Transcript Managing Uncertainty through Better Upfront Planning and

Managing Uncertainty through Better
Upfront Planning and Flexible Workplans
Northeast States’
Improving the Quality of Site Characterization
Albert Robbat, PhD
Tufts University, Chemistry department
Center for Field Analytical Studies and Technology
Medford, Massachusetts 02155
tel 617-627-3474; [email protected]
What’s the Problem
• Hazardous waste site characterization and cleanup is expensive
and time-consuming.
• Small sites to extremely large sites require the same systematic
planning and scientific assessment.
• Money is tight, yet data volume is needed to make sound
scientific decisions as to the nature and extent, if any, of
contamination.
• New sampling and analytical measurement technologies have
been that have the potential to greatly reduce cost and time.
• New processes have been developed and promoted by state and
federal agencies, but are rarely used.
• Why??
What’s The Opportunity
• Systematic Planning, Dynamic Workplans, Field
Analytics and On-site Decision Making together can:
 Provide more information at less cost and over shorter
time periods.
 Provide screening to quantitative “risk” quality data, when
and where needed.
 Increase field personnel efficiency and on-site decision
making confidence.
 Increase site-specific information and final site
characterization decision confidence.
Conversion of an Abandoned
Chemical Plant to an
Entertainment Complex
Brownfields
Redevelopment
Urban Waste Sites
Converted to
an Industrial Park
Brownfields
Redevelopment
What is Decision Making Uncertainty?
What is Sampling and Analysis Uncertainty?
How Many Wells?
What is Decision Making Uncertainty?
What is Sampling and Analysis Uncertainty?
How Many Soil Samples?
What Role Does Heterogeneity Play in
the Sample Collection, Analysis, and
Decision Making Process?
Rapid in situ
Sample Collection and Analysis
Better Contamination Depth Profiles
DAF, dilution attenuation factor
Rapid Direct MS Measurements
Direct In situ TECP-MS
Better Assessment of VOC Risk to Groundwater
Field versus Laboratory VOC Data Comparison
No degradation or loss of analyte due to time delays
S a m p l e ID
C o m po unds
S 2 -B 2 -(2 0 -2 2 )
1 ,1 - d ic h lo r o e th e n e
1 ,1 - d ic h lo r o e th a n e
c is -1 ,2 -d ic h lo r o e t h e ne
1 ,1 ,1 - tr ic h lo ro e th e n e
to l u e ne
te tr a c h lo r o e t h a n e
e th y lb e n ze n e
m /p -x y le n e
o -x y le n e
S 3 -B 1 -(1 3 -1 5 )
to l u e ne
e th y lb e n ze n e
m /p -x y le n e
o -x y le n e
S 3 -B 2 3 -(1 3 -1 5 )
1 ,1 - d ic h lo r o e th e n e
c a r b o n te tr a c h lo r id e
te tr a c h lo r o e t h a n e
e th y lb e n ze n e
o -x y le n e
F ield (p p b )
L a b o r a to r y
(pp b)
30
41
56 0
30 0
3 7 ,0 0 0
12 0
99 0
7 ,4 0 0
2 ,2 0 0
< 50
< 50
< 50
250
2 ,0 0 0
< 50
240
1 ,2 0 0
480
2 8 0 ,0 0 0
3 ,0 0 0
3 2 0 ,0 0 0
8 3 ,0 0 0
5 8 ,2 0 0
1 4 ,5 0 0
5 8 ,7 0 0
2 5 ,5 0 0
15
6
23
7
17
<
<
<
<
<
10
10
10
10
10
Projected vs Actual Number of Samples Analyzed
Dynamic Workplan Projected and Actual Number of Samples Analyzed
TypeofAnalysis
Site1
Samples
Site2
Samples
Site3
Samples
TotalSamples
Analyzed
Projected Actual Projected Actual Projected Actual Projected Actual
VOCSamples
Screened
162
210
135
177
288
214
585
601
VOCSamples
Quantified
42
51
36
58
59
49
137
158
PCB/PAHSamples
Quantified
42
46
0
12
0
10
42
68
MetalsSamples
quantified
51
22
44
54
36
45
131
121
Sample number includes field duplicates.
