persistent organic contaminant availability in …persistent organic pollutant availability in...
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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
Persistent organic pollutant availability in sediment Slide 3
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/
Persistent organic pollutant availability in sediment Slide 5
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:
Persistent organic pollutant availability in sediment Slide 6
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 (+)
Persistent organic pollutant availability in sediment Slide 7
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 (+).
Persistent organic pollutant availability in sediment Slide 8
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)
Data represent PCBs in Hunters Point sediment, Neanthesarenaceodendata (♦) and
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]
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 (+).
Persistent organic pollutant availability in sediment Slide 9
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 [-
]
Persistent organic pollutant availability in sediment Slide 10
Predicted from 6h desorption
1.E+02
1.E+03
1.E+04
Est
imat
ed L
ipid
Con
c [u
g/g]
(c)
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).
Persistent organic pollutant availability in sediment Slide 11
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
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:
not O.K.
O.K.
Persistent organic pollutant availability in sediment Slide 12
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
Persistent organic pollutant availability in sediment Slide 13
Bringing coal to Newcastle
International Project with Patras University sponsored by the Royal Society: Characterisation of natural & anthropogenic black carbon in UK estuaries.
Persistent organic pollutant availability in sediment Slide 14
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
Persistent organic pollutant availability in sediment Slide 15
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
Estimating aqueous concentrations:
7.0, aqbcfrbcaqocaocsed CKfCKfC +=
log Kfr = 0.98*log Kow + 2.21 For PCBs
log Kfr = 1.6*log Kow – 1.4 For PAHs
Persistent organic pollutant availability in sediment Slide 16
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 (+).
Persistent organic pollutant availability in sediment Slide 17
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)
Data represent PCBs in Hunters Point sediment, Neanthesarenaceodendata (♦) and
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]
Measured Lipid Conc [ug/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 (+).
Persistent organic pollutant availability in sediment Slide 18
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
Estimating aqueous concentrations:
7.0, aqbcfrbcaqocaocsed CKfCKfC +=
log Kfr = 1.016*log Kow + 0.2469
log Clip = 0.91*log Kow + 0.51 +log Caq
Estimates generally better,but underestimates free aqueous concentrations below 30 ng/L
Persistent organic pollutant availability in sediment Slide 19
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
Persistent organic pollutant availability in sediment Slide 20
Activated carbon sorption
Hale, Tomaszewski, Luthy and Werner Water Research 2009, Available online 23 June
Persistent organic pollutant availability in sediment Slide 21
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
Persistent organic pollutant availability in sediment Slide 24
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
Persistent organic pollutant availability in sediment Slide 26
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
Persistent organic pollutant availability in sediment Slide 27
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.
Persistent organic pollutant availability in sediment Slide 28
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.
Persistent organic pollutant availability in sediment Slide 29
Bioremediation vs. AC amendment
Weakly adsorbed
Bioremediation
Strongly adsorbed
Organic sediment pollution
AC amendment
Treated sediment -> geotechnical applications?
Persistent organic pollutant availability in sediment Slide 30
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
Persistent organic pollutant availability in sediment Slide 32
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
Persistent organic pollutant availability in sediment Slide 33
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
Persistent organic pollutant availability in sediment Slide 34
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
Persistent organic pollutant availability in sediment Slide 35
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.
Persistent organic pollutant availability in sediment Slide 36
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
Persistent organic pollutant availability in sediment Slide 37
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
Persistent organic pollutant availability in sediment Slide 38
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