monitoring aquatic contaminants with time- averaged

Monitoring Aquatic

Contaminants with Time-

averaged Concentrations by

Programmable In Situ Extraction

Rolf U. Halden, PhD, PE

Isaac B. Roll, PhD

October 27, 2015

1

This work was performed under

ESTCP ER-201122

Cost-Effective, Ultra Sensitive Groundwater

Monitoring for Site Remediation and

Management

2

1. Background and

Rationale

2. In Situ Sampler

3. Demonstration

4. Applicability

5. Questions and

Comments

Agenda

3

Photograph: Erin Driver

1. Background and

Rationale

4

• Characterization

drives up to 25% of

remediation

expenditures1,2

• $2 billion/year (US)

• Federal mandates to

reduce energy use,

carbon emission

Sustainability and Economics

25%

Characterization

and Monitoring

Side Remediation Expenditures

(approximately $8 billion/year)

51. Background and Rationale

Photograph: Isaac Roll

• Taking measure

– Sampling method in

the field

– Analytical method in

the lab

• Sources of error

– Sampling: >90%3

– Analytical: <10%

• Training, SOPs,

QA/QC cannot

address all sources

Environmental Characterization

Characterization

And Monitoring


Photograph: Alizee Jenck

• Preservation

• Mass and volume

– Transportation

– Hazardous waste

• Field extraction

– Improves stability of

analytes4

– Reduces mass,

handling

Liquid Sample Challenges

Characterization

And Monitoring



• Discrete sampling

may be too infrequent

• Time-integrated

sampling

– Passive samplers

(weeks)

– Active samplers

(days)

– Reproducibility

Dynamic Environments

Characterization

And Monitoring0

0.5

1

1.5

0 5 10 15 20

C/C

0

Time

Cw

CA Discrete Sample Set A

CB Discrete Sample Set B

0

0.5

1

1.5

0 5 10 15 20

C/C

0

Time

Cw

CR Accumulative Sampler


Approach• Reduce and manage sampling error

– Active sampler

– Simultaneous, replicate samples

• Eliminate liquid samples

– In situ extraction with off-the-shelf consumables

– Reduce sample mass, improve stability

• Time-integrated sampling

– Programmable sampling rate

– Sampling periods from days to weeks

Characterization

And Monitoring


2. In Situ Sampler (IS2)

10

Reduce and Manage Error• Precision,

programmable

positive-displacement

pumps

• Six parallel sampling

channels for

simultaneous

replicates

• Autoclavable glass

(5 mL) or plastic

(10 mL) syringes 112. In Situ Sampler (IS2)

Photographs: Isaac Roll

• Solid phase extraction

(SPE)

• Parallel and/or series

extraction

• Commercial, off-the-

shelf cartridges and

sorbents

• Lab methods

become field

methods

Eliminate Liquid Samples

7.5 cm



• Programmable

sampling rate

• Timed aliquots or

nearly-continuous

sampling

• Sampling periods

from days to weeks


13

Time-Integrated Sampling

0

0.5

1

1.5

0 5 10 15 20

C/C

0

Time

Cw

CR Accumulative Sampler


14

In Situ Sampler (IS2)

140 cm demonstration sampler

(including optional liquid capture)


Photograph: Sara Murch

3. Demonstration

15

• Shallow, coastal

freshwater aquifer

• Sands, sandy silts

• Chromium-VI

• Demonstration well

– 10-cm diameter

– Water at 4 ft

– Screened 9 – 19 ft

– 0.25 mg/L Cr(VI)

(July 2013)

16

Demonstration: Coronado Island

3. Demonstration

Satellite Image: Google Earth

• 24-hour sampling at

two-hour intervals

• Cr(VI) concentration

fluctuated by ±20%

of mean

• Fluctuation followed

tide

• No observed change

in depth to water

17

Pre-Demonstration Sampling

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

0.5

1.0

1.5

2.0

Tid

e (

AM

SL),

Well

(DT

W)

(m)

Concentr

ation (

mg/L

)Chromium(VI)

Tide (AMSL)

Well (DTW)

12:0

0 P

M

12:0

0 A

M

12:0

0 P

M

3. Demonstration

Demonstration Objectives

• Reduce and manage sampling error

– 1.25 mL samples at 2-hr intervals

– 420 mL total

– Triplicate samples

• Eliminate liquid samples

– Parallel SPE and liquid sampling to

demonstrate equivalence

• Time-integrated sampling

– 28-day, 420-mL composite sample

183. Demonstration

19


3. Demonstration


20


3. Demonstration

Photographs: Erin Driver (L) and Isaac Roll (R)

Reduce and Manage Sampling Error

21

• Triplicate samples

provide inter-

sample error (8%)

