Managing Uncertainty through Better Upfront Planning and Flexible Workplans

Managing Uncertainty through Better Upfront Planning and Flexible Workplans

Albert Robbat, PhD

Tufts University, Chemistry department

Center for Field Analytical Studies and Technology

Medford, Massachusetts 02155

tel 617-627-3474; [email protected]

Northeast States’ Improving the Quality of Site Characterization

• 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 Problem

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.

BrownfieldsRedevelopment

Conversion of an Abandoned Chemical Plant to an

Entertainment Complex

BrownfieldsRedevelopment

Urban Waste SitesConverted to

an Industrial Park

What is Decision Making Uncertainty?

What is Sampling and Analysis Uncertainty?

How Many Wells?

Rapid in situSample Collection and Analysis

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?

Better Contamination Depth Profiles

DAF, dilution attenuation factor

Rapid Direct MS Measurements

Direct In situ TECP-MS

Better Assessment of VOC Risk to Groundwater

Sample ID Compounds Field (ppb)Laboratory

(ppb)

S2-B2-(20-22) 1,1-dichloroethene 30 < 501,1-dichloroethane 41 < 50cis-1,2-dichloroethene 560 < 501,1,1-trichloroethene 300 250toluene 37,000 2,000tetrachloroethane 120 < 50ethylbenzene 990 240m/p-xylene 7,400 1,200o-xylene 2,200 480

S3-B1-(13-15) toluene 280,000 58,200ethylbenzene 3,000 14,500m/p-xylene 320,000 58,700o-xylene 83,000 25,500

S3-B23-(13-15) 1,1-dichloroethene 15 < 10carbon tetrachloride 6 < 10tetrachloroethane 23 < 10ethylbenzene 7 < 10o-xylene 17 < 10

Field versus Laboratory VOC Data Comparison

No degradation or loss of analyte due to time delays

T y pe o f A na ly s isS ite 1

Sa m ple sS ite 2

S a m ple sSite 3

S a m p le sT o ta l Sa m ple s

A na ly ze d

P r o je cte d A ctu a l P r o je c te d A c tu a l P ro je c te d A c tua l P ro je c te d A c tua l

VO C S am p le sSc re e n ed

1 62 21 0 13 5 17 7 28 8 2 1 4 5 8 5 6 0 1

VO C S am p le sQ u a nt ifie d

42 51 36 5 8 5 9 4 9 1 3 7 1 5 8

P C B/P A H S am p le sQ u a nt ifie d

42 46 0 1 2 0 1 0 4 2 6 8

M e ta ls Sa m p le sq ua n tif ied

51 22 44 5 4 3 6 4 5 1 3 1 1 2 1

S a m p l e n u m b e r i n c l u d e s f i e l d d u p l i c a t e s .

D y n a m i c W o r k p l a n P r o j e c t e d a n d A c t u a l N u m b e r o f S a m p l e s A n a l y z e d

Projected vs Actual Number of Samples Analyzed

Traditional Approach

Off-SiteSamples Results

1. Planning Phase

2. Sample Collection 6. Decisions Made

3. Transportation

4. Lab Analysis

5. Results Returned

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

Dynamic Workplan Approach

Planning Phase

Sample Collection Decisions Made

Field Analysis

Characteristics- Real time sample analysis- Rapid field decision making- Dynamic workplans

Advantages- Reduce cost per sample- Increase # of samples- Reduce # of field visits- Faster, better, cheaper

Requirements- Field analytical methods- Decision support in the field

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

Systematic Planning and Dynamic Workplan

Field Requirements• Collect samples quickly

• Analyze samples quickly

• Review and report results quickly

Performance-based

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

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

Field Analysis of Organics

eNose Detection of Volatiles

By Direct Measuring MSOr TECP-MS

50 compounds detected in 20 sec

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

Field Analysis of Metals

Selected Projects! Hanscom Air Force Base, Bedford, MA (Volatiles, Semi-volatiles, Metals)

! Joliet Army Amunition Plant, Joliet, IL (Explosives)

! NJ Superfund Site (Metals)

! MCAS, Yuma, AZ (Volatiles, Semi-volatiles, Metals)

! Fort Devens, Ayer, MA (Volatiles, Semi-volatiles)

! KY Pipeline Company (PCBs)

! Landfills, MA & VA (Volatiles, Semi-volatiles, Metals)

! Naval Security Station, Washington, DC (PCBs)

! New England Coal Gasification Plants (PAHs)

! Midwestern Manufacturing Co. (Volatiles, Semi-volatiles)

Comparison of Field Technologies for PCBs and PAHs

Polycyclic Aromatic Hydrocarbons Polychlorinated Biphenyls

Site-specificDQO’s and

Action LevelAttributes GC/FID TD GC/ MS

EnzymeKits

GC/ECD TD GC/MSEnzyme

Kits

Ye s Selectivity N o S p ec ia t e c la ss -sp ec ific Ye s S p ec iat e c la ss -sp ec ific

1 -pp m /P A H0.5 -p pm t ot a l P C B Sensitivity 0.5 -p pm 0 .3 -pp m

M FG . a ndC om p o un dD e p e nd e nt

0 .03 -p p m 0.2 -p pmAroc lor

D e p e nd e n t0 .5 to 1 -pp m

4 0% Precision 4 0% 40 %M FG .

D e p e nd e nt 4 0%

3 0 % 4 0%M FG .

