Persistent Organic Contaminant Availability in …Persistent organic pollutant availability in...

Persistent Organic Contaminant Availability in Sediment: Improved Risk Assessment and Novel Remediation Approachesand Novel Remediation Approaches

Dr. David Werner & many others (see acknowledgements)

Lecturer in Environmental Engineering, Newcastle University

September 23rd 2009

Persistent organic pollutant availability in sediment Slide 2

Overview

Persistent organic pollutants (POPs):

1. POP availability in sediment:

- Traditional and improved modelling concepts- Importance of organic carbon characterization- Importance of organic carbon characterization- Measurement methods- Implications for risk assessement

2. Novel remediation approaches:

- Case study of a traditional dredging approach at a U.S. superfund site- Rational for sediment remediation with activated carbon- Activated carbon amendment vs. bioremediation


PAH pollution in U.K. sedimentsEstuary Sediment type Individual EPA

PAHs(mg/kg)

Tweed Sand < 0.015

Blyth Mud 0.1 to 2.5

Tyne at Hebburn Mud 0.2 to 6 PAHsTyne at Hebburn Mud 0.2 to 6

Wear Mud 0.1 to 5

Thames Mud 0.01 to 1

According to Woodhead et al., 1999, Marine Pollution Bulletin, 38, from p. 773

Dredged sediments may be disposed of at sea without further testing only when the concentration of individual PAHs is below 0.1 mg/kg (all PAHs except 0.01 mg/kg for dibenz[a,h]anthracene)

Department for Environment Food and Rural Affairs, 2002: The use of action levels in the assessment of dredged material placement at sea and in Estuarine Areas under FEPA(II)

PAHs

Modelling the fate of persistent organic pollutants in sediment Slide 4

Sediment research network

http://www.ceg.ncl.ac.uk/insr/

International Network for Sediment Research sponsored by the Leverhulme Trust

INSR’s mission is to define the concepts for improved biogeochemical models of the pollutant fate in sediment and compile data for model calibration and testing in a shared database.

http://www.ceg.ncl.ac.uk/insr/


Traditional models (fugacity)Linear free energy relationships (LFER) for PCBs:Schwarzenbach et al., Environmental Organic Chemistry, Sec. edition, Wiley Interscience, 2003

log Caq = -0.74*log Kow - 0.15 – log foc +log Csed

Estimating aqueous concentrations:

log Clip = 0.17*log Kow + 0.36 – log foc +log Csed

Estimating lipid concentrations:

log Clip = 0.91*log Kow + 0.51 +log Caq

Estimating lipid concentrations from free aqueous concentration:


Prediction of aqueous concentrations

1.E+01

1.E+02

1.E+03

1.E+04

Est

imat

ed A

queo

us C

onc

[ng/

L]

Data represent PCBs in Hunters

1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

1.E-04 1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04

Est

imat

ed A

queo

us C

onc

[ng/

L]

Measured Aqueous Conc [ng/L]

Data represent PCBs in Hunters Point sediment (♦), Lake Hartwell sediment (○), Grasse River sediment (□), Crab Orchard Lake sediment (●), Milwaukee River location 1 sediment (∆), Milwaukee River location 2 sediment (x) and Niagara River sediment (+)


Prediction of biolipid concentrations

1.E+02

1.E+03

1.E+04

Est

imat

ed L

ipid

Con

c [u

g/g]

(a)

Data represent PCBs in Hunters Point sediment, Neanthesarenaceodendata (♦) and

1.E-02

1.E-01

1.E+00

1.E+01

1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04

Est

imat

ed L

ipid

Con

c [u

g/g]

Measured Lipid Conc [ug/g]

arenaceodendata (♦) and Leptocheirus plumulosus (◊); Grasse River sediment, Lumbriculus variegatus (□); Crab Orchard Lake sediment, Lumbriculus variegatus (●), Milwaukee River location 1 sediment, Lumbriculus variegatus(∆); Milwaukee River location 2 sediment, Lumbriculus variegatus(x); and Niagara River sediment, Lumbriculus variegatus (+).


Do aqueous conc. make eq part work?

