Chemosphere 82 (2011) 639–647

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Role of black carbon in the distribution of polychlorinated

dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils
Yunzhou Chai a,⇑, John W. Davis a, Michael Wilken b, Greg D. Martin b, Daniel M. Mowery c, Upal Ghosh d
a
Toxicology and Environmental Research and Consulting, The Dow Chemical Company, 1803 Building, Midland, MI 48674, USA
b
Environmental Analytical Sciences, The Dow Chemical Company, 1602 Building, Midland, MI 48674, USA
c
Analytical Sciences Gulf Coast R&D Support, The Dow Chemical Company, Freeport, TX 77541, USA
d
Department of Civil and Environmental Engineering, University of Maryland at Baltimore County, 1000 Hilltop Circle, Baltimore, MD 21250, USA

a r t i c l e i n f o a b s t r a c t

Article history: Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans

Received 22 July 2010 (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The
Received in revised form 3 November 2010 PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either
Accepted 4 November 2010
chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the
Available online 3 December 2010
first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles,
including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and
Keywords:
charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 lm–
PCDD/F
Black carbon
2000 lm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke
Fractionation associated with the chloralkali production process served as both the source and subsequent transporter
Petrography for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of
Nuclear magnetic resonance PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong associa-
tion of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability
thus the risk associated with these hydrophobic organochlorines in soils and sediments.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction of HOCs. Current scientific understanding divides the organic car-

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs)
are byproducts of combustion, metal smelting and refining, chem-
ical manufacturing, and possibly some natural processes (US Envi-
ronmental Protection Agency, 2006). Because some PCDD/F
congeners are persistent, bioaccumulative, and toxic, extensive re-
search has been conducted to characterize the fate and transport
(sorption/desorption), bioavailability, and risk of PCDD/Fs in soils
and sediments (Ruby et al., 2002; Yeager et al., 2007; Sormunen
et al., 2008; Garabrant et al., 2009). Understanding sorption,
desorption, and bioavailability of hydrophobic organic contami-
nants (HOCs) such as PCDD/Fs in sediments and soils is critical
for human health and ecological risk assessments. There has been
increasing recognition that elevated contaminant levels in soil and
sediment are not necessarily indicative of potential exposure risks
because the contaminants may be only partially available to recep-
tors (Koelmans et al., 2006).
The type of organic carbon in soils and sediments has been
shown to be critical in determining the sorption and availability
⇑ Corresponding author. Tel.: +1 989 636 1380; fax: +1 989 638 9305.
E-mail address: YChai@dow.com (Y. Chai).
bon in soils and sediments into natural organic carbon (relatively
labile, such as vegetation) and black carbon (BC, more refractory,
such as coke and soot) (Koelmans et al., 2006). The presence of
BC has been posited to impact the bioavailability of HOCs such as
polycyclic aromatic hydrocarbons (PAHs) and polychlorinated
biphenyls (PCBs) in sediments or soils due to the sequestration of
these HOCs and aging effects (i.e., extended contact time between
contaminants and soil or sediment) (Alexander, 2000). Black car-
bon, including naturally occurring charcoal from forest fires and
anthropogenically originated soot and coke, has a high affinity
for PAHs and PCBs. The partition coefficient of PAHs and PCBs in
these materials can be orders of magnitude higher than that in nat-
ural organic matter (Jonker and Koelmans, 2002; Ghosh et al.,
2003; Hawthorne et al., 2006). Black carbon has been shown to
cause slow desorption kinetics or desorption-resistance for these
contaminants (Jonker and Smedes, 2000; Ghosh et al., 2001; Chai
et al., 2006; Cornelissen et al., 2006). Slow desorption has been
found to be a governing process for limiting the bioavailability of
soil/sediment-bound PAHs, PCBs, and other organochlorine pesti-
cides (Lamoureux and Brownawell, 1999; Kraaij et al., 2002;
Kukkonen et al., 2004). Studies have indicated that only the rapid
desorbing fraction may be bioavailable while the slow desorbing
fraction may not be readily bioavailable, therefore the fast

