Black carbon and ecological factors affect in situ biota to sediment accumulation factors for hydrophobic organic compounds in flood plain lakes

Ecological factors may play an important role in the bioaccumulation of polychlorobiphenyls (PCBs) and polyaromatic hydrocarbons (PAHs). Geochemical and bioaccumulation behavior of these chemicals also appears to be related to the presence of black carbon (BC) in sediment. In situ PCB and PAH biota to sediment accumulation factors (BSAF) for benthic invertebrates, as well as 6h Tenax-extractable (fast-desorbing) concentrations and lake characteristics (including BC in sediment), were determined for different seasons in chemically similar but ecologically different lakes (fish-dominated turbid, algae-dominated turbid, and macrophyte-dominated). BSAFs could be explained with a model including a term for Freundlich sorption to BC and a term for uptake from fast-desorbing concentrations in ingested sediments. Freundlich coefficients for in situ sorption to BC (KF) were calculated from slow desorbing fractions and BC contents and agreed well with literature values for KF. Furthermore, in contrast to BSAFs based on total extracted concentrations, Tenax-based BSAF showed a strong positive correlation with log Kow. We therefore argue that BC caused slow desorption and limited BSAFs in these lakes. Seasonal and lake effects on BSAFs were detected, while the differences between oligochaetes and other invertebrates were small for PCBs and within a factor of 10 for PAHs. BSAFs for pyrogenic PAHs were much lower than for PCBs, which was explained by stronger sorption to BC and lesser uptake from ingested sediment.     

Strong sorption of native PAHs to pyrogenic and unburned carbonaceous geosorbents in sediments

It has recently been shown that the presence of carbonaceous geosorbents (CG, including black carbon (BC), unburned coal, and kerogen) can cause strong sorption of polycyclic aromatic hydrocarbons (PAHs) in sediments. We studied sorption of native PAHs in four Norwegian harbor sediments of which high fractions (21-56%) of the total organic carbon (TOC) consisted of CG carbon (CGC), as shown by organic petrography. PAH sorption coefficients were 1-2 orders of magnitude above predictions based on amorphous organic carbon partitioning alone. In recent studies, such strong sorption was attributed solely to BC sorption under the implicit assumption that sorption is linear for coal and kerogen. The most important result of the present study is that total sorption is better explained by considering all three nonlinearly sorbing CGC materials than by only considering BC. In addition, it was evaluated whether activated carbon (AC) amendments could be effective in reducing the freely dissolved pore-water concentrations (CW) and thus the environmental risks of the PAHs in such strongly sorbing sediments. The results indicated that an addition of 2 weight % AC reduced the Cw by factors of 21-153 for the four sediments (average values for all PAHs). Itwas shown that phenanthrene sorption to AC was, on average, reduced by a factor of 6 in sediment-AC mixtures compared to pure AC.     

Importance of black carbon to sorption of native PAHs, PCBs, and PCDDs in Boston and New York harbor sediments

The solid-water distribution ratios (Kd values) of "native" PAHs, PCBs, and PCDDs in Boston and New York Harbor sediments were determined using small passive polyethylene samplers incubated for extended times in sediment-water suspensions. Observed solid-water distribution coefficients exceeded the corresponding f(oc)Koc products by 1-2 orders of magnitude. It was hypothesized that black carbon (fBC), measured in the Boston harbor sediment at about 0.6% and in the New York harbor sediment at about 0.3%, was responsible for the additional sorption. The overall partitioning was then attributed to absorption into the organic carbon and to adsorption onto the black carbon via Kd = f(oc)Koc + f(BC)K(BC)C(w)n-1 with Cw in microg/L. Predictions based on published Koc, K(BC), and n values for phenanthrene and pyrene showed good agreement with observed Kd,obs values. Thus, assuming this dual sorption model applied to the other native PAHs, PCBs, and PCDDs, black carbon-normalized adsorption coefficients, K(BC)S, were deduced forthese contaminants. Log K(BC) values correlated with sorbate hydrophobicity for PAHs in Boston harbor (log K(BC) approximately 0.83 log gamma w(sat) - 1.6; R2 = 0.99, N= 8). The inferred sorption to the sedimentary BC phase dominated the solid-water partitioning of these compound classes, and its inclusion in these sediments is necessary to make accurate estimates of the mobility and bioavailability of PAHs, PCBs, and PCDDs.     