• Active sampling

improved sampling

rate (RS) precision

(3.4%) versus

passive

samplers7,8,9,10

3. Demonstration

0

10

20

30

40

50

60

70

80

90

100

CSS MESCO POCIS SPMD IS2

(n = 18) (n = 21) (n = 46) (n = 12) (n = 8)

RS

D (

%)

of S

am

plin

g R

ate

Range of RSD (%) Observed for

Sampling Rates

CSS: Constantly Stirred SorbentMESCO: Membrane-Enclosed Sorptive Coating POCIS: Polar Organic Chemical Integrative SamplerSPMD: Semipermeable Membrane DeviceIS2: In Situ Sampler

• 420-mL liquid

samples yielded 4-g

SPE samples

• Equivalent to 336

discrete samples

• No liquid handling by

technicians

• 99% reduction in

material leaving site

• For 250-mL samples:

22

Eliminate Liquid Samples

Hazardous

Material

Production

-98%

Cost of

Transportation6

-92%

Carbon Impact of

Transportation5

-98%

3. Demonstration

• 28-day time-

integrated average

• 75% ± 6% recovery

• 8-fold improvement in

reporting limit

23

Time-Integrated Sampling

0.01

0.10

1.00

Day 7 Day 14 Day 28 28-DayAverage

28-DayAverage

Liquid Composite Samples SorbedSamples

Co

nce

ntr

atio

n (

mg

/L)

Total Cr Reporting Limit

3. Demonstration

• Capital

– Research instrument

costs were similar to

available commercial

instruments ($4000)

• Operating

– Technician time in field

observed similar to

other instruments

– Waste and

transportation costs

reduced

24

Comparison of Costs

3. Demonstration

0

2500

5000

7500

IS2 LiquidAutosampler

6-ParameterSonde

BladderPump

US

Do

llars

Capital Cost

4. Applicability

25

• Environmental

characteristics

amenable to passive

sampling (see ASTM

D7929-14)

• Contaminant

compatibility and

degradation modes

– Many contaminants

are stabilized by field

extraction4

26

Method Development

4. Applicability


5. Conclusions

27

• In Situ Sampler

– High-precision active

sampling

– Simultaneous replicate

samples

– In situ solid phase

extraction

– Commercial off-the-

shelf consumables

– Long time-base, time-

integrated sampling

– Large sample volume28

Conclusions

Error

CO2

Waste

Cost

5. Conclusions


• ESTCP– Project Sponsor

• NAVFAC Southwest– Case Study Site at Naval

Air Station North Island, San Diego, CA

• Amec Foster Wheeler– Development Study Site

at Former Williams Air Force Base, Mesa, AZ

• ASU Center for Environmental Security Team and Collaborators

29

Acknowledgements


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DC, 2004.

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92, (4), 466-478.

4. Green, D. R.; Le Pape, D., Stability of hydrocarbon samples on solid-phase

extraction columns. Analytical Chemistry 1987, 59, (5), 699-703.

5. U. S. Environmental Protection Agency, Optional Emissions from

Commuting, Business Travel and Product Transport; EPA430-R-08-006;

Washington, DC, 2008.

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2015)

30

References7. Vrana, B.; Popp, P.; Paschke, A.; Schüürmann, G., Membrane-Enclosed

Sorptive Coating. An Integrative Passive Sampler for Monitoring Organic

Contaminants in Water. Analytical Chemistry 2001, 73, (21), 5191-5200.

8. Alvarez, D. A.; Petty, J. D.; Huckins, J. N.; Jones‐Lepp, T. L.; Getting, D. T.;

Goddard, J. P.; Manahan, S. E., Development of a passive, in situ,

integrative sampler for hydrophilic organic contaminants in aquatic

environments. Environmental Toxicology and Chemistry 2004, 23, (7), 1640-

1648.

9. Huckins, J. N.; Petty, J. D.; Orazio, C. E.; Lebo, J. A.; Clark, R. C.; Gibson,

V. L.; Gala, W. R.; Echols, K. R., Determination of uptake kinetics (sampling

rates) by lipid-containing semipermeable membrane devices (SPMDs) for

polycyclic aromatic hydrocarbons (PAHs) in water. Environmental Science &

Technology 1999, 33, (21), 3918-3923.

10.Llorca, J.; Gutiérrez, C.; Capilla, E.; Tortajada, R.; Sanjuán, L.; Fuentes, A.;

Valor, I., Constantly stirred sorbent and continuous flow integrative sampler:

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Journal of Chromatography A 2009, 1216, (31), 5783-5792.

31

Questions?

32


CorrespondanceRolf U. Halden, PhD, PE

Director, Center for Environmental Security

The Biodesign Institute at Arizona State University

781 E. Terrace Road, Tempe, AZ 85287-5904

Email: [email protected]

Phone: 480-727-0893

33

monitoring aquatic contaminants with time- averaged

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