duplicate results must be addressed
in the reviewer narrative. However,
if large differences exist,
identification of field duplicates
should be confirmed by contacting the
sampler.
- 36 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A"
PART C: PESTTCTDE/PCB ANALYSTS
1.0 Traffic Reports and Laboratory Narrative
1.1 Are Traffic Report Forms present for all r 1
samples?
ACTION: If no, contact lab for replacement of
missing or illegible copies.
1.2 Do the Traffic Reports or SDG Narrative indicate
any problems with sample receipt, condition of
the samples, analytical problems or special
circumstances affecting the quality of the data? r 1
ACTION: If any sample analyzed as a soil, other
than TCLP, contains 50%-90% water,
all data should be qualified as estimated
(J). If a soil sample, other than TCLP,
contains more than 90% water, all data
should be qualified as unusable (R).
ACTION: If samples were not iced upon receipt at
the laboratory, flag all positive results
"J" and all non-detects "UJ".
2.0 Holding Times
2.1 Have any PEST/PCB technical holding times,
determined from date of collection to date of
extraction, been exceeded? r -\
Water and soil samples for PEST/PCB analysis
must be extracted within 7 days of the date of
collection. Extracts must be analyzed within 40
days of the date extraction.
- 37 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: If technical holding times are exceeded,
flag all positive results as estimated
(J) and sample quantitation limits (UJ)
and document in the narrative that holding
times were exceeded. If analyses were done
more than 14 days beyond holding time,
either on the first analysis or upon
re-analysis, the reviewer must use
professional judgement to determine the
reliability of the data and the effects
of additional storage on the sample results.
At a minimum, all the data should at least be
qualified "J", but the reviewer may determine
that non-detects are unusable (R) .
3.0 Surrogate Recovery (Form II)
3.1 Are the PEST/PCB Surrogate Recovery Summaries
(Form II) present for each of the following
matrices?
a. Low Water
b. Soil r 1
3.2 Are all the PEST/PCB samples listed on the
appropriate Surrogate Recovery Summary for
each of the following matrices?
a. Low Water X I
b. Soil r 1
ACTION: Call lab for explanation/resubmittals.
If missing deliverables are unavailable,
document effect in data assessments.
3.3 Were outliers marked correctly with an
asterisk? r 1
ACTION: Circle all outliers in red.
3.4 Were surrogate recoveries of TCX or DCB
outside of the contract specification for
any sample or blank? (60-150%) [ ]
- 38 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: No qualification is done if surrogates
are diluted out. If recovery for both
surrogates is below the contract limit,
but above 10%, flag all results for that
sample 'J". If recovery is < 10% for
either surrogate, qualify positive
results 'J" and flag non-detects "R".
If recovery is above the contract advisory
limits for both surrogates qualify positive
values "J".
3.5 Were surrogate retention times (RT) within the
windows established during the initial 3-point
analysis of Individual Standard Mixture A? £ 1
ACTION: If the RT limits are not met, the
analysis may be qualified unusable (R)
for that sample on the basis of
professional j udgement.
3.6 Are there any transcription/calculation errors
between raw data and Form II? j; ]_
ACTION: If large errors exist, call lab for
explanation/resubmittal. Hake any
necessary corrections and document
effect in data assessments.
4.0 Matrix Spikes (Form III)
4.1 Is the Matrix Spike/Matrix Spike Duplicate
Recovery Form (Form III) present? .[ 1
4.2 Were matrix spikes analyzed at the required
frequency for each of the following matrices?
(1 MS/MSD must be performed for every 20 samples
of similar matrix or concentration level)
a. Low Water r 1
b. Soil r 1
ACTION: If any matrix spike data are missing,
take the action specified in 3.2 above.
- 39 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
4.3 How many PEST/PCB spike recoveries are outside
QC limits?
Water Soil
out of 12 out of 12
4.4 How many RPD's for matrix spike and matrix spike
duplicate recoveries are outside QC limits?
Water
out of 6
ACTION: No action is taken on MS/MSD data alone.
However, using informed professional
judgement, the data reviewer may use the
matrix spike and matrix spike duplicate
results in conjunction with other QC
criteria and determine the need for some
qualification of the data.
5.0 Blanks (Form IV)
5.1 Is the Method Blank Summary (Form IV) present?.[ ]_
5.2 Frequency of Analysis: For the analysis of
Pesticide/PCB TCL compounds, has a reagent/
method blank been analyzed for each SDG or
every 20 samples of similar matrix
or concentration or each extraction batch,
whichever is more frequent? .[ ]_
ACTION: If any blank data are missing, take
the action specified above in 3.2. If
blank data is not available, reject
(R) all associated positive data.
However, using professional judgement,
the data reviewer may substitute field
blank data for missing method blank data.
5.3 Has a PEST/PCB instrument blank been analyzed
at the beginning of every 12 hr. period following
the initial calibration sequence? (minimum
contract requirement)
- 40 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: If any blank data are missing, call lab for
explanation/resubmittals. If missing
deliverables are unavailable, document the
effect in data assessments.
5.4 Chromatography: review the blank raw data -
chromatograms, quant reports or data system
printouts.
Is the chromatographic performance (baseline
stability) for each instrument acceptable for
PEST/PCBs? r 1
ACTION: Use professional judgement to determine
the effect on the data.
6.0 Contaminat i on
NOTE: "Water blanks", "distilled water blanks" and
"drilling water blanks" are validated like any
other sample and are not used to qualify the
data. Do not confuse them with the other QC
blanks discussed below.
6.1 Do any method/instrument/reagent/cleanup blanks
have positive results for PEST/PCBs? When applied
as described below, the contaminant concentration
in these blanks are multiplied by the sample
Dilution Factor and corrected for % moisture when
necessary. _[ ]_
6.2 Do any field/rinse blanks have positive
PEST/PCB results?
ACTION: Prepare a list of the samples associated
with each of the contaminated blanks.
(Attach a separate sheet)
NOTE: All field blank results associated to a particular
group of samples (may exceed one per case or one per
day) may be used to qualify data. Blanks may not be
qualified because of contamination in another blank.
Field blanks must be qualified for
surrogate, or calibration QC problems.
- 41 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: Follow the directions in the table below
to qualify TCL results due to contamination.
Use the largest value from all the associated blanks.
Sample cone > CRQL Sample cone < CRQL & Sample cone > CRQL
but < 5x blank is < 5x blank value & > 5x blank value
Flag sample result Report CRQL & No qualification
with a "U"; qualify "U" is needed
NOTE: If gross blank contamination exists, all data
in the associated samples should be
qualified as unusable (R).
6.3 Are there field/rinse/equipment blanks associated
with every sample? [ 1
ACTION: For low level samples, note in data assessment
that there is no associated field/rinse/equipment blank.
Exception: samples taken from a drinking water tap
do not have associated field blanks.
7.0 Calibration and GC Performance
7.1 Are the following Gas Chromatograms and Data
Systems Printouts for both columns present
for all samples, blanks, MS/MSD?
a. peak resolution check
b. performance evaluation mixtures
c. aroclor 1016/1260
d. aroclors 1221, 1232, 1242, 1248, 1254 r 1
e. toxaphene [ ]
f. low points individual mixtures A & B [ 1
g. med points individual mixtures A & B .[ ].
h. high points individual mixtures A & B _[ 1
- 42 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
i. instrument blanks _[ ^
ACTION: If no, take action specified in 3.2 above.
7.2 Are Forms VI - PEST 1-4 present and complete
for each column and each analytical sequence? r 1
ACTION: If no, take action specified in 3.2
above.
7.3 Are there any transcription/calculation errors
between raw data and Forms VI? j; ±
ACTION: If large errors exist, call lab for
explanation/resubmittal, make
necessary corrections and
document effect in data assessments.
7.4 Do all standard retention times, including each
pesticide in each level of Individual Mixtures
A & B, fall within the windows established
during the initial calibration analytical
sequence? (For Initial Calibration Standards,
Form VI - PEST - 1). r 1
ACTION: If no, all samples in the entire
analytical sequence are potentially
affected. Check to see if the
chromatograms contain peaks within an
expanded window surrounding the expected
retention times. If no peaks are found
and the surrogates are visible, non-
detects are valid. If peaks are present
and cannot be identified through pattern
recognition or using a revised RT window,
qualify all positive results and non-detects
as unusable (R) .
For aroclors, RT may be outside the RT window,
but the aroclor may still be identified from the
individual pattern.
7.5 Are the linearity criteria for the initial
analyses of Individual Standards A & B within
limits for both columns? (% RSD must be < 20.0%
for all analytes except for the 2 surrogates,
which must not exceed 30.0 % RSD). See Form VI
PEST - 2. j- T
- 43 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ACTION: If no, qualify all associated positive
results generated during the entire
analytical sequence "J" and all non-
detects "UJ". When RSD >90%, flag all
non-detect results for that analyte R
(unusable).
7.6 Is the resolution between any two adjacent
peaks in the Resolution Check Mixture > 60.0%
for both columns? (Form VI-PEST - 4) r ]
ACTION: If no, positive results for compounds
that were not adequately resolved should
be qualified "J". Use professional
judgement to determine if non-detects
which elute in areas affected by co-eluting
peaks should be qualified "N" as presumptive
evidence of presence or unusable (R).
7.7 Is Form VII - Pest-1 present and complete for
each Performance Evaluation Mixture analyzed
during the analytical sequence for both
columns? _[ ]_
ACTION: If no, take action as specified in
3.2 above.
7.8 Has the individual % breakdown exceeded 20.0%
on either column. _[ ]_
- for 4,4' - DDT? r 1
- for endrin?
Has the combined % breakdown for 4,4'- DDT/
Endrin exceeded 30.0% on either column?
(required in all instances) [ ]
ACTION: l. If any % breakdown has failed the
QC criteria in either PEM in steps
2 and 17 in the initial calibration
sequence (p. D-38/Pest SOW 3/90),
qualify all sample analyses in the
entire analytical sequence as described
below.
- 44 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
2. If any % breakdown has failed the QC
criteria in a PEM Verification
calibration, review data beginning
with the samples which followed the
last in-control standard until the
next acceptable PEM & qualify the
data as described below.
a. 4,4'-DDT Breakdown: If 4,4'-DDT breakdown
is greater than 20.%:
i.- Qualify all positive results for DDT
with "J". If DDT was not detected, but
ODD and DDE are positive, then qualify
the quant it at ion limit for DDT as
unusable (R) .
ii. Qualify positive results for ODD and/or
DDE as presumptively present at an
approximated quantity (NJ) .
b. Endrin Breakdown: If endrin breakdown is greater
than 20.0%:
i. Qualify all positive results for endrin
with "J". If endrin was not detected, but
endrin aldehyde and endrin ketone are
positive, then qualify the quantitation
limit for endrin as unusable (R) .
ii. Qualify positive results for endrin ketone and
endrin aldehyde as presumptively present at an
approximated quantity (NJ) .
c. Combined Breakdown: If the combined 4,4'-DDT and
endrin breakdown is greater than 30.0%:
i. Qualify all positive results for DDT and
endrin with "J". If endrin was not
detected, but endrin aldehyde and endrin
ketone are positive, then qualify the
quantitation limit for endrin as unusable
(R) . If DDT was not detected, but ODD and
DDE are positive, then qualify the
quantitation limit for DDT as unusable (R) .
- 45 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
ii. Qualify positive results for endrin ketone
and endrin aldehyde as presumptively present
at an approximated quantity (NJ). Qualify positive
results for DDD and/or DDE as presumptively present
at an approximated quantity (NJ) .
7.9 Are the relative percent difference (RPD) values
for all PEM analytes <25.0%? (Form VII-PEST-1) r 1
ACTION: If no, qualify all associated positive
results generated during the analytical
sequence "J" and sample quantitation
limits "UJ".
NOTE: If the failing PEM is part of the
initial calibration, all samples are
potentially affected. If the offending
standard is a verification calibration,
the associated samples are those which
followed the last in-control standard
until the next passing standard.
7.10 Have all samples been injected within a 12 hr.
period beginning with the injection of an
Instrument Blank? j; 1
ACTION: If no, use professional judgement to
determine the severity of the effect
on the data and qualify accordingly.
7.11 Is Form VII - Pest-2 present and complete for
each INDA and INDB Verification Calibration
analyzed? _[ ]_
ACTION: If no, take action specified in 3.2 above.
7.12 Are there any transcription/calculation errors
between raw data and Form VII - Pest-2? I 1
ACTION: If large errors exists, call lab for
explanation/resubmittal, make any
necessary corrections and document
effect in data assessments.
under "Conclusions".
- 46 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
7.13 Do all standard retention times for each INDA
and INDB Verification Calibration fall within
the windows established by the initial
calibration sequence? j ]_
ACTION: If no, beginning with the samples which
followed the last in-control standard,
check to see if the chromatograms contain
peaks within an expanded window surrounding
the expected retention times. If no peaks
are found and the surrogates are visible,
non-detects are valid. If peaks are present
and cannot be identified through pattern
recognition or using a revised RT window,
qualify all positive results and non-detects
as unusable (R).
7.14 Are RPD values for all verification calibration
standard compounds < 25.0%? _[ ]_
ACTION: If the RPD is >25.0% for the compound
being quantitated, qualify all associated
positive results "J" and non-detects "UJ".
The "associated samples" are those which
followed the last in-control standard up
to the next passing standard containing
the analyte which failed the criteria.
If the RPD is >90%, flag all non-detects
for that analyte R (unusable).
8.0 Analytical Sequence Check fForm VIII-PEST1
8.1 Is Form VIII present and complete for each column
and each period of analyses? .[ ]_
ACTION: If no, take action specified in 3.2 above.
8.2 Was the proper analytical sequence followed for
each initial calibration and subsequent analyses?
(see CLP SOW p. D-39 & D-41/PEST) r 1
ACTION: If no, use professional judgement to
determine the severity of the effect
on the data and qualify it accordingly.
Generally, the effect is negligible
unless the sequence was grossly altered
or the calibration was also out of limits.
- 47 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
9.0 Cleanup Efficiency Verification fForm
9.1 Is Form IX - Pest-1 present and complete for each
lot of Florisil Cartridges used? (Florisil Cleanup
is required for all Pest/PCB extracts.) r 1
ACTION: If no, take action specified in 3.2 above.
If data suggests that florisil cleanup
was not performed, make note in "Contract
Problems/Non-Compliance".
9.2 Are all samples listed on the Pesticide Florisil
Cartridge Check Form? _[ ]_
ACTION: If no, take action specified in 3.2 above.
9.3 If GPC Cleanup was performed, (mandatory for all
soil sample extracts) is Form IX - Pest-2
present? _[ ]_
ACTION: If no, take action specified in 3.2 above.
ACTION: If GPC was not performed when required,
make note in" Contract Problems/Non-
Compliance" section of data assessment.
9.4 Are percent recoveries (% R) of the pesticide and
surrogate compounds used to check the efficiency
of the cleanup procedures within QC limits:
80-120% for florisil cartridge check? r 1
80-110% for GPC calibration? r 1
Qualify only the analyte(s) which fail the recovery
criteria as follows:
ACTION: If % R are < 80%, qualify positive
results "J" and quantitation limits
"UJ". Non-detects should be qualified
"R" if zero %R was obtained for
pesticide compounds. Use professional
judgement to qualify positive results
if recoveries are greater than the upper
limit.
- 48 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
NOTE: Sample data should be evaluated for
potential interferences if recovery
of 2,4,5-trichlorophenol was > 5% in the
Florisil Cartridge Performance Check
analysis. Make note in Contract Problems/
Non-Compliance section of reviewer narrative.
NOTE: The raw data of the GPC Calibration
Check analysis is evaluated for pattern
similarity with previously run Aroclor
standards.
10.0 Pesticide/PCB Identification
10.1 Is Form X complete for every sample in which a
pesticide or PCS was detected? r 1
ACTION: If no, take action specified in 3.2 above.
10.2 Are there any transcription/calculation errors
between raw data and Forms 6E, 6G, 7E, 7Df 8D.
9A, B, 10A.
ACTION: If large errors exist, call lab for
explanation/resubmittal, make necessary
corrections and note error under
"Conclusions".
10.3 Are retention times (RT) of sample compounds
within the established RT windows for both
analyses?
Was GC/MS confirmation provided when required
(when compound concentration is > 10 ug/ml in
final extract) ? _[ ]_
Action: Use professional judgement to qualify
positive results which were not confirmed
by GC/MS. Qualify as unusable (R) all
positive results which were not confirmed
by second GC column analysis. Also qualify
as unusable (R) all positive results not
meeting RT window unless associated standard
compounds are similarly biased, (see
Functional Guidelines) The reviewer should
use professional judgement to assign an
appropriate quantitation limit.
- 49 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
10.4 Is the percent difference (% D) calculated for the
positive sample results on the two GC columns
< 25.0%? r 1
ACTION: If the reviewer finds neither column
shows interference for the positive
hits, the data should be flagged
as follows:
% Difference Qualifier
25-50 % J
50-90 % JN
> 90 % R
NOTE: The lower of the two values is reported
on Form I. If using professional judgement,
the reviewer determines that the higher
result was more acceptable, the reviewer
should replace the value and indicate the
reason for the change in the data assessment.
10.5 Check chromatograms for false negatives, especially
the multiple peak compounds toxaphene and PCBs.
Were there any false negatives? _[ ]_ .
ACTION: Use professional judgement to decide
if the compound should be reported. If
the appropriate PCB standards were not
analyzed, qualify the data unusable (R).
11.0 Compound Quantitation and Reported Detection Limits
11.1 Are there any transcription/calculation errors in
Form I results? Check at least two positive values.
Were any errors found? _[ ]_
NOTE: Single-peak pesticide results can be checked for rough
agreement between quantitative results obtained on the two GC
columns. The reviewer should use professional judgement to
decide whethera much larger concentration obtained on one
column versus the other indicates the presence of an
interfering compound. If an interfering compound is
indicated, the lower of the two values should be reported and
qualified as presumptively present at an approximated
quantity (NJ). This necessitates a determination of an
estimated concentration on the confirmation column. The
narrative should indicate that the presence of interferences
has interfered with the evaluation of the second column
confirmation.
- 50 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YESNO N/A
11.2 Are the CRQLs adjusted to reflect sample dilutions
and, for soils, % moisture? _[ ]_
ACTION: If errors are large, call lab for
explanation/resubmittal, make any
necessary corrections and document
effect in data assessments.
ACTION: When a sample is analyzed at more than
one dilution, the lowest CRQLs are used
(unless a QC exceedance dictates the use
of the higher CRQL data from the diluted
- sample analysis). Replace concentrations
that exceed the calibration range in the
original analysis by crossing out the "E"
value on the original Form I and substituting
it with data from the analysis of diluted
sample. Specify which Form I is to be used,
then draw a red "X" across the entire page
of all Form I's that should not be used,
including any in the summary package.
ACTION: Quantitation limits affected by large,
off-scale peaks should be qualified as
unusable (R) . If the interference is
on-scale, the reviewer can provide an
approximated quantitation limit (UJ) for
each affected compound.
12.0 Chromatoaram Quality
12.1 Were baselines stable?
12.2 Were any electropositive displacement
(negative peaks) or unusual peaks seen? .[ 1
ACTION: Address comments under System
Performance of data assessment.
- 51 -
-------
STANDARD OPERATING PROCEDURE
Date: January 1992
Revision: 8
YES NO N/A
13.0 Field Duplicates
13.1 Were any field duplicates submitted for
PEST/PCB analysis?
ACTION: Compare the reported results for
field duplicates and calculate the
relative percent difference.
ACTION: Any gross variation between field
duplicate results must be addressed
in the reviewer narrative. However, if
large differences exist, identification
of field duplicates should be confirmed
by contacting the sampler.
- 52 -
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
CLP DATA ASSESSMENT
Functional Guidelines for Evaluating Organic Analysis
Case No. SDG No. LABORATORY SITE
DATA ASSESSMENT:
The current Functional Guidelines for evaluating organic data have
been applied.
All data are valid and acceptable except those analytes which have
been qualified with a "J" (estimated), "N" (presumptive evidence
for the presence of the material), »U" (non-detects) , "R"
(unusable),or »JN" (presumptive evidence for the presence of the
material at an estimated value). All action is detailed on the
attached sheets.
Two facts should be noted by all data users. First, the "R" flag
means that the associated value is unusable. In other words, due
to significant Q_C problems, the analysis is invalid and provides no
information as to whether the compound is present or not. "R"
values should not appear on data tables because they cannot be
relied upon, even as a last resort. The second fact to keep in
mind is that no compound concentration, even if it has passed all
QC tests, is guaranteed to be accurate. Strict QC serves to
increase confidence in data but any value potentially contains
error.
Reviewer's
Signature: Date: / /199
Verified By: Date: / /199
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
1. HOLDING TIME:
The amount of an analyte in a sample can change with time due to
chemical instability, degradation, volatilization, etc. If the
specified holding time is exceeded, the data may not be valid.
Those analytes detected in the samples whose holding time has been
exceeded will be qualified as estimated, "J". The non-detects
(sample guantitation limits) will be flagged as estimated, "J", or
unusable, "R", if the holding times are grossly exceeded.
The following analytes in the samples shown were qualified because
of holding time:
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
2. BLANK CONTAMINATION:
Quality assurance (QA) blanks, i.e., method, trip, field, or rinse
blanks are prepared to identify any contamination which may have
been introduced into the samples during sample preparation or field
activity. Method blanks measure laboratory contamination. Trip
blanks measure cross-contamination of samples during shipment.
Field and rinse blanks measure cross- contamination of samples
during field operations. If the concentration of the analyte is
less than 5 times the blank contaminant level (10 times for the
common contaminants), the analytes are qualified as non- detects,
«y". The following analytes in the samples shown were qualified
with "U11 for these reasons:
A) Method blank contamination
B) Field or rinse blank contamination ("water blanks" or
"distilled water blanks" are validated like any other sample)
C) Trip blank contamination
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
3. MASS SPECTROMETER TUNING:
Tuning and performance criteria are established to ensure adequate
mass resolution, proper identification of compounds, and to some
degree, sufficient instrument sensitivity. These criteria are not
sample specific. Instrument performance is determined using
standard materials. Therefore, these criteria should be met in all
circumstances. The tuning standard for volatile organics is
bromofluorobenzene (BFB) and for semi-volatiles is
decafluorotriphenyl- phosphine (DFTPP).
If the mass calibration is in error, or missing, all associated
data will be classified as unusable, "R". The following samples
shown were qualified with "R" because of tuning:
-------
ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
4. CALIBRATION:
Satisfactory instrument calibration is established to ensure that
the instrument is capable of producing acceptable quantitative
data. An initial calibration demonstrates that the instrument is
capable of giving acceptable performance at the beginning of an
experimental sequence. The continuing calibration verifies that
the instrument is giving satisfactory daily performance.
A) RESPONSE FACTOR
The response factor measures the instrument's response to specific
chemical compounds. The response factor for the VOA/BNA Target
Compound List (TCL) must be > 0.05 in both the initial and
continuing calibrations. A value < 0.05 indicates a serious
detection and quantitation problem (poor sensitivity) . If the mean
RRF of the initial calibration or the continuing calibration has a
response factor <0.05 for any analyte, those analytes detected in
environmental samples will be qualified as estimated, "J". All
non-detects for those compounds will be rejected ("R"). The
following analytes in the samples shown were qualified because of
response factor:
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ATTACHMENT 1
SOP NO. HW-6 page of
DATA ASSESSMENT
5. CALIBRATION:
A) PERCENT RELATIVE STANDARD DEVIATION (%RSD) AND PERCENT
DIFFERENCE (%D):
Percent RSD is calculated from the initial calibration and is used
to indicate the stability of the specific compound response factor
over increasing concentration. Percent D compares the response
factor of the continuing calibration check to the mean response
factor (PRF) from the initial calibration. Percent D is a measure
of the instrument's daily performance. Percent RSD must be <30%
and %D must be <25%. A value outside of these limits indicates
potential detection and quantitation errors. For these reasons,
all positive results are flagged as estimated, "J"; and
non-detects are flagged "UJ". If %RSD and %D grossly exceed QC
criteria, non-detect data may be qualified "R".
For the PCB/PESTICIDE fraction, if %RSD exceeds 20% for all
analytes except for the 2 surrogates (which must not exceed 30%
RSD), qualify all associated positive results "J" and non-detects
MUJ".
The following analytes in the samples shown were qualified for %RSD
and %D:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
6. SURROGATES/ SYSTEM MONITORING COMPOUNDS (SMC):
All samples are spiked with surrogate/ SMC compounds prior to
sample preparation to evaluate overall laboratory performance and
efficiency of the analytical technique. If the measured surrogate/
SMC concentrations were outside contract specifications,
qualifications were applied to the samples and analytes as shown
below. The following analytes for the samples shown were qualified
because of surrogate/ SMC recovery:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
7. INTERNAL STANDARDS PERFORMANCE:
Internal Standard (IS) performance criteria ensure that the GC/MS
sensitivity and response are stable during every experimental run.
The internal standard area count must not vary by more than a
factor of 2 (-50% to +100%) from the associated continuing
calibration standard. The retention time of the internal standard
must not vary more than ±30 seconds from the associated continuing
calibration standard. If the area count is outside the (-50% to
+100%) range of the associated standard, all of the positive
results for compounds quantitated using that IS are qualified as
estimated, "J", and all non-detects as "UJ" only if IS area is
< 50%. Non detects are qualified as "R" if there is a severe loss
of sensitivity ( < 25% of associated IS area counts).
If an internal standard retention time varies by more than 30
seconds, the reviewer will use professional judgment to determine
either partial or total rejection of the data for that sample
fraction. The following analytes in the samples shown were
qualified because of internal standards performance:
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ATTACHMENT 1
SOP NO. HW-6 page of
DATA ASSESSMENT
8. COMPOUND IDENTIFICATION:
A) VOLATILE AND SEMI-VOLATILE FRACTIONS
TCL compounds are identified on the GC/MS by using the analyte's
relative retention time (RRT) and ion spectra. For the results to
be a positive hit, the sample peak must be within ±0.06 RRT units
of the standard compound, and have an ion spectra which has a ratio
of the primary and secondary m/e intensities within 20% of that in
the standard compound. For tentatively identified compounds (TIC) ,
the ion spectra must match accurately. In the cases where there is
not an adequate ion spectrum match, the laboratory may have
provided false positive identifications. The following analytes in
the samples shown were qualified for compound identification:
B) PESTICIDE FRACTION:
The retention times of reported compounds must fall within the
calculated retention time windows for the two chromatographic
columns. The percent difference (%D) of the positive results
obtained on the two GC columns should be <25% The following
analytes in the samples shown were qualified because of compound
identification:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
9. MATRIX SPIKE/SPIKE DUPLICATE, MS/MSD:
The MS/MSD data are generated to determine the long-term precision
and accuracy of the analytical method in various matrices. The
MS/MSD may be used in conjunction with other QC criteria for some
additional qualification of data. The following analytes, for the
samples shown, were qualified because of MS/MSD:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
10. OTHER QC DATA OUT OF SPECIFICATION:
11. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT (continued on next
page if necessary):
12. CONTRACTUAL NON-COMPLIANCE:
13. This package contains re-extraction, re-analysis or
dilution. Upon reviewing the QA results, the following form
I(s) are identified to be used:
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ATTACHMENT 1
SOP NO. HW-6 Page of
DATA ASSESSMENT
11. SYSTEM PERFORMANCE AND OVERALL ASSESSMENT (continued)
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SOP NO. EJf-7
Revision * 3
DKEA VALIDATION
BY:
Leon I^zarus,^Environmental Scientist
Toxic and Hazardous Waste Section
BY:
George
Toxic andTiazardous Waste Section
OCWCUERED BY;
APERCfVED BY;
Runyth/ fioief
MonitoriJig Managsment Bcsnch
/a. h r >
ous Waste Section
-------
ALL LAND BAN TCLP ANALYSIS MUST USE SW-846 METHODS.
THIS SOP ONLY APPRAISES THE TCLP EXTRACTION PROCEDURE. TO COMPLETELY VALIDATE A
TOP ANALYSIS, YOU MUST ALSO USE THE REGION II SOPS FOR ORGANIC AND INORGANIC DATA
VALIDATION.
BEFORE VALIDATING TCLP DATA, THE DATA VALIDATOR MUST DETERMINE IF ANY TOXICTTY
CHARACTERISTIC OR LAND BAN REGULATORY ACTION LEVELS ARE APPLICABLE.
YES NO N/A
Was a ZHE vessel used for VOAs? [ ]
Was there any evidence of leakage? [ ]
Action: If a ZHE vessel leaked, or was not used,
reject (R) all- VOA data, except data which
exceeds the regulatory level for any analyte.
See attached list for TC regulatory levels.
If other analytes are being validated, the validator
must determine which, if any, Land Ban regulatory
levels are applicable. The Land Ban TCLP
regulatory levels are listed in 40CFR268.
Did the lab use proper bottles? [ _ ] _ _
Action: If a plastic bottle was used, except for PTFE,
reject (R) all nan detect organic data. All positive
organic values should be flagged as presumptively present
at an estimated quantity (ON).
Did the lab correctly coiroute % solids? [ _ ] _ _
Action: If the lab made an error, request revised data.
If appropriate, did the lab reduce particle size? [ _ ] _ _
Action: If the lab did not perform a required
particle size reduction, reject (R) all non detects.
All positive values should be flagged as
presumptively present at an estimated quantity (JN) .
Was the correct extraction fluid used?
Was the pH of the extraction fluid correct?
(4.88-4.98 for fluid #1) (2.83 - 2.93 for
extraction fluid
Action: If the extraction fluid pH was wrong, or the
wrong fluid was used, reject (R) all non detects.
All positive values 'should be flagged as presumptively
present at an estimated quantity (JN) .
-1-
-------
YES NO N/A
Was the correct weight of extraction fluid used? [ ]
Action: If the extraction fluid weight is not ±15%
of the correct value, flag all results as estimated (J).
If the extraction fluid weight is more than 30% above
the correct value, reject (R) all non detects, and
flag all positive values as presumptively present at
an estimated quantity (JN).
For volatile analytes, was the sample weight 25
grams or less? L ] —
Action: If the sample weight is more than
25 grains, flag all data as estimated (J).
Were the TCLP extracts properly preserved? [ ]
(Metals roust be preserved to a pH <2 with HNOj).
Action: If the preservative causes precipitation,
the sample should not be preserved, but the sample
should be analyzed as soon as possible after
extraction. The use of organic preservatives is optional.
If proper inorganic preservation procedures were not
followed, reject (R) all non detects, and flag all
positive values below regulatory action levels as
presumptively present at an estimated quantity (JN).
Positive data at concentrations above regulatory
action levels should not be qualified.
Is there a TCLP blank with the appropriate TCLP [ ]
fluid for every 20 samples? (This is in
addition to the method"blanks, which are required
for each analytical method).
Action: If there is no TCLP blank, call laboratory
for explanation/resubmittal. If not available,
reject (R) all associated positive data.
Contaminants in TCLP blanks should be
treated as method blank contaminants when validating
data.
Have samples been analyzed within TCLP holding
times from date of collection ? [ ]
NOTE: CLP holding times do not apply to TCLP analysis.
The following table lists TCLP holding times:
-2-
-------
TCLP Holding Times
TOP HOLDING
ITMES (DAYS)
VOA
ORGANIC
EXTRACTABLES
MERCURY
OlHEk METALS
FROM COLLECTION
TO TCLP EXTRACTION
14
14
28
180
FROM TOP EXTRACTION
TO PREPARATIVE
EXTRACTION
N/A
7
N/A
N/A
FROM PREPARATIVE
EXTRACTION TO
ANALYSIS
14
40
28
180
HOLDING TIME DECISION TABLE
Have samples been analyzed within TCLP holding time?
If Yes.
Action: Do not qualify data because of holding time.
If No.
Action: In the sample, does any analyte exceed the regulatory level?
Toxicity Characteristic regulatory action levels are listed on page 5 of this SOP.
The Land Ban regulatory action levels are listed in 40CFR268.
If No.
Action: Reject (R) all
analytes.
If Yes.
Action: Do not qualify
analytes which exceed
regulatory levels.
Mention in data
assessment that
reported value
represents the
minimum concentration
present.
Assume that TCLP analysis of TC analytes is for the purpose of determining
compliance with the TC regulatory levels (attached). If other analytes are being
validated, the validator roust determine which, if any, Land Ban regulatory levels
are applicable. The, Land Ban TCLP regulatory levels are listed in 40CFR268.
-3-
-------
ANALYTICAL DATA MUST BE VALIDATED ACCORDING TO THE REGIONAL ORGANIC AND INORGANIC
DATA VALIDATION SOPS BEFORE THE FOLLOWING QUESTIONS MAY BE ADDRESSED.
YES NO N/A
Have any acetates, acetic acid, or acetic anhydride
been reported as TICs? [ ]
Action : If yes, reject (R) TICs.
Are all organic compounds analyzed by the TCLP method
properly calibrated? [ ]
Analytes on Form I that have not been calibrated should
be qualified as follows: non-detects should be
rejected (R); positive values should be reported as
TICs, and flagged "ON".
Have multi-phasic samples been properly analyzed? [ ]
(Check to see if aqueous samples have > .5% solids.)
If not, reject (R) all data below regulatory action
levels.
Have adequate raw data deliverables been submitted? [ ]
Action: If not, contact the laboratory.
If the raw data is not available,
use professional judgement to qualify analytical
data, and mention in data assessment.
Was the method of standard additions properly [ ]
utilized for analysis of metals?
Action: If not, an metals data should be
qualified as estimated "J".
THE FOLLOWING STATEMENT MOST BE ADDED TO ALL TCLP DATA VALIDATION REPORTS:
Analytical data qualified as "JN" or "R" may not be used to demonstrate compliance
with Toxicity Characteristic or Land Ban Regulations.
-4-
-------
TC ANALYTES AND THEIR REGULATORY LEVELS
Regulatory
Constituent Level (ma/1)
benzene
carbon tetrachloride
chlordane
chlorobenzene
chlorofora
o-cresol
m-cresol
p-cresol
1 , 4-dichlorobenzene
1 , 2-dichloroethane
1, 1-dichloroethylene
2 , 4-diiuLtrotoluene
heptachlor
arsenic
barium
Gsdnumn
c^r\T^^K\\Tr\\
lead
•m^TnTr^/
seleniim
0.5
0.5
0.03
100.0
6.0
200.0
200.0
200.0
7.5
0.5
0.7
0.13
0.008
5.0
100.0
1.0
5.0
5.0
0.2
1.0
Regulatory
hexachlorobenzene 0.13
hexachloro-l,3-butadiene 0.5
hexachloroethane 3.0
methyl ethyl ketone 200.0
nitrobenzene 2.0
pentachlorophenol 100.0
pyridine 5.0
tetrachloroethylene 0.7
trichloroethylene 0.5
2,4,5-trichlorqphenol 400.0
2,4,6-trichlorqphenol 2.0
vinyl chloride 0.2
silver 5.0
endrih 0.02
lindane 0.4
roethoxychlor 10.0
toxaphene 0.5
2,4-D 10.0
2,4,5-TP (silvex) 1.0
-5-
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Appendix V
-------
Appendix V
References for Multi-phasic and Oily Waste
-------
United States
Environmental Protection Agency
Workshop on
Predicting the Environmental
Impact of Oily Materials
July 14, 1992
Eighth Annual Waste Testing
And
Quality Assurance
Symposium
Arlington, VA
-------
PREDICTING THE ENVIRONMENTAL IMPACT OF OILY MATERIALS:
INTRODUCTION AND REGULATORY PERSPECTIVE
David Friedman
USEPA Office of Research and Development
401 M Street SW
Washington, DC 20460
BACKGROUND
Prevention of groundwater contamination has historically been one of the EPA's
highest priorities in implementing the RCRA program. To that end, the Agency has
developed and promulgated test methods, fate and transport models, and regulatory
standards to control the management of wastes whose properties might pose a hazard to
groundwater. Scientists are concerned with oily waste due to its volume, toxiciry, and
potential for causing severe ecological damage. Such wastes take many forms including:
liquids of widely varying viscosity, contaminated soils, sludges, and tarry "plastic" masses.
Oily wastes have some unique properties. They can migrate Hke a liquid but appear
to be a solid. Because they result from many commercial processes and applications, they are
broadly distributed, of very large volume, and of tremendous commercial importance.
In developing the hazardous waste identification characteristics, EPA highlighted its
concerns with protecting ground water resources by developing the Extraction Procedure
Toxkity Characteristic (40 CFR 26124). The characteristic relies on laboratory procedures to
predict toxicant mobility.
Over the years a number of laboratory extraction methods have been applied to the
problem of predicting what might migrate from oily wastes managed under landfill
conditions. Among the test methods mat have been developed and employed to identify
those wastes which might pose an unacceptable hazard are: EPA methods 1310,1311 and
1330 (Extraction Procedure, Toxirity Characteristic Leaching Procedure and Oily Waste
Extraction Procedure).
The current approaches all have deficiencies with respect to predicting the mobffity of
toxic chemicals from oily wastes. Methods 1310 (EP) and Method 1311 (the TCLP)
underestimate the mobility of many oily wastes due to filter dogging problems, their
precision is less than desirable, and they have certain operational problems. Conversely,
Method 1330 (OWEP) probably overestimates mobility since it emulates a worst possible case
scenario. None of the available laboratory mobility procedures is thus totally satisfactory.
Presetted on July 14,1992 ai EPA Workshop II Pagel
on "Predicting vie Eninnnuiuuiliil Impact of Oify Mtttsriuls"
Printed on Recycled Paper
-------
PROBLEM
Given the importance of this issue/ it is imperative that accurate/ precise/ and usable
approaches to characterizing the mobility of oily materials be developed. That is what we
are here for today.
The problem of mobility estimation is too large and complicated for us to try and
solve all its aspects in a half day. Therefore, we win focus on just one aspect of the
problem - predicting the initial source term. To put it another way/ we want to predict the
highest concentration of material that might be released from the waste to the soil
immediately below the point of disposal for some reasonable amount of time. This
information would then feed into the fate and transport models used to predict the final
toxicant concentration at some distance away from the disposal area.
DISPOSAL SCENARIO OF CONCERN
The priority waste management facility scenario that EPA has selected to be modeled
in this workshop is placement of the waste into or on the ground (e,g., landfill or lagoon).
Within this scenario a number of parameters need to be considered. These include:
• Temperature (assume temperate conditions)/
• Rainfall regime/
• Biodegradation/
• Hydrolysis/
• Soil types (assume soil underlying the waste management unit has a
porosity similar to that of sand)/ and
• Amount of waste (assume amount is large enough so that it can be
considered to be infinite).
FATE AND TRANSPORT MODEL CONSIDERATIONS
To properly manage oily wastes to protect ground water sources from contamination
by waste constituents/ an adequate model to predict the fate and transport in the subsurface
environment is needed. The Agency is developing a model to simulate the migration of
aqueous and nonaqueous phase liquids and the transport of individual rhgmirai constituents
which may move by convection and dispersion in each phase.
As input parameters, the model needs information on the amount and composition of
both the aqueous and nonaqueous phase liquid portions of the waste as wen as the
composition of the leacnate that might be generated by action of surface waters on any
Presented mfrty 14,1992 at EPA Workshop n Page 2
m "Predicting the EiwiwumuUid Impact ofOOy Materials"
-------
"solid" material that may have initially been present in the waste material. At this time, the
Agency does not have a precise way of defining either an "aqueous phase liquid" or a
"nonaqueous phase liquid".
REGULATORY PERSPECTIVE
In an ideal situation, an effective approach to evaluating oily wastes would:
• Be simple to use (not require sophisticated equipment, nor constant
attention by a highly trailed technician),
• Be inexpensive to run,
• Take as little time as possible to perform (ideally no more than 24
hours),
• Be accurate (relative to predicting behavior of waste in the
environment),
• Be precise (Le., be reproducible),
• Be rugged (capable of characterizing a broad range of waste types and
constituents of concern)/ and
• Not generate wastes (e.g., generate little if any solvent waste and waste
contaminated media).
The characteristics that the approach should have (maximum desirable values for each
parameter) are:
• A high degree of freedom from false negatives (any errors tend toward
overestixnation of threat to environment),
• Precision (RSD <50%),
• Relatively low cost,
• Taking as little time as possible to perform (<24 hours), and
• Ruggedness.
Presented on Juty 14,1992 at EPA Workshop U Page 3
oti fTGCudifif the cftvtTonjttstttol ttopttct ofO&y AVUCTAUS
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OPTIONS FOR CONSIDERATION
I. Develop a two-component mobility test that determines the fraction of the
waste which is flowable (capable of physical movement under the influence of
gravity and overburden pressure) under the conditions of the test Suggested
conditions: room temperature and 50 psL Define as mobile afl material that is
flowable under terms of the test phis the aqueous extract of the non-flowable
fraction. Under mis option/ the procedures used are independent of waste
properties and disposal environment
IL Develop a single generic laboratory procedure to estimate what disposal point
concentration would result from aqueous leaching of the hazardous
constituents from both the mobile and non-mobile fraction of the material.
Under this option, the procedures used are independent of waste properties
and disposal environment
m. Employ a series of laboratory test procedures to evaluate the waste material.
These procedures would be keyed to the fate and transport model to be
employed to evaluate the data. The procedure also would be independent of
the properties of the material under evaluation.
The questions we would like you to address are:
• What would be the "best" approach to use in order to predict the nature
and concentration of the components that would leach from ofly wastes
if the waste were to be placed in an unlined landfill environment?
• If the necessary tools are not presently available, how should such a
test method or model be developed and evaluated?
• What form should a cooperative development program take? How
could it be organized? Who might the cooperators be? How long
would you expect it to take to develop the necessary tools?
If you think of any ideas, information, or suggestions mat you feel the Agency should
consider when addressing this issue, please send them to us. Send your comments to:
David Friedman
US Environmental Protection Agency
401 M St SW (RD-680)
Washington, DC 20460
We will need to receive your comments by August 21,1992 in order for them to be
incorporated into the conference final report
Presented on July 14,1992 at EPA Workshop E Page 4
on Predicting we uiuiioiutvntoi onpttct of Ouy MutentHs"
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PREDICTING THE ENVIRONMENTAL IMPACT OF OILY WASTE:
INDUSTRY PERSPECTIVE
Clifford T. Narquis
BP Research
4440 Warrensville Center Road
Cleveland, OH 44128-2837
STATEMENT OF ISSUE
Managing solid waste in an environmentally sound manner is a subject of high
concern to industry/ EPA and the public However, we must have regulatory tools which
accurately reflect the environmental hazard, and analysis tools which accurately assess the
potential impact of various management approaches. We need to bring the best science to
bear on the evaluation of the potential environmental threat from oily waste disposal,
considering the likely management scenarios. One way EPA has decided to regulate certain
oily waste in the past is by listing the waste as hazardous under RGRA. This approach
identifies a material as an environmental threat based on possible (but not necessarily
realistic) mismanagement scenarios. A second way to regulate the waste is to determine if it
is hazardous using the toxicity characteristic (TO and the Toxicity Characteristics Leaching
Procedure (TCLP) test This test is used to determine whether a waste is hazardous or not
based upon a specific teachability test and municipal landfill disposal scenario. The options
explored in this paper serve to promote thinking about new approaches for identifying the
environmental threats and thereby to better focus regulations dealing with the management
of these materials. This wfll be done by introducing and critiquing current most common
predictive methods and presenting potential avenues for more accurate methods.
Although it is nearly impossible to precisely define the term "oily waste", the
following analysis can provide a basis for further discussion:
a) An oil is generally an immiscible or relatively insoluble liquid, varying in
composition but consisting of organic constituents. Petroleum oils principally
consist of hydrocarbons; vegetable and animal oils are glycerides, and fatty
acids; and essential oils are texpenes, alkaloids, etc.
b) An ofly waste is an industrial process waste or residual bearing oil in visual
and /or measurable proportions.
c) Oil in oily wastes can occur in any matrix, including: sorbed to dry solids; in
sludges or shinies; multi-phase liquids or sludges/slurries with multi-phase
Presented an Juty 14,1992 at EPA Workshop n Page 5
m "Predicting Ae EiwiiuiuaaM Impact of OOy Materials"
-------
liquids/ if water is present Proper treatment and disposal of all such matrices
is a concern of the petroleum industry.
d) Analysis of oils in ofly wastes can be accomplished by techniques such as Total
Petroleum Hydrocarbons (TPH) (not constituent-specific) or TCLP (constituent-
specific), hi a number of contexts, the procedures of methods such as these
serve to define what is meant by "oil" and "ofly waste."
e) Oily wastes possess a wide variety of compositions and physical and
toxicological properties.
Some examples of oily waste include petroleum refinery shidges, such as oil- water
separator sludge and dissolved air floatation froth, storage tank bottom sludge/ used oil and
others. Expanded beyond the petroleum community mere are many types of oily wastes
(FOTW sludges/ polymer plants, timber processing, iron and steel pulp and paper, meat
packing, slaughterhouse, leather tanning, cofl coating^restaurants, and miscellaneous foods
including meat, dairy and vegetable based oils and fats, etc.).
Currently mere are a variety of state and local programs designed to address potential
environmental impacts of the management of various types of ofly materials, such as E&P
wastes, spill residues and U5T wastes. A number of RCRA listed and toxicity characteristic
wastes are also regulated under federal programs. EPA is currently evaluating the possible
listing of additional petroleum refining wastes.
Unfortunately, the current analytical methods for determination of the environmental
threat of petroleum constituents in wastes ^"d ofly materials via the TOLP test and model
and RCRA listing system remain controversial. USEPA, academia, and me regulated
community are continuing efforts to identify a sound, reproducible methodology to
accurately assess these threats. In fact, EPA has recently proposed a rule to address the over-
regulation of listed wastes created by EPA's "mixture" and "derived-from" rules. This
initiative, called the Hazardous Waste Identification Rule, could have major impacts on the
classifications and management of hazardous and nonhazardous industrial wastes/ including
ofly waste
An approach that the American Petroleum Institute (APD has suggested to the
Agency is concentration-based exclusion criterion coupled with contingent management It is
a two-tiered process for determining whether wastes captured under the RCRA listing rule
should or should not continue to be regulated as hazardous. One tier would allow wastes
with constituents below health based levels (with an appropriate multiplier to account for
dilution and attenuation) to be deemed nonhazardous provided the waste does not exhibit a
RCRA characteristic. A second tier would allow wastes that contain constituents-below
somewhat higher health based levels to be deemed as nonhazardous, provided these wastes
are managed in certain environmentally protective ways. This second approach would alter
the current system by basing a waste's classification on how it is actually managed and not
how it could be hypothetically mismanaged.