0045-6535/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2010.11.017
640 Y. Chai et al. / Chemosphere 82 (2011) 639–647
desorbing fraction has been suggested as an overall indicator of
bioavailability (Lu et al., 2003; Hawthorne et al., 2005).
The floodplain soil and sediment from the Tittabawassee River
(TR) in Michigan, USA have been found to contain elevated levels
of PCDD/Fs due to historic discharges from The Dow Chemical
Company’s manufacturing facilities located in Midland, MI. The
PCDD/Fs found in the TR sediments and floodplain soils are be-
lieved to be primarily associated with chloralkali manufacturing
process and chlorophenols production processes that occurred
during the early 20th century (Wilken et al., 2006a). Prior to the
installation of the wastewater treatment plant in mid 1930s,
wastes from the manufacturing operations were incinerated, dis-
charged to waste management ponds that were occasionally brea-
ched during flooding events or discharged directly to the TR.
Several studies have shown that the bioavailability of the PCDD/
Fs in the TR is much lower than would be predicted by the assump-
tion of 100% bioavailability recommended by US Environmental
Protection Agency (Ruby et al., 2002; Budinsky et al., 2008;
Zwiernik et al., 2008; Garabrant et al., 2009; Fagervold et al.,
2010), although the underlying mechanisms for the lower bioavail-
ability observed in these studies has not been thoroughly under-
stood. Some investigators have proposed that PCDD/Fs are
strongly associated with BC particles in soils and sediments based
on the partitioning characteristics of bulk sediment/soil and the
presence of BC in the sediment/soil (Lohmann et al., 2005;
Cornelissen et al., 2008), however, no direct measurement has been
made for PCDD/Fs after isolation of BC particles.
The primary goal of the present study was to identify and eval-
uate the role of BC particles in the distribution of PCDD/Fs in his-
torically impacted floodplain soils through particle separation,
characterization, and direct measurements. The specific objectives
of this study were to (1) isolate and characterize different organic
fractions, specifically BC particles, (2) determine the concentra-
tions of PCDD/Fs associated with different particle size soil
fractions and distinct particle types, and (3) understand the rela-
tionship between BC phase and PCDD/F distribution. This paper
presents the first attempt to isolate BC particles from field soils
contaminated with PCDD/Fs for the characterization of the BC
and for direct measurement of PCDD/Fs in BC particles.
2. Experimental
2.1. Soil collection
Subsurface soil samples were collected from the TR floodplain
using a hand auger at various depths [ft below ground surface,
(ft bgs)] from multiple locations with different geomorphic fea-
tures (see Supporting Information Figure SI-1 for an area map).
Sampling was performed on the same day at three locations along
a transect perpendicular to the river channel with increasing dis-
tance from the middle of the river: (1) a natural levee/intermediate
terrace, (2) a historical levee/high terrace, and (3) a wetland.
Five soils were collected from the natural levee/intermediate
terrace (SW20) at depth ranging from 3 to 8.5 ft bgs (SW20 3 ft–
4 ft, 4 ft–5 ft, 5 ft–6 ft, 6 ft–7.5 ft, and 7.5 ft–8.5 ft). These five soils
were sandy soils containing 66%–83% sand, 12%–22% silt, and 5%–
11% clay. Three soils were collected from the historical levee
(SW85) at depth ranging from 0 to 2.5 ft bgs (SW85 0 ft–0.6 ft,
0.6 ft–1.5 ft, and 1.5 ft–2.5 ft). These three soils were also sandy
soils containing 86%–90% sand, 6%–10% silt, and 4%–5% clay. Addi-
tional three soils were taken from the seasonal wetland (SW265) at
depth ranging from 0 to 3.1 ft bgs. These three soils were higher in
the silts and clay fractions containing 24%–33% sand, 42%–46% silt,
and 21%–34% clay. The soils were sieved through a 2 mm sieve
after collection to remove large objects (e.g. gravels, leaves, etc.),
homogenized, and then stored at 4 °C in sealed containers until
further use. The soils collected from these locations were used in
this study because previous studies showed that these soils exhib-
ited different soil texture and contained elevated levels of PCDD/Fs
with distinct PCDD/F congener profiles (Ann Arbor Technical Ser-
vices, 2007). Soil SW20 is typical Tittabawassee River floodplain
soil regarding both soil texture and PCDD/F profile, whereas soil
SW265 is atypical.
2.2. Fractionation of soil and isolation of particles
Soil samples were fractionated utilizing wet-sieving based on
ASTM method D 422-63 (ASTM, 2003). An aliquot of each soil sam-
ple (300 g) was fractionated to collect 250 lm–2000 lm
(>250 lm) fraction. These coarse fractions were separated further
into light and heavy fractions utilizing cesium chloride solution
(specific gravity of 1.8) as a high density medium (Ghosh et al.,
2000). The particles in the light fraction with size of >250 lm from
the natural levee soil SW20 5 ft–6 ft were further segregated since
petrographic analysis showed that this sample exhibited very high
black carbon content (see Section 3). Four distinct groups of organ-
ic particles (i.e., anthropogenic BC, charcoal, root, and wood) were
manually isolated from this sample based on similar morphologi-
cal characteristics observed by visual inspection under an optical
microscope. Anthropogenic BC appeared shiny black under the
microscope, and included coal, coal tar pitch, and coke. Charcoal
particles were black and retained some of the wood grain structure
and were likely from natural origin. Root and wood were readily
identifiable. All four categories of particles were analyzed for
PCDD/Fs.
The heavy fractions (sand, 250 lm–2000 lm) were not sub-
jected to further study because these fractions contained negligible
amount of PCDD/Fs (<2% of that in the whole size fraction of
250 lm–2000 lm). The fine fractions (<250 lm) were not studied
further due to difficulty in isolation and characterization of the
particles. Visual observation under the microscope revealed that
the finer size fraction also contained particle types seen in the
coarse range particles. Thus the observations made in the coarser
range of particles are likely translatable to the finer size fraction
as well.
2.3. Petrographic analysis
The particles isolated from the light fraction (>250 lm) from
the natural levee soil SW20 5 ft–6 ft and the wetland soil SW265
0.8 ft–1.1 ft were subjected to petrographic analysis in order to
identify their origin. These samples were selected because these
soils exhibit different soil textures and distinct PCDD/F profiles
(Ann Arbor Technical Services, 2007). Coal petrography analysis
of soil particles was performed according to ASTM standard
methods for coal analysis: D2797 (Preparing Coal Samples for
Microscopic Analysis by Reflected Light), D2798 (Microscopic
Determination of the Reflectance of Vitrinite in a Polished Speci-
men of Coal), and D2799 (Microscopic Determination of Volume
Percent of Physical Components of Coal). Photographs from petro-
graphic analysis were taken at 600X in oil with reflected light.
2.4. NMR spectroscopy
Nuclear magnetic resonance (NMR) spectroscopy was con-
ducted to determine the aromaticity of the light fraction from
the natural levee and wetland soils. The light fractions (>250 lm)
from the natural levee soil SW20 5 ft–6 ft and the wetland soil
SW265 0.8 ft–1.1 ft were subjected to solid-state 13C NMR spec-
troscopy characterization. Again, these samples were chosen be-
cause these soils exhibit different soil textures and distinct
 Y. Chai et al. / Chemosphere 82 (2011) 639–647 641