Traditional Approach
1. Planning Phase
Characteristics
- pre-planned sampling grids
- off-site lab analysis
- static work plans
Problems
- high cost per sample
- surprise results
- pressure to oversample
- multiple trips to field
2. Sample Collection
6. Decisions Made
Sa m p
les
Off-Site
s
Re sul t
3. Transportation
5. Results Returned
4. Lab Analysis
Dynamic Workplan Approach
Characteristics
- Real time sample analysis
- Rapid field decision making
- Dynamic workplans
Planning Phase
Advantages
- Reduce cost per sample
- Increase # of samples
- Reduce # of field visits
- Faster, better, cheaper
Sample Collection
Decisions Made
Requirements
- Field analytical methods
- Decision support in the field
Field Analysis
Systematic Planning and Dynamic Workplan
 Select Core Technical Team
• Designate one member with authority to make final field decisions
• Develop workplan “thought process and rules-to-follow” in the
field
• Although in Massachusetts and Connecticut upfront buy-in is not
needed, adherence to the documented “thought process” will help
insure acceptance of field data results
 Develop Conceptual Model & Decision Making Framework
• Produce map depicting vadose zone and groundwater flow systems
that can influence contaminant movement
• Establish DQO’s to ensure type, quantity, and quality of field data
 Develop Standard Operating Procedures
• Produce performance methods that support the DQO process
• Document MDL’s prior to field mobilization
Systematic Planning and Dynamic Workplan
 Develop Data Management Plan
• Integrate chemical, physical, geological, and hydrogeological data
 Develop Quality Assurance Project Plan
• Define technical team/regulators responsibilities consistent with
EPA/state policy
 Prepare Health and Safety Plan
• Establish DQO’s to monitor worker/community safety
Performance-based
Field Requirements
• Collect samples quickly
• Analyze samples quickly
• Review and report
results quickly
PBMS/Keys to Success
 Experienced, trained personnel
 Data produced must provide level of assurance that it meets
sufficient accuracy, precision, selectivity, sensitivity, and
representativeness to meet project-specific DQO’s
 Legal Defensibility, Rule 702, Determination of Reliability
• technique tested, subject to peer review, accepted by scientific
community
• method reproducible, with potential rate of error known
 Visible & well-documented practices and procedures
manuals for effective quality system
High Performance/Quality Control
 Blanks, LCS, SRMs, MS, MSDs
 Calibration & Continuing Calibration
 Peak Integration
 MDL’s
 DQO’s
 Data Useability
 Reporting
Field Analysis of Organics
 In situ or Hand-held Vapor Analyzers
• ECD, FID, PID provides signal response in seconds
 Portable GC’s with Selective Detection
• ECD, FID, PID provides screening data in seconds to 10’s minutes
 Field GC’s with Selective Detection
• ECD, FID, PID provides semiquantitative data in 10’s of minutes
 Field GC’s with Mass Spectrometry Detection
• Provides semiquantitative to quantitative data in seconds to 10’s
of minutes
 In situ Mass Spectrometry
• Provides semiquantitative data in seconds
 Immunoassay or colorimetric Kits
• Provides screening data in 2-15 min
eNose Detection of Volatiles
By Direct Measuring MS
Or TECP-MS
50 compounds
detected in 20 sec
Field Analysis of Metals
 x-ray Fluorescence Spectroscopy
• Provides screening to quantitative data in seconds to 10’s of minutes
 Inductively Coupled Plasma/Optical Emission Spectroscopy
• Provides quantitative data in minutes
 Anodic Stripping Voltammetry
• Provides quantitative data in minutes
 Immunoassay or colorimetric Kits
• Provides screening data in 2-15 min
Comparison of Field Technologies for PCBs and PAHs
Selected
Comparison of Method
andProjects
Data Quality Attributes
Polycyclic Aromatic Hy drocarbons
Polychlorinated Biphenyls
! Hanscom Air Force
Base, Bedford, MA (Volatiles, Semi-volatiles,
Metals)
Site-s pecific
Enzyme
! Joliet
Army Amunition
Plant,
IL (Explosives)
DQO’s and
Attributes
GC/FID Joliet,
TD GC/ MS
GC/ECD
Enzyme
Kits
Spec iate
class-spec ific
0.2-ppm
Aroc lor
Dependent
0.5 to 1-ppm
30%
40%
MFG.