Presented an July 14,1992 al EPA Workshop 27 Page 6
m "Predicting the Eiwuviunailul Impact of OOy Materials"
-------
On the test method side, many, including Environment Canada, ASTM and the
U5EPA, have been involved with the development of improved teachability and contaminant
fate/transport tests and models. Despite this work, predicting the potential environmental
hazard associated with oily wastes remains problematic
TCLP APPROACH
The toxidty characteristic leaching procedure (TCLP) was developed as a way to
evaluate the threat of solid waste disposal under "...a mismanagement scenario for toxic
wastes which constitutes a prevalent form of improper management—namely, the co-disposal
of toxic wastes in an actively decomposing municipal landfill which overlies a groundwater
aquifer..." (Fed. Reg., May 8,1990). The TCLP is a leaching and acidic aqueous extraction
test The test was designed to model mismanagement of the disposal of process wastes. The
Toxidty Characteristic (TO rule itself, and constituent-specific limits associated with the TC,
define wastes as hazardous on the basis of the concentrations of certain toxic constituents.
The TC and its constituent-specific limits were developed in large part to protect human
health from contamination of drinking water aquifers. The TCLP test, as currently
interpreted, is applicable to those wastes which produce a separate non-aqueous phase as
well as those which do not
Specifically the model system that forms the basis for the regulatory limits imposed
by the current toxidty characteristic is one which assumes that the waste is disposed of in a
municipal hazardous waste landfill where it is leached by acidic landfill liquids, emerges
from the landfill bottom into underlying groundwater whereupon it migrates to an
hydraulically down-gradient drinking water well (see Figure 1).
The current Toxicxty Characteristic defined-method for determining environmental
risks uses a three-part system, consisting of a physical model (TCLP), coupled to a
mathematical model (EPACML), coupled to a toxicological model The TCLP simulates
constituent leaching from a landfill, EPACML simulates constituent transport from a landfill
to a drinking water well, and the toxicological model relates drinking water concentration to
health-effects. The TCLP was not designed as, and fails as, a multi-phase model This is
because the oil phase is simply treated as water. Additionally any multi-phase capability
within EPACML was ignored due to the TCLP output
Presented on Jvty 14,1992 at EPA Workshop U page7
on Pfdttcttng mB EiunHMinfnbii Input of OSy Mstsnius"
-------
§
R.
fs
Landfill
Waste
Toxicological
models
Qroundwatar
EPA CIHL mODEL
Figure 1: Components of TC "System"
-------
Significant technical aspects of the TCLP simulation can be summarized as follows
(see Figure 2).
• No vadose zone-bottom of the landfill is in direct contact with the ground
water.
• The disposal of waste liquids (oil and water) are equally mobile
• The liquids are not leached or diluted but ehite directly from the landfill into
the ground water.
• Infinite source-liquids continue to be released forever regardless of amount of
liquids in the original waste.
• The solids are leached with a 20:1 volume of acidic "landfill leachate" which
then enters the ground water.
• Infinite source - the hazardous constituent concentration in the initial 20:1
leachate volume continues to be leached from the material forever, regardless
of mass of constituents in the original waste.
• The liquids and leachate travel through the ground water to a drinking water
well Attenuation and dilution reduce concentrations by a factor of 100.
• Oil moves as water.
• Hazardous constituent concentrations achieve steady-state in the well at which
time the well-owner drinks two-liters/day for 70 years (ofl and aH).
VALIDITY OF THE TCLP APPROACH
Oily wastes provide a great challenge to those charged with evaluating then- potential
impact on the environment Unfortunately the design of the TCLP test in concept,
methodology and fate/transport modeling, inaccurately predicts the behavior of waste
containing separate-phase oil and organic constituents. One shortcoming is that it forces a
generic disposal scenario which may be reasonable for some cases but impossible for others.
Specific problems include operational problems with the test procedure, the assumption that
oil behaves identically to water in the environment, the validity of the disposal scenario/ and
invalid contaminant fate/transport assumptions.
Presentedmjuh/14,1992atEPA Workshoptt
on "Predicting the Enviioiimuilal Impact of Ofly Materials''
-------
i'i
£J
fS
a
ig
^».a
Q^
4ifc1
I
g
Landfill
9. Individual
drinks 2 L/dan
lor 70 gun
20:1
acidic
leachate
Doth
liquidfl
and
loachate
6. Infinite source
of loachate
mlgrato
tO UJBll
7. Straight dilution 6
attenuation bg factor
of 100
B. Oil moves as mater
1. Ho vadosB zone
2. Rqueoue and non-aqueous
liquids treated identically
3. Liquids not leached or diluted
prior to entering groundurater
4. Infinite source
of maete liquids
5. Leachate enters
groundvater diractlg
Figure 2: Issues inherent in TC scenario which work to
introduce inaccuracy.
-------
The test system was not designed for multi-liquid phase materials. This results in
operational problems with the TCLP methodology including non-reproducible free oil
breakthrough, filter dogging/ and
-------
The disposal scenario as depicted by EPA is not an accurate description of current
waste disposal practices. An EPA-OSW survey, several years old already, documents that
liquid-type wastes are no longer being accepted by municipal landfills (51 Fed. Reg. 21655).
New test methods based upon actual waste management situations would give more
accurate results than those based on generic hypothetical scenarios.
Industry has commented upon the shortcomings of the current TCLP/CML model
For example/ the infinite source assumptions require contaminant mass to continue to be
available for introduction into ground water until steady state is achieved. This is
unrealistic. One improvement would be to design transient/ declining source terms into the
model Further, there is no consideration of a vadose zone although we know it exists and
future landfill regulations will require the presence of a vadose zone. The TCLP is not
designed to handle the separate organic phase flow. The current TCLP system does not take
into account aerobic biodegradation, volatilization/ or retardation. Hydrolysis is apparently
being considered at this juncture, but is not currently part of this system.
The unilateral application of TCLP to multi-phase wastes, especially those containing
oily materials/ is unsupported and inappropriate. There is no evidence that non-aqueous
liquids behave as aqueous liquids in a landfill Indeed, such liquids have an affinity for the
solid materials in the landfill which could cause contaminants to be less mobile than
predicted by the TCLP.
Until work on the behavior of non-aqueous materials and the prediction of their
movement is more mature, the non-aqueous liquids should be treated like the waste itself
and be subjected to the same extraction with acidic fluid. To the extent mat hazardous
constituents are released into the extractant, they should be combined with the aqueous
extract generated from the waste solids.
THE EFFECTS OF THE CURRENT TC SCENARIO MODEL • SOME IMPACTS
A number of wastes from the petroleum industry, such as waters from tank
drawdowns, ground-water extraction, and hydrotesting, are or may be subject to the TC rule
even though there is no conceivable way that these materials would ever find their way into
a
The RCRA Corrective Action Program could potentially generate large quantities of
petroleum-contaminated soils. On-site and in-situ management techniques are not accurately
represented by the TCLP. In addition, a number of states currently have effective response
programs for dean up of spills and other releases of petroleum into the environment States
are concerned that application of the TCLP (particularly if TCLP is a poor estimator of
environmental threat) win seriously impact operation and effectiveness of these progiauis by
adding unnecessary and unwarranted hazardous waste handling requirements to wastes
which don't pose a threat We can no longer afford to waste large sums of money handling
solid waste in a manner which over estimates the actual environmental threat
Presented mjufy 14.1992 at EPA Workshop E Awe 22
on "Predicting Oie Eiwiionmuiiul impact of Ofly Materials"
-------
A WAY FORWARD - SAB LEACHABIUTY SUB COMMUTE
Given the problems with the applicability of the TCLP to multi-phase waste, are there
any alternatives? What are the potential ways forward?
Last year, a report was issued by the Science Advisory Board (Environmental
Engineering Committee, Leachabitity Subcommittee), entitled "Recommendations and
Rationale for Analysis for Contaminant Release." It contained nine recommendations:
• A variety of contaminant release tests and test conditions which in corporate
adequate understanding of the important parameters that affect leaching
should be developed and used to assess the potential lease of contaminants
from sources of com
• Prior to developing or applying any leaching tests or models, the controlling
mechanisms must be defined and understood.
• A consistent repeatable and easily applied, physical hydrologic and
geochemical representation should be developed for the waste management
scenario of concern.
• Leach tests and conditions (stresses) appropriate to the situations being
evaluated should be used for assessing long-term contaminant release
potential.
• Laboratory leach tests should be field-validated, and release test accuracy and
precision established before tests are broadly applied.
• More and improved leaching models should be developed and used to
complement laboratory tests.
• To facilitate the evaluation of risk implications of environmental releases, the
Agency should coordinate the development of leach tests and the development
of models in which release terms are used.
• The Agency should establish an inter-office, inter-disciplinary task group,
including ORD to help implement these recommendations and devise an
Agency-wide protocol for evaluating release scenarios, tests, procedures, and
their applications.
• The task group should also be charged with recommending what the
appropriate focal point(s), responsibilities, and organizational, budgetary and
communication links should be within the Agency for the most effective,
continued and ongoing support and pursuit of research, development, and
utilization of methods and procedures.
To fully accomplish all of the recommendations will be costly and time- consuming.
However there can be no alternate to core research on contaminant release and transport
Presented on Jidy 14,1392 at EPA Workshop!! Page 12
on "Predicting UK Eiwiioiuneiilal Input of OSy Materials"
-------
methods. SAB identified approximately 30 leach tests which are used internationally to
attempt to evaluate environmental threat of wastes. Unfortunately SAB concludes that each
method suffers Lfuiii shortcomings.
APPLICATION TO OILY WASTE
If we wish to improve upon the system/ there axe two basic options:
1. Stick with the physical/mathematical model basis of the TCLP and improve
accuracy by modeling multi-phase transport and remove assumptions
predicated on long-term human consumption of immiscible product
2. Replace with a single alternative model, either physical or mathematical
We understand that EPA is exploring various enhanced modeling systems for multi-
phase disposal scenarios. These would include multi-phase flow within the unsatuzated zone/
and partitioning between aqueous/ oil, and air phases within the soft. Also included would
be saturated zone groundwater pollutant transport models which are more accurate. Industry
favors these developments as tools to better understand ofly waste disposal impact
On the other hand, we must currently deal with an inappropriate TC rule. Currently,
industry must comply with the TC rule, which means it must run TCLP tests on oily wastes.
This has resulted in a disastrous situation. The TCLP was not designed to accurately assess
the environmental threat of ofly materials. Therefore it does not However, decisions on the
"proper" management of these wastes are being made on the basis of a flawed test
Industry has had to deal with the TC for many years. We have modified our waste
management approaches and strategies, we have complied with TC and land disposal
requirements and we are preparing to fully comply with Corrective Action. Unfortunately,
changes to the TC at this point may be just as disruptive and costly as compliance with the
TC has been to date. Modifications must be done carefully and deliberately, always using
the best possible science to ensure accuracy, not just consistency.
API supports, as mentioned in the Statement of Issue section, a concentration- based
exclusion coupled with contingent management for exempting listed hazardous waste from
subtitle C requirements. This would address the "inappropriate scenario" dilemma by
incorporating elements of actual management approaches instead of one hypothetical
approach.
The regulated community has volunteered to work with EPA both as individuals,
individual companies, and through trade organizations. We win continue to offer such
assistance. For myself/1 see continued interaction between EPA- OSW and the American
Petroleum Institute. Typical industrial support to EPA includes offering tertmjraJ comment,
procuring wastes, providing waste generation and characterization data, and participating in
round-robin testing of new methods.
Presented on July 14,1992 at EPA Workshop n Page 14
on "Predicting Htc Enviiuiiinuitul Impact of OSy Materials"
-------
TABLE 1 - EXTRACTION TESTS
I. STATIC TESTS (LEACHING FLUID NOT RENEWED)
A AC ITATRD EXTRACTION TESTS
TEST METHOD
TCLP(IJII)
LEACHING FLUID
ACETIC ACID
OINACETICACID
SOLUTION, pill 9.
FOR ALKALINE WASTES
0.1 M SODIUM ACBTATB
BUFFER SOLUTION. pH 3.0.
FOR NON-ALKALINB WASTES
LIQUID-SOUP RATIO
2(11
MAXIMUM PARTICLE SEE
95 mm
PROCEDURE
(ENVIRONMENT CANADA)
NUMBER OF
EXTRACTIONS TIME OF EXTRACTIONS
II HOURS
EPTOX(IJIO)
ASTM D3987-I5
CAUFORNU WET
LEACHATB EXTRACTION
PROCEDURE (MOE.
ONTARIO)
QUEBECRSQ
(MOE. QUEBEC)
FRENCH LEACH TEST
(AFMOR. FRANCE)
EQUILIBRIUM
EXTRACTION
(ENVIRONMEN T CAN ADA)
MULTIPLE BATCH
LBACHINO
OSN ACETIC ACID
(pll=5.0)
ASTM TYPE IV REAGENT WATER
02MSODIUMC1TRATE
(pHc5.0)
ACETIC ACID
2 MEQ/0
INORGANIC 0 02 MEQ/0
ORGANIC DISTILLED WATER
DI WATER
DIS11LLED WATER
ACETIC ACID
BUFFER. pH 4 5
16:1 DURING EXTRACTION
20.1 FINAL DILUTION
201
10:1
20-1
101
101
41
4.1 OR
2:1
95mm
AS IN ENVIRONMENT
20mm
AS IN ENVIRONMENT
GROUND
9.5mm
GROUND
95mm
1 24 HOURS
1 1$ HOURS
1 48 HOURS
1 24 HOURS
1 24 HOURS
1 16 HOURS
1 7 DAYS
VARIABLE 24 HOURS
-------
TABLE I • EXTRACTION TESTS (continued)
a
IS
s>
TESTMBTHOD
MATERIAL CHARACTER-
IZATION CENTRB-4
(MATERIAL CHARACTER-
IZATION CENTRE)
OILY WASTE
(1330)
SYNTHETIC PRECIPI-
TATION LEACHING
PROCEDURE (1312)
EQUILIBRIUM
LEACH TEST
LBACHPIO FLUID
CHOICE
SOXLET WITH TIIF AND
TOLUBNBEPON
REMAINING SOUDS
VARIABLE
DISTILLED WATER
LIQUID.SOUP RATIO MAXIMUM PARTICLE SIZE
l°'l 2 FRACTIONS
74. 149 mm
1000.300 ML 9.5 nm
20:1
20-1 95mm
47 DAYS
>7 DAYS
METHOD (MATERIAL
CHACTBRIZATION
CBNTRB-2)
C. SEQUENTIAL CHEMICAL EXTRACTION TESTS
I
TEST METHOD
SEQUENTIAL
EXTRACTION TESTS
LBACHINO FLUID
0.04 M ACETIC ACID
LiqUID:SOUD RATIO
501
MAXIMUM PARTICLE SIZE
9 5 mm
NUMBER OF
EXTRACTIONS TWH OF EXTRACTIONS
I)
24 HOURS PCR
nXTRACTION
-------
Presented on July 14, 1992
R
ts
j>
L§-
K *H
9»
D. CONCENTRATION BUILD-UP TEST
TEST METHOD
SEQUENTIAL
CHEMICAL EXTRACTION
STANDARD LEACH
TEST. PROCEDURE C
(UNIVERSITY OF
WISCONSIN)
LBACHINO FLUID
FIVB LBACHINO SOLUTIONS
INCREASING ACIDITY
DI WATER
SYN LANDFILL
LBACHATB
TABLE 1 • EXTRACT
LlQUIPiSOUP RATIO
VARIES FROM
16:1 TO 40:1
10'I.Stl
7.5:1
MAXIMUM PARTICLE SIZE
150 um
AS IN ENVIRONMENT
NUMBER OF
EXTRACTIONS
TIME OP EXTRACTIONS
VARIES FROM 2
TO 24 HOURS
J OR 14 DAYS
II. DYNAMIC TESTS (LEACHING FLUID RENEWED)
A. SERIAL BATCH (PARTICLE)
TEST METHOD
MULTIPLE
EXTRACTION
PROCEDURE
(1)20)
MWBP
(MONOF1LL WASTE
EXTRACTION PROCEDURE)
GRADED SERIAL BATCH
(U.S. ARMY)
SEQUENTIAL BATCH
ASTM D4793-88
WASTE RESEARCH
UNIT LEACH TEST
(HARWELL LAB-
ORATORY. UK)
STANDARD LBACHINO
TEST: CASCADE TEST
SOSUV. NETHERLANDS
LEACHING FLUID
SAME AS BPTOX. THEN
WITH SYNTHETIC ACID
RAIN(SULFURICACID-
NITRIC ACID IN 60 40%
MIXTURE)
DlSTILLBD/DBIOmZBD
WATER OR OTHER FOR
DISTILLED WATER
TYPE IV RBAOBNT WATER
ACETIC ACID
BUFFERED pH=5
DISTILLED WATER
HNO3PH40
LIQUID-SOUP RATIO
20'I
10:1 PER
EXTRACTION
SPECIFIC SITE
INCREASES FROM
2:1 TO 96:1
20-1
IBBDVOL5ELUTIONS
10 BED VOL >«
BLUTIONS
20.1
MAXIMUM PARTICLE SIZE
9.5mm
9.6 mm OR
MONOLITH
N/A
AS IN ENVIRONMENT
CRUSHING
CRUSHING
NUMBER OF
EXTRACTIONS
9 (OR MORE)
10
TIME OP EXTRACTIONS
24 HOURS PER
EXTRACTION
II HOURS PER
EXTRACTION
UNTIL STEADY STATI
II HOURS
2 TO 80 HOURS
23 HOURS
-------
TABI.B I • EXTRACTION TESTS (continued)
D. PLOW AROUND TESTS
TEST METHOD
I ABA DYNAMIC LEACH
TEST (INTERNATIONAL
ATOMIC ENERGY AGENCY)
ISO LBACH TEST
(INTERNATIONAL
STANDARDS ORGANI-
ZATION)
ANSI/ANSI6.I
(AMERICAN NATIONAL
STANDARD INSTTTUTB/
AMERICAN NUCLEAR
SOCIETY)
DLT
LEACHING FLUID
Dl WATER/SITE WATER
DI WATER/SITE WATER
Dl WATER
DI WATER
C. FLOW THROUGH TESTS
TEST METHOD
STANDARD LEACHING
TEST: COLUMN TEST
(SOSUV.THB
NETHERLANDS)
COLUMN ASTMD487«-89
LEACHING FLUID
Dl WATER
HNOjpH-4
TYPE IV REAGENT WATER
UQUIDSOUD RATIO
N/A
N/A
N/A
WA
LlQUIDiSOUD RATIO
10:1
ONE VOID VOLUME
MAXIMUM PARTICLE SEE
ONE PACE PREPARED
SURFACE POLISHING
SURFACE WASHING
SURFACE WASHING
MAXIMUM PARTICLE SIZE
AS IN ENVIRONMENT
AS IN ENVIRONMENT
NUMBER OF
EXTRACTIONS
II
II
NUMBER OF
EXTRACTIONS
TIMBOF EXTRACTIONS
>6 MONTHS
>IOODAYS
90 DAYS
196 DAYS
TIME OP EXTRACTIONS
20 DAYS
24 HOURS
-------
in.
OTHER TESTS
TEST METHOD
LEACHING FLUID
MCC-5S SOXHLET TEST DI/SITE WATER
(MATERIAL CHARACTER-
ISTIC CENTER)
ACID NEUTRALIZATION HNO. SOLUTIONS OF
CAPACITY INCREASING STRENGTH
TADLB I EXTRACTION TESTS (umuiiitd)
, NUMBER OF
LIQUIDiSOLID RATIO MAXIMUM PARTICLE SIZE EXTRACTIONS TIME OF EXTRACTIONS
lOO'l
3:1
CUT AND WASHED
130 urn
02ML/M1N
I 48 HOURS PER
EXTRACTION
REFERENCES-
I • Compendium of Wasio Leading Te»n. Wane Water Technology Centre. Environment Canada. Final Diafi May 27.1989
2. Private discussions with Gall Hansen. Office of Solid Wasw. U S EPA
-------
PREDICTING THE ENVIRONMENTAL IMPACT OF OILY MATERIALS:
SCIENTIFIC PERSPECTIVE
Larry P. Jackson
INTRODUCTION
This paper is intended to stimulate discussion into new or better ways to evaluate the
potential release of regulated substances from oUy wastes. The paper discusses some options
to the currently approved procedures to determine the concentrations of regulated organic
chemicals released into the groundwater regime from improperly managed oily waste. The
paper also describes a proposed method to evaluate the fraction of an oily waste which is
flowable under the influence of gravity or overburden pressure if the material is improperly
disposed in a landfill The options presented cover, in part, some of the major technical
concerns of the Environmental Engineering Committee of the Environmental Protection
Agency's (EPA) Science Advisory Board (SAB) in their October, 1991 recommendations to the
EPA Administrator1
This paper is prepared from the perspective that accurate, reliable, and cost-effective
analytical procedures can be developed to properly characterize and manage potentially
hazardous oily wastes. The paper accepts the premise that the regulatory community must
proceed carefully and the "worst case scenario" will be considered in any proposed solutions.
The paper seeks to incorporate some of the suggestions of the EPA Science Advisory Board
that methods should take into consideration real world factors such as:
• source matrix properties,
• contaminant properties,
• leachant properties,
• fluid dynamics,
• chemical and physical properties of the waste,
• temporal/spatial depend*
measurement methods, and
physical models.
Presented on ]uty 14,1992 at EPA Workshop n Page 20
OH .P7CBZCRfZ£ ut£ CrttbrWUUCJufll JlHpBCt fly Ouy AdvCflUS
-------
TECHNICAL ISSUES
Neither the regulatory nor the regulated community has successfully proposed
methods to properly characterize the potential for environmental impact for oily wastes.
Existing leaching tests are known to be technically and mechanically deficient and no
method exists to measure the amount of flowable, oily material which may be released from
a waste. Solutions to these problems have not been discussed to any extent in the published
literature nor in the proceedings of symposia and workshops. These issues are recognized as
the major unaddressed problems in evaluating the pollution potential of oily wastes. Any
scenario which proposes to assess the pollution potential of this class of wastes must address
these issues. This section describes the current state of the technology in these areas.
The Oily Waste Extraction Procedure (OWEP, EPA Method 1330A)2 is designed to
evaluate the potential for an oily waste to release metals under aqueous leaching conditions.
OWEP separates the solid material from the oil by solvent extraction. The solid phase is then
leached by Method 1310A, Extraction Procedure Toxidty Test2 and the extracted oil analyzed
directly for the metals of interest. The results of the analyses of the two fractions are
combined mathematically. It is generally conceded that this overestimates the leaching
potential of the waste. If the method is applied to the analysis of regulated organic
constituents/ all of the analyte will be deemed -teachable which is incorrect It should be noted
that the OWEP has never been suggested as appropriate for organic constituents.
The current approach for analyzing the leaching potential of solid waste, EPA Method
1311, Toxicity Characteristic Leaching Procedure (TCLP)2 differs from the OWEP in that TCLP
attempts to determine die aqueous teachability of the waste for both inorganic and organic
constituents in a single leach test It is very diffi™i» to conduct in a reproducible manner.
Mechanical problems with the test make it time consuming to perform and frequent
reanalysis is required. Precision between replicate tests is very poor. Equipment cleanup is a
major obstacle to laboratory productivity. Costs can run to several thousand dollars per
sample for difficult-to-handle samples. The major problems found in conducting the TCLP
are:
• Handling of the sample is messy, effecting weighing of proper amounts into
the extraction vessels. Loss of volatiles occurs.
Proper sub-sampling of multi-phasic materials is diffRrnit. Samples frequently
contain oil, water, and solids. Isolation of solids for extraction is arduous.
The tumbling action of the two liter extraction vessels forms emulsions making
isolation of the aqueous leachatp HifRmit-
Separation of the leachate from the solid residue after extraction is frequently
impossible because the oily material clogs the filter. This is especially serious
when using the zero headspace extractor (ZHE) since the test must be repeated
if this happens.
Presented™ July 14,1992at EPA Workshopn Aye 21
an "Predicting the Environmental Impact ofOBy Materials"
-------
• Oily wastes frequently yield aqueous leachates and free organic material which
must be separated and analyzed separately, doubling or tripling the analytical
costs.
• Equipment cleanup is very time consuming, minor amounts of residual organic
material can carry over and contaminate succeeding samples.
These problems are sufficiently severe that both regulators and regulated community
have lost confidence in the utility of the method to estimate the potential environmental
hazard of oily wastes.
PROPOSED APPROACHES
This section discusses four proposed approaches to improving the technical and/or
procedural methods for determining the potential environmental impact of oily materials.
They axe
• Adopt a flowable materials test
• Modify the TCLP.
• Adopt a new method of contacting the leach medium with the waste.
• Devise a new model for determining the amount of a regulated substance
released from an oily waste by a
-------
Approach 2 - Modify the TCLP
Modification 1 - Addition of Inert Substrate.
One basic problem with the ability to conduct TCLP is the physical nature of oily
material and the impact that has on the conduct of the test as discussed above. The EPA has
addressed this type of problem in Methods 3540 and 35502, Soxhlet Extraction and Sonication
Extraction respectively/ where inert adsorbents are added to the waste to provide a free
flowing material with sufficient permeability to allow for efficient extraction. The same
approach can be taken with the TCLP.
The addition of a high surface area, inert matrix like silica beads (or sand) win
effectively immobilize the free phase organic material and provide a free flowing medium for
sample preparation (sub-sampling) and extraction. The increased surface area will promote
sohibilization of the organic components into the extraction medium. This approach wfll be
effective for both free liquids and oily solids. If an aqueous phase is also present, adsorption
of the oily material should facilitate separation of the aqueous material prior to extraction.
The presence of the substrate surface as a host site for oily material win minimize the
formation of emulsions during tumbling of the waste/leachant mixture/ provided the
viscosity of the organic material is sufficiently high that the shear forces of the tumbling
action do not separate the liquid material from the solid. After the tumbling sequence, the
solid substrate and absorbed oily material wfll settle to the bottom of the leaching vessel and
eliminate or minimize the amount of free organic liquid floating at the surface of the
solution, making the filtration step much pasipr and dogging less likely.
This type-of sorbent bed closely resembles the real world case of oily material spilled
onto or migrating through soil columns until it no longer moves under the force of gravity.
This model of oil coated soil represents the most common real world source of potential
pollutant release from oily wastes.
Modification 2-Use of Fritted Stainless Steel Filter.
Regardless of whether or not the method is modified by the addition of an inert
substrate to immobilize the oily material, the filtration step of the method can be improved.
Agency funded research of improved filtration media led to the development of a sintered
stainless steel filter that overcame many of the clogging problems6. The modification has not
been added to the method at this time, but it has been used without formal regulatory
adoption, with some intractable wastes. Other approaches to improve filtering should be
examined, such as the use of thick pads (several nuns) of non-woven glass or plastic fibers
and powdered filter aids as pre-filters. These are physical changes to the filter apparatus;
they should be permitted as long as the modifications can be shown not to alter the
composition of the filtrate by absorption of analytes or allow for the passage of particles with
a nominal size greater than 0.7 micron.
Presented mjuty 14,1992 at EPA WoriahopU Page 23
on "Predicting the Enummmentd Impact of Ofly Materials"
-------
Approach 3 - Adopt a New Leaching Technique
The mechanical forces that act on oily waste during the TOP tend to separate the oil
from the substrate that was part of the original waste material or the inert material added in
Approach 2. This leads to the formation of emulsions and/or free liquid phases which coat
and clog the fitters during the nitration step. Column leaching configurations that are less
physically aggressive than tumbling can be used as the leaching model for oily wastes. The
penneabffity of the waste material is the key property of the waste which must be controlled
if a column technique is to work (permeability also impacts the efficiency of any extraction
process). Use of inert sorbents, as in Approach 2. can provide the necessary permeability to
allow for uniform flow of the aqueous medium through the waste bed and promote effective
leaching. Unif orm flow would be provided by pumping the leachant through the system.
Flow rates can be adjusted to mmmi** the shear forces which might dislodge oily
material from the. waste. Flow direction can be changed based on the density of the organic
fluids. Downward flow for materials lighter man water and upward flow for materials
heavier than water wffl minimize the likelihood that oily material wffl separate from the
substrate during testing. If the fluids do separate, they wffl not find their way into the
leachate reservoir without passing through the substrate bed where they win re-deposit on
the surface. Mmimum flow volumes per unit mass of waste wffl become the operational
control of the test rather than the tumbling time that is now used.
The dynamic flow conditions of the column test also allow for efficiencies in
_ _ . ^ ^ m «• 4 <_____ _•_ __ •__ f __ 1 __ M.L __ * - -- .J £«* 4fe«
SUDSeQUBni scunpie oiuujraia. ivi.uvj.cixi ow«u* £»•»& sr^+mn. ii«« AW* WM> w.*^,...-.. —.•— —.—.rgcHUC
analytes can be placed between the pump outlet and the head of the column to collect and
pre-concentrate the analytes for future analysis. The use of these sorbents also allows the
introduction of "fresh teachanr to the top of the column of waste in a manner similar to the
way fresh ground or surface water would contact the waste in the real world scenario. This
would promote maximum release of the target analytes.
The column leach model proposed here resembles the real world case where ground
or surface water percolates through oily material that adheres to the soil, more closely than
does the tumbling action of the TCLP. The column leach approach can be extended to
evaluate the attenuation of solubilized materials by a representative soil, by placing a soil
layer in the same extraction column as the waste or by passing the leachate through a second
column placed in series with the waste containing column. This allows for the development
of a modular test sequence in which the same test used to characterize a waste leachate is
used as the source term for attenuation studies, which may be conducted as part of a site-
specific risk assessment This strategy is in keeping with the SAB's recommendation to the
EPA.
Approach 4 - Use a Totally Different T^arhmg Model
The current TCLP and the two options previously discussed are alternative physical
models of the leaching process. Most problems resulting from these approaches center
around sample handling, leaching, and filtering the leachate. To avoid some of these
Presented an July 14,1992 at EPA Worktop U Page**
on 'Predicting toe EnrinmmenfaZ Impact ofOOy Materials'
-------
problems, the Agency should consider using well-developed, existing theoretical and
experimental models of the leaching of materials from oily matrices as well and the migration
and interaction of the soluble components with soils. Both the EPA and the American
Petroleum Institute (APD have published significant papers on the approach7A94
and the correlation coefficient, n , dropped to 0.87. Table 1 compares the experimental data
for eleven of the compounds for which data was experimentally determined with the data
derived from equation 3. Most of the data compare favorably with the normal range of
allowable differences between replicate analytical determinations.
Presented mjiity 14,1992 at EPA Workshop U Page 25
an "Predicting the Eiaimiuiiailal Impact of Ofly Materials"
-------
TABLE 1
Comparison of Observed and Estimated Hydrocarbon Concentrations
from a Standard Gasoline in Equilibrium with Water (1:10)
HYDROCARBON
Benzene
Toluene
2-Butene
2-Pentene
Ethylbenzene
o-Xylene
m-Xylene
Butane
1 ,2,4-Trimethylbenzene
2-Methyibutane_
Pentane
CONCENTRATION
OBSERVED
58.7
33.4
2.4
2.4
4.3
6.9
11.0
2.7
1.1
3.7
1.0
ESTIMATED
58.8
37.8
3.2
1.7
32.
4.7
9.2
5.2
1.8
62
22
This type of model works well for those cases where the oily waste matrix is the
primary determinate in the partition coefficient in the matrix/water distribution. The 1984
API report discusses the situation where the amount of oil is very small compared to the
total mass of organic carbon in the soil/sediment/waste matrix and in effect represents oil
absorbed on soil6. Equation 4 applies to these situations.
(4)
where:
= soil/water partition coefficient
- the organic carbon partition coefficient
= weight percent organic carbon in the substrate.
Presented an Jufy 14.1992 at EPA Workshop E
on "Piediclmg the Eiwiiuiuntiilul Impact of O3y Materials"
Page 26
-------
The organic carbon partition coefficient, Kg,. / is related to the octanol water partition
coefficient, K^, by equation 5.
log Km - 0.317 (5)
These models are based on the physical and chemical properties of the target analytes
and the substrates with which they are associated, be it a flowable liquid, solid waste, or soil
Accurate and precise methods exist for experimentally determining the input variables to the
models. These variables include but are not limited to:
• analyte concentration in total waste,
• percent organic carbon in sofl or waste matrix,
• partition coefficients (fuel/water, soil/water, octanol/water), and
• water solubility of target analytes.
As the data base is expanded, relationships among classes of organic compounds, water,
soils, and wastes win emerge These relationships win lead to better empirical and theoretical
understanding of the physical and chemical factors controlling the release of materials to the
environment New materials can be evaluated without detailed experimental studies by
analogy with similar compounds, wastes, and soils.
Use of this type of approach helps fulfill the SAB's recommendation that more rigorous
scientific procedures be used to determine the potential for release as wen as environmental
impact This approach also meets the recommendation that rugged tests that are less
susceptible to waste matrix effects be used. The approach also uses many of the same
parameters used in determining fate and transport and important measures of dtviivniiienlal
risk; therefore, a more unified model of environmental impact can be developed.
ROLE OF THE EPA AND PUBLIC SECTOR GROUPS
The EPA can serve as a catalyst for the necessary research studies for needed to improve
and develop reliable analytical methods. EPA also can lead in measuring the important
physical and chemical properties, of the analytes, wastes, and soils, that define analyte
behavior in the environment Members of the public sector can contribute laboratory support
and technical expertise to developing the necessary methodology and demonstrating the
applicability and ruggedness of the methods.
These workshops are an ideal expression of how this should work.
Presented on July 14,1992 at EPA Workshop n Page 27
on "Predicting toe Environmental Impact ofOOy Materials"
-------
REFERENCES
1. EPA Science Advisory Board. October, 1991. Leachability Phenomena,
Recommendations and Rationale for Analysis of Contaminant Release by the
Environmental Engineering Committee, Report EPA-SAB-EEC-92-003.
2. EPA/ Test Methods for Evaluating Solid Wastes, Physical/Chemical Methods, SW-846,
3rd Edition, final Update 1, November, 1990
3. Hazardous Waste Management: Containerized LiquiflS in landfills. October 29,1991.
Federal Register, VoL 56, No. 209, p. 55646.
4. Hoffman, P.A. et aL. Development of the Liquid Release Test Research Triangle
Institute Report
5. Background Document for the Liquid Release Test (LRT): Single Laboratory
Evaluation and 1988 Collaborative Study. EPA RCRA Docket # F-91-CLLA-FFFFF.
6. Truesdale, RS. et aL. April 1990. Evaluation and Modification of Method 1311 for
Determining the Release Potential of Difficult-to-Klter Wastes. EPA Contract No. 68-
01-7075, Research Triangle Institute.
7. Kaxickhoff, S.W. and Brown, DS. 1979. Determination of Octanol/Water Distribution
Coefficients, Water Solubilities, and Sediment/Water Partition Coefficients for
Hydrophobic Organic Pollutants, EPA Report EPA-600/4-79-032.
8. Rembold, ICA. et aL 1979^Adsorption of Energy-Rebte^rOrganic Pollutants: A
Literature Review. EPA Report EPA-600/3-79-086reT
9. Hassett, JJ. et aL 1980. Sorption Properties of Sediments and Energy Related
Pollutants, EPA Report EPA/3-80-041.
10. Environmental Research and Technology, Inc. 1984. The Land TreatahQity of
Appendix VEI Constituents in Petroleum Industry Wastes, API Publication No. 4379.
11. TRC Environmental Consultants, Inc. 1985. Laboratory Study on Solubilities of
Petroleum Hydrocarbons in Groundwater. API Publication No. 4395.
Presented on July 14,1992 at EPA Workshop U Page 28
on Tretuduig Ac Etuniuiuntnlui Inifurt of Ooy Muttiuus
-------
Appendix VI
-------
Appendix VI
Office of Solid Waste Methods Section
Memoranda #35, #36
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
OFFICE OF
SOLID WASTE AND EMERGENCY RESPONSE
MEMORANDUM i 36
DATE: January 12, 1993
SUBJECT: Notes on RCRA Methods and QA Activities
From: Gail Hansen, Chief yUO*t
Methods Section (OS-331)
This memo addresses the following topics:
o 1992 Symposium on Waste Testing and Quality Assurance
o Issue Discussion Groups
o Inorganic Methods Workgroup Meeting
o Organic Methods Workgroup Meeting
o QA Workgroup Meeting
o Miscellaneous Methods Workgroup Meeting
o ICP Discussion Group
o HPLC Methods Discussion Group
o SPA Methods Discussion Group
o SFE Methods Discussion Group
o SW-846 Update and TCLP Spike Recovery Correction Removal
Notice Update
o Total Analysis Versus TCLP.
Printed on Recycled Paper
-------
The instrument manufacturers are working with the Agency to
determine the optimum SFE conditions for the major classes of
semivolatile analytes. This input will help expedite development
of a broader scope for Method 3560.
For further information on SFE topics, please contact Barry
Lesnik at (202) 260-7459.
SW-846 and TCLP Spike Recovery Correction Removal Notice
The final SW-846 Update I rule and the proposed Update II rule
packages are both currently at the Office of Management and Budget
(OMB) review step in the regulatory process. It is not known how
long this review step will take. Once the review by OMB is
complete, it is'expected that the promulgation of Update I and the
proposal of Update II will take at least 2 months.
The rule to delete the matrix spike correction requirement
from the TCLP which was finalized on June 29, 1990, has been
published (57 FR 55114-56117, November 24, 1992). This rule
withdraws the spike recovery correction requirements from the TCLP
and, except for a few technical and format changes made in the June
29, 1990 rule revising the TCLP, returns the QA provisions of the
TCLP to those promulgated on March 29, 1990 (55 FR 11796).
Specifically, this rule requires the method of standard additions
as the quant itat ion method for metallic contaminants when
appropriate as specified in the method.
For further information on SW-846 updates or the TCLP rule,
please give Kim Kirkland a call at (202) 260-6722.
Totals Analysis Versus 7*eT-p
Over the past year, the Agency has received a number of
questions concerning the issue of total constituent analysis with
respect to the TCLP. Section 1.2 of the TCLP allows for a
compositional (total) analysis in lieu of the TCLP when the
constituent of concern is absent from the waste, or if present, is
at such a low concentration that the appropriate regulatory level
could not be exceeded. A number of persons have contacted the MICE
Service and have requested clarification on this issue with respect
to a number of waste testing scenarios.
Wastes that contain less than 0.5% dry solids do not require
extraction. The waste, after filtration, is defined as the TCLP
extract. The filtered extract is then analyzed and the resulting
concentrations are compared directly to the appropriate regulatory
concentration.
19
-------
For wastes that are 100% solid as defined by the TCLP, the
maximum theoretical leachate concentration can be calculated by
dividing the total concentration of the constituent by 20. The
dilution factor of 20 reflects the liquid to solid ratio employed
in the extraction procedure. This value then can be compared to
the appropriate regulatory concentration. If this value is below
the regulatory concentration, the TCLP need not be performed. If
the value is above the regulatory concentration, the waste may then
be subjected to the TCLP to determine its regulatory status.
The same principal applies to wastes that are less than 100%
solid (i.e., wastes that have filterable liquid). In this case
however, both the liquid and solid portion of the waste are
analyzed for total constituency and the results are combined to
determine the maximum leachable concentration of the waste. The
following equation may be used to calculate this value.
[AxB] + [CxD]
B + [20-- x D]
= E
where: A = concentration of the analyte in liquid portion of the
sample (mg/L)
B = Volume of the liquid portion of the sample (L)
C = Concentration of analyte in the solid portion of the
sample (mg/kg)
D = Weight of the solid portion of the sample (kg)
E - Maximum theoretical concentration in leachate (mg/L)
To illustrate this point, the following example is provided:
An analyst wishes to determine if a lead processing sludge
could fail the TC for lead. The sludge is reported to have a low
concentration of lead, and the analyst decides to perform a
compositional analysis of the waste instead of a full TCLP
evaluation. A representative sample of waste is subjected to a
preliminary percent solids determination as described in the TCLP.
The percent solids is found to be 75%. Thus, for each 100 grams of
this waste filtered, 25 grams of liquid and 75 grams of solid are
obtained. It is assumed for the purpose of this calculation that
the density of the filterable liquid is equal to one. The liquid
and solid portion of the sample are then analyzed for total lead.
The following data are generated:
20
-------
Percent solids = 75%
Concentration of lead in the liquid phase = 0.023 mg/1
Volume of filtered liquid = 0.025 L
Concentration of lead in the solid phase = 85 mg/kg (vet weight)
Weight of the solid phase = 0.075 kg.
The calculated concentration is as follows:
[0.023-2S x 0.025L] + [85-^ x 0.075*?]
£ - >. - *2 _ = 4.18 JH
0.025 L+[20-£- x 0.075*0-] L
*
In this case, the maximum leachable concentration is below the
5 mg/1 regulatory concentration for lead, and the TCLP need not be
performed.
Non-aqueous based wastes (i.e., oily wastes) may be calculated
in the same manner as described above, except the concentration of
constituents from the liquid portion of the waste (A in the above
formula) are expressed in mg/kg units. Volumes also would be
converted to weight units (kg). The final leachate concentration
is expressed in mg/kg units.
21
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. D.C. 20460
OFFICE OF
SOLID WASTE AND EMERGENCY RESPONSE
MEMORANDUM * 35
DATE: June 12, 1992
SUBJECT: Notes on RCRA Methods and QA Activities
From: Gail Hansen, Chief
Methods Section (OS-331)
This memo addresses the following topics:
o 1992 Symposium on Waste Testing and Quality
Assurance
O SW-846 Update
- Final Rule for January 23, 1989 Proposed Rule
- Notice, Proposed Rulemaking for the Second Update to
the Third Edition
o chlorofluorocarbon 113 (CFC-113) Solvent Replacement
Update
o Environmental Monitoring Methods Index (EMMI)
o Sampling Work Group Formation
o MICE Update
o oily Waste Analysis
o Electronic SW-846 Availability.
Printed nn Recvcled Paoer
-------
oilv Waste Analysis
One of the most frequently asked questions on the MICE
Service concerns the application of the TCLP, Method 1311, to
oily wastes. Many callers request technical guidance on the
extraction of oily wastes due to the difficulty in the filtration
on these types of waste. In many cases, an oily waste does not
filter completely due to premature clogging of the glass fiber
filter. This can result in the retention of standing liquid on
the glass fiber filter. Material that do not pass through the
glass fiber filter at the conclusion of the filtration step is
defined by the method as the solid phase of the waste. The solid
phase is then subjected to the leaching procedure of the TCLP.
For oily wastes, clogging of the glass fiber filter can result in
an overestimation of the amount of solid material available for
leaching.
To solve this problem, the Agency recommends a conservative
approach, one that probably will overestimate the amount of
leaching. Rather than performing the TCLP extraction on the
unfiltered portion of the oily waste, assume the waste is 100%
liquid (e.g., will pass through the glass fiber filter) and
perform a totals analysis on the oily waste to determine if the
oil exceeds the appropriate regulatory level.
Filterable waste oil generated during the TCLP must be
analyzed for a variety of organic and inorganic analytes. The
OSW recognizes the difficulty in achieving acceptable performance
for the analysis of waste oil using methods currently provided in
SW-846. As a result, the Agency will provide several new methods
for the preparation and analysis of oil samples to the Organic
Methods Workgroup in July. In addition, a microwave assisted
digestion procedure should improve the analysis of metals and
will be proposed as part of the Second Update of the Third
Edition of SW-846. Brief descriptions of these techniques are
provided below, for additional information on the organic
procedures contact Barry Lesnik at (202) 260-7459. For
additional information on microwave digestion contact Ollie
Fordham (202) 260-4778.
The use of purge-and-trap (Method 5030) for volatiles in oil
generally results in severe contamination of analytical
instrumentation. Traps, transfer lines and chromatography
columns may become contaminated with oil. This leads to elevated
baselines, hydrocarbon background in subsequent analyses, and
cross-contamination. Headspace (Method 3810) is currently
allowed only as a screening procedure in SW-846. The Agency is
evaluating the use of headspace in conjunction with isotope
dilution mass spectrometry for the quantitative analysis of
volatiles in oil. Headspace reduces interference problems
encountered with purge-and-trap. However, headspace quantitation
can be questionable because the distribution of analytes is not
10
-------
the same in different types of samples. That difficulty appears
to be minimized by the use of isotope dilution calculations.
Headspace/isotope dilution analysis will require the promulgation
of two new SW-846 methods: Method 5022, Volatiles by Automated
Headspace, and Method 8266, Volatiles by Isotope Dilution GC/MS.
Performance data for the analysis of motor oil will be presented
to the organics Workgroup and during a platform talk at the July
Symposium. Draft methods should be available for limited
distribution by September.
Headspace/isotope dilution will require that laboratories
acquire hardware and provide additional analyst training.
Therefore, an alternate Solvent Dilution Direct Injection (Method
3585) option for Method 8260 is also being evaluated. While use
of the direct injection technique will result in more instrument
contamination, it may be appropriate for laboratories that
analyze only a limited number of oil samples. Method performance
data will also be presented for direct injection during the
symposium in July.
The analysis of semi-volatile target analytes is also
difficult with present methods. While gel permeation cleanup
(GPC) is effective, it can only be used for small oil samples
(<0.5 g). work is in progress to evaluate partition and
extraction cleanup procedures for waste oil. Partitioning oil
between dimethyl formamide (DMF) and hexane or extraction of oil
with methanol/DMF followed by acid/base partitioning has proved
successful prior to the analysis of chlorophenols in waste oil.
A similar approach is being evaluated for the analysis of
organochlorine pesticides. Work to date has demonstrated that
steam distillation and vapor/vapor extraction procedures are not
appropriate for petroleum products.