PCDD/F profiles. Solid-state 13C NMR spectra were acquired at
room temperature on a Bruker Avance 400 spectrometer operating
at a 13C resonance frequency of 100.6 MHz. Magic-angle spinning
(MAS) was employed at a spinning frequency vr = 12 kHz using a
4-mm MAS H-X-Y probe head and zirconia sample rotors. Quanti-
tative 13C DP/MAS spectra were acquired with the quantitative
pulse sequence developed by Mao and Schmidt-Rohr [Fig. 1a in
reference (Mao and Schmidt-Rohr, 2004)] for the analysis of natu-
ral organic matter. Briefly, utilizing relatively fast MAS speeds
P10 kHz, a Hahn echo is obtained at 2 tr, where tr is the MAS rota-
tion period, to avoid baseline distortions. The high spinning fre-
quencies allow the aromatic carbon spinning sidebands to be
minimized and also to be removed from the center bands of other
carbon signals. A recycle delay (time between scans) was chosen
for sufficient relaxation of the 13C magnetization between scans,
enabling quantitative peak integrals. A 30-s recycle delay was se-
lected for this study, based on the parameters utilized by Mao
and Schmidt-Rohr (Mao and Schmidt-Rohr, 2004) for similar mate-
rials. The DP/MAS experiments utilized a 4-ls 13C 90° excitation
pulse, a 30-s recycle delay, and 63-kHz TPPM decoupling during
acquisition. DP/MAS spectra of the two organic fractions of soil
samples were acquired in 5 k scans and of the humic acid sample
in 2 k scans. Chemical shifts (d, ppm) were calibrated with an
external standard of glycine (carboxyl peak d = 176.0 ppm).
Soil samples (approximately 10 g–30 g each), with the addition of
17 13C-labeled 2,3,7,8-substituted tetra- through octa-PCDD/Fs as
internal standards, were Soxhlet extracted with toluene for 20 h.
The extract was purified using a multi-step cleanup with a mixed
silica gel/acid/base column, silica gel/silver nitrate column and
activated aluminumoxide. The purified extract was exchanged to
nonane after blow-down using high purity nitrogen. The seventeen
2,3,7,8-substituted tetra- though octa-PCDD/F congeners and total
tetra- through octa-chlorinated homologs were quantified using
high resolution gas chromatography/high resolution mass spec-
troscopy (HRGC/HRMS). The following abbreviations, TCDD/F, PeC-
DD/F, HxCDD/F, HpCDD/F, and OCDD/F, are used in this paper to
address tetra-, penta-, hexa-, hepta- and octa- chlorinated diben-
zo-p-dioxins/dibenzofurans, respectively. The seventeen 2,3,7,8-
substituted tetra- through octa-PCDD/F congeners are considered
to be of toxicological significance and their relative potencies are
estimated by the toxic equivalency factor (TEF). The toxic equiva-
lent (TEQ) in this paper was calculated by multiplying the concen-
tration of a congener by the corresponding human and mammalian
TEF established by the World Health Organization (WHO) in 2005
(Van den Berg et al., 2006).
3. Results and discussion

2.5. PCDD/F analysis 3.1. PCDD/F congener patterns in bulk soil

Sample extraction, purification, and analysis were based on U.S. The floodplain soils collected from the three locations were all
EPA method 1613B (US Environmental Protection Agency, 1994). impacted by PCDD/Fs at all soil depths. The sum of the concentra-
tions of the seventeen 2,3,7,8-chlorinated tetra- through octa-
30 PCDD/Fs (total mass of 17 congeners or TM17) and the TEQ in bulk
AA SW20 5-6 soils are presented in Table 1. The concentration of the TM17 ran-
25 SW265 0-0.8
ged from 0.35 to 195 lg kg1 while the TEQ levels ranged from
Concentration, µg kg -1

0.02 to 20.8 lg kg1. These soils exhibited readily distinguishable

20 PCDD/F congener patterns. Generally, the natural levee (SW20)
soils (except for SW20 3 ft–4 ft) were predominantly impacted by
15 TCDFs, PeCDFs, and HxCDFs, with 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF,
2,3,4,7,8-PeCDF, and 1,2,3,4,7,8-HxCDF contributing approximately
10 75%–92% of the TM17 and approximately 90% of the TEQ level (re-
fer to the 17 toxic congener profile for soil example SW20 5 ft–6 ft
5 in Fig. 1). The total homolog (i.e., total TCDDs, total TCDFs, etc.) and
TEQ profile for these soils revealed similar pattern (refer to Sup-
0 porting Information Figure SI-2). This tetra- to hexa-PCDFs-domi-
nated pattern has been shown to be uniquely associated with
60 historical chloralkali production processes (Vizard et al., 2006;
B SW20 5-6 Wilken et al., 2006a). These low organic (total organic carbon frac-
SW265 0-0.8
50 tion <1%), sandy soils in the natural levee have been shown to be
more representative of the soils deposited along TR floodplain
Individual / TM17, %