Predicting PAH bioaccumulation and toxicity in earthworms exposed to manufactured gas plant soils with solid-phase microextraction

Soils from former manufactured gas plant (MGP) sites are often heavily contaminated with polycyclic aromatic hydrocarbons (PAHs). Current risk assessment methods that rely on total PAH concentrations likely overstate adverse effects of such soils since bioavailability is ignored. In this study, solid-phase microextraction (SPME) was applied to estimate bioavailable PAH concentrations and toxicity in earthworms exposed to 15 MGP soils. In addition, PAH sorption to all soils (K0o values) was determined. The results showed a several orders of magnitude variation in Koc values, demonstrating that generic organic carbon-normalized sorption coefficients will typically be overconservative at MGP sites. SPME-predicted bioaccumulation generally was within a factor of 10 of measured bioaccumulation (in earthworm bioassays), in contrast to current risk assessment model estimates that overpredicted bioaccumulation 10-10 000 times. Furthermore, on the basis of estimated total body residues of narcotic PAHs, SPME correctly predicted worm mortality observed during bioassays in the majority of cases. For MGP sites where current risk assessment procedures indicate concerns, SPME thus provides a useful tool for performing a refined, site-specific assessment.     

Sorption characteristics of polycyclic aromatic hydrocarbons in aluminum smelter residues

High temperature carbon oxidation in primary aluminum smelters results in the release of polycyclic aromatic hydrocarbons (PAH) into the environment. The main source of PAH are the anodes, which are composed of petroleum coke (black carbon, BC) and coal tar pitch. To elucidate the dominant carbonaceous phase controlling the environmental fate of PAH in aluminum smelter residues (coke BC and/or coal tar), the sorptive behavior of PAHs has been determined, using passive samplers and infinitesink desorption methods. Samples directly from the wet scrubber were studied as well as ones from an adjacent 20-year old storage lagoon and roof dust from the smelter. Carbon-normalized distribution coefficients of native PAHs were 2 orders of magnitude higher than expected based on amorphous organic carbon (AOC)/water partitioning, which is in the same order of magnitude as reported literature values for soots and charcoals. Sorption isotherms of laboratory-spiked deuterated phenanthrene showed strong (-100 times stronger than AOC) but nonetheless linear sorption in both fresh and aged aluminum smelter residues. The absence of nonlinear behavior typical for adsorption to BC indicates that PAH sorption in aluminum smelter residues is dominated by absorption into the semi-solid coal tar pitch matrix. Desorption experiments using Tenax showed that fresh smelter residues had a relatively large rapidly desorbing fraction of PAH (35-50%), whereas this fraction was strongly reduced (11-16%) in the lagoon and roof dust material. Weathering of the coal tar residue and/or redistribution of PAH between coal tar and BC phases could explain the reduced availability in aged samples.     

Biomimetic extraction of PAHs and PCBs from soil with octadecyl-modified silica disks to predict their availability to earthworms

We developed a model to predict the availability of PAHs and PCBs to earthworms (Lumbricus terrestris L.) in soils. We related the uptake of PAHs and PCBs by earthworms to the extraction with octadecyl-modified silica disks (C18 disks). Eleven soils (data set A) were used to develop the model, and 14 additional soils (data set B) were used to validate it independently. The biota-to-soil accumulation factors (BSAFs) of higher molecular weight PAHs (> or =202 g mol(-1)) and PCBs were higher than the corresponding Cl8 disk-soil partition coefficients (Kdisk) in the soils of data set A. This suggested that PAHs and PCBs were not only partitioned between soil and earthworms but also selectively ingested or metabolized. Nevertheless, we could predict the BSAFs of individual PAHs and PCBs for data set A by regression equations of log BSAF on log Kdisk (r=0.47-0.87). To predict the BSAFs of all PAHs and PCBs, respectively, we derived a model for each compound class that uses Kdisk and K(ow) values. Both the compound and the compound-class specific model were suitable to predict the BSAFs of PAHs and PCBs in data set B within a factor of 10-15.     