The Agency will propose a new digestion procedure (Method
3051) for inorganic samples in the Second Update of the Third
Edition of SW-846. The procedure uses a microwave oven to heat
the acid during digestion of sediment, sludge, soil and oil
samples. The resulting digestate can be analyzed using atomic
absorption (AA) or inductively coupled plasma (ICP) methods in
SW-846. Microwave assisted digestion is suitable for all oils
including oils that contain particulates. The only current
inorganic preparation method suitable for oils is Method 3040, a
dissolution procedure. In contrast to Method 3051, Method 3040
is suitable only for metals dissolved in oil. Method 3040 can be
used to show that an oil is hazardous based on the concentrations
of dissolved metals.
Electronic SW-846
SW-846 now can be purchased from private vendors in an
electronic format. A brief description of each known package and
information on how to obtain copies of each are given below.
11
-------
The sw-846 Authority is published in electronic format by
virtual Media Corporation. The SW-846 Authority is an
c^rehensivl electronic publication designed to track and manage
regulatory issues. By using IQTP (Intelligent Query Text
Processor), the SW-846 Authority utilizes a comprehensive index,
allowing users full text and retrieval capabilities. Users have
thousands j of ™^& ^rSJSSSuS.
featSre29of ^SW-sJf A^rity Include:
• RCRA Act (SWDA)
• RCRA 40 CFR Parts 260-265, 270-272
• SW-846 Solid Waste Test Methods Manual
• RCRA Inspection Manual.
For information on the SW-846 Authority call (800) 645-4130
or write to:
Virtual Media Corporation
14455 North Handen Road, Suite 201
Scottsdale, AZ 85260
Electronic E.P.A. Methods1" 1.1 is offered by Chemsoft*"
corporation as an electronic database of all EPA methods. This
p?ogwm is designed for rapid search and retrieval of EPA methods
by method number, analyte, title, type of instrumentation, or CAS
nLber Each program contains the full text of the methods as
SSS appea? ?nPSl appropriate EPA manual. Use of this software
requirS Windows 3.0. The following programs are available
either separately or may be purchased as a single package.
• EPA SW-846 Series Methods
• EPA 500 Series Methods
• EPA 600 Series Methods
• EPA Water and Waste Methods.
For further information on Electronic E.P.A. Methods, call
(800) 536-0404 or (707) 864-0845 or write to:
WindowChem Software, Inc.
1955 West Texas Street, Suite 7-288
Fairfield, CA 94533-4462
The Methods Section will provide additional information in
future memoranda on other sources of electronic SW-846 media when
we become aware of them.
12
-------
Appendix VII
-------
Appendix VII
Recommendations and Rationale for Analysis of
Contaminant Release by the Environmental Engineering
Committee
Science Advisory Board
October 1991
-------
United States Science Advisory Board EPA-SAB-EEC-92-003
Environmental Protection (A-101F) October 1991
Agency
>EPA Leachability
Phenomena
Recommendations and
Rationale for Analysis of
Contaminant Release by the
Environmental Engineering
Committee
Printed on Recycled Paper
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, O.C. 20460
EPA-SAB-EEC-92-003
OFFICE OF
October 29, 1991 THE ADMINISTRATOR
Honorable William X. Reilly
Administrator
U.S. Environmental Protection Agency
401 M Street, 8.W.
Washington, D.C. 20460
Subject: Leachability: Recommendations and Rationale
for Analysis of Contaminant Release
Dear Mr. Reilly:
. »ne Leachability Subcommittee (LS) of the Science Advisory
Board's Environmental Engineering Committee (EEC) has prepared
the attached recommendations and rationale on leachability, an
important release term related to solid wastes and contaminated
soils, for your consideration. —MW^TO
Over the past decade, the EEC has reviewed a number of EPA
issues involving leachability phenomena and noted several
problems relating to this release term that were common to a
variety of EPA offices. The Committee believed that these common
problems would be best called to the Agency's attention througS a
general review of leachability phenomena. «™ign a
Drafts of this report on leachability have been reviewed at
a series of Subcommittee, Committee, and Executive Committee
meetings over the past 18 months. This included both a session
on February 26, 1990, devoted to assessing the Agency's varied
needs on leachability-related information, and a Technical
Workshop on May 9, 1990. The workshop assisted in determining
how leachability phenomena should be used to determine how a
waste will leach when present under various scenarios in the
environment.
The following recommendations have been developed. First
in regard to leachability test development we recommend:
a) incorporation of research on processes affecting
leachability into EPA's core research program to better define
and understand principal controlling mechanisms; "er °erine
*» development of a variety of contaminant release tests,
rather than focusing on mimicking a single scenario,
-------
e) development of improved release and transport-
transformation models of the waste matrix to complement the
leaching tests, and
d) field validation of the tests and models, and
establishment of release-test accuracy and precision before tests
are broadly applied.
next, in regard to the application of such tests and models,
ve recommend:
e) use of a variety of contaminant release tests and test
conditions vhich incorporate adequate understanding of the
important parameters that affect leaching in order to assess the
potential release of contaminants from sources of concern. A
medical analogy is that no physician would diagnose on the basis
of one test showing only one aspect of the problem,
f) development of a consistent, easily applied, physical,
hydrologic, and geochemical representation for the phenomenon or
waste management scenario of concern,
g) identification and application of appropriate
environmental conditions for tests in order to evaluate long-term
contaminant release potential as required under varying statutes,
and
h) coordination between the Agency's programs which develop
leachability tests with those that develop the environmental
models in which the release terms are used.
Finally, we recommend:
i) establishment by the Agency of an inter-office, inter-
disciplinary task group, including ORD to help implement these
recommendations, and
j) development of an Agency-wide protocol for evaluating
release scenarios, tests, procedures, and their applications.
These recommendations are made with the anticipation that an
improved understanding of the fundamental scientific principles
that control contaminant release and transport within a waste
matrix will allow better regulatory and technical decisions to be
-------
made in cases where the potential exists for leaching of
contaminants into the environment.
We are pleased to be of service to the Agency, and hope that
you will find this effort useful. We look forward to your
response to the recommendations cited above.
Dr. Raymond C. Loehr, Chairman Mr. Richard A. Conway, Chairman
Executive Committee Environ. Engineering Committee
Dr. c. H. Ward, Chairman
Leachability Subcommittee
-------
ABSTRACT
The Leachability Subcommittee (LS) of the Environmental
Engineering Committee (EEC) of the EPA Science Advisory Board
(SAB) conducted a self-initiated study and prepared a report on
the topic of leachability phenomena. The intent of this report
is to provide reeonnendations and rationale for analysis of
contaminant release to the staff in the various offices of the
Environmental Protection Agency (EPA). The nine recommendations
from the report are highlighted as follows:
1) A variety of contaminant release tests and test condi-
tions vhich incorporate adequate understanding of the important
parameters that affect leaching should be developed and used to
assess the potential release of contaminants from sources of
concern.
2) Prior to developing or applying any leaching tests or
models, the controlling mechanisms must be defined and
understood.
3) A consistent, replicable and easily applied, physical,
hydrologic, and geochemieal representation should be developed
for the vaste management scenario of concern.
4) Leach test conditions (stresses) appropriate to the
situations being evaluated should be used for assessing long-term
contaminant release potential.
5) Laboratory leach tests should be field-validated, and
release test accuracy and precision established before tests are
broadly applied.
6) More and improved leach models should be developed and
used to complement laboratory tests.
7) To facilitate the evaluation of risk implications of
environmental releases, the Agency should coordinate the
development of leach tests and the development of models in vhich
the release terms are used.
8) The Agency should establish an inter-office, inter-
disciplinary task group, including ORD to help implement these
recommendations and devise an Agency-wide protocol for evaluating
release scenarios, tests, procedures, and their applications.
9) Core research on contaminant release and transport within
the waste matrix is needed.
Key Wordss leachability, leachability phenomena, leach tests and
methods, leaching chemistry, leaching models
ii
-------
Z. EXECUTIVE SUMMARY
In vaste management, including managing the effects of
spills or other releases which are sources of underground
contamination, a critical issue is the assessment of the
potential for constituents to leach to the environment. The
Environmental Engineering Committee (EEC) of the Science Advisory
Board (SAB) undertook a study of this issue because it noted
several common problems relating to this release term as it
reviewed, over the past decade, various leaching tests and risk
models for several EPA offices. Tests such as the Extraction
Procedure (EP) and the Toxicity Characteristic Leaching Procedure
(TCLP) had, and continue to have, scientific limitations, yet
were being inappropriately and in some cases widely used. Often
tests were developed without rigorous review. A self-initiated
study seemed appropriate to define the leachability problem
better and to offer advice on its resolution.
The EEC established a Leachability Subcommittee (L8) that
addressed:
1) Needs of the Agency and regulated communities to
quantify leachability (releases) of contaminants to the
environment.
2) state-of-the-art and science related to fundamental
principles and practice in predicting leaching of constituents
from wastes, contaminated soils, and other sources.
3) Recommendations to improve the scientific understanding
and application of leaching tests.
Workshops were held, literature was analyzed, and
findings were discussed over an 18-month period leading to the
preparation of this report.
The various needs for tests and models to predict leaching
are defined. Tests developed and used in the U.S. and Canada are
summarized. The scientific considerations important in design
and interpretation of leachability tests are presented. This
information, expert advice and analysis by workshop participants,
and reviews by SAB members, resulted in guidance which should, if
progressively implemented, significantly strengthen the Agency's
ability to assess appropriately leaching of contaminants from
hazardous wastes, contaminated soils and other sources.
This guidance, in the form of nine recommendations, is
summarized as follows:
1) A variety of contaminant release tests and test
conditions which incorporate adequate understanding of the
important parameters that affect leaching should be developed
-------
•ad used to assess the potential release of contaminants from
sources of concern.
2) Prior to developing or applying any leaching tests or
•odels, tbe controlling mechanisms must be defined and
understood.
3) A consistent, replicable and easily applied, physical,
hydrologic, and geocheaieal representation should be developed
for the waste management scenario of concern.
4) Leach test conditions (stresses) appropriate to the
situations being evaluated should be used for assessing long-term
contaminant release potential.
5) Laboratory leach tests should be field-validated, and
release test accuracy and precision established before tests are
broadly applied.
6) More and improved leach models should be developed and
used to complement laboratory tests.
?) To facilitate the evaluation of risk implications of
environmental releases, the Agency should coordinate the
development of leach tests and the development of models in vhich
the release terms are used.
8) The Agency should establish an inter-office, inter-
disciplinary task group, including OXtD, to help implement these
recommendations and devise an Agency-vide protocol for evaluating
release scenarios, tests, procedures, and their applications.
The task group should also be charged vith recommending vhat the
appropriate focal point(s), responsibilities, and organisational,
budgetary and communication links should be vithin the Agency for
the most effective, continued and ongoing support and pursuit of
the research, development and utilisation of methods and
procedures.
9) Core research on contaminant release and transport vithin
the vaste matrix is needed.
ZZ. IMTRODUCTXON
Zn both hazardous and non-hazardous vaste management, one of
the most critical issues is the assessment of the potential for
constituents contained in the source material to leach or
othervise be released to the environment. Approaches to estimate
potential release of organic and inorganic constituents and their
subsequent environmental migration and associated health risks
are important in many situations (e.g., pollution prevention,
risk reduction, restoration-remediation and hazard identi-
fication) .
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Appendix VIII
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Appendix VIM
USEPA Region II
Special Analytical Services Request
-------
SAS Number
U.S. ENVIRONMENTAL PROTECTION AGENCY
CLP Sample Management Office
P.O. Box 818 - Alexandria, Virginia 22313
Phone: (703) 557-2490 - (FTS) 557-2490
SPECIAL ANALYTICAL SERVICES
Client Request
I ' Regional Transmittal ' 1 Telephone Request
A. EPA Region/Client:
B. RSCC Representatives:.
C. Telephone Number: (_
D. Date of Request:
E. Site Name:
Please provide below description of your recent request for
Special Analytical Services under the Contract Laboratory
Program. In order to most efficiently obtain laboratory
capability for your request, please address the following
considerations, if applicable. Incomplete or erroneous
information may result in a delay in the processing of your
request. Please continue response on additional sheets, or
attach supplementary information as needed.
1. General Description of Analytical Service Requested:
Analysis of soil samples by TCLP for TC analytes.
Analysis of aqueous blanks for TC analytes.
-------
Definition and number of work units involved (specify
whether whole samples or fractions; whether organics or
inorganics; whether aqueous or soil and sediments; and
whether low, medium, or high concentration):
Number of Samples Matrix Concentration Analysis
3 Soil Low TCMplus
pyridene
and m-
cresol),
TAL,
2,4-D and
2,4,5-TP
by TCLP
Water Low TCL(plus
Field pyridene
Blank and m-
cresol),
TAL,
2,4-D and
2,4,5-TP
3. Purpose of analysis (specify whether Superfund (Enforcement
or Remedial Action), RCRA, NPDES, etc.):
4. Estimated date(s) of collection:
5. Estimated date(s) and method of shipment:
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6. Number of days analysis and data required after laboratory
receipt of samples:
Environmental samples must undergo TCLP extraction within
the following time periods after sample receipt:
Mercury 26 days
Other Metals 178 days
Volatiles 12 days
Pest/Herb/BNA 12 days (7 additional days
from TCLP extraction to
preparative extraction)
Environmental TCLP sample extracts must be analyzed within
the following time periods after extraction:
Mercury 28 days
Other Metals 180 days
Volatiles 14 days
Pest/Herb/BNA 40 days
Field and trip blanks must be analyzed within the following
time periods after sample receipt:
Mercury 26 days
Other Metals 6 months
Volatiles 10 days
Pest/Herb/BNA 5 days to extraction,
40 days to analysis
The complete data package containing all the sample delivery
groups (SDG) associated with this case must be submitted as
one data package in its entirety within 35 days from the
verified time of receipt of the last sample in this case.
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7.
Analytical protocol required (attach copy if other than a
protocol currently used in this program):
TCLP Metals
TCLP VOAs
TCLP BNAs
TCLP Pest
TCLP Herb
Metals
VOAs
BNAs
Pest
Herb
Matrix
soil
soil
soil
soil
soil
water
water
water
water
water
Preparation
SW-846
SW-846
SW-846
SW-846
SW-846
1311
1311
1311
1311
1311
Analysis
CLP ILM03.0
CLP OLM01.8
CLP OLM01.8
CLP OLM01.8
SW-846 8150A
CLP ILM03.0
CLP OLM01.8
CLP OLM01.8
CLP OLM01.8
SW-846 8150A
Only the 39 TC analytes shall be reported.
Revision l of Method 8150A, dated November 1990, shall be used to
analyze herbicides.
The July 1992 version of Method 1311 shall be used.
8. Special technical instructions (if outside protocol
requirements, specify compound names, CAS numbers, detection
limits, etc.):
All Fractions
If dilutions are necessary due to an analyte being out of
calibration range, they must be done in increments of 10.
The raw data of all the dilutions must be provided; the
final result of the analyte shall be calculated from the
least dilution that would bring the analyte concentration
within the calibration range.
A TCLP blank must be carried through the extraction,
digestion, and analytical procedures.
The maximum number of samples in a sample delivery group
(SDG) is 20.
Field blanks and trip blanks do not require MS/MSB. The
matrix spike shall be added to the TCLP extract, not the
environmental sample.
Metals
The CRDLs for the TC metals shall be twenty times the CRDL
in the current SOW, except for mercury, which will
-------
be two hundred times higher. The matrix spike analytes will
be spiked at five times the contract specified
concentrations. The TCLP Section 8.4 criteria for method of
standard additions shall be followed.
Orcranics
Volatile and semi volatile TCL fractions will be diluted
five times before analysis, which will increase the CRQLs by
a factor of five. Pesticides will be diluted ten times
before analysis, which will increase the CRQLs by a factor
of ten. The TCL surrogates will be spiked at five times the
contract specified concentrations. The TCL matrix spike
analytes shall consist of all the TC analytes except
toxaphene, and shall be spiked at ten times the contract
specified concentrations.
When analyzing BNA samples, the 2/88 CLP extraction
procedure must be used. Initial and continuing
calibrations are required for pyridine and m-cresol.
There are no calibration acceptance criteria for pyridine or
m-cresol.
Herbicides
Follow requirements in 8150A and 8000A.
Analytical results required (if known, specify format for data
sheets, QA/QC reports. Chain of Custody Documentation, etc). If
not completed, format of results will be left to program
discretion.
The following TCLP deliverables shall be supplied:
1. The TCLP and preparative extraction dates and analyses
dates. Data to justify selection of TCLP extraction
fluid.
2. A physical description of the samples.
3. The sample weights and the extraction fluids weights.
4. The final volume of TCLP extract and the volume of
extract analyzed.
5. The calculations used to compute percent dry solids and
the weight of the liquid phase (if applicable).
6. Extraction logs for each sample, indicating the volume
and pH of acid added. Were inorganic sample extracts
properly preserved?
7. A description of the materials of construction for
extraction vessels, filtration devices, and ZHE
extraction devices (i.e. glass, Teflon, PVC, stainless
steel etc.) .
8. The calculations used to compute TCLP extract
concentrations for multiphasic samples.
-------
9. When VOA samples consist of oily waste that cannot be
filtered, describe how the TCLP extract is separated
from the oily waste.
10. A copy of the sampling log.
11. Any evidence of leakage in the ZHE device.
TCLP Worksheets 1, 2, 3, and 4 (attached), must be
submitted with the analytical data.
A TCLP bank must be analyzed in addition to method
blanks.
The following analytical results shall be submitted for
Method 8150 A analysis:
The laboratory must submit all documentation including: SAS
packing lists, traffic reports, chain of custody forms, and
sample preparation information. Analytical and QC results
shall be submitted on the following modified CLP/SOW
pesticide forms: Form I (Analytical Results), Form II
(Surrogates), Form III (Matrix Spikes), Form IV (Method
Blank), Form VI (Initial Calibration), Form VII (Calibration
Verification), Form VIII (Analytical Sequence) and Form X
(Identification Summary). All QA/QC information, including
laboratory generated standards and sample chromatograms,
must be submitted. A written narrative describing problems
encountered in receipt or during analysis and corrective
actions taken (including telephone logs, etc.) must be
provided. All documents (modified CLP forms, raw data,
etc.) related to re-extraction/re-analysis must also be
submitted in its entirety.
10. Other (Use additional sheets or attach supplementary
information, as needed):
The following requirements apply to method 8150A:
The laboratory must supply any information required to
reproduce, during independent data review, all results
reported by the laboratory. The laboratory must supply a
detailed example calculation that clearly demonstrates the
manner in which the initial and final results were derived.
Where applicable, each component of the calculation must be
explained (e.g., if the calculation include a dilution
factor, it must be specified how each dilution occurred).
-------
11. Name of sampling/shipping contact:
12.
Phone: ( )
Data Requirements
For VOAs, BNAs, pesticides and metals, follow CLP criteria.
The following requirements apply to 8150A herbicide
analysis:
Parameter
2,4-D
2,4,5-TP
Detection Limit
As per method
8150A
Precision Desired
As per method
8150A
Estimated Quantitation Limits (EQL) can be computed from
Table 1 & 2 of method 8150A for various parameters.
13. QC Requirements
For VOAs, BNAs, pesticides, and metals, follow CLP criteria.
The following requirements apply to 8150A herbicide
analysis:
Audits Required
Initial Calibra-
tion
Continuing(mid-
level std) Cal-
ibration
Surrogate
Method Blank
Duplicate
Matrix Spike
Frequency of Audits
See Method 8000A
All samples, etc.
1 per 20 samples
l per 20 samples
1 per 20 samples
Limits
(% or Concentration)
Every 10 samples %D s25%
50-120% Recovery
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8
Audits Required Frequency of Audits (% or Concentration)
For VOAs, BNAs, pesticides, and metals, follow CLP criteria.
For 8150A and TCLP, follow method criteria.
14. Action Required if Limits are Exceeded
For VOAs. BNAs. pesticides, and metals, follow CLP protocol
For 8150A. reextract and reanalyze.
Please return this request to the Sample Management Office as
soon as possible to expedite processing of your request for
special analytical services. Should you have any questions, or
need any assistance, please contact your Regional representative
at the Sample Management Office.
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TCLP Worksheet No. 1
Sample Description
Laboratory Sample Mo.
Field Sample No.
ft. Sample Description
Number of phases
1. solid
2. liquid
a. lighter than water
b. water
c. heavier than water
B. Percent Sofa Pbase
1. weight of filter
2. weight of subsample
3. weight of filtrate
4. weight percent solids (wet)1
5. weight percent solids (dry)2
6 volume of initial aqueous filtrate
7. volume of initial organic filtrate
1. The weight percent wet solids is given by the equation:
weight of subsample - weight of filtrate
weight of subsample
2. The weight percent dry solids is given by the equation:
(weight of dry waste - filtei) - weight of filter
weight of subsample
X100
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10
Discussion and Recommendations
TCLP Worksheet No. 1
Sample Description
This worksheet documents important information regarding the general description of the sample and the number of
phases observed in the sample as received from the field. This information is used to determine the amount of leaching
fluid used to leach solid materials and the weighting factors used when calculating final analyte concentrations from
multi-phasic samples.
A. Sample Description
Number of phases •• The number of phases present in the sample determine how the TCLP is conducted. Solid
materials having no visible liquid phase are extracted as received from the field and the analyte concentration
found in the leachate is the reported value. Liquid materials having no measurable solids content ( < 0.5 wt. %
dry solids) are defined as the TCLP extract flf 2.1) and are filtered and analyzed directly.
Multi-phase samples must be separated ( H 7.1.1.2) and each phase treated individually. Aqueous phases may be
combined with the leachate from solid phase materials before analysis if the two aqueous materials are compatible
( H 7.2.13.2). If the two aqueous materials are not compatible, than each liquid must be analyzed by the
appropriate methods and the results combined numerically to determine the final reported value ( \7.2.14).
A.1. Solid •- record the visible presence of a solid material heavier than water. If the sample contains more than
one solid phase ( example, wood chips and sediment mixed with water) record the information in the
laboratory notebook.
A.2. Liquid •• record the number of liquid phases observed in the sample according to their apparent density. It
may be impossible to distinguish apparent density if only one liquid phase is observed and there is no
indication on the accompanying chain-of-custody form (CDC). If this is the case, record it as aqueous material
and let the subsequent analytical record show if the liquid is organic after the container is opened at the
appropriate time.
B. Percent of Solid / Liquid Phase(s) •• paragraphs 7.1.1 through 7.1.2.3 of the method describe the procedure to
follow for the determination of the percent solids of the samples. It is also convenient to measure the percent of
any non-miscible liquid phases at this point because the information is required in H 7.2.14.
Laboratory subsamplmg of the material delivered to the laboratory must be thoroughly documented. The total
contents of the sample container should be considered as "the sample" and care must be taken to ensure the
representativeness of any subsample. Heterogeneous and multi-phasic materials can be difficult to subsample
properly and frequently require significant judgment on the part of the analyst.
Discussion - At this point, h is important to review the COC and confirm the number of containers of each
sample provided to the laboratory and the types of analyses requested. If the analysis of volatile components is
requested, the determination of percent solids in multi-phasic samples must he completed hefore proceeding to the
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11
leaching of the solid material in the zero headspace extractor (ZHE) to prevent overfilling the ZHE. It is best if a
separate sample has been provided for this purpose ft 6.2). The laboratory should establish an SOP to address
how to proceed if only one container is available.
It is common that when more than one container of multi-phasic materials is received from the field, each
container will show different amounts of each phase. This provides a challenge to the laboratory which must
report the data based on percent phase composition of the sample. A practical solution is to record the depth
(measured from outside the container) of the layers in the each container after the contents have been allowed to
settle and determine the combined volume of each phase in all the containers. Then measure the phase
composition on a single container (after thorough mixing to obtain a representative subsample). Combine these two
sets of values to determine the correct volume/mass adjustments on the TCLP results.
The laboratory should also establish an SOP on how to proceed when only a limbed amount of sample is available
and the analyses requested exceed the amount of sample provided.
B.1. Weight of filter •- This value must be measured before loading the filter into the filter holder because the
mass of the filter is used in performing the calculation for percent dry solids.
B.2 Weight of sample aliquote •• a representative 100 gram sample ft 7.1.1.5) is withdrawn from the sample
container for filtration. If liquid material is decanted from the sample before subsampling, its volume/weight must
be recorded and factored into the calculations of percent solids.
Discussion - Many mufti-phasic samples are difficult to filter. This is especially true of oily wastes and
sludges. The method directs that any material retained by the filter after following the instructions is defined
as solid waste ft 7.1.18). Experience has shown that the reproducibitity of the percent solids determination
with these types of samples is highly variable. Subsequent steps in the extraction procedure ft 7.2.5 and
7.3.4.2} use the % solids value to estimate the mass of the original waste used to obtain an appropriate
sized subsample of the so/id for extraction.
The method directs that the material retained by the filter be dried at 100 ± 20'C ft 7.1.22) to
determine the percent dry solids. This may not be achievable for organic multi-phasic materials because of
safety considerations and the fact that many organic liquids boil considerably higher than water and it may
be impossible to achieve a constant weight for successive weighings (± 1%).
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12
The laboratory should establish a standard operating procedure (SOP) addressing these types of samples.
Basically, the laboratory has three choices of how to proceed. It may
• attempt to dry all samples as directed by the method;
• dry samples containing only water as the liquid phase; and/or
• define the retained material as a dry solid for the purpose of further testing.
This decision may have significant impact on the amount of material selected for leach testing and on the
reported analyte values. The laboratory should consider discussing this issue with their clients and any
regulatory groups to whom the data will be submitted.
B. 3 Record weight of filtrate.
B. 4 Weight percent solids(wet) equals:
weight of subsample - weight of filtrate x 1QO
weight of subsample
The procedure defines the material retained by the filter as the solid phase of the waste (f 7.1.1.8). This
value is used to calculate the volume of the original multi-phasic material which must be filtered to yield the
proper amount of solid waste for the extraction procedure.
B.5 Weight percent solids (dry) •• the total mass of the filtered solids and the filter are removed from the filtration
apparatus and dried at 100 ± 20 °C until a constant weight is achieved ft 7.1.2.2). This value is used to
calculate the dry solids content of the waste. Use caution when drying samples that may contain flammable
material. It is important to factor in the tare weight of the filter for samples that have low solids values.
The weight percent solids (dry) is calculated by the equation:
(weight of dry waste + filter) - weight of filter
T~T~.—,— :
weight of subsample
If the weight percent dry solids is > 0.5%, the total waste is defined as a solid waste and steps must be
taken to collect the appropriate weight of solid material for extraction (t 7.1.2.4).
B.6 Volume of initial aqueous filtrate •• this value is used in H 7.2.14 and 7.3.14 in the final calculation of analyte
concentration.
B.7 Volume of initial organic filtrate •- this value is used in 1 7.2.14 and 7.3.14 in the final calculation of analyte
concentration.
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13
TCLP Worksheet No. 2
Selection of Extraction Fluid
Laboratory Sample No.
Field Sample No.
C. Extraction Fluid Oefermiasgoii - does not apply 1« detenmtalioft of wrtatSe organic eampwe
1. particle size reduction? yes/no
2. sample weight, / if 5.0 ± 0.1 grams
3. volume of water, / if 96.5 ± 1.0 ml added
4. initial pH (after 5 min. mixing time)
5. if pH > 5.0, S if 3.5 ml IN HCI added
6. / if heated and held at 50 °C for ten
minutes
7. secondary pH (at room temp.)
nls
D. Selection of £xtraetfen fluid;
1. S if pH from C.4 or C.7 is < 5.0, use
extraction fluid No. 1.
2. S if pH from C.7 is > 5.0, use extraction
fluid No. 2
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14
Discussion and Recommendations
TCLP Worksheet No. 2
Selection of Extraction Fluid
for
Metals, Semi-volatile Organic Components, and Pesticides/Herbicides
This worksheet documents the important steps which should be followed to correctly
determine the appropriate extraction fluid for leaching solid wastes for the analysis of
metals, semi-volatile organic components, and pesticides/herbicides. This procedure does
not apply to the determination of volatiles using the zero headspace extractor (ZHE).
Discussion - the Environmental Protection Agency's "worst case" waste disposal model
assumes mismanaged wastes will be co-disposed with municipal solid waste in a 5:95
ratio. These wastes will be exposed to leaching by the acidic fluids formed in municipal
landfills. The EPA's model further assumes the acid/base characteristics of the waste will
be dominated by the landfill fluids. The TCLP laboratory procedure directs that alkaline
wastes be extracted with a stronger acidic leach fluid than acid or neutral wastes so that
the alkaline nature of the waste will not control the leaching chemistry of the TCLP test.
This is in keeping with the waste disposal model's assumption that the acid fluids in the
landfill will dominate leaching chemistry over time.
The procedure described in K 7.1.4 of the method addresses the determination of the
appropriate extraction fluid. It is a short term test whose results can have a significant
impact on the final analytical results if the wrong extraction fluid is selected. This is
especially true for metals determinations because of their sensitivity to the pH of the leach
medium. The following discussion examines each step of the procedure and points out
some sensitive technical points and how they can affect the results.
f 7.1.4.1 Particle size of test material - The requirement to use 1mm particle size material
in the test recognizes the fact that in a short term reaction between a liquid and a solid,
high surface area is the most important characteristic of the solid. The rate of the reaction
is controlled by the rate of diffusion of the liquid into the pores of the solid so a high
surface area is necessary if the results of a short term test are to be reliable. Therefore,
failure to take a representative subsample of the solid material and perform the necessary
particle size reduction can result in significant bias. This is especially true if the waste
contains a wide range of particle sizes and only the fines are selected for testing.
f 7.1.4.3 Heating of the reaction mixture - The method specifies that the waste/acid
slurry is to be held at 50°C for ten (10) minutes. Care should be taken to heat the sample
to 50 °C as rapidly as possible without overheating. When the sample has completed the
•ten minute period at temperature, it should be allowed to cool and the pH determined as
soon as possible. The longer the reaction between the acid solution and the solid waste is
allowed to continue, the more likely that a falsely high pH reading will result. This will
result in improper selection of the more acidic extraction fluid. Failure to reach and hold
the required temperature can result in an artificially low pH reading for the test solution,
leading the incorrect selection of the less acidic extraction fluid.
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15
C. Extraction Fluid Determination H 7.1.4)
C.1. Indicate if particle size reduction is required for the sample.
Discussion - the laboratory should consider establishing an SOP to address the
particle size reduction requirements for the TCLP procedure. Most solid samples will
not be received from the field with a particle size of 1mm as required for this step
of the procedure ft 7.1.4.1). Many multi-phasic samples will not be amenable to
size reduction because of the nature of the sample. Samples containing pebbles,
rocks, or debris may be difficult to size reduce if the larger particles are hard. Proper
subsampling of the waste may be difficult if the waste is heterogeneous.
C.2. Sample weight -- check the box if 5.0g of sample is used in the test. Record the
actual weight if a different sized sample is used.
C.3. Volume of water - the volume of water used in the test is dependant on the weight
of sample being tested. If the sample weight (above) is 5g and 96.5 mL of water is
added, check the box. If the weight is not 5g, record the volume of water added.
( # of grams X 19.3mL).
C.4. Initial pH -- record the pH of the slurry after a five minute mixing period. Use narrow
range pH indicator paper if organic material is observed floating on the top of the
slurry to avoid damage to pH electrodes.
C.5. Procedure for alkaline wastes - if the initial pH of the slurry is > 5.0, add 3.5 mL
of 1N HCI to determine if the alkalinity of the waste is sufficient to require the use
of the stronger acid extraction fluid.
C.6. Neutralization reaction conditions - the slurry should be heated to 50 °C and held
for ten minutes.The laboratory should consider validating their procedure to confirm
these conditions are met. A bench procedure specifying the hot plate setting (or
other source of heat), the time required to reach the desired temperature, the ten
minute time at temperature, and the time required to return to room temperature
should be established. This will assure the maximum degree of reproducibility in the
determination of the alkaline potential of the wastes tested.
C.7. Secondary pH -- record the pH of the slurry after it has completed the cooling cycle.
D. Selection of Extraction Fluid
D.1. If either the initial pH or the secondary pH is < 5.0, select Extraction Fluid #1 as
the leaching medium.
D.2. If the secondary pH is >5.0, select Extraction Fluid #2 as the leaching medium.
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16
TCLP Worksheet No. 3
Determination of Extraction Fluid Volume
for
Metals, Semi-Volatile Organic Components and Pesticides/Herbicides
Laboratory Sample No.
Held Sample No.
E. Determination of Satnpte Size for teaefc Testing - the arethocl requires. 9 mNmuBj 100
gram sample size for extraction t1 7.2.5},
1 . particle size reduction? yes/no
2. amount of dry solids (100g min.)
3. amount of multi-phasic sample1
a. weight of material
b. weight of filtrate
c. weight of solid material
F. Determination of Amount of Extraction Fluid - the selection of the correct extraction fluid
is found in Section D, Worksheet Mo, 2.
1 . for dry solids (20X sample wt.)
2. for multi-phasic samples2
G. Record of Extraction Test - the extractor
1 . extraction start time
2. extraction stop time
3. filtration complete time
4. pH of filtrate
5. volume of filtrate
t period is specified as 18 ± 2 hours.
1. The theoretical amount of multi-phasic waste necessary to yield a 100g sample is
given by:
Amount of multi-phasic material =
(104)
(wt. percent wet solids)
2. The amount of extraction fluid needed to extract the solid material from a filtered multi-
phasic waste is given by:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
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17
Discussion and Recommendations
TCLP Worksheet No. 3
TCLP Extraction Procedure
for
Metals, Semi-volatile Organic Components, and Pesticides/Herbicides
This worksheet documents the performance of the TCLP extraction procedure for metals,
semi-volatile organic compounds and pesticides/herbicides.
E. Determination of Sample Size for Leaching -- the specified size of sample for the
leaching test is a minimum of 100g (1 7.2.5). The regulatory control limit for defining if
the waste is hazardous is based on the levels of analytes reported in the leachate
based on this size sample and a twenty to one (20:1) liquid to solid ratio. If the
amount of waste subjected to extraction is not 100g, than the volume of extraction
fluid must be adjusted to preserve the liquid to solid ratio.
E.1. Amount of dry solids -- record the weight of dry solids.
E.2. Amount of multi-phasic sample -- the amount of multi-phasic waste material
necessary to produce a 10Og sample after filtration can be estimated by the
equation:
Amount of multi-phasic material =
(104)
(wt. percent wet solids)
F. Determination of the Amount of Leaching Fluid
F.1. Dry solids -- for dry solids containing no filtrable fluids, the calculation of the
correct volume of leaching fluid is straightforward. The amount is equal to twenty
(20) times the mass of solid being leached. Note that the method specifies a 20:1
ratio based on the weight of extraction fluid required (H 7.2.1.1). If the laboratory
elects to use extraction fluid volume, rigorous adherence to the method requires a
one time specific gravity correction to convert the required weight into the
appropriate volume.
F.2. Multi-phasic samples - the method says (H 7.2.11) the percent wet solids can be
used to calculate the weight of extraction fluid used to extract the solid waste
resulting from the filtration of a known weight of multi-phasic waste. The equation
for this calculation is:
Amount of extraction fluid = 0.2 (percent wet solids) (weight of waste filtered)
This assumes there is no subsampling error between the original determination of
the weight percent solid phase (wet) and the subsequent selection of a weight of
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18
the multi-phasic waste for filtration and extraction. This is frequently not so. The
nature of many multi-phasic wastes and/or the necessity to use more than one
sample container for the two determinations means that subsamplng error can be
significant. This error can be eliminated if the actual weight of filtered solids is
determined at the time the material is separated for extraction. The equation for this
calculation is:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
The actual filtration procedure is detailed in J's 7.2.2 though 7.2.8. Requirements
for sample particle size reduction are given in f 7.1.3 and 7.2.10. These should be
followed as closely as the nature of the samples will allow and all departures from
the instructions should be described in the laboratory notebook.
G. Record of the TCLP Extraction Test - the period of the extraction test is given as
18 ± 2 hours (H 7.2.12). Extraction should be started so the resulting slurry can be
filtered as soon as possible after the 18 hours has past. The filtration effectively stops
the extraction process. If the extraction fluid is left in contact with the waste for longer
than the specified period {overnight or over the weekend), the extraction process
continues and may lead to elevated levels of contaminants.
G.1. Extraction start time - record the time and date the extraction begins.
G.2. Extraction stop time - record the time and date the extraction is completed.
G.3. Filtration completion time - record the time and date the filtration is complete.
G.4. pH of filtrate -- while not required by the method, this is a good indicator of test
performance when performing duplicate laboratory analysis or analyzing field
replicates. It can be a reliable measure of sample heterogeneity.
G.5. Volume of filtrate - record the total volume of filtrate collected from the sample.
This value is required to make the appropriate volume corrections when reporting
the results from multi-phasic wastes.
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19
TCLP Worksheet No. 4
Zero Headspace Extraction (ZHE)
Laboratory Sample No.
Field Sample No.
H. Determination of Sample Size for Leach Testing - maximum 25 grams
1 . amount of dry solids
2. amount of multi-phasic sample1
Determination of Amount of extraction, n
1 . for dry solids (20X sample wt.)
2. for multi-phasic samples2
a. weight of material
b. weight of filtrate
c. weight of solid material
ukftto. 1
J. Record of ZHE Extraction Test - the extraction period is as 18 ±2 hours If 7.3.12.3).
1 . extraction start time
2. starting pressure
3. extraction stop time
4. S if positive pressure
5. filtration completion time
6. pH of filtrate
7. volume of filtrate
1. Determination of amount of multi-phasic sample for extraction:
a. if weight percent dry solids is < 0.5% (from Worksheet No. 1, B. 4), the waste is
filtered and the filtrate is defined as the TCLP leachate (1 7.3.4).
b. if weight percent wet solids is > 5% (from Worksheet No. 1, B. 4), the amount of
multi-phasic material which should be filtered to yield a 25 gram sample is given by:
Amount of multi-phasic material
(2.5 X103)
(wt. percent wet solids)
2. The amount of extraction fluid #1 needed to extract the solid material from the filtered
multi-phasic waste (H.2) is given by:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
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20
Discussion and Recommendations
TCLP Worksheet No. 4
Zero Headspace Extraction
for
Determination of Volatile Organic Compounds
This worksheet describes the important information regarding the conduct of the zero
headspace extraction (ZHE) of solid waste materials for volatile organic compounds.
Samples containing < 0.5 % dry solids are NOT subjected to ZHE leaching procedure.
They are filtered in the ZHE device and the resulting filtrate is defined as the TCLP leachate
and analyzed directly (f 7.3.4).
H. Determination of Sample Size for Leach Testing - the maximum sample size for this
test is limited by the volume of the ZHE to approximately 25g (fl 7.3).
H.1. Amount of dry solids - record the weight of dry solids charged to the ZHE but do
not exceed 25g.
H.2. Amount of multi-phasic sample -- the amount of multi-phasic waste material
necessary to produce a 25g sample after filtration can be estimated by the
equation:
Amount of multi-phasic material = (2.5 x 103)
(wt. percent wet solids)
I. Determination of the Amount of Leaching Fluid #1
1.1. Dry solids - for dry solids containing no filterable fluids, the calculation of the
correct volume of leaching fluid is straightforward. The amount is equal to twenty
(20) times the mass of solid being leached. Note that the method specifies a 20:1
ratio based on the weight of extraction fluid required {f 7.3.11). If the laboratory
elects to use extraction fluid volume, rigorous adherence to the method requires a
one time specific gravity correction to convert the required weight into the
appropriate volume.
1.2. Multi-phasic samples - the method indicates (1 7.3.11) that the percent wet solids
can be used to calculate the weight of extraction fluid used to extract the solid
waste resulting from the filtration of a known weight of multi-phasic waste. The
equation for this calculation is:
-------
21
Amount of extraction fluid = 20 &rcent wet solid$^ (wei9ht of waste filt&red>
100
This assumes there is no subsamplmg error between the original determination of
the weight percent solid phase (wet) and the subsequent selection of a weight of
the multi-phasic waste for filtration and extraction. This is frequently not the case.
The nature of many multi-phasic wastes and/or the necessity to use more than one
sample container for the two determinations means that subsamplng error can be
significant. This error can be eliminated if the actual weight of filtered solids is
determined at the time the material is separated for extraction. The equation for this
calculation is:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
The actual filtration procedure is detailed in ^'s 7.3.7 though 7.3.9. Requirements for
sample particle size reduction are given in 1 7.3.5 and 7.3.6. These should be followed as
closely as the nature of the samples will allow and all departures from the instructions
should be described in the laboratory notebook.
The addition of extraction fluid #1 to the ZHE is described in detail in 1 7.3.12.
J. Record of the ZHE Extraction Test - the period of the extraction test is given as
18 ± 2 hours (f 7.3.12.3). Extraction should be started so the resulting slurry can be
filtered as soon as possible after the 18 hours has past. The filtration effectively stops
the extraction process. If the extraction fluid is left in contact with the waste for longer
than the specified extraction period (overnight or over the weekend), the extraction
process continues and may lead to elevated levels of contaminants.
J.1. Extraction start time -- record the time and date the extraction begins.
J.2. Starting pressure -- the method requires the ZHE be pressurized to approximately
10 psi at the beginning of the test.
J.3. Extraction stop time - record the time and date the extraction is completed.
-------
22
J.4. Positive final pressure - the method requires that the ZHE retain positive pressure.
at the conclusion of the extraction period or the test must be repeated (1 7.3.13).
Loss of pressure is an indication the ZHE leaked during the test resulting in a loss of
volatile components.
J.5. Filtration completion time - record the time and date the filtration is complete.
J.6. pH of filtrate -- while not required by the method, this is a good indicator of test
performance when performing duplicate laboratory analysis or analyzing field
replicates. It can be a reliable measure of sample heterogeneity.
J.7. Volume of filtrate -- record the total volume of filtrate collected from the sample.
This value is required to make the appropriate volume corrections when reporting
the results from multi-phasic wastes. The filtration of oily wastes may be especially
difficult.
-------
Appendix IX
-------
Appendix IX
Office of Solid Waste Methods Section
Required Uses of SW 846
-------
The following information regarding required uses of SW-846
was compiled by the Methods Section, OSW, U.S. EPA Headquarters.
Several of the hazardous waste regulations under Subtitle C of
RCRA require that specific testing methods described in SW-846 be
employed for certain applications. Any reliable analytical method
may be used to meet other requirements in 40 CFR parts 260 through
270. For the convenience of the reader, the Agency lists below a
number of the sections found in 40 CFR parts 260 through 270 that
require the use of a specific method for a particular application,
or the use of appropriate SW-846 methods in general:
(1) Section 260.22(d)(1)(i) - Submission of data in support
of petitions to exclude a waste produced at a particular
facility (i.e.. delisting petitions);
(2) Sections 261.22(a)(l) and (2) - Evaluation of waste
against the corrosivity characteristic;
(3) Sections 261.24 (a} - Leaching procedure for evaluation of
waste against the toxicity characteristic;
(4) Sections 264.190(a), 264.314(c), 265.190(a), and
265.314 (d) - Evaluation of waste to determine if free
liquid is a component of the waste;
(5) Section 266.112(b)(1) - Certain analyses in support of
exclusion from the definition of a hazardous waste of a
residue which was derived from burning hazardous waste in
boilers and industrial furnaces;
(6) Section 268.32 (i) - Evaluation of a waste to determine if
it is a liquid for purposes of certain land disposal
prohibitions;
(7) Sections 268.40(a), 268.41(a), and 268.43(a) - Leaching
procedure for evaluation of waste to determine compliance
with Land Disposal treatment standards;
(8) Sections 270.19(c) (1) (iii) and (iv), and
270.62(b)(2)| (i)(C) and (D) - Analysis and approximate
quantification of the hazardous constituents identified
in the waste prior to conducting a trial burn in support
of an application for a hazardous waste incineration
permit; and
(9) Sections 270.22(a) (2) (ii) (B) and 270.66(c) (2) (i) and (ii)
- Analysis conducted in support of a destruction and
removal efficiency (DRE) trial burn waiver for boilers
and industrial furnaces burning low risk wastes, and
analysis and approximate quantitation conducted for a
trial burn in support of an application for a permit to
burn hazardous waste in a boiler and industrial furnace.
-------
Appendix X
-------
Appendix X
Stabilization/Solidification: Is It Always Appropriate?
and
Stabilization/Solidification of Wastes Containing
Volatile Organic Compounds in Commercial
Cementitious Waste Forms
Printed with permission from STP 1123 Stabilization and Solidification of Hazardous,
Radioactive, and Mixed Wastes, 2nd Volume, copyright American Society for Testing and
Materials, 1916 Race Street, Philadelphia, PA 19103
-------
VVH.CO «NU tWH IH ON SOLIOIFICATION/ST ABILIZA1.
19
Carlton C. Wiles* and Edwin Barth*
Solidification/Stabilization: Is It Always
Appropriate?
RFTKKKNCK: Wiles. C C amtnarth r "Snlldilicnlinn/Slabilbnlinn: Is II Alnays Appropri-
ate?" XiuMi:aii«H anil Xnliililii'iiiiim <>l Ha:nriliHi'. Rniliiviilnv tuul Mt\e
-------
20 HAZARDOUS WASTES
Arsenic under oxidizing conditions will be in .he pen.avalcnl form and will be soluble over a
brTad range of pH values (p.! from - 2 to . 4). Thus, in order .0 s.abiltze «•"*""**
it may be necessary to reduce it to the trivalcnt or elemental form. In this case, the pH must
be maintained below 11, as As{lll) becomes soluble at a pH of > 11.
Chromium is similar to arsenic in its chemical behavior. The ox.d.zed. soluble form of
chrome is the hexavalcnt form Cr(VI). In order to apply many of the common S/S technolo-
gieTTe operator f.rst must chemically reduce Cr(Vl) to Cr(lll). wh.ch ,s relatively insoluble
ovcrapH range ofaboutSto 13. Again, controlling final pH in the process is necessary because
Crtlll) is soluble outside this range.
Lead is amphoteric, that is, it is soluble under both basic and acidic cond.t.ons^ Lead is fa.rly
insoluble at pH values between 7 and 12 (Fig. I). At a pH below about 7 lead ,s soluble as
Pb", while at a pH above 12. it can be soluble asanionic plumbate ion. Chemical reduction
of the lead is ineffective; proper control ofpH is usually more important.
100
8 9 10
SOLUTION pH
MG. I —Soliibiliiif.'s iijiwial hydroxides us afmuliim nlpll.