40 regarding both soil texture and PCDD/F congener profile (Ann Ar-
bor Technical Services, 2007).
30 Soils from the wetland (SW265) were atypical of the soil types
found in the TR floodplain in that these soils were higher in organic
20 matter (total organic carbon fraction up to 5.6%) and contained ele-
vated levels (>70%) of silts and clays. The wetland soils, SW265,
also exhibited a more complex congener pattern (see example soil
10
SW265 0 ft–0.8 ft in Fig. 1 and Figure SI-2) which reflected a
combination of PCDD/Fs originating from both chloralkali and
0
chlorophenols production processes. For example, the typical
F
46 - Hx F
12 8- DF

3 4 -H F
12 8 - DD
3 4 -H DD

H DD
12 78- DD

3 4 -H F
12 8- DD

H F
F
12 8- DD

12 78- DF
12 8-P DF
23 8-P DF

D
D

12 789 x CD

chloralkali pattern of TCDF, PeCDF, and HxCDF congeners com-

12 678 xCD

9- D
D

D
C
C

C
2 OC

78 p C
12 78 xC
67 xC
C
37 -TC

pC

47 eC

pC
C

C
7 C

O
36 Hx
36 Hx

34 e
34 Pe

H
3 H

prised a sizeable percentage of the total PCDD/Fs in these wetland

12 78

8-

8
9

7
23

37

soils. In addition, 50%–84% of the TM17 levels were comprised of

23

HpCDD/Fs and OCDD/F which are signature congeners from chloro-

Fig. 1. PCDD/F Congener profile in natural levee soil SW20 5 ft–6 ft and wetland soil
SW265 0 ft–0.8 ft. A) Concentration of seventeen 2,3,7,8-substituted tetra- through
octa- PCDD/F congeners, B) Percentage of individual congener of the total
concentration of the seventeen 2,3,7,8-substituted tetra- through octa- PCDD/F
congeners (TM17).
phenol production (Wilken et al., 2006a; Uchimiya et al., 2007).
However, since the TEF values for HpCDD/Fs and OCDD/F are very
low, the TEQ values in these wetland soils were still dominated by
PCDFs, with 2,3,7,8-TCDF, 2,3,4,7,8-PeCDF, and 1,2,3,4,7,8-HxCDF
642 Y. Chai et al. / Chemosphere 82 (2011) 639–647

Table 1
PCDD/F concentrations and toxic equivalents (TEQ) in bulk soils and light fractions with size of >250 lm from Tittabawassee River floodplain soils.

Soil Location Depth Bulk soil >250 lm light fraction

(ft bgs)
TM17 in TEQ in bulk TOC in Mass of light TM17 in light TEQ in light TM17 in light TEQ in light
bulk soil soil lg kg1 bulk soil % fraction/mass fraction lg kg1 fraction lg kg1 fraction/TM17 fraction/TEQ
lg kg1 of bulk soil % in bulk soil in bulk soil
Natural levee
SW20 3–4 22.8 0.53 0.86 0.40 28.4 1.43 1.2 (0.02) 2.7 (0.05)
SW20 4–5 21.3 1.95 0.69 0.23 19 100 2440 898 (13.5) 1250 (18.7)
SW20 5–6 29.9 3.05 0.38 0.27 138 000 16 800 4600 (38) 5490 (45)
SW20 6–7.5 86.6 9.48 1.1 0.08 12 800 1590 148 (3.5) 167 (4.0)
SW20 7.5–8.5 195 20.8 0.36 0.18 5820 736 29.9 (0.23) 35.4 (0.28)
Historical levee
SW85 0–0.6 27.3 0.92 2.4 0.84 39.4 1.62 1.4 (0.08) 1.8 (0.09)
SW85 0.6–1.5 10.3 0.81 0.78 0.57 1090 136 105 (1.8) 167 (2.8)
SW85 1.5–2.5 0.35 0.02 0.33 0.24 1.39 0.19 3.9 (0.03) 8.7 (0.06)
Wetland
SW265 0–0.8 48.6 1.04 5.6 0.26 6.87 0.16 0.1 (0.02) 0.1 (0.02)
SW265 0.8–1.1 29.3 1.83 3.4 0.44 26.0 0.53 0.9 (0.07) 0.3 (0.02)
SW265 1.1–3.1 1.68 0.07 1.5 0.02 4.78 0.32 2.8 (0.09) 4.8 (0.15)

TM17: Sum of the concentrations of seventeen 2,3,7,8-substituted tetra- through octa-PCDD/Fs. TEQ: Human and mammalian toxic equivalency factors recommended by the
World Health Organization in 2005 (Van den Berg et al., 2006) were used; none detect was regarded as zero. TOC: Total organic carbon content. The values in the parenthesis
are ratios of the organic carbon-normalized concentrations in the bulk soil and that in the light fraction, the organic carbon content of the light fractions is estimated to be
46%.