1.E+01

1.E+02

1.E+03

1.E+04

Est

imat

ed L

ipid

Con

c [u

g/g]

(d)


1.E-03

1.E-02

1.E-01

1.E+00

1.E+01

1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04

Est

imat

ed L

ipid

Con

c [u

g/g]


arenaceodendata (♦) and Leptocheirus plumulosus (◊); Grasse River sediment, Lumbriculus variegatus (□); Crab Orchard Lake sediment, Lumbriculus variegatus (●), Milwaukee River location 1 sediment, Lumbriculus variegatus(∆); Milwaukee River location 2 sediment, Lumbriculus variegatus(x); and Niagara River sediment, Lumbriculus variegatus (+).


Using desorption dataCorrelating biolipid concentrations with the pollutants mass desorbed within 6 hours in Tenax © bead extractions, normalized by the sediment organic carbon content:

Landrum, P. F.; Robinson, S. D.; Gossiaux, D. C.; You, J.; Lydy, M. J.; Mitra, S..Ten Hulscher, T. E. M. Predicting bioavailability of sediment-associated organic contaminants for Diporeia spp. and Oligochaetes. Environmental Science & Technology. 2007, 41, 6442-6447

log Clip = 0.91*log f6h + 0.84

Estimating lipid concentrations from f6h:

0 20 40 60 80 100 1200

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

Time [days]

Mas

s fra

ctio

n de

sorb

ed [-

]


Predicted from 6h desorption

1.E+02

1.E+03

1.E+04

Est

imat

ed L

ipid

Con

c [u

g/g]

(c)


1.E-02

1.E-01

1.E+00

1.E+01

1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04

Est

imat

ed L

ipid

Con

c [u

g/g]


arenaceodendata (♦) and Leptocheirus plumulosus (◊); Grasse River sediment, Lumbriculus variegatus (□); Crab Orchard Lake sediment, Lumbriculus variegatus (●), Milwaukee River location 1 sediment, Lumbriculus variegatus(∆); Milwaukee River location 2 sediment, Lumbriculus variegatus(x).


What is wrong with foc?Linear free energy relationships (LFER) for PCBs:Schwarzenbach et al., Environmental Organic Chemistry, Sec. edition, Wiley Interscience, 2003

log Caq = -0.74*log Kow - 0.15 – log foc +log Csed


log Clip = 0.17*log Kow + 0.36 – log foc +log Csed

Estimating lipid concentrations:


Estimating lipid concentrations from free aqueous concentration:

not O.K.

O.K.


Organic carbon in sediment

Organic carbon in sediment is heterogeneousPhotos Dr. Stavros Kalaitzidis Department of Geology, University of Patras

Amorphous organic material Black carbon material

Photos Dr. Stavros Kalaitzidis Department of Geology, University of Patras

Extensive Sorption of Organic Compounds to Black Carbon, Coal, and Kerogen in Sediments and Soils: Mechanisms and Consequences for Distribution, Bioaccumulation, and Biodegradation; Cornelissen, G.; Gustafsson, O.; Bucheli, T. D.; Jonker, M. T. O.; Koelmans, A. A.; van Noort, P. C. M. Environ. Sci. Technol.; (Critical Review); 2005; 39(18); 6881-6895

Humic acid Graphite

Absorption Adsorption


Bringing coal to Newcastle

International Project with Patras University sponsored by the Royal Society: Characterisation of natural & anthropogenic black carbon in UK estuaries.


River Tyne sediment5 % of the sediment weight: modern organic matter 0.36 %, coal organic matter 3.5 %, carbonised coal particles 2.1 %, tar and oil 0.3 %

50% of the PAH massCoal

Less than 1.8 g/cm3

50% of the PAH mass

More than 1.8 g/cm3

95 % of the sediment weight

50% of the PAH mass

Bulk sediment particles

Quarz


Black carbon modelsAccount for nonlinear sorption to black carbon:Moermond, C. T. A.; Zwolsman, J. J. G..Koelmans, A. A. Black carbon and ecological factors affect in situ biota to sediment accumulation factors for hydrophobic organic compounds in flood plain lakes. Environmental Science & Technology. 2005, 39, 3101-3109