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION 21
While these shortcomings do not preclude the use of S/S for these metals, they do cmphasi/c
the importance of performing carefully controlled trcatability studies before applying specific
S/S techniques to specific waste streams. Furthermore, to improve the interpretation of treat-
ability study results, certain guidelines must be followed. Preliminary rules of thumb for assess-
ing S/S technology applied to metals, at the bench-scale level, arc as follows.
I. Characterize the original waste as well as possible. This characteri/.ation should include
chemical characteristics, mineral composition, physical properties, and so on, as well as
the normal analyses for pollutant levels.
2. Identify the target contaminants and tailor the binder system to low solubility regions of
the metal of interest.
3. Perform appropriate extraction tests on the untreated waste to serve as a benchmark for
subsequent data on the treated waste. Report extraction test data for both treated and
untreated forms. Consider incorporating leaching data into a site-specific ground water
model.
4. Analyze and record pH on the extracts from the untreated waste and treated product.
5. Analyze additives for presence of hazardous constituents. Identify critical characteristics
of all additives to establish a quality control program. Carefully control and record all
additives during Ircatability tests. Small variations in additives can greatly affect
teachability.
6. When reporting Icachate data on treated samples, show the total percent reduction
achieved and the extent to which simple dilution has contributed to such reduction.
These arc not complete guidelines for performing trcatability studies, merely some rules to
follow that will make S/S data easier to interpret and transfer. The importance of conducting
properly designed and controlled trcatability studies for any waste cannot be overemphasized.
The HPA is currently evaluating protocols for conducting such treatability studies.
S/S Applied to Wastes Containing Volatile Organics
It is common to distinguish organics as volatile, scmivolatilc, and nonvolatile. Typically,
volatile organic compounds (VOC) arc considered to be those having boiling points below
150°C (301°F). When one considers the operational steps in the S/S process, it is obvious that
during the mixing of binder, water, and waste, as well as during the curing process, VOCs arc
lost because of the mixing and because of any rise in temperature. The KPA's Ollicc of Air
Quality Planning and Standards (OAQPS) is presently developing guidance for the Resource
Conservation and Recovery Act (RCRA) Treatment, Storage and Disposal (TSD) facilities,
indicating that solidification processes, even for very low levels of volatile constituents, must
incorporate capture and control mechanisms to ensure that there is no release of volatile con-
stituents to the atmosphere. Furthermore, since the capture mechanisms of cement-bused pro-
cesses depend so heavily on physical containment, it is almost a certainly that volatiles can
escape from the solidified form, no matter how great the retardation introduced by reductions
in pore space or increases in tortuosity. Thus, as a general rule, sites contaminated with only
volatile constituents should not IK considered as candidates for S/S. Sites contaminated with
a mix of materials, including volatiles as well as other organics and inorganics, will require
careful characteri/ation before selecting S/S as the principal technology. Whether or not S/S
should he used will depend upon the relative levels of volatiles and other constituents present.
If the site contains metals or other constituents above specific levels of concern, then additional
treatment by S/S may be required.
-------
22 HAZARDOUS WASTES
The quantities of such organics acceptable for S/S should he based on a risk assessment lor
the given site and/or on the result of a iicatiihihly study llial includes u mass hulunce on the
organics before, during, and after treatment I'lic trcalability study should include u "harsh"
cxlrnciion procedure (lor example, total w.islc analysis) to evaluate the migration of orgunics
in both treated and untreated material because many organics are noi soluble in water or weak
acid media The risk assessment should assume llial none of the highest risk compounds will
he retained by Ihc S/S process and/nr that all sueli compounds will be lost via air emissions
during the S/S processing, unless an air pollution control mechiinisni is in place. This scenario
is very conservative as it does not assume any relaidalion of the compound that can ociur hy
physical mechanisms in the solidified waste form. Conversely. Ihc muss balance approach will
give some credit for physical characteristics or other bonding mechanisms in the solidified
waste form. Even so, this approach is also conservative in that a lota) waste analysis (TWA) or
similar extraction procedure requires grinding of llic sample. "I his grinding results in destroy-
ing or altering and reducing the effectiveness of some physical properties that can impede the
release of the organics under actual field conditions However, we believe these conservative
approaches arc necessary based upon available S/S data as applied to orgunics and the appar-
ent inadequacies in the sampling, analysis, and extraction tests used to evaluate the treatment
or organics ut Superfund sites.
Therefore, except For the case when 100% hazardous volatile constituents are present, the
amount of organics present may not be the most important factor in deciding whether or not
to evaluate S/S as part of the total treatment process The important factors ate the concen-
liation and characteristics of remaining constituents of concern that will requite treatment, if
ull (he volatiles were removed and/or destroyed. In other words, preticat mcnl. removal, and/
or capture and treatment of volatile oiganic constituents will be required prior to or during S/
S
S/S Applied to Wastes Containing Semlvolulile Organics
Evaluating Ihc effectiveness of S/S processes to capture and iminohih/c scmivolalilc organ-
ics is more complicated Alter mixing, Ihc solidification process that lakes place over a period
of time is called "curing." During the curing process, the water present is used in h yd tut ion
reactions. The final solidified waste form, especially for ccmcnl-bascd processes, is usually a
monolithic structure incorporating hydrated silicates and carbonates in an agglomeration of
crystalline structures thai incorporate und/or microcricapsululc the Iwardous constituents,
the original soils, and any aggregate that may have been added to enhance the product's
strength Solidification processes are normally exothermic because of Ihc hydralion reactions
Typically, the heat given off is sufficient to raise Ihc temperature of Ihc matrix by .10 to 4IFC
in the early stages of curing. In cases where kilndust or other lime-based products (that is. those
containing large amounts of quicklime (CaO)J arc used, temperature rises can be significantly
higher yet. Thus, it is possible (hat some of the low-boiling semivolulile compounds volatilize
and escape during the curing process
Once curing is complete1, the cfleeli vcncss of cement-based solidification processes to con-
lain semivolalilc organic compounds is currently unclear. 'I he application ol the IX 'LI' lest to
organically contaminated soils before and alter treatment with cement-bused solidification
processes in the Superfund Innovative Technology Evaluation (SI'I L) program lias yielded
inconclusive results This situation is due largely to the fact that the solubility of the organic*
in the extraction fluid is so low that even small quantities of these organic contaminants
iimckly saturate (he 1'CLP liquid. 1 hus, no measurable difference between the teachability of
organic contaminants from untreated soils and from the solidified soil product can be dcler-
1 - "J" "• ™«"«iirr nl the nrnhuhle mobility of these
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION 23
comamiiMim in aqueous-phase leaching processes, ,t .Iocs not address the potentril esuanu ,,l
^
I" ..... CCtP'"hlC lhrCS"0ld- ">Un S/S p">™ - -» 3™r S
rt of a complete treatment tram Slabili^tion/sohdihcatK,,, would follow some c" her
2L 1 hcTT" °r "7 T™" J"K"°r dCMrUC""n °f ""•• «*«*' «- -- votaS c,±
ucms 1 he levels of residual scmivoliinlc compounds rcm.umng ,n Ihc WMC nrior o a 1,1
ification process musi be determined based on maximum eoncen,," K^ m, s a t W-H, eS
each such consntuenl Note thai m this conte*.. S/
sm
sonn.
be demonstrated to be effective. Al present such demon
" "
evauated
Discussion of Kxirm-ifon
lixlraclion tests are used to determine or estimate the
I he harsh exlract.ons, such as total waste analysis, do no, represent real "« c Lid ZZons
al lest
Summary »f Selected Results fur Orj-anic Waslw
leach
that was allowed ,o cure for l.uee daynd Table 3
-------
24 HAZARDOUS WASTES
TABLE I—Some f \irannia r«fi uutl lor waluiuinxitaMizatuin/uiltdtJuMiiinulargante-
fiiiiitinuiiaied mute
Peer Reviewed
Extraction for Organic Utilized for evaluating
Tcsls Stabilisation Organic Stabilization
Comments
TCLP
1 CLP Cage
No
No
Several Supcrfund
Sues
ASTM Committee
D-34
Gnnding of monolith.
Codispcual scenario only may not
show orgunics
Most organic* not soluble in
Icachalc
No gnnding
Erosion caused by cage docs not
represent "real world"
Poor rcproducibilily noted by
ASTM
Most orgnnics not soluble in
leachale
TCLP Acid
Kain
rCLP Acetone
MEP
Total Waste
Analysis
(TWA)
ANSI 16.1
ANSI 16 1 plus
ground water
Acid Rain
(1312)
No
No
No
No
No
No
No
Limited number
ofSupcrfund
sites
Limned number
orSuperfund
sites
Dehsling (metals)
R&D
Several SuperCund
sites
Limited number
ofSunerfund
sites
Unknown
Used synthetic acid rain with TCLP
apparatus
Acetone to extract PCBs nul
realistic
Conservative worsl case docs not
represent "real world"
Somewhat realistic
Simulates acid rain
Metliylenc chloride or hexani-
Conservative wotsi case, docs noi
represent "real world"
May not show organic1;
May not show organic!
May not be representative of real
acid rain
May not be applicable for orgunics
for a sample thai was allowed to cure 28 days before leach testing These tables show a com-
plete mass balance indicating (he amount or phenol retained in the solidified product. The
enhanced retention in the 28-day cured product is probably due to a decrease in pore si/c in
the product as curing proceeds. Twenty-eight days is a typical curing lime forccmcnl-bascd
solidification processes. Even so, only about 40% of the phenol is retained in the solidified
product.
Bricka, Holmes, and Cullmane |6J ofthe U S Army Corps of Engineers, Waterways l-xpcr-
iment Station, in a study performed for KPA. showed a comparison of ihc tPand TCLP Icach-
ingcxlracts Tor two solidified sludges and one nonsolidificd, organic-based sludge (Table 4) A
metal hydroxide sludge (ideniified as WES) was stabilized by addition ofcemcnl. A second
material (identified as WTC) was a metal solution containing chromium chloride, cadmium
nitrate, k ' Citrate, sodium arsenile. and phenol at a pi I of 2.5. This synthetic metal solution
was sol y adding Portland cement. Type F fly ash, and soil in equal quantities to the
l. a PCE sludge, was a still-bottom wasle mulling from ihc
WILES AND BAHTH ON SOLIDIFICATION/STABILIZATION
TABI L 2—Mu\\ Imlumc leuili ie\i Nit I |5J
25
1 caching Period
Days 1 and 2 Icairulc
vapor
Days 3 and A. leachatc
vapor
Days 5 and 6: Icachalc
vapor
Days 7 and 8 Icuduic
vapor
Tola! phenol (cached from .10 g of cement product
Phenol adsorbed to liner of cement mold
Phenol mixed into 30 g of cement product
Phenol retained in cement product (calculated by difference)
Phenol
Released, mg
27 42
OOO
6 13
000
254
000
1 04
000
37 13
4000
274
l-cachunt
Volume, ml.
245
33
-------
26 HAZARDOUS WASTES
1 ABLE 4—Siiulv H an-ruge fimo/l'
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION 27
IADI.I 4— O»i/»mr|)
_ _
F.xlr.ict Concentration.
ma/l
ol
rp TCI.P
• • "
ClILOROI OHM
ft oo 1 40
0 no i Hu
11 m 57 27
1 3 97 ti ti
i MI I S.h
1 01 ' •>0
11 n 12 70
23 7 1 Jt iv
n 11 O 20
0 22 u '"
898 913
1.2-DlCIILOROETIIANE
. r -, 1 27
1 Jf ' *'
iu in 61 17
38 7O o i .1 '
i / i 4 21
J ol ^ *•
CT in 71 40
57. 3U ' ' H"
it if 0 49
0 76 u H *
4503 4423
1.1,1-TRIC.HIOROBTHANL
n <»/ I (Jl
096 • *J
i u 1 1 46 SO
IK 33 HD nu
A c< 4 RO
053 H ou
i c m ?S 07
1 5 U/ *J "'
n in 045
I) 2 v w •« j
1507 24.83
CARBON FETRACHLORinF.
n A-I 0 89
U n £ \f n f
i at 7 60
3 *J3 ' ««
/\ -ii O SO
021 11 ju
m/w\ IOOO
1 0 Oil ' u uu
n m 0 20
11 IU U AW
5 00 5 00
rRHIIIOROETIII-.NF
-. .-, A U()
I 4 / v fv
Lt A1 114 13
54 oJ i >t 1 1
1 AH 1 54
1 *tO • ^^
11 11 3997
jjfi j»^»
•> 17 2 55
£. >*
9H07 13567
l)LN7LNt
1 All 2 10
1 OU * -11'
4297 8533
_ e "JQ
2 62 5 29
t A 1 7 76 57
j*i ii 1 1» ^ «
091 n14
5523 6240
I.I. 2,2-1 UK III OROITIIANL
n 7s 0 22
O £J " £A
1 00 5 00
711 904
un-nwtl i«w ''«
__
• llirn1
_ ^ — ——
Organic Recovery, %
bP
0088
0.140
0 101
0.238
0022
0090
0157
0387
0361
0573
0076
0450
0096
0 183
0055
0 151
0029
0 151
0042
0039
0023
0 100
0010
0 050
0.347
0646
0148
0317
0 232
0981
0 160
0410
0262
0542
0091
0552
0025
0010
0731
'1 Cl.P
0 140
0273
0156
0327
0020
0091
0127
0614
0423
0714
0049
0442
0 193
0468
0480
0251
0045
024K
0089
0 076
0050
0 100
0020
0050
0 690
1 141
0154
0 400
0255
1357
0210
0853
0 529
0 766
0079
0 624
0022
0050
1) 904
1 xlruc.1 C'onicnlr.ition,
Level ol mg/L Organic Recovery. %
Spike Added,
Sludge mg/l. 1-P TOP IT ICI.P
WIC IOOO 010 020 0010 0020
10000 ,500 500 0050 0050
1 1.1 RAl III OROMIII NE
WPS IOOO 310 700 0310 0700
10000 2597 3867 0260 0387
PCI IOOO 303 319 0303 0319
10000 28.10 1337 0283 0114
WTC 1 000 1 00 1 60 0 100 0 160
1887 3987 0189 0399
lOLUENE
Wl S 1 000 3.03 443 0 303 0 443
10000 5543 9367 0554 0937
|T|- I 000 137 2 50 0 1 37 0 250
36 67 35 77 0 367 0 35K
WTC IOOO 1.24 139 0124 0139
10000 6567 8957 0657 0896
HTIIYI ni N/tNk
WIS IOOO 527 1733 0527 1733
10000 3383 4733 0338 0473
PCI. IOOO 203 211 020.1 0233
10000 3453 20.93 0345 0209
WIC IOOO 293 394 0293 0394
10000 1610 9560 0161 0956
lillTANONE
WIS IOOO 3580 1700 3580 1700
10000 18800 25667 1880 2567
PCT IOOO S l<) 519 0519 0519
10000 11113 114 M 1 1.11 1 141
WIC IOOO 959 629 0959 0629
10000 16300 16567 1610 1657
4-MLillVL-2-PrNiANONr
WLS 1 000 41 33 1333 4 113 1 131
10000 19267 11111 1927 3133
I'CL 1 000 II 61 1061 1 163 1 061
10000 21100 24700 211(1 2470
WIC 1 ODD 7 67 4 88 0 767 0 488
29800 10600 2980 1060
liciition processes, one bused on porll.md cement and fly ash. the other on lime kiln dust and
fly ash llolb are compaied with a blank wherein the organic materials were mixed with non-
re.iilive solid material to simulate the solidification mixing process 1 Ins work and additional
field tests are being used hy L'I'A to develop regulations and guidance on the control of VOC
emissions dm ing S/S lie.ilmcnt processes used ;il KCKA I'SD facilities
Recently, research witli modified clay has shown promise Ibi .1 strong Bonding between
scmivol.ilile compounds .ind orgunophihc clay material \'J] The extraction data presented in
Table 5 and bonding evaluation (cdimuucs indicated sliong bunding.
-------
28 HAZARDOUS WASTES
• phenol
4O • 3-chlorophenol
* 2,3 dichorophenol
00
I IG. 2-l.fw*
3456/8
TIME/DAYS
amKiinitiK iluinixil with adxarheilpliemil. .t-cMoropliiiuil. ami >.J-
Recommendations for Determining Appropriateness of S/S for Organic*
The following recommendations arc based upon current knowledge about using S/S for
treating organics. Generally. S/S should not be used to treat a site contammg only organic
wa, Alternative technologies (for example, incineration, steam «**•»£««"£
tion and so on) should he used to remove and/or destroy the orpines II res.due rcma n , after
hiLimary treatment thatstill require additional treatment, S/S can be eHect,vcly used J ow-
cvcr a wcl7designcd and controlled treatability study should be conducted to assess S/S dice-
tivcness and to select and design a proper S/S process.
Lime Kiln Dust/Fly Ash
30
MINUTES
FKi. 3—t 'iiniiilalivi' un'lnni- rmis.wnx
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION 29
TAIII.I: S—/-.'.v/nirfiiiM ilaia iii'on iiw.wc\liil>ili:ciln-tlli iirKtuwiiliilir elayx.
Compound
Kuw WiiMc Mcun
CiMU-cnlruliiin.
'I'rciiliil WiiMv Mean
< oncenlradon. ,
Uis-(2-chl()roisopropyl) ether
Nuphlhiilcne
Phenunlhrcne
llen/o (it) unlhracenc
K52K
IKOfiO
21) 1X4
30 .160
1445*
Nl)
Nl)
" Nl) = not ili-lrclril.
* Value corrcclcd lor dilution.
On strictly technical considerations, there may be exceptions to this general approach. I or
example, if the organic is generally not mobile through air, soil, and water [for example, poly-
chlorinated biphcnyls (PCBs)] then some approaches to S/S may be acceptable cost-ellcctivc
treatment alternatives for a given site, depending on the remediation goals. Careful attention
must be paid to any existing stale and federal environmental regulations concerning the par-
ticular organic contaminant (for example, dioxins, and so on). Trcatabilily studies must be
performed that incorporate appropriate test methods to evaluate the organic waste's potential
for escape.
Based on existing data, volatile organic compounds cannot be iinmohili/cd by current S/S
technology. Whether or not a site containing VOCs can be treated by S/S will depend upon
specific conditions existing at the silc. Available data also indicate that scmivolatilc organic
compounds cannot be effectively treated by current S/S techniques. Whether or not a silc con-
taining scmivolatilc organics, along with other wastes, should be treated using S/S also depends
upon site-specific factors.
Figure 4 provides a general decision tree for determining if S/S should be considered for
treating a site containing organics. The approach is as follows:
I. Determine the amount of organics (relative to inorganic contaminants and oilier mate-
rials) and their chemical and physical characteristics. Determine whether the organics of
concern arc above acceptable levels (for example, above regulatory limits or above levels
causing unacceptable risks to exposed populations).
2. Based upon this information and other site characterization data, further determine what
inorganic compounds, materials, and so on, would remain if all the organics were
destroyed or removed.
3. Determine the concentrations and the chemical and physical characteristics of the resid-
uals remaining if organics were removed/destroyed.
4. If the site contains only organics, do not consider S/S unless (he organics arc not mobile
(in air, water, or soil) and do not require special handling/disposal/lrcatmcnt because of
special regulations (for example, TOSCA, and so on) or the orgunics arc below some pre-
determined acceptable level based upon a risk assessment.
a. If organics arc not mobile and do not require special treatment and management
because of environmental laws, unacceptable risks, or other special considerations,
consider S/S.
b. If organics arc volatile or semi volatile, arc hazardous and are above levels of concern,
then they must be destroyed and/or removed prior to S/S. However, depending upon
the amounts of volatile and/or scmivolatilc organics present, it may he feasible to col-
lect and treat the organics as part of the S/S treatment train.
-------
HAZARDOUS WASTES
Does The Site
Contain Organic*?
no_
Are Organics Above
"Levels of Concern" ?
no
-^Consider S/S|
fyes
Does The Site
Organlce ?
fyes
Are The Organlce
Mobile, Volatile,
Semi-Volatile,
Or Soluble ?
Are There CandU
S/S Processes F<
Treating Such
Organlcs
no
1 no
~~Jyee
lote
d no
If Organlcs Are
Removed Will
Treatment ?
Perform Tr
S/S Proi
yes
Consider S/S With
And/Or Controls
pass As Required
eatablllty
Specific
:es«(ee)
fall
PIG 4—(iitii'ral ihtiutm tree lor S/S apftlietllii «rgamn
c. If organics arc mobile and/or volatile but not hazardous (which is unlikely at Super-
fund sites) then S/S is a potentially feasible trcalmcnl
Determining Levels of Volatile/Scmlvolatile Organics Acceptable to S/S
There arc two approaches for determining Ihc maximum amounts of volalilc/scmivolatilc
organics acceptable Tor S/S as Ihc whole treatment or as part of a treatment train Unc is based
on results of risk assessment and nn assumption that S/S will not provide treatment. 1 he sec-
ond is based on results ol a Instability study and a comparison of organic levels in Ihc
untreated waste with those in Ihc solidified waste using a total waste analysis or similar Icsls.
The first approach, based on risk assessment, is as follows:
1 Determine the concentration of the organics present in the waste to be treated
2 Identify the compound that poses Ihc highest health orcnvironmcntal risk (quantity and
loxicily)
3. Determine a threshold concentration of the highest risk compound below which it will
not pose a health or environmental risk at the given site
4 Assume that
a The S/S process will not treat or contain Ihc selected compound and therefore all of
il will be released from Ihc solidified waste, and/or
h I hat all of the compound will be released iis mr emissions during lite S/S process
5 If ihcscconccnlralionsarc above those levels determined lo pose a health/environmental
risk at the given site, then pielrc.ilnient to remove or destroy Ihc organics will he required
and/or air emission controls and treatment will be needed on the S/S treatment train
WILES AND BARTH ON SOLIDIFICATION/STABILIZATION 31
Regulatory limits have not yet been established but could be based on some multiples of
Ihc drinking water standards, on limits being established by EPA for air emission con-
trols, or on some oilier standard.
This approach is very conservative and docs not account far the retardation of the release
of organics caused by Ihc physical characteristics of the solidified waste form. A second
approach, based on "harsh" extraction lest concepts, can be envisioned as follows:
I Use a total waste analysis, mcthylcnc chloride, or similar harsh extraction procedure to
determine the organic content of the untreated waste
2. Perform the S/S trcalability study, but ensure that proper controls arc used to collect all
organic air emissions Continue collection of air emissions during the curing phase.
\ Perform extraction/leaching tests on solidified waste forms after curing. Collect organic
air emissions
4 By comparing the organic levels in the untreated waste, the collected air emissions, the
solidified waste form, and in the extract from the extractions lest, one can determine if
acceptable treatment has been achieved and also whether VOC emission controls will be
necessary during full-scale application of the S/S process
5 Compare the levels of organics in the extract from the solidified waste form to some pre-
determined level (for example, 100 times drinking water standards)established as accept-
able for the site If Ihc levels arc acceptable, then S/S can be used. However, one must
also determine if controls are necessary lo collect and t real VOC emissions during the S/
S process.
This second approach is also conservative, but will give some credit lo any S/S processes
winch claim to be able to treat organics. Because of the grinding required for the harsh extrac-
tion tests, this approach provides little credit for physical retardation of releases of the organics
that may result from the improved physical properties of the solidified waste form.
Summary
I Ins paper discussed some approaches for determining whether or not organic contami-
nated soils should be treated by S/S technologies. The approaches arc conservative and give
little recognition to the physical characteristics of the solidified waste forms in the immobili-
/alion process. These approaches arc also based upon technical rather than regulatory consid-
erations after reviewing available information on the S/S of organic wastes. Several instances
h.ivc been reported where processors have claimed treatment of organics by S/S. In most, if
not all of these, the experimental approach was too limited. Measuring organic content before
treatment and after treatment without controls to collect and analyze air emissions is not
.irccpiablc. Many, if not all, of the volatile and semi volatile organics will "disappear" during
Ihc process because they volatilize. Much more sound scientific evidence is required before S/
Snfnrgamc contaminated waste can become routine practice. I he EPA is addressing this issue
•K well as the development of reasonably quick and inexpensive protocols for conducting S/S
Irc.n.ibility studies involving organics.
Also presented were sonic general rules lor conduct ing Irculnbihly studies for mcliil-beanng
Basics The need for this has become evident in reviewing many studies, including data from
ilic conduct of trcalability studies at Super! und sites The purpose of these rules is lo improve
llic quality and applicability of the data.
-------
HAZARDOUS WASTES
The authors wish to thank Dr. Joseph T Swartrhaugh. PEER Consultants, P.O., and Dr.
Jeffrey Means. Hattcllc Memorial Institute. Tor their assistance in preparing tins paper.
References
\l\ fold. I* I. .Caldwcll. R .amIChao.C C,"l'liysiealandrhcmicalC«inlainmcnlofOrganicConlam-
i nanism Solidified WjMc." Wave ManaKfiwat. Vnl 10. 1990. pp 95-102
|,?] Shivcly, W f and Crawford. M A in l.minminenial A \pit lit <>l .Miiliili:uiiim and Solidification of
Utt:
-------
bu HAZARDOUS WASTES
| »| IX1 Pen-in. I' K .mil Sawyer. S . I'IIH n-ilin\;\ nl Kr\ran h .Sim/wiium l llti:tii|>.r.iiii Demonstration lest
lnlcrnalion.il W.istc I ccluuilngirs In Situ Sl.ihih/.ilion .md .Solitlilii.ilmii llialc.ih. Honda." FPA/
540/5-89/004a. U S I nvironiiienl.il I'roleelion Agrncv. C incinn.ili. OH. June 1989
|rt| Weil/man. I . llamcl. I. I". anil ll.irtli. T . f'niuvtliiw <>t Kc\tiinli .\\miin\iiini IMIH!l)i\innal
Kfiiifilinl.il inm Im inmiiiim anil I miimnil nl Hii:iinliin\ llu\ii- Vol 14.1.PA/nOO/9-88/021
US Lnvironmcnlal Protection Agency.C'incinn.ili. Oil. July 1988. pp S42-5S7
|7| Weil/in.in. I. ll.nncl I. I".. IX- IVrein I' .iiul Hl.niey I) /Yin m/mi>wif Kr\nmli .?r»i/jmmiii.
I ami l)i\IH>\nl Kfintilial •lilinn IHIIIII-IIIIIIIH mill Irctilmciil iif Ha:uttli>in lln\ii: Vol IS. LPA/
600-9-90/006 US riivironiiiciil.il Protection Agcmy (ini.iiiii.ili Oil. Ich 1990. pp 448-438
|(V| Rowc Ci. "I valuation of Irc.ilincnl technologies for I islcd Petroleum Rclincry Wastes, I'mal
Kcpod." No 4465. American Petroleum Institute. Washington. PC. M.iy 1988
|V| Ciihhons J J .iml.Soundariirni.in R ..tnieru tin I alinriitnn: Vol 20. No 7. July 1988. pp 18-46
|/»j Ciihhons. J J and Soundararninn. R.../lineman I.aliiirtiitin: Vol 21. No 7. July I9K9, pp 7U-79
j / / j SniiiKl.ir.ir.ij.in. R . Rdrth. E . .mil Gibbons. J J . llii:iint,iu\ Muii'ntil\ < 'nniriil. Vol 3, No. 1.1989
pp 42-45
[12] M.mi.ikcr J W and Thompson J M . in Orxanu (ln-inii ul\in ilir Siul I nrmnimrni Marcel Dck-
ker. Inc. New York. 1972. pp 49-143
| /.»| Chiou. C I . Peters. L. J., and I rccd. VII. Hiifim: Vol. 206. Nov 1979. pp. 811-832 I
\I4\ Chiou.C I .Porter P E. .nut Schmcddiiig. I) W . l-.nvininnn-nlnl Stit-mvunil Inlmnhgv Vol
17 No 4. 1981 pp 227-230
|/^| llnyd S A .Slumhni.S.Lcc.J-r.amlMortland. M M .CIav\anhHKNCK:Spcncc.R.I>.c;illiam.T M.Morgan.l L.andOshornc S C "Stabilization/
SoNdilicntion of Wastes Con.aininR Volatile Organie Compounds In Commerelal Cemenlitlous
WMetmmi«*iMiMiHmamlMul,lm,niin,illla:ai^^
MV^.WMSTIIU.7 M CiilltamandC C W.les. Eds . American Soc.ey for Tcsti
ing nnd Materials. PliiUlclphiu. 1992. pp 61-72.
AHSIHACI: Stiihili7ation/solidiHcalion (S/S) is one of the most widely used tcchmaucs for
waste treatment and remedial actions, but docs not have rcguLitory approval for treating organ-
ics Application with voladlc organic compounds (VOTs) is particularly controversial since U
was hclicvcd that the necessary mechanical mixing and exothermic cemcntitious reactions
would vapon/e the VOCs I he objective of this study was to establish whether S/S is a v aWe
.illcrnalivc lor a sludge heavily contaminated (about 1%) with relatively immobile metals hut
hghlly contammjlcd ( <0 04%) w,ll, VOCs that were contammatmg the groundwatcr The ma»
balance md.ca.ed that > 50%oflhe VOCs were retain^ m the Iaboratory8prepa™hon orccmer^
titiou, samples cured for 28 days The performance tests indicated the commercial Kuc?s
r-r^. ,c ?^1 m M '^ 'ndlCCS ^m I '° >9 for "1C eighl VOCs sludlcd •""« d'smbution coef-
riricnlsof > 10 could be attained for all eight and > 100 for some compounds
,M"' solldlfie!I"on- VOCs. organic, immobilization, cement, grout.
, nchloroctlicnc acetone, methyl ethyl kctonc. 1 .2-dichlorocthenc. chloroform ben^
/cnc. chlorobcnzcnc. pcrchloroclhcnc
Suhili/alion/solidtncalion (S/S) is one ofthc most widely used techniques for the treatment
.md ultimate disposal of both radioaclt vc and chemically ha/ardous wastes because oflow pro-
icssing costs, compatibility with a variety of disposal scenarios, and ability to meet stringent
pnxcnng and performance rcqu.rcmcnts S/S is accepted as the best demonstrated available
technology (RDA I ) for many applications involving metals contamination, but not involving
«.rg.inic contaminatton [ 1.2] The .sludge used in this study was contaminated (sec Table I )
mainly with metals, to a lesser extent with scmivolatilc organtcs. and to an even lesser extent
volume organic compounds (VOCs) Only the VOCs were observed to be migrating in the
proundwalcrat the site from which the sludge was excavated: hence. VOCs were the focal point
"i me study. In situ S/S is an attractive remedial action alternative in this case because incin-
eration ml I result in little or no volume reduction for this sludge, incineration may result in
more mobile metallic species, excavation may icsull in evaporation of most of the VOCs and
m situ i/j> may achieve the environmental protection desired with the least disturbance to the
„ , *nvi1ronmcnl and lhc maximum prelection to operating personnel and residents I o
pursue this alternative, the sponsor needed to demonstrate the im mobilization potential of the
Chemical lechnology Division. Oak Ridge National Laboratory. Oak Ridge. PN 37831-7271
61
-------
62
HAZARDOUS WASTES
SPENCE ET AL ON VOLATILE ORGANIC COMPOUNDS
63
TABLE \-Mitiiiin-il i umrnlraluHH in the umpikeil \liulm'
(Nun- Stunt- mlanlft new last in lhei>nm'\\ til r \iavaliiiK anil
litmtogenizinx llu- large \ainplr The luhlr ra/iirt rcflnl what wa\
;iroiW HI the lubnraliirv prior 10 \pikmg)*
Compound
Concentration.
mg/kg
Sue
Maximum
VOLATILE ORGANIC COMPOUNDS (VOC)
Accione I 7 9
1,2-DCE 002 100
Chloroform 17 17
MCK 56 4
TCf 15 130
Dcnzcnc 0 55 3
PHRC 7.5 59
Chlornhcnzcnc 39 20
BASE/NEUTRAL/ACID ORGANIC COMPOUNDS (DNA)
Phenol 3 7
I.VDichlorobcnzcne 130
1,4-Dichlorohcnzcnc 120
1,2-Oichlorobcnzcne <6 I
2.4-Dimclhylphcnol 110
1,2,4-Tnchloronen/ene 100
2-Mclhylniiphlhalene 190
Di-n-bulylphlhalatc 160
Bis(2-elhylhcxyl)phthalalc 190
MfcTALS
Dan urn
Cadmium
Chromium
Lead
Silver
Nickel
Aluminum
Calcium
Iron
Phosphorus
Silicon
140
560
A 200
760
47
210
28000
3000
82 000
3400
1 500
"A 464 wl% loss was observed upon drying the unspikcd
sludge
commercially available waste forms Fortunately, recent investigations have indicated true
bonding between organic wastes and sonic binders as required in the Environmental Protec-
tion Agency's(EPA) interpretation of the I luzardous and Solid Waste Amendments (I ISWA)
to the Resource Conservation and Recovery Act (RCRA) [ 1.3.4].
This paper presents the results ofu study done at Oak Ridge National I .ahonitory (URNL)
on the VOC immobilization potential of commercial ccmcntilious waste forms through the
Hazardous Waste Remedial Actions Program (HAZWKAP) in support of the sponsor.
Although the toxicity characteristic leaching procedure (1 CLP) is the regulatory lest for these
orgamcs. it was not considered a satisfactory lest of the immobili/iilion potential for these
waste forms because this test was not designed for waste that had been slabili/ed/solidilied.
and, at the time ol this study, regulatory guidance was not clear on sample handling and prep-
aration when VOCs were involved (that is, VOC losses prior to the initiation of the extraction
procedure may have given erroneously good results). A static leach lest was utilized that
enabled the calculation of both the mass transfer resistance of the waste forms and the affinity
of the waste forms for the VOCs Crucial to the accuracy of this test was the development of
techniques to estimate the VOCs actually retained in the sample at the start of leaching. This
was accomplished indirectly by measuring the VOCs that evaporated during sample prepa-
ration Although the TCLP was done and is reported in this paper, the main measure of immo-
bilization potential is considered to be the teachability index and distribution coefficient
reported for each VOC and each of the following four vendors: Vendor A, RMC Environ-
mental and Analytical Laboratories Co.; Vendor B, Wastcch, Inc.; Vendor C, International
Waste 'I cchnologics; and Vendor D, Silicate Technology Corp
Procedures
It is standard practice in studies of this type to compare the TCLP performance of the waste
before and after treatment. This approach was not used in this study because much of the
VOCs were lost in the process of taking the large sample needed, and the objective of the study
was measurement of the VOC immobilization potential In the former approach, it isquitcall
right, desirable even, to have Icachatc, or extract, concentrations below the detection limits as
a gross measure of effective treatment for a specific site; but one learns little about the true
immobilization potential of a particular waste form that can be extrapolated to other condi-
tions or sites. Since the VOC concentration of the waste sample in the laboratory was not rep-
resentative of the site VOC concentration, spiking of the laboratory sample was required, and,
to ensure obtaining measurable concentrations in the Icachatcs, spiking was designed to give
concentrations not only higher than the site average concentrations, but also higher than site
maximum concentrations. Eight VOCs—acetone. 1,2-dichlorocthcnc (1.2-DCE), chloro-
fonn, methyl ethyl kctone (MEK), benzene, trichlorocthcne (TCE), chlorobcnzcnc, and
pcrchlorocthcnc (PERQ—were selected among the possible candidates to be spiked into the
sludge and studied
The procedure consisted of spiking the sludge using a I lobart mixer outside the glove box,
taking three sludge samples foi analysis by standard U S. Environmental Protection Agency
(LTA) Contract L.ihoiatuiy Program (Cl P) protocols (P.PA CLP Statement of Work for
Orgamcs Analysis Multimedia, Muliicompoiicnt), immediately placing the spiked sludge
inside the glove box. mixing the spiked sludge with the vendor materials according to the ven-
dor instructions (grout), filling the stainless steel molds with the grout and covering with stain-
less steel endplales. removing the molds from the glove box and quickly scaling inside the
stainless steel curing pipe, measuring the VOC concentration of the glove box air using a gas
chromalograph with a It.imc loni/ation tleiixtor (tiC-HD), curing the samples for 28 days,
mcasiinnglliL- VOC concentration of the curing pipe air with the CC-HD, removing the cured
samples from the pipe, and quickly removing the endplales. weighing, and sealing inside a
/ero-lie.ids|>.ive extraction vessel (ZMI.'V). (Ciroul means the cemcnlitioiis waste form in this
document.) The amount of VOCs retained in the sample prior to leaching was estimated by
subtracting the amount of VOCs that evaporated into the glove box and curing pipe from
the amount me.isiucd in the sludge by the I-PA protocol. (Rubbers and plastics, including
Tellon*. should lie avoided )
-------
64
HAZARDOUS WASTES
SPENCE ET AL ON VOLATILE ORGANIC COMPOUNDS
65
Sieiiic
The static leaching procedure consisted of suspending each cured sample in 603 g of deion-
izcd water inside u ZIII£V. liuch sample consisted of a Hal disk (6 2-cni diameter by 1.6-cm
thick) inside a stainless steel ring with no covering on cither Rat face (the leaching sui faces)
Two types of static leaching were done. First, three samples were leached separately Tor the
entire time period with periodic m-housc Icachale analysis Second, five separate samples were
leached, each for a different lime period. At the end of the time period, the Icachate was
removed and submitted to an El'A approved laboratory for analysis.
Lmchaie Analy\n
The in-house analysis was done using a Tckmar liquid sample concentrator (LSC) in con-
junction with a Pcrkm-ElmcrGC ion trap detector (ITD)capahlc of measuring concentrations
as low as I mg/Mg(PPB) within 1 5% ofthc true value. The submitted samples were measured
using an LSC with GC mass spectrometer following CPA contract laboratory procedures
(CLP), capable of measuring concentrations as low as I mg/Mg within 10% of the true value
Results
Grout Compoulion and Properties
Only about 10 to 50% of the VOCs added during spiking was mixed into and retained in the
sludge; presumably, the remainder evaporated during the process of mixing the spike into the
sludge This was expected based on the development tests and was the reason analysis of
the sludge VOC concentration was required after spiking The sludge analysis technique con-
sisted of extraction followed by analysis ofthc extract. Hie cxtractant (typically hcxanc) did
not always extract all of the VOCs in the sludge; thus, the VOC content of the spiked sludge
tended to be underestimated for this study. Tables 2 and 3 list the average VOC concentra-
tions, and their standard deviations, measured in the spiked sludge used to make the static
leach samples and the TCLP samples, respectively The acetone concentration was left as an
unknown for the Vendor A static leach samples because its concentration was measured to be
negligible, well below the amount that leached during the static leaching. I'he concentrations
listed in Table 3 were more representative of maximum site concentrations, as intended The
concentrations listed in Table 1 were designed to give measurable Icachate concentrations dur-
ing static leaching
TABLE 2— The VOC iluJge ciinceniralwiu mvawretl ajicr \pikmn fur the \lnlu Inuli wim/i/rv.
(average o) three with the \iantlunl dtvmliim in pamuhe\e\)
'IAHI I. 3—I In- !'()( \liulKfiiiiin-niKiiiiHH meauimt «//«•/• \inkniKInr tin- ICI /' WHM/J/CI. ing/kg
(awraitf i>l l/iri'C with I lie Mtimliinl ilrvinlmn in i>urcnllie\e\)
Compound
Acetone
1.2-1x1:
Chloroform
MF.K
TCK
licn/ene
PLKC
Chlorobcnzcnc
Vendor A
927(139)
1033(125)
253 ( 69)
623 ( 56)
787 ( 98)
963(119)
550 ( SI)
Vendor II
123 ( 25)
170 ( 16)
190 ( 16)
I37( 9)
193 ( 12)
I73( 17)
537(115)
S47( 52)
Vendor C
223 ( 9)
485 (304)
313(180)
4.30 ( 59)
I84( 94)
327(188)
767(201)
220 ( 64)
Vendor D
210(119)
953(143)
1150(147)
257 ( 74)
573 ( 82)
820 ( 91)
8X7 (246)
477 ( 37)
Compound
Acetone
1.2-IXT.
riilornlorm
MIK
III-
Dcn/cnc
PIRC
Chlorohen/ene
Vendor A
148 ( 74)
457(127)
31 ( 1)
763 ( 29)
101 ( 63)
6( 2)
233 ( 66)
48 ( 4)
Vendor II
IKO( 2K)
313 ( IV)
29 ( 2)
198(128)
I8(l( 24)
6(03)
197 ( 17)
3K( 4)
Vendor C
I83( 24)
303 ( 47)
27 ( 1)
210(262)
l«3( 21)
4(04)
106 ( 21)
36 ( 4)
Vendor 1)
I63( 26)
363 ( 9)
27 ( 3)
637 (202)
103 ( 12)
8(05)
I70( 36)
40 ( 3)
than while curing for 28 days inside the curing pipe. Although the vapor VOC concentration
inside the curing pipe was significant, little mass was lost to the small headspace of these pipes
The concentration retained in the cured grout was estimated from the concentration measured
in the spiked sludge correcting for the evaporation losses measured during mixing and curing
and for the dilution of the spiked sludge in the grout product I able 4 lists the grout compo-
sition for each vendor's product along with some other physical properties The estimated
VOC concentration retained in the samples after curing and percent retention is listed in
1 ahlcs 5 and 6 for the static leach samples and the 'I CLP samples, respectively
Figure I illustrates the scatter in the leaching data Despite the scatter, the general trend in
Fig I was obvious and was typical of this data This trend was analy/cd using the average
Icachate concentration for all the samples at a given time. 1 he Icachate for Vendor B's product
foamed during analysis, resulting in invalidation of much of the early data for in-house anal-
ysis until this problem was solved As a consequence, only the single set of data for the sub-
mitted samples exist for this early lime period for Vendor 13
TARI L 4—Ccnieniiliniit ttmrc Inr in IUIHIHIMIHIII anil iilmual i>n>iicrlie\
Vendor A Vendor 1)
Vendor C
Vendor D
COMPOSITION, WT%
Sludge*
Water added
Solid additives
1 i(|uid additives
Density. kg/I.
Volume increase. %
2X-d.iy uncontined compressive
strength, kl'a
39 K
159
44 1
00
I'KOPI R TILS
1 61
121
6447 12
9 1
IKS
63 3
9 1
162
784
797
62 S
69
139
167
1 22
93
83
735
81
184
00
1 39
40
414
° l-cd
-------
66 HAZARDOUS WASTES
TABI.E $—Ksiimaieil I'()(.' fiiiueniralion (»ix/kx) retained in ilif eured ivmenliiiinix samples fur lite
static leach ie\l. (Tin- mine in parentheses ;'.v the ir;«« <>///«• I '(><•' linn mix estimated l» In- nlaimil
through ini.\iiiK mill
SPENCE ET AL. ON VOLATILE ORGANIC COMPOUNDS
ORNL DWG 90A-1367
67
Compound
Acetone
1,2-DCl-
Chloroform
MI3K
TCE
Benzene
PERC
Chlorobcnzcnc
Vendor A
a
277 (67%)
352 (76%)
81 (73%)
226(81%)
270(77%)
412(95%)
233 (95%)
Vendor I)
9 (75%)
8 (44%)
13(66%)
1 1 (76%)
13(64%)
12(67%)
39 (72%)
50 (90%)
Vendor C
148(98%)
245 (75%)
144 (68%)
286 (98%)
101 (Kl%)
174(79%)
510(98%)
122(82%)
Vendor I)
108 (63%)
482 (62%)
710(76%)
146(70%)
392(84%)
480 (72%)
702 (97%)
370 (95%)
° Left as an unknown.
TCLP
Table 7 lists the results of the TCLP test. (Table 7 lists only the VOCs that were spiked, but
the other compounds were below their TCLP limits.) The extract for Vendor A did not exceed
any TCLP limits. The TCE limit was exceeded for Vendors B, C, and D, and the PP.RC limit
was exceeded for Vendor C. Referring to Tables I and 3, the spiked concentration exceeded
the site maximum concentration in all cases, except for TCE for Vendors A and D. The ratio
of the site maximum to the spiked sludge concentration of TCE for Vendor A was 1.29. Mul-
tiplying the TCE extract concentration for Vendor A by this factor yields 0.032 mg/L, still
below the limit of 0.07 mg/L. The equivalent factor for Vendors B and C was 0.72, giving a
reduced TCE concentration of 0.051 mg/L (below the TCLP limit) for Vendor B and 0.22
mg/L (still above the TCLP limit) for Vendor C. A similar pro rata reduction for PERC and
Vendor C gave 0.06 mg/L compared to the limit of O.I mg/L. Thus, correcting the TCLP
extract concentrations by the ratio of the site maximum concentration to the measured sludge
concentration resulted in concentrations below the TCLP limits for Vendors A and B. but
TCE was still above the TCLP limit for Vendors C and D. The ratio of the TCE limit to the
measured extract concentration was 0.23 and 0.37, respectively, for Vendors C and D. Assum-
ing the extract concentration is proportional to the measured sludge concentration, the sludge
concentration would have to be lower than 43 mg/kg (33% of the site maximum) for Vendor
C and 38 mg/kg (29% of the site maximum) for Vendor D. The average of the TCE concen-
trations measured for the samples taken from the buried lagoon during site charactcri/ation
i
o
o
<
TIME (d)
l-ICi. I—Viatic Icarhinit tifTl'Kfnnn I'eiuliir.-l'xpriiduri.
was 5.8 mg/kg (4% of the site maximum). Thus, all of the vendors may pass the TCLP test
depending on what basis ofcomparison is allowed by the regulatory agencies.
Regardless of these number games about the TCLP limits for this particular site, it is impor-
tant to note that llus level of sludge concentration (10 lolOOO mg/kg) did lead to measurable
extract concentrations (0.004 to 0.3 mg/L), in some cases in the vicinity of the TCLP limits
for these compounds. Undoubtedly, the performance of these products could be improved,
for example, by targeting the additive for a specific compound or compounds, but it does seem
to imply that application to some organic species present at as high as, or higher than, 0.1 wt%
would be questionable, at least for this sludge. On the other hand, the performance was impres-
sive for some compounds (for example, MILK, was spiked in the sludge as high as 763 mg/kg,
but never exceeded 0.5 mg/L in the extract, despite being a hydrophilic compound) compared
to others (for example, the extract TCE concentration was uncomfortably close to or greater
than the TCLP limit, despite being a hydrophobic compound). An additive such as orguno-
TABI.E b—Ksiimauil \'OC ctmceiuratwn (niK/kg) niuined In the aired cemenlitiiHis sample\fur the
'II 'I.I' U-xt. (Tin- value in parentheses is the wl% iiflhe t-'OC' ilial was estimated retained ilinnixh
nti.\itiK ami turing.)