Dependent
40 %
Yes
No
No
Yes
No
20-min
10-min
10-min
19
32
32
Kits
Action Level
! NJ Yes
SuperfundSelectivity
Site (Metals)
No
!
TD GC/MS
Speciate
class-spec ific
Yes
1-ppm/P AH
MFG. and
0.5-ppm
total PC
B
Sensitivity
0.5-ppm Semi-volatiles,
0.3-ppm
Compound
0.03-ppm
MCAS,
Yuma,
AZ (Volatiles,
Metals)
Dependent
MFG.
! Fort
Devens,
Ayer,
MA
(Volatiles,
Semi-volatiles)
40%
Precision
40%
40%
Dependent
40%
! KY Pipeline Company
(PCBs)
Accuracy
No
! Landfills,
No
! Naval
! New
biase d to ward:
false positive
Yes
MA
&
VA
(Volatiles,
false negative
No
Analysis
Rate/Sample
Security
Station,
No
Yes
Semi-volatiles,
No
No Metals)
No
20-min
10-minDC (PCBs)
10-min
Washington,
Total Number of
Sam ples
19
EnglandAnalyzed
Coal
Gasification
per
10-hr Work Day
32
32
Plants
(PAHs)
! Midwestern Manufacturing Co. (Volatiles, Semi-volatiles)
VOC Analysis of Soil by Purge and Trap GC/MS
QC Parameters
Field PBMS
SW-846 Modified Method 8260A
Laboratory Analysis
SW-846 Method 8260A
Instrument Performance
Tests MS Tuning
perform instrument check, minimum
requirement once to initiate shift
perform instrument check, minimum
requirement once to initiate 12-hr shift
Initial Calibration
5-point
DQO dependent; match SW 846 or all RF
%RSDs 40% with no more than a > 30%
or all RF %RSDs 30%
calibration check compounds (CCC)
%RSD’s < 30%, if all RF %RSD 15%
then use Ave. RF else use linear regression
Laboratory Control
Standard
sample throughput dependent,
can match SW 846
after each initial calibration;
percent accuracy within 80% to 120%
Continuing Calibration
Verification
DQO dependent; match SW 846 or begin &
end of day, % Diff for all compounds 
40% and no more than a > 30%
one per 12-hr shift; (calibration check
compound) CCCs < 20%. All analytes
within ± 25% of expected value
Method Blank
once per day and after highly contaminated
sample; all target compound conc. < PQL
one per analytical batch;
all target compound conc. < PQL
Surrogate Spike Analysis
DQO throughput rate dependent; for each
sample, blank, standard or other QC run
for each sample, blank, standard or other
QC run, laboratory established recovery
limits (e.g. 80-130 %)
Sensitivity
5-2500 ppb levels, matrix dependent
5-2500 ppb levels, matrix dependent
Selectivity
can do up to 97 VOCs 2-6 ions per analyte;
minimal chromatographic separation,
selectivity achieved by IFD software
can do up to 97 VOCs with 1-6 ions per
compound; adjust chromatography to
separate VOCs of interest
Precision
replicate analysis
QC acceptance criteria
replicate analysis
QC acceptance criteria
Accuracy
sample throughput dependent; can match
SW 846; laboratory control check sample
(LCS) once per day
surrogate dependent recovery within 70120%; laboratory control check sample
(LCS) once per 12-hr shift
Other
carryover monitored by analysis of blanks,
watch baseline on chromatograms
carryover monitored by analysis of blanks,
watch baseline on chromatograms
SVOC Analysis of Soil by Thermal Desorption GC/MS
QC Parameters
Field PBMS
SW-846 Modified Method 8270C
Laboratory Method
SW-846 Method 8270B
Instrument Performance
Tests MS Tuning
perform instrument check, minimum
requirement once to initiate shift
perform instrument check, minimum
requirement once to initiate 12-hr shift
Initial Calibration
5-point
DQO dependent; SW 846 or all RF %RSDs
40% and no more than a > 30%
calibration check compounds (CCC)
%RSD’s < 30%, if all RF %RSD 15% then
use Ave. RF else use linear regression
Laboratory Control
Standard
DQO throughput dependent; after each initial
calibration, percent accuracy 80% to 120%
after each initial calibration; percent
accuracy
within 80% to 120%
Continuing Calibration
Verification
DQO dependent; can match SW 846 or begin