7.0, aqbcfrbcaqocaocsed CKfCKfC +=

log Kfr = 0.98*log Kow + 2.21 For PCBs

log Kfr = 1.6*log Kow – 1.4 For PAHs


Prediction of aqueous concentrations

1.E+00

1.E+01

1.E+02

1.E+03

1.E+04

1.E+05

Est

imat

ed A

queo

us C

onc

[ng/

L]

1.E-01

1.E+00

1.E+01

1.E+02

1.E+03

Est

imat

ed A

queo

us C

onc

[ng/

L]

(b)

1.E-04

1.E-03

1.E-02

1.E-01

1.E-04 1.E-02 1.E+00 1.E+02 1.E+04

Est

imat

ed A

queo

us C

onc

[ng/

L]

Measured Aqueous Conc [ng/L]

Data represent PAHs in River Tyne sediment (♦)

1.E-04

1.E-03

1.E-02

1.E-04 1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03

Est

imat

ed A

queo

us C

onc

[ng/

L]Measured Aqueous Conc [ng/L]

Data represent PCBs in Hunters Point (♦), Lake Hartwell (○), Grasse River (□), Milwaukee River location 1 (∆), Milwaukee River location 2 (x) and Niagara River sediment (+).


Prediction of lipid concentrations

1.E+01

1.E+02

1.E+03

1.E+04

Est

imat

ed L

ipid

Con

c [u

g/g]

(b)


1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

1.E-04 1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04

Est

imat

ed L

ipid

Con

c [u

g/g]


arenaceodendata (♦) and Leptocheirus plumulosus (◊); Grasse River sediment, Lumbriculus variegatus (□); Milwaukee River location 1 sediment, Lumbriculus variegatus(∆); Milwaukee River location 2 sediment, Lumbriculus variegatus(x), and Niagara River sediment, Lumbriculus variegatus (+).


What is wrong?Account for nonlinear sorption to black carbon:Moermond, C. T. A.; Zwolsman, J. J. G..Koelmans, A. A. Black carbon and ecological factors affect in situ biota to sediment accumulation factors for hydrophobic organic compounds in flood plain lakes. Environmental Science & Technology. 2005, 39, 3101-3109


7.0, aqbcfrbcaqocaocsed CKfCKfC +=

log Kfr = 1.016*log Kow + 0.2469


Estimates generally better,but underestimates free aqueous concentrations below 30 ng/L


Linear two carbon types sorption modelFree aqueous concentrations Biolipid concentrations

( ) aqbcfrbcaocaocsed CKfKfC ⋅+= ,

log Kfr = 0.91*log Kow + 1.37log Kaoc = 0.74*log Kow + 0.15


Activated carbon sorption

Hale, Tomaszewski, Luthy and Werner Water Research 2009, Available online 23 June


Lauritzen Channel

DDT

Richard Luthy Jeanne Tomaszewski

Biogeochemical models of the pollutant fate in sediments Slide 22

Remediation plan

- Dredge DDTs polluted Young Bay Mud (and dispose in landfill in Texas)

- Place 30 cm sand cap as clean habitat

Young Bay Mud, DDTs

Old Bay Mud, clean

On Shore Structures

Mussels, DDTs

Sand, clean

Old Bay Mud, clean

On Shore Structures

Mussels, clean

1990 1997

Biogeochemical models of the pollutant fate in sediments Slide 23

Post remediation survey

- DDT polluted young bay mud is found in the top 10 to 20 inches of the sediment

- Sand absent or mixed with young bay mud on top of old bay mud

- Dredging is the traditional sediment remediation approach- It is difficult to achieve complete removal of polluted sediments

Old Bay Mud, clean

On Shore Structures

Mussels, DDTs

2003

sediments- Dredging may uncover more polluted sediment layers

Tomaszewski, Werner and Luthy, Activated Carbon Amendment as a Treatment for Residual DDT in Sediment from a Superfund Site in San Francisco Bay, Richmond, CA, USA. Env. Toxicol. Chem. 10 (2007), 2143-2150


AC addition to DDT-polluted sediment

Mussel tissue concentrations(ng/g dry weight)