Compound
Acetone
1,2-OCI-
Chloroform
MI:K
ICE
Benzene
PERC
Chlorobcnzcn''
Vendor A
68 (98%)
146(68%)
13(85%)
360(100%)
28 (58%)
2 (67%)
107 (97%)
21 (94%)
Vendor B
18 (92%)
25 (73%)
2 (74%)
22 (99%)
10 (52%)
0.4 (36%)
19 (88%)
4 (93%)
Vendor C
124(99%)
160(78%)
16 (89%)
142(100%)
98 (79%)
3 (76%)
67 (93%)
23 (9%)
Vendor 1)
131 (98%)
212(71%)
19(87%)
520(100%)
56 (66%)
5 (83%)
135(97%)
31 (95%)
TAHI .1: 7—t'tincenlraliiinx im-dxured in the extracts for the '/'< 'I.I' u:il (mx/IJ.
Component
Acetone
1.2-DCI:
Chloroform
MIK
TCI:
Ben/ene
PERC
Chlorohen/ene
ViMulnr A
0.15
0.13
0.005
0.014
0.025
0.002
0.026
0.074
Vendor B
0.18
0.08
0.004
0.008
0.071
0.009
0.02X
0.027
Vendor C
0.25
0.10
0.009
0.048
0.30
0.0115
0.11
0.11
Vendor 1)
0.18
0.19
0.004
0.032
0.19
0.007
0.083
0.14
ICI.P 1.
0.59
d
0.07
7.2
0.07
0.07
0 1
1.4
imil
" No limit has hcen set lor this compound.
-------
68
HAZARDOUS WASTES
plnlic clay could be targeted Tor TCE to improve performance; in Tact, the clay could he mod-
ified into two or more different forms to target different types of organic molecules. The per-
formance or such an approach needs to be studied and the economics compared to other
alternatives.
Analysis of Results
This section concerns estimation of the effective diffusion coefficients and distribution coef-
ficient from the static leach results The static leach test involved leaching Irom the surfaces of
a slab I he initial concentration was assumed to be uniformly distributed in the slab and zero
Tor the Icachatc The leaching is assumed to be simple diffusion from the slab as defined by
Tick's second law. with the diffusion coefficient for the slab much less than the leachalc film
diffusion coefficient. The Icaclutcs were not replaced (static leaching), and. hence, leaching is
assumed to approach an equilibrium distribution of each specie between the slab and the
Icachate. Crank gives the following solution for this diffusion problem (.5 ]
('I. - ''/)
l I + « +
„,,„„
(I)
where the / I/IP mim irun\lvr />«r«»ii'icr\ (llic mm- May ftir Vendor U i\ given
Vendor
A
ll(|7 6 days)
C
1)
A
R( 16 7 days)
C
D
A
11(18 8 days)
C
D
A
D ( 1 2 2 days)
C
1)
A
II (17 4 days)
C'
U
A
II (12 9 days)
C
D
A
II (12 8 days)
r
1)
A
R (0 5 days)
C
1)
». cm'/s
30 X l of
I X 10 *, which is not realistic, especially combined with the high A I his value is left unknown until
a more thorough analysis will hopefully give a defensible vulue
' NI.WI1OX estimated a siispuiously high I) ol I X 10 " using I ho graphical estimate for .I/, but
Nl WIIOX's estimate lor liolli (.1 I) of I X 10 " and u neuheihlc -I,) was considered even worse.
-------
70
HAZARDOUS WASTES
SPENCE ET AL ON VOLATILE ORGANIC COMPOUNDS 71
dul.i scatter, a value ofzero to u lew units for K means little or no significant mleniclion of the
specie with the solid body. A value or about 10 probably means there was significant interac-
tion with the solid body. 'I he equivalent of the analytical solution is included in NFWBOX,
a computer program tliut estimates the least squares lit for up to five parameters lor leaching
problems and that includes the equivalent lor several analytical solutions to Pick's second law
jrt] In general, the average mass measured in the Icachate Tor each vendor and specie at each
time and the mass of each specie estimated retained in the slab (Table 5) were used as input to
NLWBOX to estimate two parameters. I) and -I, 'I he distribution eocllicient. A.', was calcu-
lated from this/I/and the mass estimated retained in the sample after curing. /(„ One exception
to this approach was for the acetone in Vendor A's product In this case /I,, was Icfl unknown
and estimated by NEWBOX. and /I,was assumed to be ?ero.
1 he trend for Vendor B's product was to leach little or no muss for a few days, followed by
leach rules comparable to the other vendors Tins was not a simple diflusion process and could
not be handled by NEWBOX. The NEWBOX model was modified for Vendor B by assuming
no leaching for a set time, followed by a simple diflusion, that is. a time oll'scl in 1-q I. The
lime delay was estimated as the lime intercept ofthc least squares fit for the linearized form of
the data. The linearized form of the data comes from the much simpler solution ofthc diffu-
sion model for dynamic leaching of semi-infinite medium, from this solution, a plot of the
total amount leached versus the square root oftimc is linear. Finite geometries and static leach-
ing will deviate significantly from linearity, but the early leaching behavior will mimic this
model Thus, the quantity leached was plotted against the square root of time, the linear por-
tion subjectively selected, and least squares analysis used on tins portion to find the time inter-
cept for each specie. These time delays were subtracted from the times for Vendor B's data and
these corrected times used as input to NEWBOX to get estimates for I) and A.'. Table 8 lists
NEWBOX's estimates for D and K. as well as the teachability index defined as
L = - log(O) (3)
where
/. = teachability index with /> in cm'/s.
Discussion
The teachability index for these commercial products varied from 6 0 to 9 4. and the distri-
bution eocllicient vancd from 0 to 628 l-rom past experience with mobile species such as
nitrate and some radionudidcs, a Icachabthty index of 6 to 7 is not very good for these waste
forms and indicates that unless a strong interaction exists the specie will readily leach out of
the porous solid body (usually there is a correlation between the teachability index and the
distribution coefficient). Ccmcntilious waste forms usually can achieve a teachability index of
7 to 8 and the belter ones can gel as high as 9 or belter for the more difficult species. Some
species arc more readily immobilized in ccmcntitious waste forms, or arc just not very mobile,
and have a teachability index of 10 or higher.
Taking each specie individually, one would expect acetone to be quite difficult to control
because of its affinity for water, and this indeed proved to be the case. The teachability index
and distribution coefficient were low for three (although Vendor B had a fair Icachability index
of 7 5) out of the four vendors, but Vendor C's product never leached much of the acetone
estimated retained. The Icachate concentration stabilised at a low level quickly, indicating
both a high interaction and low leachability index. (In fact, it stabilized so quickly that IMF.W-
BOX estima'- ' -l«c teachability index as 5. This seemed unreasonably low because water has
a teachability index of about 5 and the distribution coefficient was estimated so higli)
Although NT!WROX estimates the two as independent parameters. I) and K are expected to
be related as follows
/.»=
(4)
where
l)f = true difTusivity in the pore solution, cm'/s, and
K = geometric factor, dimensionless.
Tlnscxpcct.ilion raised questions about why the acetone concentration stabilised at this low
value so quickly for Vendor C's product. Several explanations arc possible, including the
amount retained was in error und very little wus actually in the sample, the original acetone
was divided into two or more species, one of which was "unleachablc" (strongly sorbcd or
disappeared by reaction); and the concentration was actually slowly increasing but the ana-
lytical technique wus unable to detect this (the analytical variability has already been men-
tioned and acetone was one ofthc harder compounds to follow at these concentrations) There
is not enough evidence at this time to rule out or verify any of these explanations or other
possible explanations All that is known is that little ofthc acetone estimated retained in the
Vendor C sample leached into the water according to analysis of the leachute.
Tor chloroform, although three of the teachability indices were still less than 8. Vendor D
hud u high K of 75 and Vendor A was even better at 628. NEWBOX estimated the teachability
index at 11 for Vendor A, quite high for ccmcnlitious waste forms. 1 his case was similar to
the one for acetone with Vendor C in that not much leached Considering the variability and
low concentrations, the index estimates for these two cases may be in considerable error.
The best performance for 1,2-dichloroclhcnc was observed for Vendor A's product with a
teachability index of 7.2 und a K of 9.0 Methyl ethyl kctone, like acetone, has an affinity for
water, but had u belter performance than 1,2-dichlorocthcne with an index of 8 and a K of
16 8 for VcndorC. The best performance for tnchlorocthcnc was for Vendor A with an index
of 7.7 and \ of 23.3. Vendor B had an index of 7.5 for benzene and a A'ofO. but Vendor A
had an index of 7 2 and a Kof 11.5 The performance for pcrchlorocthenc und chlorobcn/cnc
wus better than for the other compounds, ;ip to 9.4 und <>.0. respectively, for the index and 431
and 59 for K
Conclusions
The TCLP was judged not satisfactory for testing the immobilization potential of ccmen-
tilious waste forms Consequently, the immobilisation potential was tested by static leaching
and subsequent estimation ofthc teachability index und distribution coclficicnl.
Although open mechanical mixers were required to mix the sludge und tiealmcnt solids, the
resulting reactions were exothermic, and the products were cured for 28 days; most of the
VOCs wore retained in the cured samples. The large uncertainty in VOC analysis means
the ei ror burs were large for the parameter estimation. The estimated error for leachate analysis
was from 5 to 15%. depending on the compound, hut the error in the parameter estimation
wus ulso affected by the errors in spiking and subsequent sludge analysis. Part ofthc problem
wus (he inability of the standard extraction technique to extract some compounds completely
from the sludge for analysis As u consequence, the VOCs tended to be underestimated in (he
sludge and the subsequent testing and parameter estimation tended to be conservative because
more VOCs were actually present in the samples than estimutcd It is not unusual for the teach-
ability index to vaiy by 0 2 without such large analytical errors The Icachabil' \-x range
-------
72 HAZARDOUS WASTES
Tor (his sluily may be 1 0 or more, with I he rcpoi led estimates .it the low end. and the estimates
for K should probably be considered order of magnitude estimates.
Strong interactions were estimated Tor acetone, chloroform, and pcrchloroclhcnc .mil sig-
nificant interactions for 1 ,2-dtchlorocthcnc. methyl ethyl kelone, irichloroclhcnc. hcn/.enc,
and chloroben/enc. but no single product appears to interact significantly lor .ill eight com-
pounds This implies th jt it is possible Tor the vendors to formulaic for a combination of VOCs
using a mixture of additives unless the different .iddilivus used by the vendors interfere with
each other. Despite the evidence or interaction, the estimated teachability indices were dis-
appointingly low except for pcrchlorocthenc and chloroben/cnc. It is possible that some, hut
not all, of a given VOC was strongly sorbcd and thai the 'Tree" VOCs quickly leached out,
giving a relatively low index but a high 01 moderate A' Nevertheless, these low or moderate
indices agree with the observation that the sludge concentration must be limited at about the
spiked levels or less (< 1000 mg/kg) to pass the TCLP test The TCLP results proved that a
commercially available ccmcntilious waste form can pass the TCLP criteria Tor sludge con-
centrations indicative of this site. Based on these results, stabilization/solidification is a viable
alternative Tor a sludge or soil that is heavily contaminated with metals and lightly contami-
nated with VOCs. In such a case, incineration is an expensive alternative (hut will likely con-
vert the metals into a more mobile form requiring further treatment of ihc incinerated sludge/
soil. Currently available additives proved capable or handling VOCs with limited success,
albeit good enough to pass TCLP for this site. Perhaps better additives will he developed that
will handle even higher organic concentrations if S/S is accepted lor such applications.
This research was sponsored by the Office of Defense Waste and I ransportalion Manage-
ment. Defense Programs, U S Department of Lncrgy, under Contract DE-AC05-840R2 1400
References
| /] "SlabiliMlion/Sohdificalion ol ChKCLA and KCKA Wattes. Physical I csls, Chemical Testing Pro-
cedures. technology Screening, and Held Activities," I- PA/625/6-89/002. Center lor l-.nvironmenial
Research Information and Risk Reduction engineering Laboratory, U S l.nvironincnlal I'rolci lion
Agency. Cincinnati, OH, May 1989
[2] Wcilzman, L , Hamel, L. f .and Barth, C , "Evaluation ofSolidilicalion/Slahili/.ilionasii Rest Dem-
onstrated Available Technology," I4lh Annual lla/ardous Waste Lnginccring I ahoratory Confer-
ence. Cincinnati. OH. May I9KX
|.f] Gibbons, J J and Snundararajan. R , Anicruan Laboratory, Vol 20, No 2. I9HX. pp 1K-46
\4\ "Prohibition on Ihc Disposal of Bulk I iquicl lla/ardous WaMc in Landfills — Statutory Interpretive
Guidance," OSWER Policy Directive No 9487 (XI2A, r.PA/510-SW-OI6, U S l-jwiromncnlal Pro-
tection Agency. Cincinnati, OH, June 1986
|5| Crank, J, I lu- Muilu'iiuinmiJ DiJJii\u>n. Oxford University Press. I nndon, 1956. pp 52-56
[nj Nestor, C W..Jr..Godbcc. II W., and Joy, D S, NMttOX. A Cunipnuv Cuilr l,ir 1'uninMcr i:\n-
iniiliiin in DiJJiniiin l'nihlt-m\ ORNI /I M- 10910. Oak Ridge National Uboraloiy, Oak Ridge. I N
(in preparation)
Nancy J Sell.1 Mark A. Revall.2 William Kent ley.1 and
Thomas 11. Mclnlwh1
Solidification and Stabilization of Phenol and
Chlorinated Phenol Contaminated Soils
:: Sell. N J . Kevall. M A . llcntlcy, W . and Mclnlosli. Ill, "Sulidiliiuliun and
Slabili/uliiin of Pliunol and Chlorinated Phunnl Contaminated Soils," Stabilization ami SH/K/I-
IHUIHIII nl Hii:iirilnii\. Hiiilinailivt: ami Mi\nl \\u\le\. 2ml 1-nliinn: /IS/A/ S'//' II2J. I M
Cjilli.iin anil ( C Wiles. Lds . American Society lor Testing and Materials, Philadelphia. 1992.
pp 71-K5
AIISIK AC'I • Phenol and chlorinated phenols arc liixn compounds found in many treated wood
products such as fence posts and railroad lies, hence soils near such treatment facilities or near
old railroad yards can be quite contaminated "I Ins study investigated Ihc results of using sodium
hentonile clay modified will) dimethyl di(hydrogcnatcd tallow)ammonium chloride mixed with
I ype I poilland cement to immobih/e u series ol phenols (phenol. 2.4.6-lrichloroplienol. and
pcnlaihlorophciinl) from a sandy Shawano II hori/on (lypic Udipsamnicnl) soil
I he lest soil was mixed with the various phenols at a contaminant concentration of 1000 mg/
kg An admixture ol contaminated soil and modified ilay (0 to 10% w/w organoclay) was pre-
pared I inal solidification was done by adding cement at concentrations of 16 to 39% w/w I ox-
icily iharacterislic leaching procedure (TCI P) and uneonlined comprcssivc strength determi-
nations were made I lie lesulls of these tests indicate potential lor using these organoclay
admixtures for treating soils contaminated with various chlorinated phenols
KhV WORDS org.moclay, phenols.chlorinated phenols, stabilisation, solidification, site reme-
diation, toxic wastes
Unintentional contamination ol soil with toxic chemicals is a continuing problem. The U.S.
General Accounting Olhce estimates that as many as half ol the 5000 ha/ardous waste sites
regulated by the U S l:nvironmcnl.il Protection Agency (EPA) may be leaking ha/ardous
materials into local earth materials und then to groundwatcr | /1
Many of these toxic chemicals arc organic in nature, sonic with potentially severe adverse
effects I hey cun be carcinogenic or mutagcnic or both in man and animals, toxic to aquatic
life, and generally degrade the quality ol water for human consumption I Icnce, there is a need
to develop new and alternate control let hnologics capable of preventing these toxic chemicals
from dispersing tlnough soil into aquifers
A variety of different slahiliAition und solidification technologies have been developed in
recent yeais|2) Suggestion h.ishccn nude that site remediation can be accomplished by using
an organically modified clay (oigunoi lay) I -'I This study focuses on the possibility of using an
organoclay to sl.ilnli/u phenol .mil chlorinated phenols in contaminated soils
I o he feasible forsliihilmnganil solidifying contaminants, u treatment procedure must pro-
duce a waste thai (I) withstands a pressure ol 0.144 MPu (SO psi) when applied in an uncon-
1 Professor, research assistant, and piolessor. respectively. University ol Wisconsin—Green flay. 2420
Nicolct Drive. Circcn Hay, Wl 54111-7001
' Viic-prcsidcm. Research and Development. J V Manufacturing Co , PO Box 170. DcPerc. Wl,
S4| 15
73
-------
Appendix XI
-------
Appendix XI
Army Waste Classification Guidance for Building
Demolition Debris Containing Lead Based Paint
-------
01 OCT 1993
WASTE CLASSIFICATION GUIDANCE
FOR BUILDING DEMOLITION DEBRIS
CONTAINING LEAD BASED PAINT
PURPOSE! This guidance provides two different acceptable
methods for the characterization of the solid waste generated
during demolition operations through sampling and Toxicity
Characteristic Leaching Procedure (TCLP) analyses. Using either
method, demolition debris can be characterized as hazardous or
non-hazardous waste as defined by RCRA. These methods apply to
demolition debris only and do not apply to heavy metal bearing
wastestreams that are generated from other specific operations
(e.g., paint scrapings, sandblast residues, etc.). Throughout
this document, lead contamination, the most common TCLP debris
concern, is used as an example, although these methods can be
used to classify other TCLP wastes as well.
METHODS; Method I- The Sampling/statistical Analysts Kethod
requires sampling and TCLP analyses of both the paint and
building material. The data is analyzed using conventional
statistical methods to transform the results to a confidence
interval (CI) of 80%. Method II- The Mass Balance TCLP Method
requires only sampling and TCLP analyses of the paint and adjusts
the TCLP data by a factor based the calculated uncontaminated
mass in the total debris.
Method I. Sampling/Statistical Aaalvsass
SCOPE;
a. Before characterizing the waste, it is necessary to define
the wastestream. The wastestream is the debris generated during
a given demolition project at a given site/installation. While
all buildings/structures generating demolition debris constitute
the wastestream, only a percentage of these buildings need be
sampled. Details on how to determine the appropriate number of
buildings to sample are presented in the "PROCEDURE" section
below.
PROCEDURE: During demolition debris waste characterization,
several site-specific determinations need to be made. The
following steps explain how:
a. Defining Individual Wastestreares/Populations; As
defined above, the wastestream consists of all the debris
generated during a specified demolition project. A list of the
buildings should be recorded, including the building components
undergoing demolition , and notations of buildings that will be
generating the same type of debris because they are the same or
similar design and construction and are undergoing the same type
of demolition or rehabilitation. Information should also be
gathered regarding the demolition and disposal procedures.
-------
2
For instance, if the structures are set on cement foundations it
would be necessary to determine whether the cement is to be
demolished and disposed of with the rest of the debris. If such
foundations were to be left in place they would not be considered
as debris; otherwise, they would be included in the vastestream
and would be sampled in accordance with the procedures discussed
below.
b. Determining the munbey of samples; Based on
EPA guidance (EPA/600/8-89/046, March 1989, Soil Sampling Quality
Assurance User's Guide, 2nd Edition), a statistical approach will
be used to determine the number of buildings that need to be
sampled. This approach is based on the assumption that the
buildings are all relatively uniform and that the analytical
results of the study will be normally distributed. The EPA
manual SW-846— Test Methods for Evaluating Solid Wastes, Section
9.1.1.3, Basic Sampling Strategies (Attachment A), requires that
the number of samples used to characterize a wastestream ensure
an 80 percent confidence level in the resulting determination (in
this case, hazardous or nonhazardous waste determination) . The
enclosed Table 1 is based on these guidelines and should be used
to determine the number of buildings to be sampled at a given
project site.
c. Sample Buildings Selection; Once the number of
buildings to be sampled has been determined, the specific
buildings to be sampled need to be identified. For buildings
generating identical or similar debris (made v i the .ame
construction materials and painted with the same paint) a random
approach should be used in the selection process. Buildings may
be randomly selected using building numbers or placement on maps.
However, when one or more groups of buildings generating
identical or similar debris constitutes a separate and distinct
segment within the total number of buildings, an appropriate
percentage of buildings should be selected from the individual
group (s) .
d. Sampling Strategy; The objective is to obtain one
representative composite sample from the debris wastestream from
each building selected for sampling. The composite sample must
include appropriate proportions of each debris that the
wastestream is made of. Figure 1 depicts various areas of a
building that may be constructed of different materials and must
be sampled if they are part of the debris wastestream. Areas
that will not be part of the debris wastestream do not have to be
sampled.
-------
(1) Debris components, such as glass, screen,
or wiring, that are difficult to sample and comprise a very small
(de minimis) percentage of the debris vastestream, do not have to
be sampled. Also materials such as aluminum siding,, large metal
ductwork, light ballasts, utility equipment, and asbestos
insulation need not be sampled if these materials are separated
from the demolition debris and recycled/reused (e.g., scrap
metal). In general, the aost commonly sampled components will be
wood, brick, cement and plaster/wallboard.
TABLE 1- STATISTICAL DETERMINATION OF THE NUMBER OF BUILDINGS TO
BE SAMPLED
NO. OF TOTAL BUILDINGS
AT ONE PROJECT SITE
NO. OF BUILDINGS TO SAMPLE*
1-9
11 - 15
16 - 20
21 - 30
31 - 40
41 - 100
> 100
ALL
10
13
16
21
26
32
* It should be noted that a sample is defined as a composite of
subsamples from one building. 20-30 subsamples should be
sufficient to make one sample.
2) The proportional size of the various building
debris components based on (estimated) square footage must be
determined. For instance, a building may be 70 feet long, 40
feet wide and 12 feet high; if all four of the exterior vails are
to be demolished and are made of the same material, there is 2640
ft2 of that debris component. Window and door space should be
subtracted out from the exterior-interior vails and considered as
separate debris components. The estimated area of each debris
component (e.g., exterior wall, interior plaster board vail,
interior plywood/panelling wall, floor, cinder block supports,
-------
etc.) should be compared to one another in order to establish
ratios. The ratios will determine the number of subsamples to
obtain from each individual component. For instance, if 20% of
the area is cinder block, than 20% of the subsamples should
consist of cinder block samples.
Generally, 20 to 30 subsamples are necessary to make-up one 110-
gram composite sample for each building. This number will vary
based on the number of components that make up the debris. For
instance, if building demolition debris consists of 60% vails,
30% floor and 10% doors (based on surface area), 18 subsamples
(60/100 x 30} could appropriately be from the vails, 9 from the
floor and 3 from the doors.
e. Sampling Methodology;
(1) Using a 1-inch bit drill or similar device,
•core" subsamples should be obtained from each component of the
building demolition debris. The number of subsamples taken for
each debris component relative to the other debris components
will be based on the ratios calculated above. The subsamples
should be collected into a disposable container (such as large
sheets of paper) as the drilling is done. The sampling crew
should — to the extent possible — drill through the entire
thickness of each component (e.g., doors, floor, etc). For
building debris components such as cinder block or cement, a
hammer drill should be used. The number of drill holes obtaine*
from each component should be recorded. If the amount of
material collected for the total composite sample for the
building is not enough (i.e., less than 110 grams) for the TCLP,
additional subsamples should be obtained from each of the
specific components, with the number of additional subsamples
based on the above calculated ratios. [NOTE: For at least 5
percent of the samples (and a minimum of 1 sample) taken for each
demolition project approximately 300 grams should be obtained for
adequate split laboratory analyses.]
(2) Field duplicates, equaling 5 percent of the number
of actual composite samples (at a minimum of one), taken after
each demolition project, should be obtained to check the sampling
practice. The duplicate(s) should be obtained by simultaneously
filling two sample containers during the sample process (i.e.,
for each subsample within a sample building, two adjacent cores
should be obtained and placed into two separate containers).
f. collection and Labelling! The sample material from each
building debris should be collected onto a (disposable) container
(such as sheets of unused paper, paper plates, etc.). From this
collection container, the materials should be emptied into clean
(new) plastic baggies and labelled with the project/installation
name and or identification number, sample (building) number,
sample date, and sampling personnel's name.
-------
9* Decontamination: Nondedicated sampling equipment
such as the drill bit should be decontaminated between sampling
of individual buildings. The sampling crew should first brush
excess material from the equipment and then wash using tap water
and soap. This should be followed by a final rinse with
distilled, deionized, filtered (DDIF) water. To ensure the
equipment was properly decontaminated, a used rinse water sample
should be taken and analyzed.
LABORATORY ANALYSES!
a. Packaging and Transportation? All samples should be
properly packaged before transporting them to the certified
analytical laboratory.
b. Laboratory Preparation; To ensure thorough mixing of
the composite sample, the laboratory should be requested to
thoroughly mix/homogenize the sample before preparing it for
analyses. This will minimize the "settling** that may occur
during transportation. This procedure is extremely important
when excess sample has been obtained and the laboratory will only
be using a portion of the overall sample.
c. Analytical Methodology; All solid material being analyzed
(wood/pi aster/paint chip, etc.) should be extracted using EPA
Method 1311 (TCLP). The samples should be analyzed using either
EPA Method 6010A [Inductively Coupled Plasma (ICFj-Atomic
Emission Spectroscopy] or EPA Method 7421, the Atomic Absorption-,
Furnace Technique for lead. The ICP procedure is recommended due
to lover cost, but either method will satisfy EPA requirements.
The rinsate sample should also be analyzed using one of these
methods.
DATA ANALYSES;
a. The TCLP laboratory results should be statistically
analyzed to assess the variability among the buildings of the
demolition or rehabilitation project and overall normality of the
TCLP lead concentration distribution. If the analytical results
do not indicate a normal distribution (i.e., the arithmetic mean
is not greater than the variance), the raw data should be
transformed. After normality has been achieved through an
appropriate transformation, the 80 percent confidence interval
(CI) should be calculated and compared to the (similarly
transformed) regulatory threshold (RT) of 5.0 mg/L for lead. (See
SW-846--Test Methods for Evaluating Solid Wastes, Section
9.1.1.3, pasie Sampling Strategies!.
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b. Additional procedures may be necessary to address
potential "statistical outliers," or buildings that yield
unusually high TCLP lead concentrations that dramatically skew
the 80 percent CZ. If necessary, such buildings nay be addressed
as a separate population.
An example of a sampling/data analyses program is attached below
(Example 1.0}. See Test Methods for Evaluating Solid Waste, EPA
Manual SW-846, Vol. II, Chapter 9, November 1986 (Attachment A)
for detailed calculations.
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EXAMPLE 1.0
STATISTICAL ANALYSES
Buildina Debris Sanoles: Collected May-June 1992
Bldg
Pb Values
square root of Pb values
4711
4900
4901
4905
4713
3644
3626
3635
3641
3628
3639
3640
3629
3632
3637
3627
4904
3634
mean
std deviation
std err
normal
80% CI*
trsfd RT
Hazardous
waste
1.08
1.11
14.7
10.0
1.35
3.11
1.40
1.63
1.53
1.76
1.38
0.50
0.51
1.06
0.91
0.82
2.56
0.50
2.55
3.61
0.85
No
N/A
N/A
N/A
1.039
1.054
3.834
3.162
1.162
1.764
1.183
1.277
1.237
1.327
1.175
0.707
0.716
1.030
0.952
0.907
1.600
0.707
1.38
0.80
0.19
Yes
1.63 *80% Confidence
Interval «= mean +
2.24 (tjo*std err); where
tjtpl.333 for df=17
No
By performing a square root transformation
of the values, the data shows a NORMAL
distribution (the mean > the STD squared).
Since the 80% CI is LESS than the square root of the
regulatory level of lead (5 mg/1) the vaste is not
hazardous.
Reference: Test Methods for Evaluating
Solid Haste, EPA Manual SW-846, Vol. II,
Chapter 9, November 1986. (Attachment A)
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8
II. MASS BMAMCE TCLP CALCULATION METHOD;
a. This method is based on the assumption that for building
demolition debris, only the paint will contain heavy aetals
(e.g., lead) while the unpainted building construction materials
will contain no heavy metals. In this instance, TCLP sampling
and analyses of only the paint is required. If the above
assumption is not valid, then the* Sampling /Statistical Analyses
Method (Method I) must be used.
b. Before characterizing the waste, it is necessary to define the
wastestream. The wastestream is the debris generated during a given
demolition project at a given site/ installation. While debris from all
buildings /structures being demolished or rehabilitated constitute the
wastestream, only a percentage of these buildings need be sampled.
Details on how to determine the appropriate number of buildings to
sample are presented in the "PROCEDURE" section below.
PROCEDURE; During a demolition debris waste characterization study,
several site-specific determinations will need to be made. The
following steps are detailed to the extent possible.
a. Defining Individual Wastestreams /Populations; As
defined above, the wastestream consists of all the debris generated
during a specified demolition project. A list of i:Ue buildings should
be recorded, including the building components undergoing demolition,
and notations of buildings that will be generating the same type of
debris because they are the same or similar design and construction and
are undergoing the same type of demolition or rehabilitation.
Information should also be gathered regarding the demolition and
disposal procedures.
For instance, if the structures are set on cement foundations it would
be necessary to determine whether the cement is to be demolished and
disposed of with the rest of the debris. If such foundations were to
be left in place they would not be considered as debris; otherwise,
they would be included in the wastestream and would be sampled in
accordance with the procedures discussed below.
b. pertaining +** rnrnber of Samolest Based on EPA guidance
(EPA/600/8-89/046; March 1989, Soil Sampling Quality Assurance User's
Guide, 2nd Edition) , a statistical approach will be used to determine
the number of buildings that need to be sampled. This approach is
based on the assumption that the buildings are all of a relatively
uniform construction and that the analytical results of the study will
be normally distributed.
-------
The EPA manual SW-846—Test Methods for Evaluating Solid Wastes,
Section 9.1.1.3, Basic Sampling Strategies (Attachment A), requires
that the number of samples used to characterize a wastestream ensure ar
80 percent confidence level in the resulting determination (in this
case, hazardous or nonhazardous waste determination).' Table l (Method
I) is based on these guidelines and should be used to determine the
number of buildings to be sampled.
c. Sample Buildings Selection; Once the number of
buildings to be sampled has been»determined, the specific buildings to
be sampled need to be identified. For buildings generating identical
or similar debris (made of the same construction materials and painted
with the same paint) a random approach should be used in the selection
process. Buildings may be randomly selected using building numbers or
placement on maps. However, when one or more groups of buildings
generating identical or similar debris constitutes a separate and
distinct segment within the total number of buildings, an appropriate
percentage of buildings should be selected from the individual
group(s).
d. Sampling Strategy; The objective is to obtain one
composite sample of paint from each building selected for sampling.
Only samples of paint from the building components that will be part of
the debris vastestream should be sampled.
e. Sampling Methodology:
(1) Using a scraper or similar device, paint samples should be
r^taine^ from each component of the demolition debris. Typically, one
tuiould -ample each component of the debris that contains lead paint and
combine the samples into one composite sample (knowing that at least a
100-llOg composite sample is needed for a TCLP analyses and that at
least a 10-15g sample must be obtained from each debris component).
The choice of and number of samples should be approximately in
proportion to the areas of each building component that has been
painted with the lead paint and that will make up the debris
wastestrearn. Table 2 below provides an example of the percentage of
total building debris area that each debris component comprises and the
number of grab samples that should be taken of each component. Again,
if any of these building components will not be part of the debris
wastestream, they should not be sampled. [NOTE: For at least 5
percent of the samples (and a minimum of 1 sample) taken for each
demolition project approximately 300 grams should be obtained for
adequate split laboratory analyses.]
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10
TABLE 2- PERCENTAGES OF AREAS COVEREU BY tEAD PATNT
Category
Interior
Ceiling
Halls
Doors
Windows
Cabinets
Shelves
_Area
519.6
1137
352.4
132
46
55
Percentaae
13%
28.4
8.9
5.8
f of Subsamcles
3
6
2
1
1
1
Exterior
Siding, Attic 201.6
Siding, Walls 1000
Roof, Underside 200
Porch 355.5
5.0
25.0
5.0
Totals
3999.1
100.0%
1
5
1
23
(2) Field duplicates, equaling 5 percent of the number
of actual composite samples (at a minimum of one), taken during each
demolition project, should be obtained to check the sampling practice.
The duplicate(s) should be obtained by simultaneously filling two
sample containers during the sample process (i.e., for each sample
within a sample building, an adjacent grab sample should be obtained
and placer* into « separate container).
f. Collection and Labelling; The sample material from
each building debris should be collected onto a (disposable) container
(such as sheets of unused paper, paper plates, etc.). From this
collection container, the materials should be emptied into clean (new)
plastic baggies and labelled with the project/installation name and or
identification number, sample (building) number, sample date, and
sampling personnel's name.
g. Decontaminationr Nondedicated sampling equipment
such as the drill bit should be decontaminated between sampling of
individual buildings. The sampling crew should first brush excess
material from the equipment and then wash using tap water and soap.
This should be followed by a final rinse with distilled, deionized,
filtered (DDXF) water. To ensure the equipment was properly
decontaminated, a used rinse water sample should be taken and analyzed.
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11
LABORATORY ANALYSES;
a. Packaging and Transportation; All samples should be
properly packaged before transporting them to the certified analytical
laboratory.
b. Laboratory Preparation; To ensure thorough nixing of
the composite sample, the laboratory should be requested to thoroughly
mix/homogenize the sample before preparing it for analyses. This will
minimize the "settling" that may'occur during transportation. This
procedure is extremely important when excess sample has been obtained
and the laboratory will only be using a portion of the overall sample.
c. Analytical Methodology; All paint being analyzed
should be extracted using EPA Method 1311 (TCLP). The samples should
be analyzed using either EPA Method 6010A [Inductively Coupled Plasma
(ICP)-Atomic Emission Spectroscopy] or EPA Method 7421, the Atomic
Absorption, Furnace Technique for lead. The ICP procedure is
recommended due to lover cost, but either method will satisfy EPA
requirements. The rinsate sample should also be analyzed using one of
these methods.
DATA ANALYSES;
I) TCLP DATA ANALYSES;
a. If only one bui .ding was sampled (e.g., the same paint was used in
the other buildings) no statistical analyses need be performed oh the
TCLP data. If more than one building was sampled the TCLP laboratory
results should be statistically analyzed to assess the variability
among the buildings of the demolition project and overall normality of
the TCLP lead concentration distribution. If the analytical results do
not indicate a normal distribution (i.e., the arithmetic mean is not
greater than the variance), the raw data should be transformed. After
normality has been achieved through an appropriate transformation, the
80 percent confidence interval (CI) should be calculated.
b. Additional procedures may be necessary to address
potential "statistical outliers," or buildings that yield unusually
high TCLP lead concentrations that dramatically skew the 80 percent CI.
If necessary, such buildings may be addressed as a separate
wastestream.
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12
II) TOTAL WASTESTREAM TCLP DETERMINATION;
After obtaining statistically acceptable TCLP of the paint from step I,
above (where only one building had to be sampled, the ,TCLP value for
the one composite sample is used), the TCLP level of the total debris
vastestrean can then be estimated from a TCLP sample. The key
relationship can be derived as follows:
TCLPwaste = TCLPpaint x mp / mw,
Where mp is the mass of the paint on the building surfaces,
and mw is the total mass of the debris wastestream generated.
This simple proportion will provide a reasonable estimate of
the TCLP for the debris wastestream which can be directly
compared to the regulatory standard (e.g., 5.0 mg/1 for
lead).
a. Estimation of the Mass of Paint and Total Wastes;
Two basic formulas will be defined to estimate the parameters, mp and
mw:
mp(kg) « Ap(ft2) x dp(ft) x rp(g/cc) x 28.3 (kg/ft3)
where Ap is the surface area of paint; dp is the depth of the paint
surface; and rp is the paint density and 28.3 (kg/ft5) is the density
of water.
Bw(kg) = vi(ft3) x ri(g/cc) x 28.3 (kg/ft3)
where i are the various debris components, such as wood, concrete,
brick, etc, Vi is the volume and ri is the .density of each debris
component. The mass of each of the separate components are estimated
using standard construction estimation techniques.
Estimation values for the densities of materials and the depth of the
paint surface can be obtained from many sources. The density values
given below are from "The Handbook of Chemistry and Physics" and the
experience of the agency. Estimated average paint depth was obtained
from the Denver Bousing Authority.
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13
Estimated values for ri, rp and dp:
Density of Concrete
Density of Wood
Density of Glass
Density of Steel
Density of Plaster
Density of Gypsum Board
Density of Brick
Density of Stone (typical)
Density of Soil (dry)
Density of Pipe
Density of.Paint
Average Paint depth
2.5 g/cc
.6 - .8 "
2.5 ' "
7.5
1.5
.8
2.0
2.5 '
1.4
7-8
1.2
1/100 inch
(8.33 X 10-* ft)
The paint depth value is considered reasonably representative, but if
the TCLP sample contains abraded material (such as wood or plaster),
the average depth should be measured on-site and the mass of paint plus
abraded material calculated.
The estimation of the volume of waste materials and the area covered bj
the paint surface will take the greatest amount of time. As an example
of bow this can be done, a typical one story house design was created
for calculation purposes (Table 3). Where a number of similar
buildings are involved, a single "representative" building could be
used. If architectural drawings happen to be available, much of the
information can be obtained directly from them.
Lead-painted surfaces are assumed to include all interior walls and
ceilings as well as interior trim, windows, doors and kitchen cabinets.
It is also assumed that the outside walls of the house and porch were
painted with lead based paint.
Many of the volumes for the foundation, framing, and plaster surfaces
can.be estimated from geometric properties. Density values and the
specific weight of water in kg/ft3 are multiplied by the volume to
obtain the weights for each material. The complexity due to the number
of items involved is characteristic of residential housing. Federal
installation buildings may be somewhat simpler.
Table 3 summarizes the calculation results for the basic structural
categories. Area calculations are provided only where it is assumed
that lead based paints were applied. The total estimated weight of the
house and associated materials was 72,173 kg, which constitutes the
debris wastestream. The total painted interior surface area was 2242
ft2; the outer painted surfaces totalled 1757,1 ft2. It was assumed
that the paint thickness was. .01* on average. The estimated weight of
paint was 113.1 kg, the total mass of sample containing lead.
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14
TABLE 3. HOUSE ESTIMATION VALUES BY CATEGORY
Estimate of Total Debris Mass
Concrete
Brichinney ;5 * ? •* x "-J - «,88l kg
Wood, Framing Si1. X 2:° x 28'3 • 3'3<5
Asphalt Roo??ng J£j§ x 1% x III Z
3
100 . 4X 3
eJ?3° / AV.Si1.- I'.ltl
72,372 kg
Estimate of Paint Areas and Mass:
Interior Area fft»)
Ceiling 519.6
walls 1137
Doors 352.4
Windows 132
Cabinets 45
Shelves gs
Totals 2242
paint weight (kg) = paint area (ft*) x paint depth x paint density
- 1.868 ft3 x 1.2 X 28.3 = 63.4 kg
Area
Siding, Attic 201.6
Siding, Walls 1000
Roof, Underside 200
Porch 355.5
Totals 1757.1
Sum of all building ^ainJ" in?erio? ? Skerior^pa'int mass -
63.4kg + 49.7kg « 113.1 kg
b. Calculations of the TCLP for the
rstr jr»iis
or 32°° x
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figura i
nvwii T. r" j?'i$rim *f • BuBding
WWII TtrrjpDrary Barracks Slatad for DtmoDtion)
: Pinftlen Want
Imtr Strueturt: 'Studt •
Support Btams
HOOF
!
D D
ODD
f
DOORS
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Appendix XII
-------
Appendix XII
1992 Workshop on Characterizing Heterogeneous
Materials
-------
r/EPA
United Statas
Environmenlal Protection
Agency
Office of Research and
Development
Washington. DC 20460
EPA/600/R-93/Q33
March 1993
Environmental Monitoring
Issues
Results of Workshops
Held in July 1992 as
Part of EPA's Eighth
Annual Waste Testing and
Quality Assurance Symposium
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5. CHARACTERIZING HETEROGENEOUS MATERIALS
5.1. BACKGROUND
In both the RCRA and CERCLA programs, a material often must be characterized to
»
determine if it possesses some property of concern or interest. Types of questions that may
require answering include:
• Is the material hazardous?
• Can it be safely or successfully managed using a specified treatment technique?
• How much supplemental fuel must be added to incinerate the waste?
When the material being characterized is homogeneous, conventional sampling and
subdividing approaches can be employed. For example, in a truckload of used foundry sand
with an average phenol concentration of interest, the material is in the form of relatively fine
particles with the phenol uniformly distributed on the surface. Conventional compositing and
subsampling can provide representative samples with an average composition very close to that
of the entire load. The actual task of obtaining each subsample from the appropriate point in
the truck may be very difficult, but the approach used is relatively straightforward.
However, insurmountable problems can develop when faced with a heterogeneous
material. Heterogeneity is a relative term and, among other factors, is a function of the
objectives of the characterization and the analytical sample size. This workshop was concerned
with wastes of such various particle size, waste consistency, or extraordinary concentration
gradients that the sampling and analytical objectives could not be met using traditional
approaches and standard techniques. This is an important and difficult problem that has been
of concern to many organizations involved in waste management.
38
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The workshop goal was to advance the state-of-the-art techniques for characterizing
difficult to sample wastes. This covers wastes with a highly variable nature, (e.g. wide ranges
of particle size, large concentration gradients, and mixtures of different waste materials (e.g.
dredge materials containing sludge, tiies, construction debris, bottles, cans, etc.)). These types
of materials present challenges that traditional sampling and analysis approaches cannot meet
with the level of certainty required for modern waste management decisions.
RCRA has historically taken the position that the sample actually being analyzed does not
have to be representative of the material being characterized, but rather that the sum total of the
data must represent the property of interest. The problem presented was how to develop
practical solutions to characterize these difficult situations. In this session, the participants
discussed how to cost-effectively characterize materials that are inherently very heterogeneous
and present characterization difficulties.
5.2. SUMMARY OF POSITION STATEMENTS
5.2.1. Regulatory Program Perspective
Mr. Charles Ramsey, EPA's National Enforcement Investigation Center (NEIC),
reviewed some issues involved in implementing the RCRA regulatory requirement that a
"representative" sample of the waste be collected and analyzed. 40 CFR, Part 260.10 stipulates
that a representative sample, '... means a sample of a universe or whole (e.g., waste pile,
lagoon, ground water) which can be expected to exhibit the average properties of the universe
or whole." This definition has two aspects.
1. What is an average property?
2. How is the universe or whole defined?
The inability to answer these questions in clearly defined scientific terms leads to most of the
problems surrounding the characterization of heterogeneous wastes.
39
-------
Mr. Ramsey Proposed that hazardous waste characteristics are not "averageable1*
properties. For example, corrosivity is expressed as pH that is a logrithemic function, while
ignitibility can be expressed as passing or failing the 60°C ignition test. With these
characteristics, the numerical mean is not meaningful; therefore, an average value cannot be
obtained.
Using the average value as a measure of hazard with respect to the toxicity and reactivity
characteristics may also present potential problems. When the material to be evaluated consists
of both a contaminated phase and an inert phase, use of the mean may result in a waste being
classified as nonhazardous even though a substantial portion of the waste might be above the
regulatory threshold and pose an environmental hazard.
Using "the most likely result" approach (also known as attribute testing) avoids many of
the above problems. It requires that a certain percentage (e.g., 50%, 75%, 95%) of the
individual sample results fall below the regulatory decision value. This avoids problems
associated with determining average values. Use of this approach, however, will require a
change in the regulations.
Even when the property of concern is a continuous variable and, therefore, averageable,
collecting representative samples of heterogeneous wastes is often extremely difficult. Many
heterogeneous wastes are discontinuous in terms of physical/chemical properties and, given the
small size of analytical samples relative to the discontinuity, it is not possible to collect (and
demonstrate) representative samples of the wastes. Therefore, to ensure that an adequate
characterization is conducted, a clear definition is needed of what constitutes the "universe or
whole" to be characterized and what constitutes an acceptable level of characterization (i.e.,
What degree of confidence, that the property is below the regulatory threshold, must be obtained
to characterize the waste as nonhazardous.). The universe of the whole must also be defined
to determine the period of time and space in which the samples must be collected.
40
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5.2.2. Regulated Community Perspective
An industrial perspective was prepared by Mr. David Reese, Safety-Kleen Corp., and
presented by Mr. Gene Klesta, Chemical Waste Management Corp. The presentation focused
on the types of samples received at recycle and waste disposal centers and the different types
of problems these materials represent relative to heterogeneous wastes found in the field. The
industry receives large quantities of containerized wastes from different sources which in the
aggregate form a very heterogeneous set.
Industry strongly supports considering the method of management when establishing
analytical requirements. The current requirement for full-scale analysis is, in many cases, not
necessary and represents a significant financial burden for generators and the waste management
industry. The industry recommends that wastes destined for recycling or treatment be exempted
from rigorous analysis if the waste management process and end products are thoroughly
characterized during operations and prior to disposal.
It is further recommended that the Agency permit the use of methods other than those
in SW-846 when conducting acceptance testing of wastes for treatment and recycling. Using
proper QA/QC procedures is adequate to ensure that reliable analysis are conducted. Again,
process monitoring and end product analysis provide sufficient protection of the environment.
The industry will work with the Agency to bring industry-generated methods into the public
sector.
The industry position is similar in concept to the Agency's interest in moving towards
performance-based methods using sound project QA plans, data quality objectives.and accepted
QA/QC procedures as the quality assurance tools to monitor performance.
41
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5.2.3. State-of-Science Perspective
Dr. John Maney, a private consultant, presented a detailed strategy for random and
nonrandom sampling of heterogeneous wastes. The presentation, described a unified way of
looking at all types of waste based on the source and degree of heterogeneity of the material.