D e p e nd e n t 4 0 %

N oN o

Accuracy biase d to ward:

false positivefalse negative

YesN o

N oN o

YesN o

Ye sN o

N oN o

Ye sN o

AnalysisRate/Sample 2 0 -m in 1 0- m in 1 0 -m in 20 -m in 1 0 -m in 1 0 -m in

Total Number ofSam ples

Analyzed per10-hr Work Day

1 9 32 32 1 9 32 3 2

Comparison of Method and Data Quality Attributes

QC ParametersField PBMS

SW-846 Modified Method 8260ALaboratory Analysis

SW-846 Method 8260A

Instrument PerformanceTests MS Tuning

perform instrument check, minimumrequirement once to initiate shift

perform instrument check, minimumrequirement 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 ControlStandard

sample throughput dependent, can match SW 846

after each initial calibration;percent accuracy within 80% to 120%

Continuing CalibrationVerification

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 checkcompound) CCCs < 20%. All analytes

within ± 25% of expected value

Method Blankonce per day and after highly contaminatedsample; all target compound conc. < PQL

one per analytical batch;all target compound conc. < PQL

Surrogate Spike AnalysisDQO throughput rate dependent; for eachsample, blank, standard or other QC run

for each sample, blank, standard or otherQC run, laboratory established recovery

limits (e.g. 80-130 %)

Sensitivity 5-2500 ppb levels, matrix dependent 5-2500 ppb levels, matrix dependent

Selectivitycan 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 percompound; adjust chromatography to

separate VOCs of interest

Precisionreplicate analysis

QC acceptance criteriareplicate analysis

QC acceptance criteria

Accuracysample throughput dependent; can matchSW 846; laboratory control check sample

(LCS) once per day

surrogate dependent recovery within 70-120%; laboratory control check sample

(LCS) once per 12-hr shift

Othercarryover monitored by analysis of blanks,

watch baseline on chromatogramscarryover monitored by analysis of blanks,

watch baseline on chromatograms

VOC Analysis of Soil by Purge and Trap GC/MS

QC ParametersField PBMS

SW-846 Modified Method 8270CLaboratory Method

SW-846 Method 8270B

Instrument PerformanceTests MS Tuning

perform instrument check, minimumrequirement once to initiate shift

perform instrument check, minimumrequirement 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 ControlStandard

DQO throughput dependent; after each initialcalibration, percent accuracy 80% to 120%

after each initial calibration; percentaccuracy

within 80% to 120%

Continuing CalibrationVerification

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 Blankonce per extraction batch; all targetcompound concentrations < PQL

one per extraction batch; all target compound concentrations < PQL

Surrogate Spike Analysissample throughput dependent; for eachsample, blank, standard or other QC run

for each sample, blank, standard or other QCrun, laboratory established recovery limits

(e.g. 20-130 %)

Sensitivity 100-ppb to 1000-ppb 660-ppb to 3300-ppb

Selectivitycan 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 peranalyte; adjust chromatography to separate

SVOC of interest

Precision replicate analysis QC acceptance criteria replicate analysis QC acceptance criteria

Accuracysample throughput dependent; can match SW

846 for surrogate and MS/MSD recoveriessurrogate recovery compound dependent;

MS/MSD per extraction batch

SVOC Analysis of Soil by Thermal Desorption GC/MS

Cost Comparison and Data Turnaround Times

Analyte Current Laboratory Approach

Data Turnaround: 14 to 30 daysFaster Turnaround: 50-150% surcharge

PBMS TDGC/MS with IFD

Data Turnaround: < 7 days

VOCs$125/sample

SW 846 method 8240/826025-min/sample analysis

$75/samplemodified 826020-min/sample

PCBs

$100/sampleSW 846 method 8080

20-min/sample analysis;sample preparation

2-hr/batch of 20 samples

$100/samplemodified 8270

10-min per analysis;sample preparation


PAHs

$145/sampleSW 846 method 8100/8310;

20-min/sample analysis,sample preparation


Explosives

$180/sampleSW 846 8330/USAED 3020-min/sample analysis;

sample preparation18-hr/batch of 20 samples

Semi-VOCs







Analyte Current Laboratory Approach

Data Turnaround: 14 to 30 daysFaster Turnaround: 50-150% surcharge

PBMS TDGC/MS with IFD

Data Turnaround: < 7 days

VOCs$125/sample

SW 846 method 8240/826025-min/sample analysis

$75/samplemodified 826020-min/sample

PCBs







PAHs

$145/sampleSW 846 method 8100/8310;

20-min/sample analysis,sample preparation


Explosives

$180/sampleSW 846 8330/USAED 3020-min/sample analysis;

sample preparation18-hr/batch of 20 samples

Semi-VOCs







Contaminated ?

Delineate zone of contamination

1) Focus sampling and analysis targeting only those contaminants found in step 1.

Step 3Locate vertical and horizontal boundaries by stepping-out at 4 locations and 2 depth.

Step 2

2) Employ geostatistical sampling tools and adapt strategy based on the data obtained.

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

contaminated zone. Total 8 samples.Analyze 4 samples at 2 depths from outside

Sampling Based on Initial Conceptual ModelStep 1

2) Conduct soil and soil gas survey

for all CLP TCL contaminants.

1) Conduct geophysics survey based on areas known to contain contaminants.

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 samplesto laboratory .

To tal 4 sam ples.

Send 4 split samples to laboratory. Total 4 samples.

Phase 1Site Screening

Phase 2On-Site Verification

Phase 3 Lab Verification

Yes

No

Sampling and Analysis Flow Chart

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

• 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

Documents

Managing Uncertainty through Better Upfront Planning and Flexible Workplans