Young Bay mud + 3.2% virgin AC

+ 3.2 % regenerated AC

DDTs-uptake by mussels for young bay mud from Lauritzen Channel without and with activated carbon addition to the sediment

weight)

4,4 DDT 1.4 1.7 1.9

2,4 DDT 0 0 0.2

4,4 DDD 346 55 29

2,4 DDD 120 16 7

4,4 DDE 15 3 3

Sum DDTs 483 76 41

Incorporating the microscale in pollutant fate models Slide 25

Mass transfer model, mixed systems

Strong sorption domain

- Strong particle-water partitioning coefficient Kstrong- Slow diffusive release rate Dstong /rstrong

2

Activated carbon

uptake

slow release

Strong sorption domain

Weak sorption domain

- Weak particle-water partitioning coefficient Kweak- Fast diffusive release rate Dweak/rweak

2

- Activated carbon-water partitioning coefficient Kac- AC radius rac- Intraparticle contaminant diffusivity Dac

Water

uptake

fast release

Werner, Ghosh, and Richard G. Luthy. Modeling Polychlorinated Biphenyl Mass Transfer after Amendment of Contaminated Sediment with Activated Carbon. Environmental Science & Technology 2006, 40(13), 4211-4218


Biogeochemical modelActivated carbon particles

Slow PCB releasing particles

Fast PCB releasing particles

Activated carbon particles

Slow PCB releasing particles

Fast PCB releasing particles

Water L. variegatusDermal absorption

Particle ingestionIntraparticle diffusion

elim

inat

ion

Water L. variegatusDermal absorption

Particle ingestionIntraparticle diffusion

elim

inat

ion

Xueli Sun, David Werner and Upal Ghosh. Modeling PCB Mass Transfer and Bioaccumulation in a Freshwater Oligochaete Before and After Amendment of Sediment with Activated Carbon. Environ. Sci. Technol. 2009, 43, 1115 -1121


Biogeochemical model results(a) Grasse River

50

60

70

80

90

100

Per

cent

red

uctio

n in

Cbi

o fo

r 2.

6% A

C

Experimental

Model, alpha AC = 0

Model, alpha AC = 0.01

Model, alpha AC = 0.02

0

10

20

30

40

50

tri (1

8,19

,26,28

)

tetra

(40,45

,47,4

9)pe

nta (8

5,91

,97,

99,1

01,105

,118

)

hexa

(128,

132,

136)P

erce

nt r

educ

tion

in C

bio

for

2.6%

AC

Uptake efficiency from AC must be significantly less than uptake from sediment to explain the experimental observation, in the order of a few percent uptake or less for AC-bound PCBs, which is consistent with prior observations.


River Tyne

Tyne river estuary sediment exceeds PAH guideline values for safe disposal at sea (< 0.1 mg/kg) by about a factor of 10. Soil guideline values are much less stringent.


Bioremediation vs. AC amendment

Weakly adsorbed

Bioremediation

Strongly adsorbed

Organic sediment pollution

AC amendment

Treated sediment -> geotechnical applications?


Availability measurement

0.14

0.16

0.18

0.2

Mas

s fra

ctio

n de

sorb

ed [-

]

Tenax© bead extraction of Tyne river sediment:

Only between 1-16 percent of the total PAH

0 20 40 60 80 100 1200

0.02

0.04

0.06

0.08

0.1

0.12

Time [days]

Mas

s fra

ctio

n de

sorb

ed [-

]

mass are desorbed within 4 months.

phenanthrene ( ●, ─), fluoranthene (+, - - - -), pyrene (○, ─ ─ ─) and benzo[b]fluorene (*, — - — -)

Bioremediation and activated carbon amendment Slide 4

Biodegradation experiments

Cotton wool

Unamended

Cotton wool

Biostimulated

Cotton wool

Bioaugmented

7 g of sediment30 mL Tyne river water

7 g of sediment30 mL Tyne river waterNutrient solution

7 g of sediment30 mL Tyne river waterNutrient solutionPseudomonas putida


Sediment concentrations

3.00

3.50

4.00

µµ µµ

Time zero

Time 1 week

Time 1 month

(i)

3.00

3.50

4.00

µµ µµ

Time zero

Time 1 week

Time 1 month

(ii)

3.00

3.50

4.00

µµ µµ

Time zero

Time 1 week

Time 1 month

For all treatments: No significant change in the sediment PAH concentration after one week and one month.