Using flow charts and an extensive set of definitions and examples, the paper presents
concrete examples of options available to the field sampling team and the analytical chemist to
generate reliable analytical data from complex, heterogeneous materials. However, unless the
sample undergoes extensive comminution, Dr. Maney indicated that obtaining an analytical size
representative sample of a heterogeneous waste is almost impossible. (See the full paper in
Appendix A for details.).
5.3. CHARGE TO THE WORKSHOP PARTICIPANTS
Before breaking into three workgroups, the participants were asked to address three
questions:
1. Should EPA change from current practice (average testing) to attribute testing for
properties that are not averageable?
2. If so, what is the highest practicable degree of confidence (%) that could be required?
3. Should there be an override that says that if some samples are greater than "X", the
waste is hazardous even if the number of such samples are below the percentage
established in question 2?
A large part of each workgroup's time was devoted to discussion of the practical
definition of attribute testing and how it differs from average property testing. This decreased
42
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the time available to discuss the three issues, so no effort was made to address the third issue
within any workgroup.
5.4. RESULTS OF THE WORK GROUP DELIBERATIONS
5.4.1. Should the Agency Change to Attribute Testing for Properties that are Not
Averageable?
Approximately 90 percent of the participants believed that attribute testing should be
adopted for properties that are not averageable. This approach is more costly than average
property testing in those situations where the average property was determined by compositing
a series of field samples prior to analysis. There was some discussion that compositing of
samples prior to analysis is one way to determine an average property that avoids many of the
technical problems associated with averaging the results from a series of discrete sample
analyses.
Neither the attribute testing nor the average property testing approach eliminates all the
problems associated with the sampling of wastes prior to analysis. The nature of attribute testing
can make the sampling in many situations easier. The group agreed that approximately 80
percent of the error in characterizing waste arises from field sampling error that effects both
approaches equally.
The Agency should focus its efforts on providing sampling guidance for heterogeneous
wastes. Special efforts should be made to provide guidance for specific types of wastes such as
tires, telephone poles, construction debris, and military ordinance. Also, knowledge of the
process that generated the waste is an important part of the decision to use attribute testing and
would be a primary driver in selecting the sampling strategy.
43
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5.4.2. What is the Highest Practicable Degree of Confidence that can be Required?
Several participants felt the answer to this question should take into account the degree
of health and ecological risk associated with the material and the amount (mass or volume).
Therefore, each site should be considered unique and receive individual consideration. A site-
specific degree of confidence should be carefully developed as pan of the data quality objective
process and be codified in the site-specific QAPjP.
It was generally agreed that a maximum of 10 percent of samples collected should be
allowed to fail the regulatory criteria. Sixty-six percent of the participants felt that a 4 to 6
percent failure rate was the most appropriate. All participants felt the Agency should publish
clear guidelines on determining if attribute testing should be applied to a specific situation.
5.5. AGENCY FOLLOW TO WORKSHOP
Subsequent to the workshop, Agency staff met to discuss what steps to take to address
the issue and the ideas presented during the session. It was decided that quantitative data are
needed to determine:
What the practical effect would be if the attribute testing approach was used
instead of the current arithmetic mean.
How the number of samples needed to achieve a defined degree of confidence
would vary across the different types of materials characterized in the RCRA and
CERCLA programs.
During the next year, the Agency plans to examine its data in an attempt to answer the
above questions. However, the Agency will greatly appreciate receiving any additional
information that will help determine if a change in approach will either improve the quality or
lower the cost of decision making. If anyone has data that might assist in this effort, EPA will
appreciate receiving such information. Such information should be sent to the author at the
address indicated in the FORWARD to this report.
44
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CHARACTERIZING HETEROGENEOUS MATERIALS:
INTRODUCTION
David Friedman
USEPA Office of Research and Development
401 M Street SW
Washington, DC 20460
BACKGROUND
Throughout the RCRA and CERCLA programs, one is raced with the task of
characterizing a material to determine if it possesses some property of concern or interest.
Types of questions one may be answering include:
• Is the material hazardous?
• Can it be safely or successfully managed using a specified treatment technique?
• How much supplemental fuel might I have to add to incinerate the waste?
PROBLEM
When the material being characterized is homogeneous, conventional sampling and
subdividing approaches can be employed. For example, take the case of a truckload of used
foundry sand whose average phenol concentration is of interest. The material is in the form of
relatively fine particles. Conventional compositing and subsampling will provide relatively small
representative samples whose average composition is very close to that of the whole load. The
actual task of obtaining each subsample from the appropriate point in the truck may be very
difficult, but the approach used is relatively straightforward.
PraauedatEfA Voriahop m Juty 16.1992
'Otaraeunanf Heterogeneous l/aenab ' C~ 1
-------
However, what happens when one is faced with a heterogeneous material? When we
speak of heterogeneity, we need to keep in mind that this is a relative term and is a function of
the objectives of the characterization and the analytical sample size. The concern of today's
workshop is generally with wastes of such various particle size, waste consistency or
extraordinary concentration gradients that the sampling and analytical objectives cannot be met
using traditional approaches and standard techniques. When it is not possible to obtain a
representative sample, what shall we do?
This is an important and difficult problem. It is one that has been of concern to many
organizations involved in waste management. For example, in March 1991, the Environmental
Protection Agency, the Department of Energy, and ASTM's Committee D-34 conducted a
workshop to examine how to characterize heterogeneous wastes that were also contaminated with
radioactive materials. A report has recently been issued that describes the results of the
workshop . However, many problems and issues remain to be addressed and we have
convened today's workshop to address some of the issues.
We would like your help with addressing the following specific issues.
Identify characterization situations that present difficult problems (genetically identify
both the type of material and situation).
Develop specific guidance laying out the process to be used to adequately and
cost-effectively address the problem. Describe what criteria should be used to
guide development of solutions/approaches to specific problem situations. Please
be as quantitative as possible on when trade-offs may need to be made and how
to select among options.
If research work needs to be done to develop a solution, please identify what
work needs to be done.
1 Characterizing Heterogeneous Wastes: Methods and Recommendations, EPA/600/R-92/0,
February 1992.
at EPA MWbfcp OlJffy 16.1992
rfEMf Hamgatau ItaurUs' C-2
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Since EPA would like to solve monitoring problems through cooperative ventures,
what form should a cooperative development program take? How can it be
organized? Who might the cooperators be?
If you think of any ideas, information, or suggestions that you feel the Agency should
consider when addressing this issue, please send them to us. Send your comments to:
David Friedman (RD-680)
US Environmental Protection Agency
Washington, DC 20460
We will need to receive your comments by August 21,1992 in order for them to be incorporated
into the final conference report.
Prattled at EPA Workshop WJmfy 16. 1992
•Oaioaami Haerogauxms Maurials• C-3
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CHARACTERIZING HETEROGENEOUS MATERIALS:
REGULATORY PERSPECTIVE
Charles A. Ramsey
USEPA National Enforcement Investigations Center
Box 25227 Building 53 Denver Federal Center
Denver, Colorado 80225
INTRODUCTION
Characterization is the process used to determine whether solid waste is also a hazardous
waste. Characterization is arrived at by Mowing "testing structure." A testing structure is the
particular sampling, analysis, and data interpretation steps that are employed to measure a waste.
The purpose of this paper is to examine the testing structure used to measure characteristics
(ignitability, corrosivity, reactivity, and toxicity) of heterogeneous solid waste that would make
it hazardous waste as defined in 40 CFR part 261.21-24.
To date, there has been little progress in developing a testing structure to characterize
heterogeneous waste. EPA regulations state that characterizing waste includes determining the
average property of the "universe or whole", 40 CFR part 260.10. The problems with the
regulations are that "average" lacks scientific validity and "universe or whole" is not defined.
These two items are an integral part of the testing structure.
To address these problems, two areas must be explored: 1) policy, regulations, and
guidance issues and 2) scientific concerns. This paper focuses on heterogeneous solid waste
because it is a worst case scenario. A testing structure that works for heterogeneous solid waste
will work for any solid waste.
Praaaai or EPA Worfafap tDfffy 16.1992
Haemgouau Hataieli'
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POLICY, REGULATIONS, AND GUIDANCE ISSUES
Many problems with characterization of heterogeneous materials under RCRA can be
traced to the definition of what type of sample must be collected and analyzed. The required
sample is a "representative" sample which is defined in 40 CER part 260.10. "representative
sample means a sample of a universe or whole (e.g., waste pile, lagoon, ground water) which
can be expected to exhibit the average properties of the universe or whole." At least two
problems arise with this definition: what is the average property and what is the universe or
whole?
Average
Does average signify the arithmetic average or the "most likely result" of the target
population? To illustrate, if the data points are 5.7, 5.7, 5.8, 5.9, and 0.2, the arithmetic
average is 4.7. If the regulatory limit is 5.0, the best point estimate of the average is that it is
below the regulatory limit. However, if confidence intervals were required, there would be little
confidence in this conclusion.
If average, however, signifies the "most likely result" (the point at which one half of the
values are above or below-the median) one would conclude that 80% of the data points are
above the regulatory limit. This conclusion is also an expression of a higher degree of
confidence than the conclusion with arithmetic average. More of the values agree with this
conclusion (4 of 5 are above the limit) than agreed with the conclusion based on arithmetic
average (1 of 5 were below the limit).
With the arithmetic average approach, it is possible to have well over half the population
above the regulatory limit and still achieve compliance. With the "most likely result" approach,
not more than one half of the population can be above the regulatory threshold and be in
compliance. The "most likely result" is sometimes referred to as "attribute" testing. An
Presented at EPA Wortshap BMufy 16. 1992
•Oianaentaig Heterogeaami Maitnalt- C~5
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attribute testing structure enables one to conclude if a waste is or is not hazardous-not the
degree of hazard.
For clarification of what is meant by average, the Agency provided Chapter Nine of
"Test Methods for the Evaluation of Solid Waste, Physical/Chemical Methods' (SW-846). This
guidance suggests that average signifies the arithmetic average.
A problem with this definition can be illustrated by the Mowing scenarios. One of the
RCRA characteristics is ignitability which includes analyzing samples for flashpoint. The
characteristic is present when the waste flashes at a temperature less that 60° C. In many cases
a number is not recorded, only the presence of a flash. The regulations do not state that a waste
which flashes at 10° C is any more hazardous than one that flashes at 59° C. This logic fits
well with -most likely result" or percentage (which does not require numeric results), but is
inconsistent with the arithmetic average. With ignitability testing sometimes the analysis
produces numbers and other times it does not. Without numbers, arithmetic averages can not
be calculated, but the "most likely result" can be determined. Another characteristic is
corrosivity which can be determined by pH. Several pH values cannot be averaged to determine
the average property of a waste. First of all they are log values and adding them to derive an
arithmetic average is actually a multiplication, thus yielding the wrong information.
Furthermore, from chemical principles, the final pH depends on the buffering capacity of the
individual components. If a waste in question has pH measurements of 2 and 4 (the regulatory
limit under RCRA is 2.5), it is incorrect to conclude that the average pH is 3 and therefore the
waste is not hazardous. Arithmetic average is also not scientifically valid for either toxicity or
reactivity.
Alternatively, the "most likely result" approach will produce valid results for each RCRA
characteristic test. If five samples were randomly selected from a waste and four flashed, then
80% of the samples exceeded the regulatory limit. If "most likely result" is synonymous with
greater than 50%, then the conclusion that the waste is hazardous can be made with confidence.
Praaatd at EPA WerUtap m Jmfy 16.1991
ootaemi Jtaerfab- C-6
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Universe or Whole
The waste population to be characterized is not defined in the regulations. If the
"universe or whole" is undefined with respect to both temporal and spatial requirements, it is
not possible to design a valid testing structure. This is illustrated through some of the following
scenarios.
If there are several piles of waste, must a decision be made for each pile or for the whole
of all the piles. What if one pile is above the regulatory limit and the other pile is below? What
if several piles are below the regulatory limit, but a few are above? What if the average is
below; are any of the piles hazardous?
What if the average property of a pile is below the regulatory limit? Some portions of
the pile could be above the limit, and others below. What if the portion of the pile above the
limit was loaded into a truck to be hauled to a non-hazardous waste landfill and this was
sampled? Is this waste which was not hazardous in the pile now hazardous when in the truck?
What if the waste produced today is above the regulatory limit, but the waste produced
yesterday and the waste produced tomorrow is below the regulatory limit, is the waste below
the regulatory limit on average or not?
"Universe or whole" must be defined or it is impossible to know where to sample and
how to interpret the results.
SCIENTIFIC CONCERNS
While it is always possible to sample, analyze and produce data for any waste, the
problem with heterogeneous materials is the confidence that a correct compliance decision was
made based upon a valid testing structure. A compliance decision is affected by the purpose of
Praaiud a EPA Worktop m JOy 16.1992
"Oianaeraaig HaerogeieaaMaterials' C~7
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the measurement, use of proper sampling and analytical methods, and correct interrelation of
the results. The variability within heterogeneous materials exacerbates the bias and imprecision
of the results. As bias and imprecision increase and the average approaches the regulatory limit,
compliance decisions become more difficult. If, however, the proper testing structure was
employed, it would dramatically improve the decision making process and increase the
confidence in the results.
A proper testing structure should have the following characteristics:
It must be scientifically valid. Basic scientific principles must not be violated. There
are instances where the ideal scientific solution can be adjusted for simplicity, politics,
and economics, but the solution must remain scientifically valid. Agency regulations,
policy, and guidance must never be inconsistent with basic scientific principles
("Safeguarding the Future: Credible Science, Credible Decisions", EPA/600/9-91/050).
It must be consistent. All elements of the testing structure are dependent on each other
for their validity. Sample collection must anticipate the analyses and data interpretation
to be performed to ensure that the proper samples are collected. Likewise, without
detailed knowledge regarding sample collection, data interpretation is meaningless.
Proper Sampling
Proper sampling primarily depends on the regulatory question (e.g., presence, trends,
absence, etc.), the universe or whole (population), and the confidence that the correct
compliance decision can be made. These three considerations-question, population,
confidence-must be definitively addressed before a sampling plan is developed and implemented.
PraaiUdaEPA Wartattap OUtfy U, 1992
•OmaaioKg Haerogouau Matalals- C-8
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Proper Analysis
Proper analysis for RCRA characteristics is not an issue, because three of the four
characteristics have required test methods referenced in the regulations (reactivity methods are
only guidance at this time). The correct analytical result is the one obtained by following the
prescribed analytical method.
Proper Data Interpretations
Proper data interpretation is important for making correct decisions. Data interpretation
ties the analytical results back to the population with some specified degree of confidence to
determine if the sampling and analysis answered the question about the waste. Proper data
interpretation includes:
Making the proper type of confidence statement. The statement does not need to be
statistical; it can be an expression of professional judgment. If statistical statements are
made one must recognize that there are many types (e.g., confidence interval of the
mean, tolerance limits, prediction intervals, etc.). Not all statistical statements are valid
for any particular compliance problem and care must be chosen to select the correct one.
Establishing degree of confidence in the statistical statement. It is possible that one can
make a certain statistical statement (or use professional judgment), but if one is not very
confident in the statement it serves no purpose proving compliance or non-compliance.
With many types of statistical statements, certain assumptions are made regarding the
distribution of the data. If incorrect assumptions are made, the resulting statistical statement and
degree of confidence might not be correct. The guidance given in SW-846 makes certain
assumptions regarding the distribution of data (normally distributed) which are usually incorrect.
By definition, heterogeneous waste (as well as most environmental data) defies these assumptions
fraaaedaiEPA Wortriep mjufy 16.1992
•OmuumiHg Haemgoiomi Malcriaii • C-9
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to a degree that can make the decision and confidence statements based on arithmetic averar-
incorrect. The usual indicators of non-normal data are outliers and skewed distributions. Wu
the "most likely result" no distribution is assumed (non-parametric) and therefore the problems
with heterogeneous waste do not affect the accuracy and confidence of the decision.
CONCLUSIONS
Characterization of heterogeneous waste depends on the development on a valid testing
structure. Currently, only portions of the testing structure are in place. Two items that need
to be addressed are:
Th? -m^t lively results" (percentage^ is the valid statistic for making compliance
decisions to characterize waste. The current use of arithmetic average is scientifically
invalid for the RCRA characteristics and can lead to wrong compliance decisions. There
are at least two percentage options that currently exist in the RCRA regulations. One is
the empty drum regulation (40 CFR part 261.7) which states that drums with a capac
of less than or equal to 1 10 gallons are considered empty if no more than 3% is left (and
the contents have been removed using common practices). Drums with a capacity of
greater than 110 gallons are allowed 0.3%. The other percentage option is found in the
Land Ban regulations (49 CFR part 268) which requires that no more than 1% of the
population can be over the treatment standard.
With this new system, the Agency must decide what percentage of the waste it
will allow to be over the regulatory limit and still classify the waste as non-hazardous.
To be the most protective of the environment, 0% should be adopted although it is
probably an unrealistic standard.
"Universe of whole" must be ciffldy fefined. This is not a scientific issue, but rather
a policy issue, The term requires clarity and specificity as to both time and space. Some
Proofed at EPA Wortshep nUmfy 16.1992
'wtt'i fftftTturm **-***!•' C-10
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examples might be: one day of production, one week of production, one pile, all piles
currently on the property, 100,000 Kg, etc. Defining 'universe or whole* as one waste
stream would ignore the temporal problems. Without knowledge of exactly what the
waste population is in terms of both time and space, it impossible to develop a testing
structure to characterize it
Presetted a EPA Wortshop JD Jtfy 16.1992
•Otanatnaag Heungaieau Mataials' CM1
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HETEROGENEOUS WASTE CHARACTERIZATION:
INDUSTRY PERSPECTIVE
David Reese
Safety-Kleen Inc.
PO Box 92050
Grove, IL 60009-2050
INTRODUCTION
Heterogeneous as defined by Webster in the context of a waste is "consisting of dissimilar
or diverse ingredients or constituents". The complexity of this issue is illustrated with a drum
of heterogeneous waste in figure 1.
Characterization of heterogeneous wastes presents a number of unique challenges for th
industrial community. The principal challenges are: sampling, methodology of analysis,
frequency of testing, and controlling/ reducing costs.
SAMPLING TECHNIQUES
Routine sampling techniques consisting of sample segregation, compositing,and particle
size reduction are often inappropriate when trying to homogenize a heterogeneous waste.
Collecting the sample can become a formidable task when the waste is comprised of multiple
large particle size components. SW-846 sampling containers often are not suitable for sample
containment and larger vessels are required. Loss of volatiles due to headspace in the vessels
affects the validity of the results. Present particle size reduction techniques such as grinding
only exacerbates the problem by driving off volatiles.
PraeuedaEfA WoitihcpmJafy 16.1992
•aivuaaiuig Haengauau Haloids • C-12
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TESTING REQUIREMENTS AND
State and Federal regulations often require extensive testing protocols in Waste Analysis
Plans (WAPs) and permits. Regulators routinely require the use of SW-846 analytical methods.
These methods often are not appropriate for a variety of waste streams (organic solvents, oily
wastes, by products of recycling such as distillation bottoms). The use of methods other than
SW-846 should be accepted for alternative test procedure approval and not rejected on the sole
basis they are not SW-846. Most of the quality assurance/ quality control principals and
guidelines can be incorporated into alternative test methods resulting in improved data with only
procedural and or hardware modifications. Unfortunately these methods are not considered valid
by regulators.
The present sampling and testing requirements fail to consider the volume and frequency
of the waste being handled. It is extremely costly to test every fifty-five gallon drum according
to SW-846 guidelines, while testing every incoming rail car might be feasible. Current sampling
frequencies often overlook one of the key issues racing a heterogeneous hazardous waste
handler, that being, the end use of the waste. If small volumes of wastes are going to be mixed
with other wastes for processing in terms of recycling, and the facility is permitted to handle the
waste, the result will have no impact on the process, thus, sampling and testing need to reflect
the use of the waste while providing a safe working environment. The product of the process
should become the focus of testing.
Continuing the status quo will drive many companies out of business and create large
companies which will monopolize hazardous waste handling while passing the costs on to the
generator and ultimately the consumer. This is due to the excessive costs associated with testing
every handled waste. Multiple testing of the same waste is redundant and provides no greater
assurance of safety, process control, product quality.
fraaaed at EPA Workshop JD July 16. 1992
•Oaraamang Haerogtaeata Maunelt' C~13
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CONCLUSIONS: DEVELOPING ALTERNATIVES
Recognize Alternative Test Methods
State and federal regulators must become accepting of industry generated methods of
analysis for complex waste streams handled on a daily basis.
Develop New Methods
EPA in conjunction with industry should work together to facilitate the rapid development
and approval of new methods. This could be accelerated by using industry developed methods.
Encourage Recycling
Recycling needs to be encouraged by minimizing input testing and focussing on
by-products of the process. When a facility is My permitted to handle wastes, analysis d
-------
Obstacle to Implementation
The largest obstacle for implementation of the above alternatives is the magnitude of the number
of individual state regulators with differing view points. The result of negotiating fifty different
WAPs in fifty states poses limitations on industries ability to comply fully at all times. It is
impossible for a business to operate fifty different ways on the same type of waste stream.
REFERENCE
Characterizing of Heterogeneous Wastes: Methods and Recommendations; EPA 600/R-92/033,
Feb. 1992
PnsaaeictEPA Wortshap UUOy 16.1982
•Oianaamt Haerogaiams Mattriali • C-15
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CHARACTERIZING HETEROGENEOUS MATERIALS-
SCIENTIFIC PERSPECTIVE
John P. Maney, Ph.D
Environmental Measurements Assessments
5 Whipple Road
Hamilton, MA 01982
INTRODUCTION
A discussion of heterogeneous waste characterization is best started with a brief review
of definitions.
of
m*!!^?^ ^T™6 " ""P**0" throughout.
(Webster s 7th Collegiate Dictionary)
After studying the above definitions and applying them to waste characterization it
becomes apparent that stapling of an ideal honlogeneous waae will always result in a ^
that represents the properties of the waste (assuming that the sampling process itself does not
introduce contamination or allows for selective loss of waste components).
Praaaat a EPA MMbfep mj^ U. 1992
-o^aatlmtaatnta>taattaltnilt. c_16
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Heterogeneous: consisting of dissimilar ingredients or constituents. (Webster's 7th
Collegiate Dictionary)
Unfortunately, many of the real-world wastes are not homogeneous, but are
heterogeneous, which makes collection of a representative sample a challenging task. Prior to
discussing the representativeness of heterogeneous wastes, the following points can be made
regarding homogeneity and heterogeneity.
• Homogeneity and heterogeneity are diametric terms.
• Homogeneity and heterogeneity are relative to objectives.
• Homogeneity and heterogeneity are related to spatial and temporal distribution.
• Homogeneity and heterogeneity are sample size dependent.
A determination regarding the homogeneity and heterogeneity of a waste is made by
comparing the visual, physical or chemical composition or properties of different samples. The
more heterogeneous a waste is, the less homogeneous it is and vise-versa. Thus, when either the
homogeneity or heterogeneity of a waste is defined the other is also defined. This relationship
should be kept in mind, since for the sake of readability, the remainder of this discussion will
often refer to only one term.
Heterogeneity is relative to objectives and perspective. A non-random mixture of fine
silver nitrate powder and large crystals of silver nitrate will be considered to be heterogeneous
by the analyst performing particle size determination while the analyst performing the TCLP for
lead would consider the material homogeneous. Likewise, while the chemical properties of
99.99999% pure uranium are homogeneous, a nuclear chemist may consider it highly
heterogeneous on an isotopic level.
fraaaed at EPA Workshop IB July 16.1992
'Otaraaeremg Haerotaieaa Materials' C-17
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Tto spaoal or temporal distribution of dissimilar „ omcmta&ms
grad-ents can aUo affect the measured heterogeneity of a waste. If a reprove dtah
over a greater ar« or length of time than that represented in a
rraponeats
of --«.*-. concerto of phe*,, ^ cyc.es fton, lOOppm to 5ppm „ ba
«» ^pm every ^o nunu.es. ^ be a tadon of wha, portions, or if u,e entire cyde is
included in sequential samples.
sample he.erogeneiry ^ depend on whether a sampk is not
enough u,
^
„ e enough to accommodate representative amounts of the various sized
to sample heterogeneity of the ^ste win vary dranati caUy and wi
whethertnesampkdidordidnotconuinacadmiumnugge,. H^ever, me he
. be subsuntiany kss if 30 gram samples are coUected and anaiyzed
.2e
^oth^ta^^
a waste wUl be
ity of
average properties .«. chemical ^^ rf „„
no,
A
:
C-18
-------
Representative Database: a database, generated by the collection and analysis of more
than one sample, which together represent the average properties of the universe or
whole.
It is often impossible to collect a single sample which is representative of a heterogeneous
waste. The average properties of a heterogeneous waste are better represented by collecting a
number of waste samples such, that all portions of the waste under study have an equal chance
of being sampled. Analyses of these samples can be compiled into a database which should be
representative of the waste. It is more correct to think of a representative sample in terms of a
representative database, which is closer to the statistical use of the term, sample.
In light of all the attention directed towards heterogeneous waste, it is important to note
that from a sampling perspective, the significance of heterogeneity is not in this quality, itself,
but in the fact, that heterogeneity hinders or prevents the generation of a representative database.
The need for representativeness is the driver behind the interest and studies into heterogeneous
waste characterization.
Random: being a member of, consisting of, or relating to a set of elements that have
a definite probability of occurring with a specific frequency; being or related to a set
whose members have an equal probability of occurring. (Webster's 7th Collegiate
Dictionary)
Randomness is a critical factor in the characterization of hazardous waste. Accurate
characterization requires that the sampling process reflect the randomness or lack of randomness
of the waste. If the waste parameter of interest is distributed in a random fashion a proper
randomly designed sampling program should generate a representative set of samples. If the
waste parameter is not randomly distributed (refer to discussion of strata in the following
section) then a simple random sampling plan may not accurately characterize the waste.
Praaued at EPA Worktop m July 16. 1992
•Onuaaenaig Heteragauaa Materials' C-19
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TYPES OF HETEROGENEOUS WASTE
If the avenge propel of the waste unit of interest is not reproducibly represented in
analytical samples, then the material is considered heterogeneous. Such heterogeneous wastes
can exist in many forms;
RANDOM HETEROGENEOUS
• Randomly heterogeneous in composition/property.
• Randomly heterogeneous in particle size.
• Randomly heterogeneous in particle size and composition/property.
NON-RANDOM HETEROGENEOUS (STRATIFIED)
• Non-randomly heterogeneous in composition/property.
• Non-randomly heterogeneous in particle size.
• Non-randomly heterogeneous in particle size and composition/propeny.
EXCESSIVELYNON-RANDOMHE^^
• Excessively non-randomly heterogeneous in composition/property.
• Excessively non-randomly heterogeneous in particle size.
*«••"»« 1- Panicle size and
Assu-niag that all panicle sizes in the waste can be accommodated by the
size and that the analytical method is applicable to all waste comment,, then
Proofed a EPA HMbkp m Jaty It. 1992
p&g Hatngeiamt ItataUt' C-2Q
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and non-randomly heterogeneous waste can be characterized by a database generated from the
collection and analysis of random or systematic samples. Regarding non-randomly heterogeneous
waste a more precise estimate of mean (representative) concentrations can be obtained with a
stratified sampling approach.
Excessively non-random heterogeneous wastes are defined as those wastes that have
such dissimilar components, that it is not practical to use traditional sampling approaches to
generate a representative database. Nor would the mean concentrations reflected in such a
database be a useful predictor of a given subset of the waste that may be subjected to
evaluation, handling, storage, treatment or disposal, (i.e. the level of uncertainty is too
great).
Stratum: a portion or subgroup having a consistent distribution of the target
parameter, and a different distribution than the rest of the waste.
Waste strata can be thought of as different portions of a waste population, which may
be separated in time or space or by waste component, and each portion has internally similar
concentration distributions of the target parameter, through-out. A landfill may display
spatially separated strata, since old cells may contain different wastes than new cells. A
wastepipe may discharge temporally separated strata, if night shift production varies from the
day shift.
There are wastes which do not display any identifiable temporal or spacial
stratification, yet the target compound distribution is excessively erratic. For these wastes it
may be helpful to consider a third type of stratification - stratification of the waste by waste
component.
Component: A waste component is any identifiable article, discrete unit or
constituent of the waste, which is randomly or non-randomly distributed through-out
the waste.
Praeaed at EPA Wortsliap m Jity 16.1992
'Oamaenang Heserogateaa Ualeneli • C~21
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Stratification by waste component is easily applied to wastes that contain easily
identifiable particles such as large crystals or agglomerates, rods, blocks, gloves, pieces of
wood, concrete, etcetera. Strata separated by waste component is a different but key concept.
Separating a waste into strata according to waste components is useful when a specific kind
of waste component is not randomly distributed through-out the waste and when a
contaminant or property of interest is correlated with the waste component. This type of
strata is different since the components are not necessarily separated in time or space but are
usually intermixed and the properties or composition of the individual components are the
basis of stratification. For example, automobile batteries which are mixed in an unrelated
waste would be a waste component which could constitute an individual strata if lead was a
target parameter. If one were to sequester the batteries they would have a consistent
distribution which was different from the rest of the waste. However, if the concentration of
the target parameter is similar in different components and the particle size is such that all
the components are represented in the chosen sample size, then there is no purpose in
stratifying by waste component. Strata, by component is an important mechanism for
understanding the properties of excessively non-random heterogeneous waste and for
designing appropriate sampling and analytical efforts for these types of waste.
Table 1 summarizes mechanisms for segregating strata as well as the discriminating
qualities of strata. Since the mechanism and qualities are independent of each other there are
a total of 9 possible types of stratified wastes.
fnsaaedatEfA Wariahap IB July 16.1982
orciauniMUrt*- C-22
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TABLE 1. Strata Considerations
Mechanism for Segregating Strata
Discriminating Qualities
Spatial
Composition/Property
Temporal
Particle Size
Component
Composition/Property and Particle Size
The contamination in different strata are often generated by different processes. The
different geneses of the contamination will usually result in a different concentration distribution
and mean concentrations. Thus, each strata will have their own distribution and mean
concentration levels. If a waste having strata of distinctly different concentration distributions
is sampled using a simple random sampling approach, the concentration distributions of the
different strata may result in a bi-modal or multi-modal distribution. Homogeneous and randomly
heterogeneous waste, which are not stratified will display a normal unimodal distribution. See
Figure 1.
Non-randomly heterogeneous waste will usually have a limited number of strata which
can be identified and sampled individually or sampled as one waste. When different strata are
sampled as one population, the properties of the different strata are averaged. If the different
strata are similar in composition, then the average concentrations will be a good predictor of
composition for subsets of the waste and will often allow the program objectives to be achieved.
As the difference in composition between different strata increase, the average values become
less useful in predicting composition/properties of individual portions of the waste, which may
be handled separately. In this later case, it is advantageous to sample the individual strata
separately and if an overall average of waste composition is needed, it is best calculated
mathematically using statistical information from each strata.
Excessively non-random heterogeneous waste has numerous strata, each of which contain
different distributions of contaminants and/or particle sizes, such that an average value for the
Presented at EPA Worttfep HI July 16.1992
ogeneou Mtuenals' C-23
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i
g
e
&
o
Concentration
Concentration
Concentration
Normal Bell Distribution
(Gaussian)
Bimqdal
Distribution
Figure 1: Types of Concentration Distributions
Praoued at EPA Werfafep m J*fy 16.1992
gauau Uatenals'
C-24
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waste would not be useful in predicting the composition or properties of individual portions of
the waste (i.e. statistically speaking the variance and standard enor of the mean will be large).
The line of demarcation between non-random heterogeneous and excessively non-random
heterogeneous waste is not hard and fast. A waste can be considered excessively non-random
heterogeneous when mean values will not be representative of most portions of the waste and
when it is so heterogeneous that the waste cannot be cost-effectively sampled using traditional
sampling approaches and meet the project objectives.
A theoretical example of an excessively stratified waste could consists of commingled
waste from:
Source A - which generated a waste of varying particle size with a mean antimony
concentration of 20ppb and a standard deviation of 7ppb.
Source B - which generated a waste of varying particle size with a mean antimony
concentration of TOOOppm and a standard deviation of SOOOppm.
Source C - which generated a waste of varying particle size with a mean antimony
concentration of 3% and a standard deviation of 2%.
Source D - which generated a waste of varying particle size with a mean concentration
of 81 % and a standard deviation of 17%.
To further complicate the above waste, imagine the waste being commingled with other
materials of various particle size that may or may not contain various contaminants in addition
to antimony.
To improve readability, the remainder of the document will refer to non-random
heterogeneous waste as stratified waste and excessively non-random heterogeneous waste as
excessively stratified waste.
framed at EPA Woriahop mj*fy 16.1992
•Chanacrmg Heterogeneous Materials ' C-25
-------
composition, property. vpartdesfea^Jnfef^^
Letters
different tenets.
Homogeneous
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BAABAAAABBAA'
/ABABABABABABAB'
/BABABABABABABABl
IABABABABABABABA)
IABABABABABABAI
VBBBBBBBBBBBBB,
IBBBBBBBBBB
Stratified
Excessively Stratified
or
Random Heterogeneous
:xicxfk
X X'
: x x x * x | x x x
: x x x xr "*
x x x x x>
'YYYY^-IYYYYYY
/YYYYYY*|'VYYYYY'
'YYYYY^tYYYYYYJ
'YYYYYJ £YYYYY'
^ZtZZ
Stratified
As can be seen in the stratified
heterogeneous waste above,
heterogeneity can vary over
time.
Figure 2: Types of Positional Distributions for
a Waste Unit Such as a Landfill
Praaati a EPA Worfafep mJmfy 16,1991
Haerofatetm} Uaienais'
C-26
-------
This figure depicts the process
by which a waste is classified
as a particular waste type.
This classification wiJl be
based upon knowledge of the
waste, observations, or ideally
- preliminary sampling of the
waste.
If no significant vanalion e
detected between random
samples, the waste can be
considered homogeneous.
The waste is a heterogeneous
waste it there is variation
between individual samples
If the waste constituents are
randomly distrfxjted
through-out the waste, the
waste would be a randmoly
heterogenous waste, if
information describes a
correlation between waste
variation and time or spatial
variations or with certain waste
components or particle size,
then the waste would be
classified as a stratified or
excessively stratified waste.
Wastes that can be
cost-effectively sampled to
meet project objectives would
be classified as stratified
wastes. Those wastes which
consist of such strata that they
cannot be cost effectively
sampled are classified as
excessively stratified waste
Knowledge
Observations
Preliminary Sampling
Homogeneous
Waste
Variation between
Samples
Randomly
Heterogenous
Vanalion Correlates with
Time, Space, Particle
Size, or Components
Stratified
Waste
Can Waste Be Cost-effectively
Sampled to Meet Objectives
Excessively Stratified
Waste
Figure 3: Process for Classifying Wastes
Presented a EPA Wortshap IB July 16.1992
'Characterizing Heterogeneous Materials'
C-27
-------
Table 2 details some of the issues and concentration distributions that are pertinent to the
different types of heterogeneous wastes. For example, sample size, the number of sample?
sample locations are not an issue when sampling a homogeneous waste, while they are critical
issues when attempting to collect a representative sample of a heterogeneous waste.
PARTICLE SIZE AND SAMPLING THEORY
As a result of a continuing need to improve environmental data, it has been recognized
that sampling is presently the greatest contributor to imprecision and inaccuracy. To minimize
this error, many have correctly turned to the mining industry, which has a relative wealth of
sampling theory and expertise. The theory and applicable expertise of the mining industry has
recently been documented by a recognized expert on sampling, Francis F. Pitard, (Pitard,
Francis F., "Pierre M. Gy's Sampling Theory and Sampling Practice, CRC Publishers). This
theory, which not only applies to field sampling but also to subsampling performed in the
laboratory - determines sample mass/volume as a function of the maximum particle size of the
material being sampled..
Based on the maximum particle size of a material, sampling theory suggests minimum
sample sizes (refer to Table 3.) and particle size reduction of the sample to minimize sampling
error. For example, a waste having a maximum particle size of 0.5 inches would require
collection and analysis of a minimum sample size of 2 Kilograms to keep the sampling error less
than 17%. Since a 2 kilogram sample is too large to be subjected to analysis, it would have to
be subjected to particle size reduction prior to analysis.
It would be very costly to routinely use existing sampling theory to minimize sampling
error. These increased costs would be driven by the large sample sizes and the requirement to
reduce particle size.
The large sample sizes, specified to minimize sampling error, would increase costs since;
Pnsatal a EPA Wontrtcp OUufy 16.1992
•Oraanro He***,**, Jterfab* C-28
-------
• Sample containers and coolers would be larger and more numerous
• Larger samples would be shipped
• Larger sample storage and sample handling areas would be needed
• Large volume of unused samples would increase disposal costs.
• Health and Safety costs associated with exposure to larger samples.
Particle Size Reduction, (PSR), also has a substantial impact on cost because of the
manpower and capital investment for the required crushing and pulverizing equipment. In
addition the following are reasons for concern if particle size reduction was to be implemented
on a large scale;
• Laboratory contamination from fines.
• Damage to instrumentation from fines.
• Difficulty in cleaning PSR equipment to prevent cross-contamination.
• Loss of volatile and labile compounds and elements.
• Generation of a sample which has different properties and thus yields different
analytical results than the original sample.
• Increased Health and Safety Costs
Fortunately, the costs of employing large sample sizes and particle size reduction can
often be minimized if the waste history and Data Quality Objectives are communicated to and
discussed with the lab staff and field personnel.
Prtsouat a EPA Workshop WJdy 16.1992
'Oanacnang Haerogenetmi Materials • C-29
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SUBSAMPLE SIZE
(grams)
1
2
3
4
5
10
20
30
40
50
75
100
MAXIMUM PARTICLE SIZE
(centimeters)
.1
.13
.14
.16
.17
.21
.27
.31
.34
.37
.42
.46*
other
Wa.cn , and s** can be contamina«ed
in numerous ways, fe most common
"
«*«*« described in
and multi-phased matures.
. lm
C-30
-------
How a contaminant will be dispersed in the matrix will be determined by the mechanism
of contamination, the type of contamination, the surface area and adsorptive properties of the
sample matrix, gravity, physical manipulation and the physical size of the contaminant at the
time of contamination. (Eventually, fate and transport will substantially affect dispersion of
contaminants.) The physical size of the contaminant can be referred to as the contaminant unit
and can be measured in centimeters. Liquids, dissolved contaminants and gases have a
contaminant unit on a molecular or atomic level, (e.g. atoms can be on the order of 1 X 10-8
centimeters in diameter). Solids and suspended solids contaminate on a microscopic to
macroscopic level, (i.e. their Contaminant Unit is equal to their particle size).
Particle size can have an impact on sampling error even when the contaminant unit is on
the atomic scale, if matrix particles are of different sizes and have different adsorptive
properties. If adsorptive properties are similar for different size particles, then the dramatically
larger surface area of smaller particles/volume would result in more atomic scale contaminants
being adsorbed to smaller particles. (Thus one could eschew particle size reduction, (PSR), and
still employ a smaller subsample size by excluding large particles, if the ease of using a smaller
sample size out-weighed the chance of a false-high concentration.)
When the contaminant unit is on a larger, particle scale then adsorptive properties of the
matrix will not affect contaminant distribution in the sample. For microscopic and macroscopic
particles, an accurate representation in the subsample will be affected by the number of particles
and the relative size of the particles to the subsample size. Microscopic particles will have a
contaminant unit substantially smaller than the sub-sample size and these small particles should
not be discriminated against during subsampling.
When the contaminant unit is macroscopic and approaches the size of the sample, the
error in sampling will increase, if large sample sizes or PSR is not employed. If the largest
particle size in the sample correlates with the contaminant unit, then the large sample size
specified by sampling theory pertains to the waste. As the contaminant unit becomes smaller as
Presetted a EPA Wortshap m Jufy 16. 1992
'Oianatreuig Heerogmtau Maenals • C-31
-------
compared to the size of the sample, the greater the opportunity to avoid PSR and to selectively
exclude larger particles from the sample without introducing substantial error., (If desirec
weight of the excluded particles can be used in the calculation of a final concentration. However,
this could result in a false low result, since the contamination, if any, associated with the large
particles is not accounted for.)
The mechanism of contamination, the type of contaminant and the contaminant unit will
impact the complexity and potential error of sampling. These impacts may be better understood
by reading the following examples.
Example 1
TYPE OF CONTAMINANT: Particles contaminated with lead
MECHANISM: Direct discharge of particle to soil
CONTAMINANT UNIT: Particles as large as 0.3 centimeters
AVERAGE LEAD CONCENTRATION: lOppm
HISTORY: A manufacturer of lead-alloy babbitt lining for bearings, stored its machining
waste in piles behind it facility. Periodically the machining wastes would be recycled into
new babbitt linings. After 50 years of employing this practice, the soil became
contaminated with particles of babbitt having a maximum particle size of 0.3 centimeters
The contaminated soil consisted mainly of fine silts with less than 10% consisting of
gravel with stones having diameters ranging from 2 to 3 inches. The sampling team
uncovered a problem when they referred to the specified "minimum sample size" for 3
inch particles (i.e. 450kg). The problem of large sample size was avoided, since the
sampling team was aware of the "Type of Contaminant" and the "Mechanism" of
contamination and the "Contaminant Unit". Knowing that lead contaminated particles
were discharged directly to the soil, the sampling team was able to discard the large
stones with the realization that by discarding the stones, the resulting lead concentrations
would be a worst case. (The small lead contaminated particles would preferentially exist
in the fine silts as opposed to being adsorbed to the large stones and if lead had
dissolved, the dissolved lead would tend to adsorb to the silt which has the much larger
surface area.) The sampling team collected approximately 250 mis of soil and delivered
them to the laboratory for analysis.
frotmled at EPA Variakaf IttJtfy U. 1992
******* tlcuHab- C-32
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The analyst referred to sampling theory (refer to Table 3.) and determined that the
minimum sample size for a sample with a maximum particle size of 0.3 centimeters was 30g.
(The small percentage of larger gravel was not used to determine the maximum particle size.)
The analyst split the sample into 30g aliquots and randomly chose one for analysis. Since
the analyst did not have particle size reduction equipment and the largest sample volume he
could analyze was approximately 10 grams, he split the chosen aliquot in thirds and analyzed
all three for lead. After analysis, the concentrations were averaged.
Example!
TYPE OF CONTAMINANT: Ionic lead dissolved in an aqueous solution (Atomic scale)
MECHANISM: Direct discharge to soil
CONTAMINANT UNIT: Atomic scale, (approximately 1 X 10-8 centimeters for atoms
and somewhat larger for ion diameters)
AVERAGE CONCENTRATION: 10 ppm
HISTORY: The above described babbitt manufacturer also employed an acid-treatment
process. The aqueous waste was discharged into a tank which allowed the lead
contaminated water to leach into the surrounding soils. The surrounding soils consisted
of fine silt with 15% of its volume consisting of stones ranging in size from 0 25 to 5
inches. The sampling team collected a 2 Kilogram sample to minimize the sampling
error. The samples were sent to the laboratory for analysis. Since the analyst knew that
the soil was contaminated by lead on an atomic scale, he discarded the small stones, split
the sample and analyzed a 2 gram aliquot. (The analyst knew that the much higher
surface area of the silt would have adsorbed orders of magnitude more lead than the
stones, so that this approach yielded a worst-case analysis. To check this hypothesis the
analyst performed an acid leach on a few stones and no detectable quantities of lead were
measured.)
The above examples show how, with knowledge of the type and mechanism of
contamination and the contaminant unit the sampling team and the analyst can decrease the costs
of handling large samples and particle size reduction without substantially increasing sampling
Presented at EPA Wortshcp m July 16.1992
'OaroaenuHg Heterogeneous Itaenali* C~33
-------
error. Without the site history, large sample sizes or particle size reduction would have
required or one would risk the introduction of a substantial error into the measurement process.
TTius communication with the analyst regarding the type and mechanism of contamination is an
important means of controlling costs and minimizing errors.
The above sampling strategies are not ideal since they allow for assumptions and
interpretation and these assumptions and interpretations could lead to substantial intentional and
unintentional errors. However, the above sampling strategies are more practical, more likely to
be implemented and may be a significant improvement over the alternatives. Lastly, when these
sampling strategies are implemented by an experienced personnel who are aware of the DQOs,
site history, the types and mechanisms of contamination and the contaminant unit, the errors
associated with interpretation and assumptions should decrease substantially.
It is important to note, that application of these sampling strategies to wastes is much
more difficult than for soils and subsampling of wastes may frequently require a strict
application of sampling theory. Wastes are a more difficult media, since the complexities
waste generation often preclude knowledge of how a contaminant of interest is dispersed within
a waste and whether distribution will be a function of particle size.
EXCESSIVELY STRATIFIED WASTES
The remainder of this discussion will concentrate on excessively stratified wastes the
most difficult wastes to characterize. Compositional or particle size heterogeneity or a
combination of both compositional and particle size heterogeneity can be the cause of excessive
stratification. This discussion will address each of these causes and will concentrate on sampling
issues, since sampling is now recognized as the greatest contributor to imprecision and bias.
However, before addressing the different causes of heterogeneity, it will be useful to
consider an issue which should be common to all waste characterization efforts.
Prattled a EPA Weriahep mjufy 16.1982
•Oanaa&tg Hemgaeau Maunals'
-------
The first step in characterizing any heterogeneous waste is to gather all available information on
the;
• Need for waste characterization,
• Objectives of waste characterization,
• Pertinent regulations, consent orders, and liabilities,
• Sampling, shipping and laboratory health and safety issues,
• Generation, handling, treatment and storage of the waste,
• Existing analytical data and exacting details on how it was generated,
• Treatment and disposal alternatives.
These types of information will be used fa the planning of the sampling and analytical
effort The planning process should be detailed and address the issues defined in EPA's data
quality objective (DQO) process. Tne differ disciplines ( e.g. sampBng, chemisay
engmeenng, statistics needed to properly understand and exploit the above types of information
must be present during the planning process. If enough information is available, the planning
process will uncover
objects. If information is lacking, a preliminary sampling effort would be advisable and if
done properly should detect the existence of excessively stratified wastes.