contributing approximately 73%–87% of the total TEQs. The histor-
ical levee (SW85) soils exhibited congener patterns similar to that
for wetland soils although somewhat less impacted by HpCDD/Fs
and OCDD/F homologs (data not shown).
The occurrence and conger pattern of PCDD/Fs along deposi-
tional areas in the floodplain of the TR were well-associated with
the geomorphic features of the river. The floodplains along the
TR include a number of geomorphic features, e.g., the natural levee
for SW20, the historical levee for SW85, and the wetland for
SW265, that have developed over time due to the dynamic flow
of the river. The grain size distribution of the soils present in differ-
ent geomorphic features are determined by water velocity, sedi-
ment load and distance from the river such that the build up of
coarser grained sediment deposit are present in geomorphic fea-
tures adjacent to the river (e.g. natural levee SW20 soils) while
low energy depositional areas such as wetlands have finer grained
sediments (e.g. SW265 soils). The transport and deposition of par-
ticles, including sand, silt, clay and organic carbon particles, in the
river and its floodplain directly impact the distribution of PCDD/Fs
along various geomorphic units of the TR.
3.2. PCDD/F distribution in density separated subfractions and in
distinct types of organic particles
Selected floodplain soils collected from the natural levee were
separated into different size fractions using wet-sieving. The coarse
fraction (>250 lm) from this process were further separated
into light (organic) and heavy fractions (sand) utilizing CsCl2
solution as a density gradient. In general, the TM17 and TEQ levels
in the light fraction (>250 lm) of the natural levee (SW20) soils
were much higher than those in the bulk soil (Table 1). The
TM17 in the light fractions of the natural levee soils ranged
from 28.4 to 138,000 lg kg1, while the TEQ ranged from 1.43
to 16,800 lg kg1. The corresponding enrichment factors
(TM17light fraction/TM17bulk soil) ranged from 1.2 to 4600. These
observations contrasted with results of the wetland (SW265) soils
where the TM17 values in the light fraction (>250 lm) more clo-
sely reflected the levels found in the bulk soil with enrichment fac-
tors ranging from 0.1 to 2.8. The lower TM17light fraction/TM17bulk soil
values for the wetland soils suggest that PCDD/Fs might be more
evenly distributed in the different particle fractions from these
soils.
The isolation of the light fraction from these soils was simply a
process for the enrichment in organic mater. As a result, the
enrichment of PCDD/Fs in the light fractions was expected due to
stronger sorption to organic matter. However, several of the
enrichment factors were so elevated that they could not be ex-
plained simply by the enrichment in organic matter. The organic
carbon content (TOC) of the light fractions is estimated to be 46%
(approximately 80% of the light fraction is organic matter with
an organic carbon content of 58%). The ratios of the organic car-
bon-normalized concentrations (TM17) in the bulk soil and that
in the light fraction were estimated to range from 0.02 to 38 (Table
1). This result clearly showed that some organic particles contained
much higher concentration of PCDD/Fs because these ratios were
expected to be near unity (e.g. TOC-normalized TM17light fraction/
TM17bulk soil = 1) if the PCDD/Fs were evenly distributed in the or-
ganic matter in the soil.
To better elucidate the source of the PCDD/F enrichment, the
light fraction from the natural levee soil SW20 5 ft–6 ft
(250–2000 lm) which showed high enrichment were manually
separated and grouped according to their morphological character-
istics. Four distinct morphological groups of organic material
(anthropogenic BC, charcoal, root, and wood) were obtained and
photographs of the different organic carbon particles were taken
under optical microscope at 15 magnification (refer to Support-
ing Information Figure SI-3). The concentrations of PCDD/Fs in
these four categories of particles are shown in Table 2. The highest
concentrations of PCDD/Fs were associated with anthropogenic BC
particles, with an enrichment factor (i.e., the concentration of
PCDD/Fs on anthropogenic BC versus the concentration in bulk
soil) of approximately 1000. These anthropogenic BC particles con-
tributed approximately 60% of the PCDD/Fs in the bulk soil while
they only comprised of 0.06% of the bulk soil mass. The congener
patterns of the seventeen 2,3,7,8-substituted tetra- through octa-
PCDD/Fs in these particles are shown in Fig. 2. The total homolog
and TEQ profile for these particles are shown in Supporting Infor-
mation Figure SI-4. These particles contained exclusively PCDFs
and practically no PCDDs were detected which is consistent with
the signature pattern associated with the chloralkali process. It ap-
pears that in the natural levee close to the river, anthropogenic BC
particles (>250 lm) originating from the chloralkali process and
containing PCDFs, were deposited during flooding events and acted
as the major source of the contaminants in the soil.
 Y. Chai et al. / Chemosphere 82 (2011) 639–647 643

Table 2
PCDD/F and toxic equivalent (TEQ) levels in different categories of particles from the light fraction with size of 250 lm–2000 lm from natural levee soil SW20 5 ft–6 ft.

ID TM17 Sum of 7 2,3,7,8-substituted Sum of 10 2,3,7,8- Sum of 7 2,3,7,8- Sum of 10 2,3,7,8-

(lg kg1) PCDDs (lg kg1) substituted PCDFs (lg kg1) substituted PCDDs/TM17 (%) substituted PCDFs/TM17 (%)
Concentration
Bulk soil 29.9 2.0 27.9 6.7 93.3
Anthropogenic BC 29 780 11 29 769 0.04 99.96
Charcoal 185 0 185 0 100
Root 943 5 938 0.5 99.5
Wood 82.1 0 82.1 0 100
TEQ
Bulk soil 3.05 0.003 3.05 0.1 99.9
Anthropogenic BC 3754 7 3747 0.2 99.8
Charcoal 22.5 0 22.5 0 100
Root 111 0.15 111 0.1 99.9
Wood 10.1 0 10.1 0 100

TM17: Sum of the concentrations of seventeen 2,3,7,8-substituted tetra- through octa-PCDD/Fs.

TEQ: Human and mammalian toxic equivalency factors recommended by the World Health Organization in 2005 (Van den Berg et al., 2006) were used; none detect was
regarded as zero.