0.00

0.50

1.00

1.50

2.00

2.50

0.00

0.50

1.00

1.50

2.00

2.50

0.00

0.50

1.00

1.50

2.00

2.50

Unamended Biostimulated Bioaugmented

4.00

5.00

6.00

Ph

enan

thre

ne m

ass

[ µg

]

Amount added


Freely dissolved concentrations

Evidence for rapid degradation of phenanthrenespiked into

0.00

1.00

2.00

3.00

0 2 4 6 8

Time [days]

Ph

enan

thre

ne m

ass

[

Sterile ControlUnamendedNutrient amendedNutrient & P. putida amended

spiked into sediment free filtrate from unamendedsediment microcosms


Pseudomonas putida% Similarity

10050

Unamended, t = 0

Unamended, t = 1 week

Nutrient amended, t = 1 month

Unamended, t = 1 month

% Similarity

10050

Unamended, t = 0

Unamended, t = 1 week

Nutrient amended, t = 1 month

Unamended, t = 1 month

Nutrient- & P. putida-augmented , t = 1 month

Nutrient amended, t = 1 week

Nutrient- & P. putida-augmented, t = 0

Nutrient- & P. putida-augmented, t = 1 week

Nutrient- & P. putida-augmented , t = 1 month

Nutrient amended, t = 1 week

Nutrient- & P. putida-augmented, t = 0

Nutrient- & P. putida-augmented, t = 1 week

Pseudomonas putida bands were present at time zero and after one week, but have disappeared after one month in bioaugmented microcosms

5.00

6.00

7.00

8.00

g/g]

Unamended

Nutrient amended

Nutrient & P. putidaamended2% AC amended(mostly not detectable)Model prediction no


Available PAHsHighest uptake by polyethylene samplers embedded in the bioaugmentedmicrocosms.

0.00

1.00

2.00

3.00

4.00

NA

P

AC

EN

Y

AC

EN

FLU

PH

EN

AN

TH

FA

NT

H

PY

R

B[a

]A

CH

R

B[b

]F

B[k

]F

B[a

]P

I[1,2

,3-c

d]P

D[a

h]A

B[g

hi]P

CP

E [

µµ µµg/

g] Model prediction nodegradation no AC microcosms.

After addition of 2% dry weight AC PAH-uptake by polyethylene samplers is hardly detectable.


Conclusions risk assessment

- Traditional log Koc calculations overestimate the accumulation of persistent organic pollutants (POPs) by sediment dwelling organisms

- This is most likely due to the presence of black carbon which sorbs POPs more strongly than amorphous organic carbon at low free aqueous concentrationsaqueous concentrations

- At low free aqueous concentrations adsorption of POPs to black carbon appears to be linear

- Free aqueous POP concentrations or the readily desorbed fraction of the sediment bound POP mass give good predictions of biolipidconcentrations


Conclusions sediment remediation

- Dredging does not always achieve the remediation objectives

- Addition of activated carbon to sediment reduces the POP exposure of sediment dwelling organisms

- Sediment remediation with activated carbon is being field-tested- Sediment remediation with activated carbon is being field-tested

- Strongly sorbed POPs are not readily bio-remediated

- Addition of activated carbon to Tyne River sediment appears to be an effective means of further stabilising the already strongly sequestered pollutant residue, thus enhancing the sediment quality and potential for re-use, for instance as a geotechnical material


Acknowledgment

This presentations summarizes several years of work at Stanford University and Newcastle University, and was made possible by the many collaborators who shared their data with me:

R.G. Luthy, U. Ghosh, J. R. Zimmerman, X. Sun, J. Tomaszweski, R. Millward, M. Cho, S.E. HaleMillward, M. Cho, S.E. Hale

Financial support came from:

The UK Engineering and Physical Science Research Council (EPSRC), grants EP/D079055/1 and EP/F012934/1

The Royal Society, grant 2008/R1The Leverhulme Trust, grant F/00125/AA

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