Excessively saatified waste can not be cos^ffectively characterized by traditional
memods and this fee, usually becomes apparent during the planning process. Tne Mowing
Ascussion will consider approaches which in effea will lessen the level of stratification and
allow for more cost-effective characterization. Some of these approaches will require changes
» objectives, waste handhng or disposal metals, and some will require compromises bu, aB
approaches will require the above types of information.
ProaaaleiEfA Wertshep OUtfy 16.1992
'Onmaeaang Heterogeneous Maurtali •
-------
Of the following types of excessively stratified waste, the difficulty in characterir
waste increases from those that have strata based solely on particle size, to those which cc
of compositional strata to those which have strata of varying composition and particle size. In
fact, the difficulty in characterizing waste, which consists of strata of different particle size, is
simply a matter of determining that composition is constant across different particle sizes. If the
composition is found to be constant across the different particle sizes, the waste should be easily
characterized.
The more problematic types of waste, which have enumerable strata of different
composition or a combination of different composition and particle size are much more difficult
to characterize. The approach to characterizing these wastes usually has to be determined on an
individual and unique basis.
Excessive Strata of Different Sized Particles
Wastes having excessive stratification due only to different sized particles will
definition have the same composition or property (i.e. homogeneous orrandomly heterogeneous)
through-out its different strata. The strata can be separated in space or in time. Unless one is
attempting to measure particle size, this waste is the simplest of the excessively stratified waste
types to characterize. All particles in these types of wastes are usually generated by the same
process, (e.g. smelter slag and the previous example of silver nitrate powder and crystals),
which is the reason for similar composition across all particle sizes.
The complexity of dealing with these types of wastes is in proving that the waste has
similar composition, (i.e. mean levels and concentration distribution of the parameter of interest)
across the varying particle sizes. This determination can be made by using knowledge of the
waste or by sampling the different sized particles to determine if there are significant
compositional differences. If the determination is made using knowledge of the waste, it is
advisable to at least perform limited sampling to confirm the determination.
Praeaal at EPA Worfafep OlJiify 16.1992
•Oanaamg Haengeaeaa Uamal* • C-36
-------
The characterization process is greatly simplified, once a determination has been made
that the waste has similar composition or properties across the various particle sizes. The
sampling and subsequent analysis can be performed on particles which are readily amenable to
the sampling and analytical process and the resulting data can be used to characterize the waste,
in its entirety.
It is important to periodically verify the assumption that the different particle sizes are
composed of materials having the same concentration levels and distributions of the contaminant
of interest. This verification is especially important when there are any changes to the waste
generation, storage, treatment or disposal processes. Similarity of composition between particles
has to be verified for each parameter of interest. The effect of different particle size must also
be considered when measuring properties such as the Toxicity Characteristic Leaching Procedure
(TCLP).
Excessive Strata of Different Composition or Composition and Particle Size
Wastes having excessive stratification due only to composition or property will have
similar particle size through-out its different strata. The strata may be separable in space, time
or by component or source. Stratifying the waste should simplify the characterization process.
Wastes having excessive stratification due to both composition/property and particle size
are usually the most difficult wastes to characterize. The strata can be separated in space, in
time, or by component or source.
Figure 4. summarizes an approach to characterizing these types of excessively stratified
wastes. If a waste is excessively stratified, traditional methods of sampling will not allow
objectives to be cost-effectively achieved. To cost-effectively sample an excessively stratified
waste, one must use a non-traditional approach. The non-traditional approach may involve
modification to the sampling, sample preparation or analytical phase of the process. If after
Presented el EPA Woi+shop OlJufy 16.1992
'Oiaraamang Haeragauaa Materials' C-37
-------
Figure 4. Approach for the Characterization of Heterogeneous Waste
Is Waste
Excessively Stratified?
I
Can Sampling Be Modified?
•I-
Can Sample Prep
Be Modified?
Change Handling,
Treatment,
Disposal of Waste Or
Target Parameter
Change Sampling
and
Analysis
Objectives
N
N
N
N
Use Traditional Random,
Stratified or Systematic
Sampling
Will Modified
Approach
Allow Waste
to Be
Cost-Effectively
Sampled
And
Objectives
To Be Met?
Sample
Waste
Figure 4: Approach for the Characterization of Heterogeneous Waste
PraauataEPA WorUiop m Jufy 16.1992
Oaemgouoa UataUi"
C-38
-------
modifying the approach to sampling and analysis the objectives still can not be achieved in a
cost-effective manner, then the original plan of waste handling, treatment or disposal has to be
examined and changed so the waste can be characterized according to new and achievable
objectives.
The following subsections discuss approaches that can be employed to make excessively
stratified waste more amenable to a cost-effective sampling approach.
Design of the Sampling Approach
The first efforts to resolve the difficulty in characterizing an excessively stratified waste
are usually focused on the sampling aspects of the project. This is a logical place to start and,
if a successful sampling approach is designed, the project objectives can be cost effectively
achieved.
The difficulty in sampling excessively stratified waste can result from:
1) Various particle sizes and waste consistency which makes sampling difficult and
traditional sampling approaches cost prohibitive.
2) Extraordinary concentration gradients between different components or
enumerable strata that lead to such excessive variance in the data, that project
objectives can not be achieved.
3) Wastes which exhibit both of the above properties.
A strategy for designing a sampling plan for such excessively stratified waste includes
the following five steps;
fraaaed a EPA Worishop m Jufy 16. 1992
•Ounaenaig Hettrogeuaa Matenoli • C-39
-------
1) Select the target parameters.
2) Determine whether these parameters are correlated with; particle size space time
components, or sources.
3) Determine if any waste components or strata can be eliminated from sampling
because they do not contribute significantly to the concentration of the target
parameter.
4) Determine if small particles in a stratum represent the stratum as well as large
more difficult to sample particles. If yes, sample the smaller particles and only
track the volume contribution of the larger particles. (See Particle Size and
Sampling Theory).
5) Determine if contamination is innate or surface adsorbed. Is the contamination
surface adsorbed which would allow the material to be representatively sami
by wipe sampling? Can large particles be wiped and smaller particles extracted,
leached or digested. Can waste be stratified according to impervious and non-
impervious waste and sampled and analyzed accordingly?
To understand how this strategy would work, consider a hypothetical scenario - a storage
area containing 4000 drums of waste generated over a 15 year period. The drum contents are
excessively stratified and contain a myriad of wastes from process waste; destruction and
construction debris such as wood, concrete; lab wastes including broken glassware, paper, empty
bottles; etcetera. The appearance of the combined drum contents could best be described as a
municipal landfill in drums which appears impossible to characterize.
Praaaed at EPA Wartahop OUtfy 16.1991
aerogouaa Materials- C-40
-------
1) WHAT ARE THE TARGET PARAMETERS?
None of the waste contents are known to be listed waste so the target parameters are the
TCLP and other hazardous waste characteristics. In addition, groundwater modeling has
indicated that the storage area is the source of a plume contaminated with solvents and
beryllium.
2) ARE THE TARGET PARAMETERS CORRELATED WTTH AN IDENTIFIABLE
STRATA OR SOURCE?
The source of beryllium is traceable to one process, whose waste should be easily
identifiable if drum markings are not legible enough to determine the source. The solvents are
likewise traceable to a machine shop which would have disposed of its waste in easily identified
drums.
Testing will have to be performed to determine if there is any correlation with particle
size, space, time or components in the waste.
3) CAN ANY WASTE COMPONENTS OR STRATA BE ELIMINATED?
Historical information indicated that 400 drums of construction debris were generated
during construction of a new warehouse. The information indicates that the virgin nature of the
materials may make these drums candidates for not sampling or less intensive sampling.
Likewise, the source of beryllium contamination is a beryllium sludge which exists in
drums by itself or in drums commingled with shredded packing material and laboratory wastes
that were generated during physical testing of the beryllium product. If the materials commingled
with the beryllium waste are known not to be a source of contamination, the commingled
Wortshop HUufy 16.1992
ngauaa Maunati • C-41
-------
material can be discriminated against during sampling and only the beryllium sludge
and the volume contribution of the commingled material noted.
4) ARE CONTAMINATION LEVELS CORRELATED WITH PARTICLE SIZE?
Some of the older beryllium sludge has dried and formed a cementaceous aggregate of
different particle sizes. Since the sludge is known to be homogeneous within a batch by process
knowledge and preliminary sampling data, sampling can be restricted to the more easily sampled
- smaller particles sizes.
5) IS CONTAMINATION INNATE OR SURFACE ADSORBED
The waste from the machine shop consists of varied material from fine metallic filings
to large chunks of metal and out-of-specification metal product. Since the only contamination
in the machine shop is solvents and cutting oils and the waste matrix is impervious,
contamination is surface adsorbed in nature. Thus sampling of these wastes will consists of the
sampling of fines which will be subjected to extraction, wipe sampling of the large metallic
objects and notation of the volume contributions of the different particle sizes.
It is essential that all assumptions , (i.e. any correlations), be verified by at least
knowledge of the waste and preferably confirmed by exploratory sampling and analyses.
In the above hypothetical case, the proposed strategy for characterizing the 4000 drums
resulted in:
The identification of two large strata that constitute the majority of the waste (i.e. the
beryllium sludge and the solvent and cutting oil contaminated machine shop waste).
The elimination of the need to sample 10% of the drums, (i.e. the construction debris),
if preliminary testing verifies waste disposal information.
Framed at EPA Wartihop aUtfy 19.1992
•Oanaemt Hamgaiam, lia*nali' C-42
-------
Simplified sampling of the beryllium commingled waste by restricting sampling to the
beryllium sludge and not the other commingled materials.
Simplified sampling of the cementaceous beryllium sludge by limiting sampling to the
more easily sampled small particles.
Simplifying the sampling of the machine wastes since the source of contamination is
surface adsorbed and not innate to the waste materials.
A less expensive and doable sampling design which will result in a more precise estimate
of the mean and will generate strata specific information which will be valuable if the
strata are eventually treated separately.
The following subsections describe additional strategies that can be employed if the above
sampling strategies are not applicable to a waste or if they are applicable but by themselves will
not allow the project objectives to be cost-effectively met.
Modification of the Sample Preparation Method
As discussed in the Introduction, heterogeneity is analytical sample size dependent. The
greater the particle size and the greater the variance of the concentration of the target parameter,
the greater the heterogeneity for a given analytical sample size. To minimize the measured
heterogeneity and to accommodate large particle sizes, traditional sample preparatory methods
can be altered.
In the laboratory, the term "sample preparation" is commonly meant to include two
separate steps; 1) the subsampling of a field sample to generate an analytical sample, and 2) the
preparation of the analytical sample for subsequent analysis.
Regarding subsampling, the previously discussed logic for field sampling (refer to Section
3.1.1) is also applicable for the generation of analytical samples. That is, knowledge of
concentration distributions within the waste can be used to simplify subsampling by:
PresentedaEfA Workshop OlJiJy 16.1992
'Otamaersaig Heterogeneous Uolenois ' C-43
-------
1) Eliminating any waste components or strata that do not contribute significant- »o
the concentration of the target compound;
2) Discriminating against large particles and only select small particles if small
particles represent the waste as well as large particles; and.
3) Surface wiping larger particles and extracting or digesting fines if surface
contamination is the source of the target parameter.
If the above approaches are not applicable to a field sample, the field sample will have
to be subjected to particle size reduction (PSR) prior to subsampling or the sample preparation
method will have to be modified to accommodate the entire field sample.
PSR is useful for handling field samples, which have particles too large for proper
representation in an analytical subsample. The intent of PSR is to decrease the maximum particle
size of the field sample so that the field sample can then be split and or subsampled to gen
a representative subsample. The difficulties in applying PSR to waste samples are:
1) Not all materials are easily amenable to PSR (e.g. stainless steel artifacts);
2) Adequate PSR capabilities and capacities do not normally exist in environmental
laboratories;
3) PSR can change the properties of material (e.g. teachability)
4) PSR can be a source of cross-contamination; and
5) PSR is often not applicable to volatile and labile compounds.
fraaaed at EPA Wortahe? HtJify 16.1992
gauaui Haaiels' C-44
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Modification of sample preparative methods can include the extraction, digestion or
leaching of much larger sample masses than specified. The advantage of this approach is that
the resulting extract, digestate or leachate are relatively homogeneous which simplifies
subsampling. This approach is particularly important for volatile organic compounds which may
suffer from substantial losses if subjected to PSR. For volatile organic compound analysis, larger
portions of the wastes can be subjected to methanol extraction or possibly the entire field sample
could be subjected to heated headspace analysis as one sample or as a series of large aliquots.
Prior to modifying a sample preparatory method, especially a method associated with a
property such as the Toxitity Characteristic Leaching Procedure (TCLP), it is advisable to
consult the end-user of the data and the pertinent regulator if appropriate.
Modification of Analytical Method
The analytical phase of a sampling and analytical program allows another opportunity to
simplify the characterization of an excessively heterogeneous waste. Examples of different
classes of analytical methods are ;
Screening methods,
Portable methods,
Field Laboratories methods,
Non-intrusive methods,
Innovative methods, and
Fixed laboratory methods.
Screening, portable and field laboratory methods have the distinct advantage that they
allow for the cost-effective analysis of more samples. These methods not only generate more
precise data but the greater number of samples make it easier to detect correlations between
concentration levels and waste strata or components. Also some screening methods may analyze
a larger sample volume than what is traditionally submitted to a fixed laboratory.
fraaaei at EPA Worts/up flj Jufy 16.1992
'Qumaersmt Heterogeneous Uaunalt • C-45
-------
Non-intrusive methods can be useful when there are health and safety issues regarding
exposure to the waste. These methods may also be used to qualitatively or semi-quantitaH—'v
evaluate large volume wastes.
An EPA Document entitled "Characterizing Heterogeneous Wastes EPA 600/R-92/033"
has a solid discussion of non-intrusive methods and new methodologies that are being developed
for the characterization of heterogeneous wastes.
Modification of the Waste Handling, Treatment Disposal Plan
If the modifications discussed in the previous subsections are not applicable to a given
waste or when they are applicable but still do not allow the objectives to be cost-effectively met,
then the reasoning behind the original program must be examined. The original need behind the
waste characterization objectives has to be examined and an approach for simplifying the
characterization process must be devised.
For example, assume that the need behind waste characterization objectives for a ce
program was the common requirement to determine if a waste is hazardous prior to waste
disposal. An initial attempt to characterize the waste; 1) railed to meet the objective, 2) indicated
that the waste was excessively stratified, and 3) proved that portions of the waste are hazardous.
After reviewing this preliminary information and the costs to attempt a defensible
characterization of the waste, it could be decided that all the waste will be assumed to be
hazardous and treated as hazardous waste. Under this scenario, the needs change and now
compliance with the land-ban requirements may become the issue. Assume that the waste was
incinerated, then the less heterogeneous and more easily sampled incinerator ash would be
sampled in lieu of the original excessively stratified waste.
An other example would be a large laboratory operation that generates drums of gas-
chromatography (GC) vials containing dissolved standards, solvents and numerous contaminants
fraaaed a EPA WorfaAop OlJafy 16.1992
•Ounaavmg Hoerogtnami Mauriolt- C-46
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extracted from samples of different origins. Although, the vial contents were individually
analyzed by GC for certain parameters, the contents were not analyzed for enough parameters
to characterize the waste. A quick review of this waste would preclude further and cost
prohibitive analyses of every vial. Thus, an alternative approach would have to be devised. An
alternative approach could require that the vials be crushed and the vial contents and the solvent
used to rinse the broken vials would be collected in a receiving drum. This approach would
convert drums which contained hundreds of different vials, each of which could have their own
independent concentrations of contaminants, into two relatively homogeneous waste strata, i.e.
solvent rinsed glass and contaminated solvent.
CONCLUSIONS
The previous discussion reviewed heterogeneity issues and proposed a single and
systematic approach to the characterization of hazardous waste. This approach is based upon the
evaluation of wastes in terms of their degree and type of stratification - a factor which drives
the degree of difficulty in sampling a particular waste.
This discussion also proposed stratification in an additional dimension than the traditional
spatial and temporal dimensions. The stratification of waste according to waste components and
sources can simplify the characterization process and provide needed strata information.
This systematic approach and the additional mechanisms for stratifying waste is intended
to aid in the characterization of wastes especially those that are excessively stratified.
Prague! at EPA Wortsliap OlJiify 16.1992
'Otaraaotaag Heterogeneous Hotmail• C-47
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Appendix XIII
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Appendix XIII
Improper Hazardous Waste Characterizations:
Financial and Compliance Implications
-------
WILLIAM F. COSULICH ASSOCIATES, P.C.
ENVIRONMENTAL ENGINEERS, SCIENTISTS AND PLANNERS
QUALITY ASSURANCE IN
ENVIRONMENTAL MONITORING
IMPROPER HAZARDOUS WASTE CHARACTERIZATIONS
FINANCIAL AND COMPLIANCE IMPLICATIONS
By
RICHARD M. WALKA
WILLIAM F. COSULICH ASSOCIATES, P.C.
WOODBURY, NY
(516) 364-9880
FRANK A. LANGONE
INTERNATIONAL BUSINESS
MACHINES CORPORATION
RICHARD P. RUSSELL
WILLIAM F. COSULICH ASSOCIATES, P.C.
ERC013
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IMPROPER HAZARDOUS WASTE
CHARACTERIZATIONS—FINANCIAL AND
COMPLIANCE IMPLICATIONS
Richard M. Walka
Richard P. Russell
Frank A. Langone
This paper is not a "how to" on when or under what circumstances one is required to
make a hazardous waste determination, or a primer reviewing a step by step approach to
rendering a proper characterization. Rather, the purpose of mis paper is to illustrate why
generators of waste should render accurate and well-founded determinations as to whether the
material is a hazardous waste pursuant to appropriate federal and/or state requirements. The
paper will also review the potential financial and compliance implications of managing
nonhazardous waste as hazardous waste in New York State. When waste is classified as
hazardous, its management requires the use of a manifest for off-site transportation. Utilizing a
manifest results in a number of explicit and implicit protections and liabilities. The implications
of using the hazardous waste manifest will be a major portion of the discussion.
The recognition of the uniform hazardous waste manifest among waste generators across
the nation is probably second only to the IRS 1040 Form. Since its creation by the
Environmental Protection Agency in the late 1970's, the hazardous waste manifest and the vast
information network it supports, remains the cornerstone of RCRA's national "cradle to grave"
hazardous waste tracking system. We will explain why the manifest possibly has more
responsibilities man protections associated with its use.
It has been our experience that some clients firmly believe that "when in doubt" waste
should be classified as hazardous. These clients assume that transporting the material as a
hazardous waste, with an accompanying manifest, is always "safer", affording them some
protection that ordinarily would not otherwise exist. This "protective filer" mentality has a
number of enforceable regulatory liabilities, as well as financial implications, associated with it
which can be burdensome when the facility actually does not generate any hazardous waste.
These considerations are in addition to the high cost of hazardous waste disposal.
Obviously, this paper supports utilizing the hazardous waste manifest when appropriate,
and fosters the concept of proper and judicious hazardous waste characterizations. However, we
are opposed to using hazardous waste manifests when solely generating/transporting,
nonhazardous industrial waste.
Before we discuss the financial and compliance liabilities associated with transporting
manifested nonhazardous waste, we will briefly describe the hazardous waste program.
010RMWJUT
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WHEN IS A WASTE A HAZARDOUS WASTE?
Section 1004(5) of RCRA defines hazardous waste as a "...solid waste, or combination
of solid wastes, which because of its quantity, concentration or physical, chemical or infectious
characteristics may:
(A) cause or significantly contribute to an increase in mortality or an increase in serious
irreversible, or incapacitating reversible illness;
or
(B) pose a substantial present or potential hazard to human health or the environment
when improperly treated, stored, transported or disposed of, or otherwise managed."
While this statutory definition is subjective, it clearly states that in order for a material
to be a hazardous waste, it must first be a "solid waste", as defined by RCRA. In order for a
solid waste to be defined as a hazardous waste, it must meet the following conditions:
Is not excluded from regulation as a hazardous waste, and;
Exhibit any of the characteristics of a hazardous waste, and/or;
• Be named a hazardous waste and listed by regulation as such, or;
• Is a mixture containing a characteristic waste/listed hazardous waste and a
nonhazardous solid waste, unless the mixture is specifically excluded or no longer
exhibits any of the characteristics of hazardous waste. A mixture containing a
nonhazardous waste and a listed hazardous waste will remain a listed hazardous
waste.
In the preceding section, we provided a general definition of hazardous waste. However,
there are two principle mechanisms to determine whether a waste is a hazardous waste. First,
one must determine if it is a "listed waste," so named because it is specifically listed as such by
the EPA or a State as part of its hazardous waste regulations. Secondly, based on knowledge or
laboratory analysis, one must determine if it exhibits any characteristics of a hazardous waste:
ignitability, corrosivity, reactivity and toxicity.
CHARACTERISTIC WASTE
Ignitabilirv
A solid waste that exhibits any of the following properties is considered a hazardous waste
due to its ignitability:
• A liquid, except aqueous solutions containing less then 24 percent alcohol, that has
a flash point less than 60°C(140°F);
010RMW.RPT
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• A nonliquid capable under normal conditions of spontaneous and sustained
combustion;
• An ignitable compressed gas in accordance with Department of Transportation
(DOT) regulation;
• An oxidizer per DOT regulation.
EPA's reason for initially including ignitability as a characteristic was to identify waste
that could cause fires during transport, storage or disposal.
Corrosivitv
A solid waste that exhibits any of the following properties is considered a hazardous waste
due to its corrosivity:
An aqueous material with pH less than or equal to 2.0 or greater than or equal to
12.5;
A liquid that corrodes steel at a rate greater than 0.25 inch per year at a temperature
of 55°C (130°F).
EPA chose pH as an indicator of corrosivity because waste with high or low pH can react
dangerously with other waste or cause toxic contaminants to migrate from certain waste. Steel
corrosion was chosen because waste capable of corroding steel can escape from its container.
Reactivity
A solid waste that exhibits any of the following properties is considered a hazardous waste
due to its reactivity:
• Normally unstable and reacts violently without detonating;
• Reacts violently with water;
• Forms an explosive mixture with water;
• Generates toxic gases, vapors or fumes when mixed with water;
• Contains cyanide or sulfide and generates toxic gases, vapors or fumes at a pH of
between 2 and 12.5;
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• Capable of detonation if heated under confinement or subjected to strong initiating
source;
• Capable of detonation under standard, temperature and pressure;
Listed by DOT as Class A or B explosive.
Reactivity was chosen as a characteristic to identify unstable waste that can pose a
problem at any stage of that waste management cycle.
Toricity
The toxicity characteristic test is designed to identify waste likely to leach particular toxic
constituents into the groundwater as a result of improper management.
To ascertain if a solid waste is hazardous because of the toxicity characteristic,
constituents are extracted from the waste in a manner designed to simulate the leaching action
which occurs in landfills. The extract is then analyzed to determine if it possesses any hazardous
constituents listed in Table 1. If the concentrations of the toxic constituents are equal to or
exceed the regulatory levels listed, the waste is classified as hazardous.
Characteristic hazardous wastes are defined by certain physical/chemical criteria which
may require a representative waste sample analysis by the generator. The Toxicity subcategory
is more likely than the other characteristics to require chemical analysis. Consequently, a waste
generator must be very careful in selecting/paying for the correct protocols to characterize his
waste for Toxicity.
There are financial implications tied to Toxicity wastes in two areas. First, the prescribed
leaching protocol (Toxicity Characteristic Leaching Procedure - TCLP) is an expensive protocol
to run. However, it may not be required if the waste is a 100% solid matrix or a solid/water
matrix, for which a total constituent analysis has been performed. The extraction is also not
required if the waste is a liquid with no solid phase. Thus, an understanding of when the TCLP
is needed has a significant influence on the cost of waste characterization.
Secondly, it is important to compare the appropriate Toxicity analytical result with the
regulatory level to avoid incorrect hazardous waste determinations (false positives) which will
result in the compliance/financial implications that will be discussed below. For example, the
total constituent analysis of a 100% solid waste sample would be reduced by a factor of 20,
before comparing it to the regulatory level (the 1 to 20 factor is derived from the 1 to 20 dilution
factor that is part of the TCLP protocol).
A good source of information on the entire Toxicity category and, in particular, on
correctly using the TCLP procedure/interpreting analytical results is: "Technical Assistance
Document for Complying with the TC Rule and Implementing the Toxicity Characteristic
Leaching Procedure (TCLP)", May 1993, U.S. EPA-Region H.
010RMWRPT
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Table 1
TOXICITY CHARACTERISTIC CONTAMINANTS
AND REGULATORY LEVELS
EPA Hazardous
Waste Number
D004
DOOS
D018
D006
D019
D020
D021
D022
D007
D023
D024
D02S
D026
D016
D027
D028
D029
D030
D012
D031
D032
O033
D034
0008
DOI3
0009
D014
D035
D036
D037
D038
D010
D011
D039
O01S
D040
D041
D042
D017
D043
Amse
Cadmium
Carbon tamchlonde
Chunhne
Chlonbenxene
Chloroform
Chromium
o-Cnaol
m-Cresol
p-Ciool
Cresol
2.4-D
I ,2-Dichloroethane
1.1 -Dtchloroethy lone
2,4-Dmarotohjene
Endrm
Heptachlor (and m hydroxide)
Hexachloro-1,3-butadiene
Lead
Lmdme
Mettoxyelor
Methyl ethyl ketone
Nitrobenzene
Pyridino
Silver
TQtncUorocthyjcno
Tncbloroetfaylene
2.4,5-Tnchlorophenol
2.4,6-Tnchlorophenol
2.4,5-TP (Sdvex)
Vmyl chlonde
Ctutmlc Toxicily Ref-
! Level (me/tt
005
10
0.005
001
0005
00003
1
006
005
2
2
2
2
01
0075
0005
0007
00005
00002
0.00008
00002
0005
0.03
0.05
0004
0002
01
2
0.02
1
004
001
0.05
0007
0005
0005
4
002
0.01
0.002
MCI.
MCL
MCL
MCL
MCL
RSD
R£D
RSD
MCL
RfD
RfD
RfD
RfD
MCL
MCL
MCL
MCL
RSD
MCL
RSD
RSD
RSD
RSD
MCL
MCL
MCL
MCL
RfD
RfD
RfD
RfD
MCL
MCL
RSD
MCL
MCL
RfD
RSD
MCL
MCL
* MCL - Maximum Contaminant Level or National Interim Primary Drinking Water Standard
RSD - Risk-Specific DOM
RfD • Reference Dose
* The regulatory level equab the chrome toxicity reference level mnei a dilution/attenuation factor (DAF) of 100, unle
Regulatory
Levdftng/B*
5.0
100.0
0.5
10
0.5
0.03
100.0
60
SO
200.0*
200.0*
200.0*
200.0*
100
7.5
0.5
07
013'
0.02
0008
0.13'
0.5
30
5.0
04
0.2
100
2000
2.0
1000
SO"
10
50
07
05
05
4000
20
10
02
oted
' If o-, m-. and p-
Oil
aona cannot be differentiated, the total creaol (D026) concentration a used Note that D026 was added to the final rule for this
purpose, but is not a new constituent.
* The quamitanco limit (i e. five tunes the detection limit) is greater than the calculated regulatory level; thus, the quanntation limit becomes the regulatory level
Source: 55 QL 11804 and 11815-11816
1-24-94
010RMW.RPT
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LISTED WASTE (SPECIFIC/NONSPECIFIC)
As we mentioned above, solid waste is considered hazardous waste if it is "listed" as one
of the following:
• Nonspecific source waste - These are generic wastes, commonly produced by
manufacturing and industrial processes. Examples from this list include spent
halogenated solvents used in degreasing and wastewater treatment sludge from
electroplating processes.
• Specific source waste - This list consists of wastes from specifically identified
industries such as wood preserving, petroleum refining and organic chemical
manufacturing. These wastes typically include sludges, still bottoms, wastewaters,
spent catalysts and residues; e.g., wastewater treatment sludge from the production
of pigments.
• Commercial chemical products - The third list consists of specific unused
commercial chemical products or manufacturing chemical intermediates. The key
criterion for this category is that the waste is unused, e.g., off-spec or spilled
materials. This list includes chemicals such as chloroform and creosote, acids such
as sulfuric acid and hydrochloric acid, and pesticides, such as DDT and kepone.
These lists were developed by examining different types of waste and chemical products
to ascertain if they:
• Exhibit one of the four characteristics of a hazardous waste(listed above);
Meet the statutory definition of hazardous waste;
• Are acutely toxic or acutely hazardous;
• Are otherwise toxic.
It should be noted that individual States may designate additional materials as listed
hazardous wastes. For example, New York State regulates PCB wastes as listed hazardous
wastes (B-codes).
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REGULATORY REQUIREMENTS
If a facility produces hazardous waste based on the regulatory criteria discussed above,
it may be classified as a hazardous waste generator. Hazardous waste generators are the first link
in the "cradle to grave" hazardous waste management system established pursuant to the Resource
Conservation and Recovery Act (RCRA). Generators of 100 kilograms of hazardous waste or
1 kilogram of acute hazardous waste per month must comply with certain enforceable generator
standards.
The pretransport regulatory requirements for hazardous waste generators include:
• Obtaining an EPA ID number. One way that EPA monitors and tracks generators
is assigning each generator a unique identification number. Without this number,
the generator is barred from treating, storing, disposing, transporting or offering for
transport any hazardous waste to any transporter or treatment, storage or disposal
facility;
• Adhering to procedures for handling hazardous waste before transport;
• Manifesting hazardous waste for off-site transportation;
• Maintaining a 24-hour Emergency Contact for each shipment;
• Record keeping and reporting;
• Proper packaging to prevent leakage of hazardous waste during normal transport
conditions and in potentially dangerous situations (e.g., when a drum falls out of a
truck);
• Identifying the characteristics and dangers associated with the waste being
transported through labeling, marking and placarding of the packaged waste;
• Preparing applicable Land Disposal Restriction (Land Ban) shipping notices.
It is important to note that these pretransport regulations only apply to generators shipping
waste off-site.
In addition to the requirements outlined above, EPA and authorized states also developed
pretransport regulations for accumulation of waste prior to transport. A generator can accumulate
hazardous waste on-site for 90 days or less without a permit, as long as the following
requirements are met:
Proper Storage - The waste is properly stored in containers or tanks marked with the
words "Hazardous Wastes" and the date on which accumulation began. The waste
must also be inspected at least weekly and inspections records maintained.
010RMW.RPT
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• Emergency Plan - A contingency plan and emergency procedures to use in an
emergency must be developed.
• Personnel Training - Facility personnel must be trained in the proper handling of
hazardous waste.
• Preparedness and Prevention Measures - Providing adequate security measures,
signage, and communication systems.
The 90-day period allows a generator to collect enough waste to make transportation more
cost-effective; that is, instead of paying to haul several small shipments of waste, the generator
can accumulate waste until there is enough for one large shipment.
THE HAZARDOUS WASTE MANIFEST
The manifest is the fundamental element of the hazardous waste tracking system. The
uniform hazardous waste manifest is the document which accompanies shipments of waste and
tracks the material from the generator (the cradle) to the ultimate disposal facility (the grave).
The RCRA manifest requires the following information:
• Name and EPA identification number of the generator, transporter(s) and the facility
where the waste is to be treated, stored or disposed;
U.S. DOT description of the waste being transported;
• Quantities of waste being transported; and
• Address of the treatment, storage or disposal facility to which the generator is
sending the waste.
• 24-hour emergency contact telephone number.
It is especially important for the generator to prepare the manifest properly, since the
generator is responsible for the hazardous waste produced and its ultimate disposition.
Waste Minimization
When Congress passed the Hazardous and Solid Waste Amendments (HSWA) in 1984,
it established a framework aimed at eliminating specific forms of waste management such as land
disposal, in favor of more technologically advanced, permanent destruction methods, such as
incineration.
Among its complex and far reaching provisions, the HSWA contained a statutory
provision which initiated waste minimization criteria. Sections 3002(a)(6), regarding the
preparation of biennial waste reduction reports, and 3002(b) of HSWA, entitled, "Waste
Minimization", require generators of hazardous waste to practice and report on waste
minimization activities. It requires generators of hazardous waste to sign a specific certification
010RMW.RPT
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on the manifest indicating that they are doing all that is "economically practicable" towards
reducing the volume or quantity and toxicity of the hazardous waste generated at a facility. It
is a signed certification that generators are in full compliance with HSWA waste minimization
criteria.
Section 3002(b) of HSWA, entitled "Waste Minimization", reads as follows:
"(b) Waste Minimization - Effective September 1, 1985, the manifest required by
subsection (a)(5) shall contain a certification by the generator that -
(1) the generator of the hazardous waste has a program in place to reduce the
volume or quantity and toxicity of such waste to the degree determined by the
generator to be economically practicable; and
(2) the proposed method of treatment, storage, or disposal is that practicable
method currently available to the generator which minimizes the present and
future threat to human health and the environment."
With regard to the requirement for biennial reporting of waste reduction efforts to
regulatory agencies, Section 30021(a)(6) reads as follows:
"(6) submission of reports to the Administrator (or the State agency in any case in
which such agency carries out a permit program pursuant to mis subtitle) at least
once every two years, setting out -
(A) the quantities and nature of hazardous waste identified or listed under this
subtitle that he has generated during the year;
(B) the disposition of all hazardous waste reported under subparagraph
(C) the efforts undertaken during the year to reduce the volume and toxicity
of waste generated; and
(D) the changes in volume and toxicity of waste actually achieved during the
year in question in comparison with previous years, to the extent such
information is available for years prior to enactment of the Hazardous and
Solid Waste Amendments of 1984."
In addition to these enforceable waste reduction mandates brought about by the HSWA
manifest certification, many states have already passed additional statutes and regulations to
address pollution prevention and waste reduction.
For example, in August 1990, New York State passed a law requiring facilities that
generate and have the potential to release hazardous wastes and toxic substances into the
environment reduce, to the maximum extent possible the volume or quantity and toxicity of
wastes, whether emitted into the air, discharged into the waters, or treated and disposed of in a
010RMW RPT
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permitted facility. The waste reduction may be achieved by implementing technically feasible
and economically practicable waste reduction technology, process or operation changes. The
legislature declared that implementing such measure will help the State achieve an overall
reduction in the generation and release of hazardous waste of fifty percent over the next ten (10)
years.
This law requires generators of hazardous wastes to prepare, implement and submit a
Hazardous Waste Reduction Plan (HWRP) to the New York State Department of Environmental
Conservation (NYSDEC). The HWRP, which is reviewed for acceptance by NYSDEC, must be
updated biennially and annual status reports must be submitted. Failure to submit an acceptable
plan precludes the generator from signing the hazardous waste manifest certification.
The requirements of the Hazardous Waste Reduction Plan include, but are not limited to,
the following:
• Quantification of hazardous waste(s)
• Description of hazardous waste source(s) of generation and disposal method(s)
• Indices of hazardous waste generation to production (i.e. output from, or input to,
the process generating the waste stream)
• Submission of a hazardous waste generator summary
• Cost estimate(s) for managing each waste
• Evaluation of technical feasibility and economical practicability of implementing
waste reduction options
• Listing of technically feasible and economically practicable waste reduction
measures and schedule for implementing identified waste reduction measures
Description of corporation's and facility's waste reduction policy
• Identification of party responsible for implementation of waste reduction plan
• Identification of waste reduction measurement(s)
• Identification of employee training programs
• Estimate of anticipated hazardous waste reduction
• Estimate of anticipated transference of hazardous waste into other environmental
media
Submission of Hazardous Waste Reduction Program Summary (HWRP)
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Biennial updates of HWRP
• Annual status reports
In addition, to the state statute, EPA has published its interim final rule regarding waste
minimization program requirements. Although published in the Federal Register as an interim
final rule, the guidance puts "additional enforcement teeth" behind the hazardous waste manifest
certification requirements mandated by the Hazardous and Solid Waste Amendments.
TAX ASSESSMENT/REGULATORY FEES
In addition to the regulatory/compliance implications discussed above, there is an
additional liability when hazardous waste is generated at your facility and properly managed via
a manifest, or a nonhazardous waste is accompanied by a manifest. That liability is a special
assessment and regulatory fee. In New York State, these assessments and fees are administered
by the New York State Departments of Taxation and Finance and Environmental Conservation,
respectively. The "bottom line" is that the generation of hazardous waste in New York State can
affect your "bottom line." Another good reason to make sure your hazardous waste is in fact,
hazardous. Let's briefly review the two revenue programs.
As mentioned above, the first tax, entitled, "Special Assessments on Generation, Treatment
or Disposal of Hazardous Waste in New York State" is administered by the Department of
Taxation and Finance and is self reported by generators and TSDFs within the state on Form TP-
550. This self reporting program is managed comparable to other state taxes, that is, it is
prepared and reported by the generator and subject to review and audit by the Department of
Taxation and Finance. In its simplest form, the Special Assessment, or "waste end assessment"
as it is commonly referred to, is calculated by generators based on the tons of hazardous waste
generated in New York State that received on site treatment or disposal or that were designated
for removal or removed from the site of generation for treatment or disposal or for storage prior
to such treatment or disposal during the reporting period. With regard to treatment and/or
disposal facilities, these entities are only required to report the tons of hazardous waste received
from generators outside New York State for treatment disposal or for storage prior to such
treatment or disposal (this avoids double counting.)
In accordance with the Environmental Conservation Law (§27-0923 Special Assessments
on Hazardous Wastes Generated) the following assessment rate schedule currently applies:
Assessment Rate
Category fin dollars per Ton)
Tons disposed of in landfill on-site of generation $27
Tons designated for removal or removed from the site of
generation for disposal in a landfill or designated for
removal or removed from the site prior to disposal in a landfill . . . $27
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Tons designated for removal or removed from the site of generation
for treatment or disposal (except by landfill or incineration), or for
storage prior to such treatment or disposal $16
Tons designated for removal or removed from the site of
generation for incineration or for storage prior to incineration $ 9
Tons incinerated on the site of generation $ 2
Tons received from out-of-state for landfill
disposal or for storage prior to such disposal $27
Tons received from out-of-state for treatment or disposal other than
landfill or incineration, or for storage prior to such treatment
or disposal $16
Tons received from out-of-state for incineration or
for storage prior to incineration $ 9
As can be seen from the table above, the rates are structured to provide an incentive for
disposal/treatment of waste by incineration and discourages disposal via landfilling. A deduction
may be taken for waste that is reclaimed.
These special assessments are paid quarterly and are due to the Department by the 20th
day of the month after the end of each calendar quarter. While the fees may not seem onerous
at first glance, it does not take much material to achieve a ton of waste. For instance, a 55
gallon drum of water (the density used to calculate the fee) weighs approximately 459 Ibs or
approximately .23 of a ton. So one can see how quickly the special assessments can take a bite
of your bottom line.
The second financial implication of generating hazardous waste is the Regulatory Fee,
which is administered by the New York State Department of Environmental Conservation
pursuant to 6 New York Codes, Rules and Regulations Parts 480 through 486 (Revised 1991).
Unlike the "waste end assessment" discussed above, the Hazardous Waste Program Fee
prescribed in Part 483 is an invoice prepared and sent by the Department based on data from
annual generator reports and manifest documents submitted.
Basically, for generators of hazardous waste, the hazardous waste program fee is currently
determined as follows:
• $1000.00 for generators of equal to or greater than 15 tons per year and less than
or equal to 100 tons per year of hazardous waste,
• $6,000.00 for generators of greater than 100 tons per year and less than or equal to
500 tons per year of hazardous waste,
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• $20,000.00 for generators of greater than 500 tons per year and less than 1,000 tons
per year of hazardous waste, and
• $40,000.00 for generators of greater than 1,000 tons per year.
In addition to the above, generators of equal to or greater than 15 tons per year of
hazardous wastewater are assessed $3,000.00.
The use of a manifest New York State should only accompany shipments of hazardous
waste as defined under Part 371. In fact, Part 372.2(b)(6) states ..."Use of a Uniform Hazardous
Waste Manifest constitutes a determination by the generator that the solid waste is a hazardous
waste in New York and/or the state of generation."
Therefore, the utilization of a manifest accompanying a waste material that is clearly not
a hazardous waste material may be interpreted as a violation of New York State hazardous waste
regulations and therefore could be enforceable.
SUMMARY
We have just reviewed a number of regulatory and financial requirements that generators
of hazardous waste in New York State and elsewhere across the country are obligated to comply
with in order to protect human health and environment. Presentations such as this are typically
offered to assist hazardous waste generators in achieving and maintaining regulatory compliance...
and thereby... minimize liability from regulatory violations and associated fines.
However, as we stated at the outset, the objective of this presentation is quite the opposite.
The focus here is to identify how one's liability is actually increased by utilizing the same
regulatory system discussed above (i.e. manifest document etc.) when it simply is not required
because the waste is not truly a hazardous waste.
Example. Facility A uses a water soluble alkaline powdered product to aid in degreasing
engine electric motors and transmission parts prior to rebuilding as part of its scheduled
maintenance program. Rather than establish a proper waste characterization program with
appropriate data quality objectives and quality assurance/quality control program, the facility
manager characterizes the spent solution as a characteristic hazardous waste and ships it off-site
via a licensed transporter with a signed manifest. The waste is characterized as corrosive
(D002). This practice continues for a number of years, with manifests documenting 10's of
thousands of gallons of "hazardous waste" being generated at the facility. (In fact, subsequent
analytical data and proper waste characterization determined the material not to be hazardous).
What are the liabilities associated with this scenario?
First, the use of a manifest signifies that the entity is a hazardous waste generator and,
as such, is required to comply with appropriate federal and state generator requirements. Most
important among these requirements is obtaining an EPA ID number. The ID number must be
010RMW.RPT
-------
obtained by the generator in order to use a manifest. Now that you have declared generator
status, the following enforceable requirements are applicable:
• compliance with specific procedures for handling waste
• record keeping and reporting
• proper labeling, marking and placarding
• develop and implement an emergency plan
• personnel training
• Preparedness and prevention measures
• annual generator report.
The above requirements are enforceable and may be subject to fine if determined not to
be satisfactory to government inspectors. However, if the generator manifests wastes as "non-
hazardous," the above requirements are not applicable.
Remember, the signature box on the manifest provides for a certification indicating that
the generator has a program in place to reduce the volume and toxicity of waste, and that the
method of treatment, storage or disposal minimizes present and future threats to human health
and the environment. While these are commendable objectives, they are not applicable for a
small manufacturing facility that does not generate hazardous waste in the first place.
There are also hazardous waste reduction plan requirements. Hazardous waste manifest
documents are utilized to quantity the amounts of hazardous waste being generated at a facility.
This process can include an otherwise non hazardous waste generator on the list of hazardous
waste generators required by state law to prepare a Hazardous Waste Reduction Plan. The use
of manifests and the submission of annual generator reports at a facility that does not generate
hazardous waste in the first place can be an unnecessary regulatory burden. It costs resources to
develop, submit and implement a hazardous waste reduction plan.
Last but not least, there are the "waste end assessments" reportable and payable to the
Department of Taxation and Finance in New York State and regulatory fees assessed directly by
the Department of Environmental Conservation. While perhaps not perceived as an
overwhelming burden, when taken as a whole in consideration with the other prescribed
regulatory requirements, improper hazardous waste characterizations can take a bite from your
bottom line.
In short, the time, money and resources spent up front in proper waste characterizations
including the development and implementation of clear data quality objectives and a quality
assurance/quality control program, can go a long way toward reducing environmental compliance
and financial liability.
010RMW RPT
-------
References
Technical Assistance Document for Complying with the TC Rule and Implementing the
Toxicity Characteristic Leaching Procedure (TCLP), May 1993, US EPA Reg. H, DCN EPA 902-
b-93-001.
010RMW RPT
-------
Appendix XIV
-------
Appendix XIV
Region II State TCLP Guidances
-------
Scott A. Wemer
Commas/oner
State of New Jersey
Department of Environmental Protection and Energy
Environmental Regulation
Hazardous Waste Regulation Program
CN4Z1
Trenton. NJ 08625-O421
Phone# 609-633-1418
Frank Coolick
Administrator
M
EMORANDUM
JU/J 04 1993
TO:
FROM:
SUBJECT:
Leon Lazarus, Environmental Scientist
USEPA, Monitoring Management Branch
Richard Johnson, Supervising Env. Specialist
Bureau of Advisement and Manifest, DEPE
Position Coordination for EPA's TCLP
Workshop on June 21, 1993
I. Spike Correction
On November 24, 1992, the Environmental Protection Agency
(EPA) removed the TCLP spike recovery correction and required
the method of standard additions be used for metals. This
change occurred at 40 CFR 261, Subpart D.
The New Jersey Department of Environmental Protection and
Energy (DEPE) requires that the test methods described in
Appendix II of 40 CFR 261, Subpart D be used for performing
the toxicity characteristic leaching procedure. Therefore,
since the quality control change has been completed at the
federal level, it is effective in New Jersey by reference.
II. Totals Analysis Versus TCLP Extract Analysis
This Bureau recommends following the guidance given in the
January 12, 1993 memo from the EPA Office of Solid Waste which
explains Section 1.2 of the TCLP. In brief, for hazardous
waste classification purposes, this Bureau will accept a total
constituent analysis value which has been divided by a factor
of twenty, in place of a TCLP value.
New jersey Is an Equal Opportunity Employer
Recycled Paper
-------
However, our preference is the use of the TCLP instead of a
total constituent analysis for hazardous waste classification.
The reason for this is that a total constituent analysis such
as a priority pollutant analysis does not include all of the
TCLP constituents. A laboratory that submits a priority
pollutant analysis in place of a TCLP analysis, must be
careful to submit any additional analyses which might be
needed to compliment any missing analytes from the priority
pollutant test. The inclusion of these additional analyses
are usually omitted in packages which are submitted to us,
which causes unnecessary delays in completing a
classification.
III. Status of EPA Land Ban Regulations in New Jersey
The EPA -land ban regulations were authorized as part of the
EPA Hazardous and Solid Waste Amendments (HSWA). EPA will
enforce these requirements until New Jersey adopts this
regulation. Therefore, the EPA land ban requirements are
enforced at the federal level at this time. The DEPE is
planning to adopt an equivalent set of regulations in the
future. When this occurs, DEPE personnel will enforce the
land ban requirements.