& end of day, % Diff for all compounds
40% with no more than a > 30%
one per 12-hr shift;
%D for all compounds 20%
Method Blank
once per extraction batch; all target
compound concentrations < PQL
one per extraction batch;
all target compound concentrations < PQL
Surrogate Spike Analysis
sample throughput dependent; for each
sample, blank, standard or other QC run
for each sample, blank, standard or other QC
run, laboratory established recovery limits
(e.g. 20-130 %)
Sensitivity
100-ppb to 1000-ppb
660-ppb to 3300-ppb
Selectivity
can do up to 350 SVOC 2-6 ions per analyte;
minimal chromatographic separation,
selectivity achieved by IFD software
can do up to 350 SVOC with 2-5 ions per
analyte; adjust chromatography to separate
SVOC of interest
Precision
replicate analysis QC acceptance criteria
replicate analysis QC acceptance criteria
Accuracy
sample throughput dependent; can match SW
846 for surrogate and MS/MSD recoveries
surrogate recovery compound dependent;
MS/MSD per extraction batch
Cost Comparison and Data Turnaround Times
Analyte
Current Laboratory Approach
Data Turnaround: 14 to 30 days
Faster Turnaround: 50-150% surcharge
PBMS
TDGC/MS with IFD
Data Turnaround: < 7 days
VOCs
$125/sample
SW 846 method 8240/8260
25-min/sample analysis
$75/sample
modified 8260
20-min/sample
PCBs
$100/sample
SW 846 method 8080
20-min/sample analysis;
sample preparation
2-hr/batch of 20 samples
PAHs
$145/sample
SW 846 method 8100/8310;
20-min/sample analysis,
sample preparation
2-hr/batch of 20 samples
Explosives
$180/sample
SW 846 8330/USAED 30
20-min/sample analysis;
sample preparation
18-hr/batch of 20 samples
Semi-VOCs
$375/sample
SW 846 method 8270
40-min/sample analysis;
sample preparation
4-hr/batch of 20 samples
$100/sample
modified 8270
10-min per analysis;
sample preparation
1-hr/batch of 20 samples
$100/sample
modified 8270
20-min per analysis;
sample preparation
1-hr/batch of 20 samples
Sampling and Analysis Flow Chart
Phase 1
Site Screening
Phase 2
On-Site Verification
Phase 3
Lab Verification
Sampling Based on Initial Conceptual Model
Step 1
1) Conduct geophysics survey based
on areas known to contain contaminants.
2) Conduct soil and soil gas survey
for all CLP TCL contaminants.
No
Contaminated ?
Yes
Delineate zone of contamination
Step 2
1) Focus sampling and analysis targeting
only those contaminants found in step 1.
2) Employ geostatistical sampling tools and
adapt strategy based on the data obtained.
Step 3
Locate vertical and horizontal boundaries by
stepping-out at 4 locations and 2 depth.
Verify "Clean Sites"
Analysis of 4 depth samples from
5 random locations.
Field quantitive analysis of all
contaminants. Total 20 samples.
Verify non-detect at boundary
Analyze 4 samples at 2 depths from outside
contaminated zone. Total 8 samples.
Verify the TARGET list
Analyze inside contaminated area
for all CLP TCL analytes at 4
random locations and at 4 depths.
Quantitate full suite of contaminants.
Total 16 samples.
Send 5 split samples from
random locations to
Total 5 samples.
Send 4 split samples
to laboratory .
Total 4 samples.
Send 4 split samples to
laboratory. Total 4 samples.
Barriers
Why is the Same Technology Readily
Accepted in Other Regulated Markets?
Answer
They have learned how to deal with
measurement and decision making
uncertainties!!
Research Funding & Logistical Support
•
•
•
•
•
•
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U.S. Environmental Protection Agency
Army Environmental Center, Joliet Ammunition Plant
Hanscom Air Force Base
Department of Energy
Agilent Technologies
State Regulatory Agencies
OHM, CH2MHill, Jacobs Engineering, Bechtel
Charles River Laboratories, Pharmacopeia