3.3. Black carbon identification and characterization
The light fraction contains mostly organic particles (82% for
SW20 5 ft–6 ft and 86% for SW265 0.8 ft–1.1 ft) with the remainder
being mineral particles (sand). Photographs from the petrographic
analysis of the various organic particles from the light fraction
(>250 lm) from the natural levee soil SW20 5 ft–6 ft are shown
19000
A Anthropogenic BC
17000 Charcoal
Concentration, µg kg-1
in Fig. 3. The organic particles were identified as woody plant
material, green plant material, charcoal, coal, oxidized coal, coal
tar pitch with normal quinoline insoluble, metallurgical coke,
depositional carbon (pyrolytic or sooty), and cenosphere. The vol-
ume percentages of these particles are shown in Table 3. Anthropo-
genic BC particles (including coal, oxidized coal, metallurgical coke,
depositional carbon, coal tar/pitch, and cenosphere) plus natural
BC (charcoal) comprised approximately 30% by volume of the or-
ganic particles in the light fraction with size of 250 lm–2000 lm
from the natural levee soil SW20 5 ft–6 ft. In contrast, the organic
particles in the light fraction with size of 250 lm–2000 lm from
the wetland soil SW265 0.8 ft–1.1 ft contained mostly plant mate-

Root rial (>99%), while the only BC particles found were cenosphere and
5000
Wood charcoal, and they comprised <1% by volume. The other anthropo-
3000
genic BC particles present in the natural levee soil, including coal,
1000 oxidized coal, metallurgical coke, depositional carbon, coal tar/
500
pitch, were not observed in this light fraction from the wetland
400 soil. Thus, petrography analysis confirmed that anthropogenic BC
300 particulates containing PCDFs from chloralkali production were
200 deposited in the levee closer to the river and were one of the pri-
mary contributors to the contaminants in the floodplain soil. At
100
an increased distance away from the river in the wetlands, there
0
is less evidence of the direct influence of anthropogenic BC source
70 from chloralkali production.
B Anthropogenic BC The 30-s 13C DP/MAS NMR spectra and relative abundance of
60 Charcoal organic carbon functional groups for the light fractions from the
Root
Individual / TM17, %

natural levee soil SW20 5 ft–6 ft and the wetland soil SW265
50 Wood
0.8 ft–1.1 ft are shown in Fig. 4. The chemical shift ranges were
40 assigned to various organic carbon functional groups (Johnson
et al., 2001): aliphatic (0 ppm–50 ppm), carbohydrate (50 ppm–
30 105 ppm), aromatic (105 ppm–165 ppm), carboxyl (165 ppm–
187 ppm), and carbonyl (187 ppm–220 ppm). The concentration
20
values for various functional groups were obtained by integrating
each NMR spectrum in selected chemical shift ranges from 0 to
10
220 ppm and normalizing the integral of each range by the total
0 integral.
The light fraction from the natural levee soil SW20 5 ft–6 ft
36 -H DD

12 378 xC D

H D

F
34 - P D

23 OC D
37 -T D

36 -H DF

12 67 HxC F
78 p F
46 -H F

12 378 HxC F

H F
e F

F
34 -P F
67 Hx D

D
34 9- D
34 8-H D
23 78 xCD
12 78 x CD

9- CD
23 8-P CD

D
12 7 8 CD
8- CD
12 78 TCD

12 78- C D

D
12 78 D
34 9- D

C
12 7 8 eC

showed greater aromatic carbon content compared to the light

pC
pC
12 78 eC
x
3 -

H
12 7 8

fraction from the wetland soil SW265 0.8 ft–1.1 ft. Conversely,
23

the light fraction from the wetland soil exhibited a significantly

Fig. 2. PCDD/F congener profile in different categories of particles from light
fraction with size of 250 lm–2000 lm from natural levee soil SW20 5 ft–6 ft. (A)
Concentration of seventeen 2,3,7,8-substituted tetra- through octa- PCDD/F cong-
eners, (B) Percentage of individual congener of the total concentration of the
seventeen 2,3,7,8-substituted tetra- through octa- PCDD/F congeners (TM17).
greater carbohydrate carbon concentration. The ratio of aromatic
carbon to aliphatic carbon for the light fraction from the natural le-
vee soil was much higher than that for the light fraction from the
wetland soil. Overall, these NMR results indicate that the soil or-
ganic matter with size of >250 lm from the natural levee soil has
644 Y. Chai et al. / Chemosphere 82 (2011) 639–647

Fig. 3. Photographs from petrographic analysis of light fraction with size of 250 lm–2000 lm from natural levee soil SW20 5 ft–6 ft. Photographs were taken at 600 in oil
with reflected light. A: woody plant material; C: coal; D: depositional carbon; E: epoxy adhesive; G: green plant material; HP: Groundmass minerals or sediment mixed with
coal tar pitch; K: metallurgical coke with coating of depositional carbon (P0 : pyrolytic, T: sooty); P: coal tar pitch with normal quinoline insoluble; S: cenosphere; Y0 : pyrite in
coal.