PR75(Sl):nb
c: John Barry, Enforcement, SFO
Tom Sherman, BHWE, DEPE
Phil Flax, HWCB, USEPA
Cathy Grimes, BEERA
Henry Hoffman, Laboratory Certification
-------
New York State Department of .Environmental Conservation
50 Wolf Road, Albany, New Ybrk 12233
Thomas C. Jortlr
ComoUcsioMr
MEMORANDUM
TO: Distribution Below
FROM: \ ^Norman H. Nosenchuck, Director
ivision of Hazardous Substances
SUBJECT:' EPA Revised Disposal Standards for F001-F005 Spent *^H
^Solvent Wastes
DATE: JAN * l 1S93
The United States Environmental Protection Agency (EPA) has
revised the disposal standards for the regulated hazardous
constituents of P001-FOOS > spent solvent wastes.
These revisions were promulgated as part of the Land
Disposal Restrictions (LDRs) for Newly Listed Wastes and
Hazardous Debris that were published in the Federal Rcaiet^-r on
August 18, 1992. Due to the volume and widespread occurrence of
spent solvent wastes, it was necessary to prepare this guidance,
as our Part 376 standards are now different from the revised 40
CFR 268 standards. The attached table will, for each
constituent, identify which agency's regulation is more stringent
and must be followed. Also included are the new standards as
they were promulgated by the EPA. This unfortunate but
unavoidable dual regulation will exist until the revised
standards can be adopted and promulgated by New York State.
current projections have this adoption of revisions at least 14
to 18 months away.
Other changes, and certain exclusions included"IiT this final
rule, have created some confusion as to which agency's (EPA or
DEC) regulation is more stringent and, therefore, the one to be
enforced. All newly listed wastes are unique to the federal
regulations.
If you have any questions concerning these revisions to the
LDRs, please contact Mr. John D. Miccoli, of my staff, at
(518) 485-8988.
Attachment
Page 1 of 2
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PTSTRTBDTION;
R. Becherer, Region 1
s. Jagirdar, Region 2
A. Shah, Region 3
C. Van Guilder, Region 4
D. Curtis, Region 5
T. Morgan, Region 6
S. Eidt, Region 7
D. Rollins, Region 8
F. Shattuck, Region 9
bee: w/att: N. Nosenchuck (2)
M. O*Toole
D. Mafrici
L. Kadler
J. MiddeDcoop
P. Counterman^
R. Haggerty
J. Desai /
J. Miccoli/
JT3M:NHN:gz
Page 2 of
-------
CONSTITUENT WASTEWATER MOHWASTEWATER
Acetone
Benzene
n-Butyl alcohol
| carbon disulf ide
Carbon tetrachloride
Chlorobenzene
Cresol (m-and-p isomers)
o-eresol
Cyclohexanone
o-Dichlorobenzene
Ethyl acetate
Ethyl benzene
Ethyl ether
Zsobutyl alcohol
Methanol
Methylene chloride
Methyl ethyl ketone
Methyl isobutyl ketone
Nitrobenzene
Pyridine
Tetrachloroethylene
Toluene
1,1, 1-Trichloroethane
1,1,2 -Tr ichloroethane
40 CFR Part 268
Same in both
40 CFR Part 268
Same in both
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
Sane in both
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
Same in both
40 CFR Part 268 1
40 CFR Part 268 1
40 CFR Part 268 1
40 CFR Part 268 1
40 CFR Part 268 1
40 CFR Part 268 1
40 CFR Part 268 |
40 CFR Part 268 1
Same in both I
H Part 376
Isaac in Both
II 40 CFR Part 268
Isame in both
140 CFR Part 268
| Part 376
| 40 CFR Part 268
B40 CFR Part 268
Isame in both
| Part 376
1 Part 376
Part 376
Part 376
Part 376
Same in both
Part 376
Part 376
!part 376
Part 376
Part 376
Part 376
Part 376
40 CFR Part 268
Same in both
-------
)US CONS!
DISPOSAL STMTOXRD TO BE FOLLOWED
1,1, 2-Triehloro-l ,2,2-
trifluoromethane
Triehloroethylene
Trichloromono-
fluoronethane
Xylenes (total)
2 -Nitropr opane
2 -Ethoxycthanol
40 CFR Part 268
40 CFR Part 268
40 CFR Part 268
40 CFR Fart 268
Sane in both
Same in botb
Part 376
Part 376
Part 376
Part 376
Sane in both
Sane in both
-------
New York State Department of Environmental Conservation
50 Wolf Read, Albany. N«w Ybck 12233
MEMORANDUM ThomM C. JerflAfl
TO: Distribution Below
FROM: Norman H. Nosenchuck, Director ,
Division of Hazardous Substances Regulation
SUBJECT: Revised Toxicity Characteristic Leaching Procedure
(TCLP)
°»™ HAY £41993
The United States Environmental Protection Agency (EPA) has
revised the Toxicity Characteristic Leaching Procedure (TCLP) in
a revision to the Toxicity Characteristic (TC) rule.
The revision, promulgated on November 24, 1992, is the
result of the EPA's reassessment of the matrix spike correction
requirement, promulgated on June 29, 1990 as a final rule
technical correction to the TC rule. At that time, EPA's
intention was to achieve consistency with the SW-846 chapter One
requirements, proposed on February 8, 1990, which EPA anticipated
would be promulgated as a final rule prior to the effective date
of the TC rule.
However, to date, EPA has not promulgated the SW-846
Chapter One requirements. Therefore, in response to public
comments originally received on the February 8, 1990 proposed
changes, the EPA decided not to proceed with the proposed .spike
recovery correction requirements for Subtitle C analytical
methods.
EPA stated in the November 24, 1992 preamble to their
revision that authorized states are given the option to adopt
this change to the TCLP procedure.
New York State, as did other states authorized for Land
Disposal Restrictions (LDR), included the TCLP as a requirement
to implement these LDR regulations. As part of our current
rulemaking process to update our hazardous waste regulations, we
will include the revised TCLP for the TC rule and the LDR
regulations.
Page. 1 of 2
-------
In the meantime, to eliminate confusion regarding specific.
in the TCLP testing methods in the interim, DEC will accept the
EPA version currently in place as Appendix IX to 40 CFR Part 261,
designated as Method 1311, as an alternative to the TCLP
(Appendix 35) currently found in Part 376 to implement the LDRs.
Attached for your convenience and use, is both a copy of the
Federal Register notice of November 24, 1992, and the draft
changes to Appendix 35 found in Part 376. The draft Appendix 35,
Section 8.0 - Quality Assurance, has brackets [ ] surrounding
words or formulas being removed, and underlines all additions.
Please call John D. Miccoli, of my staff, at (518) 485-8988
if you have any questions concerning the possible ramifications
of this change to our LDR program.
Attachment
R. Becherer, Region 1
S. Jagirdar, Region 2
R. Aldrich, Region 3
C. Van Guilder, Region 4
D. Curtis, Region 5
T. Morgan, Region 6
S. Eidt, Region 7
D. Rollins, Region 8
F. Shattucfc, Region 9
cc: w/att: E. Sullivan
N.6. Kaul
M. O'Toole
G. Kelly
bcc: w/att: N. Nosenchuck (2)
D. Mafrici
L. Nadler
D. Aldrieh
J. Middelkoop
P. Counterman
R. Baggerty
J. Desai
J. Miccoli
JDK:DLA:NBH:gz
Page 2 of 2
-------
Appendix XV
-------
Appendix XV
Risk Assessment for Disposal of Solidified/Stabilized
Waste and Contaminated Soil
-------
flPR-12-1994 08:24 p.02
Texas A&M University
CIVIL
Department of Civil Engineering • Texas A&M University » College Station, TX 77843-3136
Bill Batchelor. Professor* (409)845-1304 . FAX (409)862-1542- EmailbflHatchetoretamu.edu
April 11,1994
FAX MEMORANDUM
To: Leon Lazarus
USEPA
FAX: 908-321-6622
From Bill Batchelor
4
Subject: Risk Assessment Paper
Attached is the paper I presented on risk assessment of materials treated by
solidification/stabilization. It is now under review for publication, but can be
referenced in the interim as:
Batchelor, B., "A Framework for Risk Assessment of Disposal of
Solidified/Stabilized Wastes and Contaminated Soils", Symposium on
Treatment and Modeling of Hazardous Waste Processes, 24th Annual
Meeting of the Fine Particle Society, Chicago, Blinds, August 24-28,
I'm looking forward to downloading your TCLP manual from the Clu-Ih
BBS.
-------
Texas A&M University
CIVIL
Department of Civil Engineering • Texas A&M University » College Station, TX 77843-3136
Bill Batchelor • Professor * (409)845-1304 • FAX (409)862-1542* Emailbill-batchelor@tamu.edu
April 19, 1994
Mr. Leon Lazarus
USEPA
2890WoodbridgeAve.
Edison, NJ 08837
Dear Leon:
I am enclosing a copy of the risk assessment paper that I previously faxed to
you. I hope it is useful to you.
Bill Batchelor, Ph.D,P.E.
Professor Director
Environmental & Water Res. Engr. Institute for Environmental Engineering
Civil Engineering Dept. Texas Engineering Experiment Station
-------
A Framework for Risk Assessment of Disposal of
Solidified/Stabilized Wastes and Contaminated Soils
Bill Batchelor
Civil Engineering
Texas A&M University
College Station, TX 77843
ABSTRACT
Quantitative risk assessment is the tool used at hazardous waste sites to evaluate the need
for treatment and to determine which control strategies are most effective. A general approach to
conducting quantitative risk assessments at contaminated sites is reviewed and a framework for
applying it to evaluating risk associated with ground water contamination by disposal of materials
treated by solidification/stabilization is presented. The approach is based on a material balance
around the disposal zone and the ground water flowing past it Two limiting cases are identified
that can control the concentration of contaminant leaving the leaching zone. The first case occurs
when the flow past the solid is low and the its concentration can approach that in equilibrium
with the pore water in the solid. The second case occurs when the flow past the solid is
sufficiently large that the concentration of contaminant in the flow is negligible. In this case, the
flux from the solid can be predicted by simple leach models. Examples of applying this
framework to materials treated by solidification/stabilization are presented.
INTRODUCTION
Risk assessment is becoming increasingly important to the practice of environmental
engineering. More and more it is becoming the technique used to determine the level of treatment
required and the resources to be allocated to different environmental problems. Its use for
environmental decision making is analogous to the use of costs and benefits expressed as dollars
in economic decision making. In this way, quantitative estimates of risk can be considered the
"currency" of environmental decision making.
Risk assessment is particularly important in remediation of hazardous waste sites. Federal
legislation requires decisions to be made on a site-specific basis, rather than on the basis of
national standards. The latter approach is more common in protecting water and air quality.
Three types of risk assessments are made during the process of developing a plan to remediate a
site.12 First a baseline risk assessment is made to evaluate the danger of the site as it exists. This
risk assessment is then improved in the process of determining preliminary remediation goals that
are used to screen remediation options. Finally, risk assessments are used to evaluate the remedial
alternatives in the processes of selecting the most appropriate ones.
Risk assessments are required to evaluate the impact of the site on human health and on
the environment The approaches for assessing human health impacts are much simpler, because
they do not need to deal with the complexities of environmental ecosystems. Work is underway
-------
to identify indicators of ecological health that can be easily used in environmental risk
assessments.
There is a great deal of uncertainty in quantitative risk assessments. The results of such
assessments should not be considered important because they accurately predict quantitative
impact on human health, but rather as methods to compare different alternative actions. They are
valuable in the relative sense of providing a comparison of the risk at one site to that at another,
or the risk of using one technology rather than another.
This paper will present a framework for applying risk assessment to evaluating the effect
on human health of disposal of materials treated by solidification/stabilization. It will begin with a
review of the steps typically taken in a quantitative risk assessment It will then develop the
approach for applying them to solidification/stabilization. Finally, it will provide example
calculations of how the approach could be used. The approaches to risk assessment described
will be those promulgated by the U.S. EPA,1-2 however, the opinions expressed will be those of
the author.
STEPS IN RISK ASSESSMENT
Data Collection and Evaluation
The first step in a quantitative risk assessment is to collect the data upon which the
analysis will be based. Much of this data would normally be obtained for other purposes,
however, some additional data may be required. The types of data required will become clear as
the other steps are discussed.
Exposure Assessment
The exposure assessment step involves determining the extent to which the contaminants
of concern will be taken up by exposed individuals. This process begins by evaluating the physical
setting. This will allow identification of the exposed populations and the pathways by which they
will be exposed. Exposed populations could include those that live near a site, those that work at
a site, or casual visitors to a site. Adults, children or other groups could be defined as distinct
populations for calculating risks. Exposure pathways could include inhalation of contaminants
released to the air, drinking of ground water contaminated at the site, consumption of food that
was contaminated by material released from the site, or consumption of soil transported from the
site by air.
When exposed populations and pathways are identified, the concentrations to which the
populations are exposed can be calculated. This often includes the use of transport and fate
models to estimate the concentrations of contaminants near the exposed population. These
calculations are based on the concentrations of contaminants at the site and the relevant
characteristics of the physical setting at the site. For example, a diffusion-reaction model could be
used to estimate release of volatile contaminants from soils at a site and an air dispersion model
could be used to estimate the concentration of contaminants in air at the boundary of the site
where individuals would be exposed. In another case, a vadose zone transport model could be
used to predict movement of a contaminant at a site down into the saturated zone and another
ground water transport model could be used to predict movement off-site to a drinking water
-------
well. Both models could include descriptions of the processes of advection, dispersion, sorption,
and degradation to predict transport and fate.
Good judgment should be used in determining the complexity of the models used to
calculate exposure concentrations. A complex model will not necessarily provide better estimates
of concentrations, particularly when the model requires more data than is available. Furthermore,
complex models generally are more difficult to use. An important factor to consider in choosing
an appropriate level of model complexity, is that it is not necessary to model precise conditions in
the future. For example, the wind speed and direction will not be known for the future, so exact
calculations of concentration at any time in the future are not possible. Rather, it is important to
develop a realistic way to evaluate risk that can be used to compare risks at one site to another,
and to compare risks associated with one remedial alternative to those associated with another.
Consistency across different sites and remedial alternatives is more important than accuracy for a
specific set of conditions.
When exposure concentrations are obtained, intakes of the exposed population can be
calculated. This requires assumptions about factors that affect the extent of exposure, such as the
volumes of air, water or soil consumed per day by an exposed individual. Intakes are expressed
as the mass of contaminant taken into an exposed individual per mass of the individual per unit
time.
Toxicity Assessment
The toxicity assessment involves determining the relevant lexicological data to be applied
and values for exposure periods that are reasonable for the specific case under study.
Toxicological data for many compounds have been compiled in a form that is readily applied to
risk assessments in a data base called IRIS (Integrated Risk Information System). It is available in
electronic format, and is updated regularly.3
Toxicity of compounds believed to be carcinogenic is expressed differently than for those
compounds that are not believed to be carcinogenic. A proportionality is assumed between the
intake of a carcinogen and the probability of developing a fatal cancer over the lifetime for the
exposed individual. The proportionality factor is called a slope factor and can be considered the
lifetime cancer risk associated with a unit intake of the compound. Therefore, higher slope
factors indicate more toxic compounds.
Toxicity of compounds that are not believed to be carcinogenic is expressed as a reference
dose. This is the upper limit on intake of the chemical for which adverse effects are not expected.
Therefore, lower reference doses indicate compounds that are more toxic.
Risk Characterization
This stage integrates the exposure and lexicological assessments to determine quantitative
estimates of risk. First, risk estimates are calculated for each contaminant of concern, each
pathway, and each exposed population. The lifetime cancer risk for a given pathway and chemical
is calculated for carcinogenic compounds as the product of the calculated intake and the slope
-------
factor. A hazard quotient is calculated for each pathway and each exposed population as the
intake divided by the reference dose. Lifetime cancer risks and hazard quotients are summed over
all pathways and all chemicals for each exposed population to determine the total lifetime cancer
risk and the hazard quotient. Lifetime cancer risks are to be reduced to the range between 10"4
and 10"6 and hazard quotients are to be reduced to a level below l.O.4
The last step in risk characterization is to assess the uncertainty in the risks. This is an
important step because there are many uncertainties associated with risk assessment It is
important that the range of reasonable values of risk be communicated to interested parties along
with the value of risk calculated to be the most probable. This will give an important context to
the estimates of risk. For example, a hazard index of 0.5, with a confidence interval of 0.4 to 0.6
carries a different meaning from one with the same value but a confidence interval of 0.01 to 50.
There is typically a great deal of variability in contaminant concentrations at a site. Some
areas are highly contaminated, while others are lightly contaminated or have no measurable
contamination. The physical characteristics of a site that affect the movement of contaminants
can be nighty variable at different locations at the site. For example, hydraulic conductivities and
contaminant distribution factors have been found to have scales of variation on the order of a few
meters in aquifers.5-6 Processes that can affect the fate of contaminant at a site can be highly
variable. Weather is highly variable, as can be processes such as biological degradation. Many
assumptions must be made to calculate chemical intakes that are known with little certainty.
Finally, the response of humans to the toxic compound must often be predicted based on response
of laboratory animals to high doses of the chemical. Extrapolating this lexicological data to
humans exposed to low doses is a highly uncertain process.
Uncertainty in risk analysis is quantified by repeating calculations using different but
reasonable values for the variables. This can take the form of a sensitivity analysis where values
of individual variables are changed over their expected ranges and the effect on calculated risk are
evaluated. A more extensive procedure is to conduct a Monte Carlo analysis in which probability
distributions of all variables are used to estimate the probability distribution of the calculated
risks.7
However, there is a problem in the way risks typically are calculated at sites. Guidance
from the U.S. EPA requires that conservative assumptions be made in calculating the risk.
Therefore, the value of risk determined by this method is not the most probable risk, but a risk
that is likely to be somewhat higher than is most probable. It would be better, to make the most
reasonable assumptions possible in the basic risk assessment process and then to provide a range
of more conservative values of risk on which to base decisions. A stochastic risk assessment
could be made so that decisions could be based on whatever level of conservatism desired. This
would bring the question of the desirable level of protection into the public discourse, rather than
hide it in the model calculations.
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RISK ASSESSMENT FOR S/S
Exposure Assessment
The purpose of this step is to estimate quantitative intakes of those chemicals identified as
being major risks to human health. First, the physical setting for s/s activities should be defined.
S/S could cause short-term adverse health effects during the treatment stage or long-term effects
after disposal. The potential exposed populations and pathways by which chemicals could affect
them should be identified. Potential pathways of short-term exposure include fugitive dust
emissions during transport of the material to be treated and volatile organic emissions during
treatment. However, in many cases the long-term risk of exposure through the pathway ground
water contamination is of greatest concern. Figure 1 shows a schematic of how leachate could
transport chemicals to the ground water underneath a disposal site.
Figure 1 shows in a very simplified manner the way in which leachate could pass by
Leach ate Flow
Ground Water Flow
material treated by s/s and become contaminated with the chemical contained within the treated
material. This leachate could then mix with underlying ground water. The procedure described
below will provide a method for estimating the risk to a nearby resident who might consume this
ground water.
A simple material balance can be used to estimate the concentration of contaminant in the
ground water. This balance states that the mass flow of contaminant leaving the zone where the
treated material has been disposed plus the mass flow of contaminant in the ground water
approaching the mixing zone equals the mass flow of contaminant leaving the mixing zone.
2gv/ + Qi)C'"a (1)
J~^Q~ (2)
where: Q = flow passing through disposal zone
Cj = concentration of contaminant in leachate leaving disposal zone
= flow of groundwater approaching mixing zone
-------
£ = concentration of contaminant in groundwater approaching mixing zone
- concentration of contaminant leaving mixing zone
Equation 1 demonstrates the importance of the leachate flow and leachate concentration.
The leachate flow can be changed by changing the design for disposal of the treated material.
Isolating the treated material within caps and liners will greatly reduce the flow of water passing
through the disposal zone. The value of the flow to be used in this risk assessment must be
determined based on site-specific factors. Tools such as the Hydraulic Evaluation of Landfill
Performance model8 or other ground water transport models applied to the site could be used to
estimate such flows.
Choosing a value for the ground water flow approaching the mixing zone determines the
extent to which title contaminant will be diluted in the ground water. Choosing a single value is a
great simplification of the ground water transport situation, but it can be suitable for a risk
assessment if good judgment is used. Simple mixing models or more complex ground water
transport models can be used to facilitate choosing this variable.
Many complex processes including chemical reaction and mass transport could affect the
concentration of contaminant in the leachate leaving the disposal zone. However, two limiting
cases can be examined to facilitate calculations. The first limiting case is when equilibrium
conditions control. This could happen when the leachate flow is relatively low and the leaching
rate is relatively high. Under these conditions, contaminants would leach rapidly enough so that
the contaminant in leachate leaving the site would be in equilibrium with the contaminant in the
waste forms.
Q = C* (3)
The value of the equilibrium concentration could be obtained by conducting a batch
leaching test in which the volume of leaching solution is small relative to the mass of treated
material and the leaching time is long.
A second limiting case would occur when the concentration of contaminant in the leachate
is controlled by leaching kinetics. The concentration of contaminant in the leachate could be
calculated for this case by recognizing that the mass flux of contaminant leaving the disposal zone
must equal the mass flow of material from the waste forms.
, = Ft (4)
where: /J = mass flow of contaminant in leachate leaving disposal zone
A variety of leaching models could be used to calculate the mass flow for Equation 4, but
those based on the "infinite bath", "infinite solid" and "rectangular geometry" assumptions are
simple and often appropriate.9 These models assume that the concentration of contaminant in the
leachate near the waste form is negligible relative to the concentration of leachable contaminant in
the waste form (infinite bath), that leaching has not progressed to the point where the interior of
-------
the solid has been leached (infinite solid) and that leaching has not progressed to the extent that
curvature of the waste form is important. The infinite bath assumption will be valid when leachate
flow past the solid is high enough to sufficiently dilute the contaminant to concentrations that are
low relative to the concentration within the pore water of the solid. The infinite solid assumption
will be valid as long as the model is not applied to leaching times for which a large (>20%)
fraction of the contaminant has been leached.
These models can be used to describe leaching affected by chemical reactions through the
use of an observed diffusivity. The observed diffusivity for a contaminant in a waste form can be
determined by leaching tests, or it can be estimated by more complex models that quantify the
reactions.10 These models show that the mass rate of leaching is inversely proportional to the
square root of leaching time.
(5)
(6)
where: M0 = mass of contaminant in disposal zone
L = ratio of volume of treated material to external surface area exposed to leachate
Dobs = observed diffusivity of contaminant in treated material
t= time since leaching began
The mass of contaminant in the disposal zone can be calculated based on characterization
of the material before treatment and the amount of material treated. The observed diffusivity can
be determined by dynamic leach tests or estimated from results on similar materials.11 The ratio of
the volume of treated material to its external surface area is a measure of the average particle size.
If the treated material retains its physical integrity, this variable could be large, maybe several
meters. If the material disintegrates over time, it could be as small as 1 to 10 millimeters. Note
that the mass rate of leaching depends on time, so that the concentration of contaminant in the
ground water leaving the mixing zone will vary over time.
After the concentration in the ground water leaving the mixing zone is determined, it can
be used to calculate the chemical intake of an exposed person. The following method can be used
to calculate chemical intake from drinking water.1
where: 7 = intake of chemical (mg / kg - day)
Cw = concentration of chemical in water(mg/l)
I, = ingestion rate of water (1 / day)
Ef = exposure frequency (days / year)
Ed = exposure duration (years)
Bw = body weight (kg)
At = averaging time, period over which exposure is averaged (days)
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The concentration in the water would be taken as the concentration calculated in the
ground water leaving the mixing zone. Typical values for the other variables are: 2 I/day ingestion
rate of water, 365 days/year exposure frequency, 70 years exposure duration, 70 kg body weight,
and 70 years averaging time.1
Toxicity Assessment
Toxicity assessments are carried out differently for chemicals that are believed to be
carcinogenic and those that are not The potency of suspected carcinogens is expressed as a
slope factor, which gives the lifetime cancer risk per unit of chemical intake. Potency of non-
carcinogens is expressed in terms of a reference dose. This is the estimate of chemical that is
likely to be without an appreciable risk of deleterious effects during a lifetime and is similar to an
acceptable daily intake. Values for these variables can be obtained from standard sources.3
Risk Characterization
The process of risk characterization combines information on toxicity with that of
chemical exposures to determine overall risks at a site. The risk of a chemical believed to be
carcinogenic is obtained by multiplying the slope factor for that chemical times its calculated
intake to obtain the lifetime cancer risk for that chemical. Summing over all chemicals and all
pathways gives the lifetime cancer risk for that site.
The risk of exposure to non-carcinogens is calculated as the non-carcinogenic hazard
quotient, which is the ratio of the calculated intake for a chemical to its reference dose. Hazard
quotients are summed for all chemicals and all pathways to obtain the hazard index for this site.
There are many uncertainties with any risk assessment and they should be specifically
addressed. The extent to which this is done depends on the importance of the risk assessment
Evaluation of uncertainty of the risk assessment can be done qualitatively by describing the
uncertainties in each parameter value assumed, and each assumption in the risk assessment
procedure. Quantitative evaluation of risk can be done by conducting sensitivity analyses in which
different values of parameters are used to determine the range of expected risks. This can be
done more completely with Monte Carlo simulations which will provide an estimate of the
probability distribution of calculated risks.
EXAMPLE
The following example shows how the calculations could be conducted for a carcinogen
and a non-carcinogen. The following general assumptions will be used:
ground water flow approaching mixing zone = 30 m3/d
concentration of carcinogenic and non-carcinogenic contaminants in ground water
approaching mixing zone = 0
mass of carcinogen = Sxl07g
slope factor for carcinogen = 0.05 kg-day/mg
mass of non-carcinogen = 6xl07g
8
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reference dose for non-carcinogen = 0.001 mg/kg-day
size of individual waste form (cube) = 1 m
ingestion rate for water = 2 I/day
exposure frequency = 365 day/year
exposure duration = 70 years
body weight = 70 kg
averaging time = 365 days/year x 70 years = 25,550 days
The following assumptions will be made for the case of equilibrium-controlled conditions:
leachate flow = 0.5 mVd
equilibrium concentration of carcinogen =1.0 g/m3
equilibrium concentration of non-carcinogen = 0.1 g/m3
The following assumptions will be made for the case of kinetic-controlled conditions:
leachate flow = 20 mVd
time after placement (leaching time) = 100 d
observed diffusivity of carcinogen = 10-13 mVd
observed diffusivity of non-carcinogen = 10-15 mVd
ratio of waste form volume to external surface area exposed to leaching = length of
cube/6 = 0.167 m (i.e. all of external area of waste form is exposed to leachate
flow)
Carcinogen with equilibrium control
(0) = 0 ,,
Q + Q 30+0.5 e
Risk = Intake x Slope Factor =(4.69^10-4)(0.05) =
Carcinogen with kinetic control
C = oos _ ->^,^v *v i 0 2fi7 mo /I
'"^'TtrJ ~(20X0.167)I (3.1"^^"^ ' "' 8
(20)(0. 267) + (30)(0) = Q m
30 + 20
Risk = Intake x Slope Factor = (3. 05jclO~3)(0. 05) = 1.53x10
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Non-carcinogen with equilibrium control
l- - = 4-68**°
Reference Dose 10
Hazard Quotient = - - - = - - Q. 0468
Non-carcinogen with kinetic control
C-^o.paL = "—— _ =0.0321 mg/1
1 ~T| tat) (20)(0.167) I (3.1416)(100) J s
rma QCt + Q^C^ (20)(0.0321)+(30)(0)
c_, = = = u. ui/omg/i
^ ^ --a 30+20
Hazard Quotient = - - - = 3-66*10 = 0. 366
Reference Dose 10
SUMMARY
Quantitative risk assessment can be used as an environmental currency to evaluate the
relative risks associated with different environmental problems and the relative effectiveness of
different control strategies. A standard approach has been proposed for use at sites contaminated
by hazardous wastes and this approach has been applied to provide a framework for evaluating
risks associated with disposal of materials treated by solidification/stabilization. This framework
is intended to provide a flexible approach for conducting such assessments. More complex or
simpler approaches may be appropriate for any given site. In all cases, a risk assessment must be
conducted by those who understand the physical, chemical and biological factors that affect the
actual risk at a site.
The framework for risk assessment proposed here considers the pathway of ground water
contamination and is based on a material balance around the disposal zone and the ground water
flowing past it. Two limiting cases are identified as controlling the concentration of contaminant
leaving the leaching zone. In one case, the concentration approaches the concentration that
would be in equilibrium with the contaminant in the solid. This case would be applicable to cases
in which the flow past the solid is low. The second limiting case would occur when the flux of
contaminant leaving the solid can be approximated by leaching models that assume negligible
concentrations in the leachate. This case would be applicable to conditions of high flow past the
solid.
10
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REFERENCES
1. U.S. Environmental Protection Agency, "Risk Assessment Guidance for Superfund, Volume I:
Human Health Evaluation Manual, Part A", EPA/540/1-89/002,1989.
2. U.S. Environmental Protection Agency, "Risk Assessment Guidance for Superfund, Volume
H: Environmental Evaluation Manual", EPA/540/1-89/001,1989.
3. U.S. Department of Energy, "Integrated Risk Information System", RCRA/CERCLA Division,
DOE/EH-0194, (NTIS DE0101850), 1991. (also available in updated microcomputer data file
format as NTIS PB91591330).
4. U.S. Environmental Protection Agency, "National Oil and Hazardous Substances Pollution
Contingency Plan; Final Rule, Code of Federal Regulations, 40(300), 1990.
5. Robin, M.J.L., Sudicky, R.W., Gillham, R.W., Kachanski, R.G., "Spatial Variability of
Strontium Distribution Coefficients and Their Correlation with Hydraulic Conductivity in the
Canadian Forces Base Borden Aquifer", Water Resources Research, 27(10): 2619-2632,
1991.
6. Woodbury, A.D., Sudicky, E.A., "The Geostatistical Characteristics of the Borden Aquifer",
Water Resources Research, 27(4): 533-546,1991.
7. McCone, T.E., Bogen, K.T., "Predicting Uncertainties in Risk Assessment", Environmental
Science and Technology, 25(10): 1674-1681,1991.
8. U.S. Environmental Protection Agency, "Hydrologic Evaluation of Landfill Performance
(HELP) Model, Volumes I, H, m, IV, Users Guide for Version 2, EPA 530/SW-84-010,
Office of Solid Waste and Emergency Response, 1984.
9. Batchelor, B. "Leach Models: Theory and Application," J Hazardous Materials, 24(2,3): 255-
266 (1990).
10. Batchelor, B., "A Numerical Leaching Model for Solidified/Stabilized Wastes", Water Science
and Technology, 26(1/2): 107-115,1992.
11. Stegeman, J.A., C6te, P.L., "Investigation of Test Methods for Solidified Waste Evaluation -
A Cooperative Program", Report EPS 3/HA/8, Environment Canada, Ottawa, Ontario,
Canada, 1991.
11
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Appendix XVI
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Appendix XVI
Barbara Metzger's 1992 Speech on
Environmental Data Use -
Meeting the Customer's Need
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Environmental Data Use - Meeting the Customer's Need
Introduction:
Good morning. When Llew Williams asked me to be the kickoff
speaker for this conference, I wasn't sure whether I should be
flattered or intimidated. For those of you who know me, I think
you realize that I chose to be flattered with the invitation. On
a more serious note, I am really pleased to have the opportunity
to address an audience that is interested in making quality
assurance work. As an Environmental Services Division Director
at EPA, I'm often called upon to champion QA, but most of the
time it's standing up for it because it's the "in thing", TQM and
all, and fighting for the need and the costs of appropriate
quality assurance practices. In today's climate of static or
shrinking resources to collect adequate environmental information
to support hazardous waste site cleanup or remediation decisions,
competition for available resources is intense, and getting more
so. It is imperative that we, the quality assurance
professionals, are able to support the appropriateness and the
effectiveness of the quality assurance practices we put in place
to provide useful information, not just qualified data, for our
respective program decisionmakers' use. Quality assurance for
quality assurance's sake is no longer a viable option. Quality
assurance practices must, in TQM terms, truly meet the customer's
needs to be appropriate.
As most of you are aware, this isn't as easy as it sounds.
When I ask the customer what he needs, he may be able to tell me
what compounds he is concerned about, but not much more.
Detection level, precision, and accuracy are words without
meaning to the discussion at hand.
As we look at the different phases of any environmental data
collection effort, we can see the importance of incorporating
quality assurance considerations if we are to provide our
customers with useful information.
There are five generic phases of any environmental data
collection effort:
TABLE I
1. Planning
2. Sample Collection
3. Laboratory Analysis
4. Data Review/Validation
5. Data Assessment
For each of these generic phases, there are corresponding
quality assurance activities:
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TABLE 2
Env.Data Collection
Activity QA Activity
1. Planning 1. Data Quality Objectives
(DQO's), Quality Assurance
Project Plans (QAPP's)
2. Sample Collection 2. Standard Operating
Procedures (SOP's), Audits
3. Laboratory Analysis 3. SOP's, Contract Specs,
Audits
4. Data Review/Validation 4. SOP's
5. Data Assessment 5. DQO's
At EPA, we have put a great deal of effort in quality
assurance for Superfund. Unfortunately, when Superfund started,
Quality Assurance was not an integral component of EPA engineers'
culture. Quality Assurance was a laboratory thing. Quickly,
Superfund RPM's found that contractors were fallible. Data
coming back - when it finally did arrive - couldn't be used. It
failed the guality assurance criteria, whatever they were. At
the outset of Superfund, over 65% of the data was outright
unusable, 25% due to sampling problems, and 75% due to laboratory
performance. My Regional Administrator's image in Niagara Falls
was certainly not that of the great American Eagle, but more like
Ben Franklin's choice for the symbol of America, the turkey.
Once a month for 6 months, Chris Daggett had to go to a public
meeting in Niagara Falls for the infamous Love Canal site and
tell the good Sister Margeen, the affected public, Lew Steele,
and housewife, now activist, Lois Gibbs that EPA, the
organization that was supposed to correct the problems caused by
toxic/hazardousl wastes, could not tell the assembled crowd what
was in the samples taken over eight months ago, and six months
ago, etc. Somebody in the Region had to get religion, that is
Quality Assurance Religion, and start practicing it fast. A cadre
of chemists were pulled together (an EPA euphemism for stealing
resources from other programs), and EPA was immersed in the Stage
4 QA activities of Data Review/Validation. There were no
contracts available to review other contractor's data; it was an
EPA function. It seemed every available resource had to be
thrown into the Data Validation/Data Review process if the
customer's needs for data were to be met. This is not to say
that other phases were ignored, but they sure didn't get the
attention in resources or priority that would lead to a better,
more balanced, program.
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Simply put, the Regional Administrator didn't enjoy hanging
out there in Niagara Falls, or anywhere else for that matter, and
it was QA's job to ensure that this wouldn't happen again.
Recently, QAMS and others have openly questioned if it isn't time
to start paying more attention to the remaining QA activities in
other phases of the data collection process. I agree.
Parenthetically, I will use Region II examples during this
presentation partly because I know us best, but also because I
recognize that most of what occurs in Region II happens in other
regions to a greater or lesser extent. We're in that 95%
confidence interval of who does what most of the time.
Planning Phase:
As I mentioned, we do expend effort and attention, albeit
insufficient,, on the planning phase of our environmental data
collection activities. Currently,our planning phase QA is
carried out through the requirement for, and review of, Quality
Assurance Project Plans (QAPP's) or Sampling and Analysis Plans
(SAP's). Although we feel confident that our guidance and
training for consistent planning requirements meet our objectives
for development of relevant plans; reviews are conducted by
knowledgeable staff professionals to assure that appropriate
QA requirements are incorporated. We have not been able to
participate effectively in scoping meetings held by the RPM and
the contractor who prepares the QAPP or SAP. Resources are the
issue. "Prevention is the cure" is not a concept readily accepted
if resources are required for implementation. These meetings, if
they were held, would help us to understand the purpose of the
data collection activity and identify what questions the
generated data, converted into useful information, are supposed
to help answer. Lack of understanding the reason for collecting
data sometimes leads to a false sense of security. In more than
one case where the Quality Assurance Project Plan was acceptable,
the resulting data did not meet the informational needs of the
decision maker.
Region II has a dioxin site in the Ironbound section of
Newark, New Jersey. The site was essentially cleaned, along with
the adjacent streets and markets. The collected dioxin from the
cleanup was, and still is, securely stored on site. The site is
on the banks of the Passaic River. Many of you may recall the
headlines on this site. Many discussions were held with the
Superfund program staff and biological/technical staff to
appropriately design a study to define the magnitude, extent, and
impact of the dioxin contamination on the Passaic River/Newark
Bay ecosystem. Field procedures and analytical methods were
specified to assure that biological impact criteria levels would
be measurable, etc. The QAPP was approved, and the field
sampling and laboratory analyses were conducted in accordance
with the plan, yielding data within biological criteria levels.
Unfortunately, the critical, most demanding data users were not
part of the staff designing the study. The bioaccumulation
concept was not considered in the planning phase, and when the
risk assessment derived concentrations were calculated, it was
discovered that the analytical detection levels were orders of
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magnitude above those necessary to make an appropriate ecological
assessment. The study had to be redone to meet the needs of the
data user.
As you can readily see from this example, an excellent QAPP
yielded good quality data that did not meet the information
requirements of the decision makers. " The operation was a
success, but the patient died."
Let's try an analogy: You've gotten a new job that
requires you to drive to work and consequently, you need a new
car. You're moving your family, and with the night school class,
you just don't know when you're going to find time to shop for
the car. Good old mom comes to the rescue. She'll shop around,
and when you come to dinner next week, she'll have it all scoped
out. Sure enough, next week, even before she served any food, she
proudly announces that she's decided that you should buy the new
little Cadillac convertible. It's powerful, and quick, and
sporty, absolutely gorgeous, and, or course, it's a Cadillac.
You then ask, "But Mom, doesn't that cost an awful lot, and
does it have room for two kid seats (I maybe forgot to tell you
it's going to be twins), and can it pull a trailer with all of
the camping stuff, and does it have two air bags, and does it get
good gas mileage, and what about reliability, and how about
safety?" Well, Mom doesn't actually have any answers to these
questions. You then start yelling and screaming about how you
need the car and she ought to know what you need, and at least
she ought to know not to rely on company ads..."
Finally, at that point your brother, Quincy Adams Ogilvy, or
"QAO," interrupts. "Hold it, hold it," he says, "It's not her
fault. How could she know what you need, or what is important to
you, or even when you need the information. You didn't tell her
any of that. What you both really need is a Quality Assurance
Plan to ensure that your needs are stated clearly up front and
that her methodologies will satisfy them. You need to tell her,
up front, that you need an inexpensive, efficient, safe, car that
can pull a trailer, etc. You also need to agree that Consumer
Reports is enough, or that test drives are needed, or that a
chart comparing different models is required, or whatever." And
so forth.
I think I've made my point up 'til now without discussing
the term Data Quality Objectives (DQO's). What is the purpose of
collecting the data? What questions have to be answered?. What
are the user needs? Everyone agrees that DQO's are necessary,
yes, even of utmost importance. But what are DQO's? If I asked
each of you to write down your definition of DQO, I would
probably have as many definitions as there are people in this
room. Most would be somewhat similar, but they would range from
the rigorously statistical definition on one end of the spectrum
to the general conceptual definition on the other end of the
spectrum. If DQO's are as important as we feel they are (and I
agree with that assessment), then we in the business of QA need
to develop a definition that is comprehensible and consistent
across agency and organizational boundaries, one that is user
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friendly (ie someone other than a statistician can understand and
use), and a definition that allows the information user
sufficient understanding so that they can appropriately
participate in the development of the DQO's. Unless they are
active participants, we are likely to continue to have repetition
of the example scenario which I have shared.
We must develop a mechanism which assists the customer in
clarifying and communicating his needs.
Sample Collection Phase:
Field sampling phase activities can only be quality assured
by a combination of appropriate, planned and documented field
procedures or SOP's which are designed to meet all the
informational, requirements of the data user. But as the saying
goes "The best laid plans of mice and men ". On site audits
are essential to provide us with the assurance that the sampling
plan and field procedures described, are, in reality, being
followed. Not all deviations from the QAPP or SAP occur as an
attempt to circumvent or shortcut the planned procedures. Anyone
who has been in the field recognizes that Murphy's law is always
in operation on any field sampling project. For example, how
often does the field sampling plan identify the conditions under
which the sampling event is aborted. It should. The field team
should know whether one well not recovering within the specified
time after evacuation in the QAPP is a valid criteria for
aborting the sampling event. Maybe the water bearing layer will
never permit the well to recover within the specified timeframe.
The point I wish to make here is that the plan should not be
followed just because it is "the approved plan". The sampling
team must understand the rationale, the "why", of the
requirements of the sampling and analysis plan, so that they can
appropriately modify the plan when circumstances require such
modification, and annotate the plan without compromising the
information requirements of the data user.
As QA auditors, if we observe field practices which will
compromise data quality, we must immediately inform the data
user, not wait and write a report qualifying or rejecting the
data several weeks or months down the road. In a recent audit, a
PRP field contractor was observed by our QA staff auditors to
grossly violate the planned protocol for VGA sampling. We
notified the RPM and the PRP immediately, and a very grateful PRP
was able to immediately resample while the contractor was on
site, and only pay to have appropriate samples analyzed, thus
realizing great cost savings over having to remobilize, resample,
and reanalyze in the future.
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Laboratory Analysis Phase:
Here we go again with laboratory analysis. How many times
can it be said. You have to make sure the method you select will
give you what you need! If you need low ppb level organic data,
then you better be using the appropriate low level organic
methods. Familiarity with the concepts of detection limits and
quantitation limits and Contract Required Detection Limits,
...etc, is extremely important. I am familiar with a case in
Region II where the project manager for a treatability study
needed detection levels below the 1-5 ppb concentration of
concern who requested low level analyses. He was told by the
"helpful" QA staff that the available methods were good for
concentrations in the 10-25 ppb range. He had his kazillion
samples, oops! an exaggeration (over 3000 in reality), booked and
analyzed and the data validated. Beaucoup dollars and months
later, upon receipt of the validated data, the manager called the
quality assurance officer totally devastated. The data were all
below detection levels in the 10-25 ppb range. The quality
assurance officer was pretty satisfied with the lab's
performance. "What was this guy's problem?" The project manager
told the QA person that he really needed information in the 1-5
ppb range, and this data was useless to him. Further discussion
revealed that the project manager thought that the method he had
indicated as acceptable would really get down to the 1-5 ppb
level if the laboratory did everything right. Lesson
learned Not all project managers have a good feel for
analytical chemistry. Just as I barely passed organic chemistry
because the professor called it a "black art", project managers
look at analytical chemistry as a very black art.
We cannot assume that the requestor is familiar with the
options available to him. In Region II, the QA staff and the
laboratory chemists handle the majority of advice and decisions
regarding what analytical protocols are used. We have let the
project managers "off the hook", and now the QA folks are
responsible.
Care needs to be taken in choosing the appropriate
analytical method, and the chemists who will perform the
analyses. The laboratory doing the non-routine method should
"play" with the method and the sample matrix to be analyzed to be
sure that the method chosen will yield the results anticipated.
Too often, we send the entire set of site samples off to a
laboratory with only blind faith that all will go well. As I
discussed in the field sampling phase, we should know when to
abort the mission.
As with field sampling, there must also be audits to verify
that the laboratories are, in fact, following their stated SOP's.
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Data Review/Validation Phase:
The principal purpose of data validation is to assure that
the number on the paper really represents what is in the sample.
How precise and accurate is the data,, etc.? As I indicated
earlier in this presentation, EPA spends an inordinate proportion
of time and effort on this phase of the process. We've developed
SOP's on how to validate organic, inorganic, and dioxin data
sets; we've given training courses to our support contractors and
to any other interested parties, especially for validation of
RCRA data sets.
Data validation produces for the customers a data set that
indicates the quality of the data, ranging from an indication of
"the data is exactly what it is shown to be" to "the data is so
flawed as to render it useless". The user understands these two
ends of the spectrum, but if the data is qualified with
conventional flags like "the actual value is known to be greater
than (or less than) the reported value" or "the presence of the
target analyte is verified, but not quantified", the user becomes
confused and unsure of the effect of the qualifier on the use of
the data. As a result he generally either disregards the data or
ignores the qualifiers. The latter approach seriously
compromises Records of Decision (ROD'S) when qualifiers are
deleted from backup documents. Similarly, if the qualified data
is disregarded, potentially useful information is lost.
Clearly, the data review process that only produces a
product that eliminates constructive use of the data is not
meeting the needs of the customer.
Data Assessment Phase:
Data Assessment is the phase that remedies the uselessness
of the product resulting from data review/validation. We've
probably spent less than 1% of our effort on this phase. These
activities incorporate the sum total of all environmental data
and qualifying information into the basis for the decision which
must be made by the data user. The conversion of data into useful
information is critical to the decision maker's success. He
needs the QA staff to relate all the qualifying information to
data usability; to advise on what the qualifiers mean; and to
establish a measure of confidence for the data to be used as the
basis for decisionmaking. As the QA experts, we must help to
"close the loop" for the decision makers, and provide them with
the quality framework within which they can interpret the
environmental data collected.
It is our obligation to inform them of any data limitations,
and the risks associated with using specific data sets.
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How can we best accomplish these tasks? What mechanisms are
there to involve the users in this phase of the process? Did we
provide the customer what he identified as necessary to make the
most informed decision? If we did all the "right" QA activities
in each phase of the project, and are unable to use these
activities to provide useful information to the data user, then
we have failed. On the other hand,if we build user focus and
customer involvement into each phase of the project, we are
assured at every milestone of the project that we are on the
"right" road.
There are two endings to this presentation - the first and
less kinder and gentler is the message - COMMUNICATE,
COMMUNICATE, COMMUNICATE At almost every step of the way
there is a crying need for communication. Without meaningful
communication.between the usere and supplier, there will never be
other than accidental success.
As a second, more formal ending, I hope I have been able to
stimulate your thinking on how appropriate QA might be developed
through active customer involvement; how we might better build a
11 user focus" into quality assurance activities during every
phase of any environmental data collection effort. Your active
participation in the upcoming sessions is important if we are to
develop a consensus approach which will yield useful information,
not just qualified data, to our customers, the decision makers of
our respective agencies. Thank you.
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