higher aromatic moiety in the organic matter which can be attrib- Table 3
Petrographic analysis report for organic particles in light fraction with size 250 lm–
utable to higher BC content (Simpson et al., 2004). The NMR results 2000 lm from the natural levee soil SW20 5 ft–6 ft and the wetland soil SW265
corroborate the findings of petrography analysis that the lighter 0.8 ft–1.1 ft.
density fraction from the natural levee soil SW20 5 ft–6 ft con-
Description Natural levee Wetland soil
tained higher black carbon content. soil SW20 SW265
The higher BC content agreed very well with higher PCDD/F 5 ft–6 ft 0.8 ft–1.1 ft
enrichment factor (TM17light fraction/TM17bulk soil). Highly elevated volume% volume%
PCDD/F concentrations measured in these BC particles provided di- Coal 6.6 Not observed
rect evidence that BC particles are responsible for the elevated Oxidized coal 2.0 Not observed
enrichment factors in the natural levee soils. Metallurgical coke 3.5 Not observed
Depositional carbon (pyrolytic) 0.6 Not observed
Coal tar/pitch with quinoline Insoluble 10.8 Not observed
3.4. Black carbon as a source for PCDD/Fs Cenosphere 4.6 0.5
Charcoal 1.7 0.2
The PCDD/F congener profile found in the anthropogenic BC Plant material with woody cell walls 10.0 8.2
Plant material with cell walls 60.1 91.1
particles identified from the natural levee soil, including coal tar/
from green plants (Cellulose)
pitch, coal, oxidized coal, metallurgical coke, depositional carbon,
 Y. Chai et al. / Chemosphere 82 (2011) 639–647 645

SW20

SW265

250 200 150 100 50 0 PPM

NMR spectra

Relative abundance (%) of various functional groups

Aliphatic Carbohydrate Aromatic Carboxyl Carbonyl
Sample (0 – 50 ppm) (50 – 105 ppm) (105 – 165 ppm) (165 – 187 ppm) (187 – 220 ppm)
SW20 5-6 17.1 19.4 53.4 7.6 2.6
SW265 0.8-1.1 16.1 38.6 37.5 7.1 0.7
Fig. 4. Solid-state 13C DP/MAS NMR spectra and relative abundance of functional groups for organic matter from light fraction with size of 250 lm–2000 lm from natural
levee soil SW20 5 ft–6 ft and wetland soil SW265 0.8 ft–1.1 ft. A 30-s recycle delay and MAS frequency mr = 12 kHz was employed for quantitative peak integrals.

and cenosphere particles, are consistent with characteristics of the
chloralkali process (i.e., exclusively dominated by PCDFs while
containing practically no PCDDs). The formation of high levels of
PCDFs from the chloralkali process is associated with the use of
coal tar pitch as binder in synthetic graphite electrodes and/or coal
tar pitch impregnated wooden electrolysis cell (Rappe et al., 1991).
In a recent laboratory study, Wilken and coworkers simulated the
electrolysis of brine amended with dibenzofuran (present in coal
tar pitch) and observed PCDF profile consistent with the congener
pattern observed in the TR floodplain soil (Wilken et al., 2006b).
Wilken et al. provided a mechanistic explanation for the PCDF-
dominated congener pattern from the chloralkali process. The
chemistry of the historical chloralkali process suggests that the
major fraction of the PCDD/Fs in the TR floodplain soils was formed
and embedded in the anthropogenic BC particles during the chloro-
alkali manufacturing process. This notion is further substantiated
by the observation of much lower concentrations of PCDF congen-
ers in the natural BC particles (e.g., charcoal). Thus, these PCDF
congeners were primarily not sequestered by the anthropogenic
BC particles over time in a contaminated aqueous environment,
rather, these PCDFs during their genesis were entrapped in the
anthropogenic BC particles. Anthropogenically originated BC parti-
cles such as pitch and coke associated with the chloralkali produc-
tion process served as the source and subsequent transporter for
these relative immobile and hydrophobic compounds. Once in
the river these anthropogenic BC particles were mixed and diluted
with amorphous natural organic carbon, natural BC, and inorganic
particles. Since PCDFs exhibit very strong affinity with black car-
bon particles, the majority of contaminants would be associated
with their original host particles in the river system, although a
small fraction of the PCDD/Fs would have desorbed and re-sorbed
onto other organic particles. Relative large size anthropogenic BC
particles enriched with PCDFs along with sand particles would be
deposited in the natural levees. As a result, the natural levee
(SW20) soils were dominated by the PCDFs that are associated
with historical chloralkali production process.
The subsequent transport, distribution, and slow desorption of
PCDD/Fs from these black carbon particles has contributed to the
lack of spatial continuity (discrete samples with elevated TEQ lev-
els) often observed in the TR and floodplain. Previous studies in the
Tittabawassee River have looked for a potential relationship be-
tween sediment or soil TOC and TEQ concentrations, because such
a relationship could serve as a simple indicator of potentially ele-
vated PCDD/Fs concentrations in river sediment or soils. No corre-
lation has been observed between TOC and total PCDD/F
concentrations for sediments across different locations in the TR
(Michigan Department of Environmental Quality, 2002; Hilscher-
ova et al., 2003). In the TR sediments, elevated PCDD/F concentra-
tions are associated with coarse-grained sediment and bedload
transport characterized by low TOC concentrations.
The PCDD/F congener profile for the wetland (SW265) soils
showed a combination of chloralkali pattern seen in natural levee
(SW20) soils and a substantial contribution from a source associ-
ated with the chlorophenols production processes (Wilken et al.,
2006a; Uchimiya et al., 2007). Although little BC was obtained in
the light fraction with size of >250 lm from one of the wetland
soils (SW265 0.8 ft–1.1 ft), BC particles below 250 lm were likely
present in the fine fraction of the wetland soil resulting in elevated
PCDF levels with noticeable chloroalkali pattern. In contrast to chl-
oralkali source, the PCDD/Fs from chlorophenols processes were
generated and discharged as a liquid waste which subsequently
partitioned to organic matter in the river such as fine BC particles,
dissolved organic matter, colloidal matter, and other natural or-
ganic matter. During flooding events these finer sized particles
(<250 lm) were transported further distance from the river to
areas such as wetlands. Therefore, a mixture of chloralkali pattern
and chlorophenol pattern was seen in wetland (SW265) soils.
3.5. Implication of black carbon on PCDD/F bioavailability
The strong association and entrapment of the PCDD/Fs within
anthropogenic BC can limit bioavailability. Black carbon exhibits
646 Y. Chai et al. / Chemosphere 82 (2011) 639–647
a very high sorption affinity for HOCs with partition coefficients
ranging up to three orders of magnitude higher than that in the
natural organic matter (Ghosh et al., 2003; Lohmann et al., 2005).
Cornelissen and coworkers (Cornelissen et al., 2008) used a BC-
inclusive sorption model to demonstrate that more than 90% of
the PCDD/Fs in soils impacted by chlorophenol wood preservatives
was associated with BC. This strong sorption directly limits the bio-
availability of these highly hydrophobic compounds (Koelmans
et al., 2006).
The present study for the first time isolated and characterized
the BC particles in soils impacted by PCDD/Fs, which provided in-
sights for previous observations that the PCDD/Fs in the floodplain
of TR exhibit reduced bioavailability. In a recent study, Fagervold
and coworkers (Fagervold et al., 2010) used earthworms (Eisenia
fetida) to study the bioavailability of PCDD/Fs in the TR floodplain
soils. The bioavailability of the dominant furan congeners indicated
by biota to soil accumulation factors ranged from the highest value
of approximately 0.1 for 2,3,7,8-TCDF to 0.02 for OCDF in a natural
levee soil (SW20 5 ft–6 ft) and a wetland soil (SW265 0 ft–0.8 ft).
Budinsky and coworkers (Budinsky et al., 2008) showed that the
relative bioavailability (the oral absorption of PCDD/Fs from soil
relative to the absorption from corn oil as a readily available dosing
vehicle) of PCDD/Fs in the floodplain soils are 20%–25% in juvenile
swine and 60% in rat. In a separate study, Zwiernik and coworkers
(Zwiernik et al., 2008) used a multiple-lines-of-evidence approach
to evaluate the exposure and effects of PCDD/Fs to mink (Mustela
vison) along the TR basin. Mink is a top mammalian predator which
consumes large amount of fish and is one of the species more sen-
sitive to the effects of PCDD/Fs. Zwiernik and coworkers found no
adverse effect on resident mink along the TR caused by the
PCDD/Fs exposure. A human exposure study in Midland and Sagi-
naw counties of Michigan was also conducted by Garabrant and
coworkers (Garabrant et al., 2009). They reported on human serum
PCDD/F levels in individuals in the vicinity of TR and Saginaw Riv-
er. The study concluded that there was little contribution to serum
PCDD/Fs from exposures in Midland and Saginaw counties during
the last 25 years to either contaminated soil, household dust, or
recreational habits.
The majority of the PCDD/Fs in the TR floodplain have been
present for approximately a century. This extended aging period
(i.e., contact time between contaminants and soil) also contribute
to limit the mobility and bioavailability of PCDD/Fs. For instance,
the bioavailability indicated by the biota-sediment accumulation
factors of 2,3,7,8,-tetrachloro- and octachlorodibenzo-p-dioxin for
the oligochaete Lumbriculus variegates were 1.5- to 2-fold lower
in sediment after 21 months of aging compared with the newly
spiked sediments (Loonen et al., 1997). The mammalian oral intake
of aged contaminated soil resulted in minimal or even undetect-
able absorption of the contaminants (Hack and Selenka, 1996;
Umbreit et al., 1986).
4. Conclusions
The PCDD/F profiles of soils in the Tittabawassee River flood-
plain exhibited distinct congener patterns consistent with byprod-
ucts from either chloralkali manufacturing or chlorophenols
productions. Black carbon particles were isolated for the first time
from floodplain soil impacted by PCDD/Fs. Petrographic analysis
showed that BC particles, including coal, oxidized coal, metallurgi-
cal coke, depositional carbon, coal tar/pitch, cenosphere, and char-
coal, comprised approximately 30% by volume of the organic
fraction with size range of 250 lm–2000 lm from a typical flood-
plain soil. The BC particles with anthropogenic origin such as pitch
and coke associated with the chloralkali production process served
as both the source and subsequent transporter for the highly
hydrophobic PCDD/Fs. These anthropogenic BC particles were en-
riched with high levels of PCDFs, containing approximately 1000-
fold the concentration found in the bulk soil. This study provided
direct evidence that BC in field-contaminated soil plays a pivotal
role in sequestrating PCDD/Fs. The strong association of PCDD/Fs
with anthropogenic BC directly impacts the physicochemical and
biological availability thus the risk associated with these hydro-
phobic organochlorines in soils and sediments.
Acknowledgment
This research was funded by The Dow Chemical Company. The
authors thank Dr. Dan Gray at Koppers for providing petrography
analysis. The authors thank two anonymous reviewers for their
constructive comments for this manuscript.
Appendix A. Supplementary material
Additional information is available on soil sampling site, indi-
vidual PCDD/F compound TEQ and homolog concentrations in soil
and particles, and photos of various organic particles. This material
is available free of charge via the Internet. Supplementary data
associated with this article can be found, in the online version, at
doi:10.1016/j.chemosphere.2010.11.017.
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