Role of black carbon in the sorption of polychlorinated dibenzo-p-dioxins and dibenzofurans at the Diamond Alkali superfund site, Newark Bay, New Jersey

The sorption of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to organic carbon (OC) and black carbon (BC) was measured in two sediment cores taken near the Diamond Alkali superfund site (DA) in the Passaic River and Newark Bay, New Jersey (U.S.A.). An OC partitioning model and a BC-inclusive, Freundlich distribution model were used to interpret measurements of freely dissolved PCDD/Fs using passive samplers in sediment incubations, together with measured sedimentary concentrations of OC, BC, and PCDD/Fs. Samples were also analyzed for polycyclic aromatic hydrocarbons (PAHs) as controls on the two distribution models. The OC partitioning model underpredicted the distribution of PAHs and PCDD/Fs by 10-100-fold. The Freundlich model predicted the distribution of PAHs at the DA to within a factor of 2-3 of observations. Black carbon-water partition coefficients (K(iBC)) for PCDD/Fs, derived from literature results of both field and laboratory studies differed up to 1000-fold from values derived from this study. Contrary to expectations, PCDDs displayed stronger sorption than either PCDFs or PAHs relative to their subcooled liquid aqueous solubilities. Even though the presence of BC in the sediments reduced the overall bioavailability of PCDD/Fs by >90%, the sediments at 2 m depth continue to display the highest pore water activities of PCDD/Fs.     

Measuring and modeling adsorption of PAHs to carbon nanotubes over a six order of magnitude wide concentration range

Understanding the interactions between organic contaminants and carbon nanomaterials is essential for evaluating the materials' potential environmental impact and their application as sorbent. Although a great deal of work has been published in the past years, data are still limited in terms of compounds, concentrations, and conditions investigated. We applied a passive sampling method employing polyoxymethylene (POM-SPE) to gain a better understanding of the interactions between polycyclic aromatic hydrocarbons (PAHs) and multiwalled carbon nanotubes (CNTs) over a 6 orders of magnitude wide concentration range. In the low-concentration range (pg-ng L(-1)), sorption of phenanthrene and pyrene was linear on a nonlogarithmic scale. Here, sorption could thus be described using a single sorption coefficient. Isotherm fits over the entire concentration range showed that (i) monolayer sorption models described the data very well, and (ii) the CNTs sorption capacity was directly related to their surface area. Sorption coefficients for 13 PAHs (11 of which have not been reported to date) were also measured at environmentally relevant low concentrations. No competition seemed to occur in the low-concentration range and sorption affinity was directly related to the solubility of the subcooled liquid of the compounds.     

Bioavailability of PAHs in aluminum smelter affected sediments: evaluation through assessment of pore water concentrations and in vivo bioaccumulation

Bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) from coal tar pitch polluted sediments was predicted by (1) a generic approach based on organic carbon-water partitioning and Gibbs linear free energy relationship (between K(OW) and K(OC)), and (2) measurements of freely dissolved concentrations of PAHs in the sediment pore water, using passive samplers and solid phase extraction. Results from these predictions were compared with those from in vivo bioaccumulation experiments using Nereis diversicolor (Polychaeta), Hinia reticulata (Gastropoda), and Nuculoma tenuis (Bivalvia). Measured sediment/water partition coefficients were higher than predicted by the generic approach. Furthermore, predicted biota-to-sediment accumulation factors (BSAFs) derived from measured pore water concentrations were more in agreement with the bioaccumulation observed for two of the three species. Discrepancies associated with the third species (N. tenuis) were likely a result of particles remaining in the intestine (as shown by microscopic evaluation). These results indicate the importance of conducting site-specific evaluations of pore water concentrations and/or bioaccumulation studies by direct measurements to accurately provide a basis for risk assessment and remediation plans. The importance of knowledge regarding specific characteristics of model organisms is emphasized.     

Quantitative high-resolution mapping of phenanthrene sorption to black carbon particles

Sorption of hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) to black carbon (BC) particles has been the focus of numerous studies. Conclusions on sorption mechanisms of PAH on BC were mostly derived from studies of sorption isotherms and sorption kinetics, which are based on batch experiments. However, mechanistic modeling approaches consider processes at the subparticle scale, some including transport within the pore-space or different spatial pore-domains. Direct evidence based on analytical techniques operating at the submicrometer scale for the location of sorption sites and the adsorbed species is lacking. In this work, we identified, quantified, and mapped the sorption of PAHs on different BC particles (activated carbon, charcoal and diesel soot) on a 25-100 nm scale using scanning transmission X-ray microscopy (STXM). In addition, we visualized the pore structure of the particles by transmission electron microscopy (TEM) on the 1-10 nm-scale. The combination of the chemical information from STXM with the physical information from TEM revealed that phenanthrene accumulates in the interconnected pore-system along primary "cracks" in the particles, confirming an adsorption mechanism.     

Bioaccumulation of perfluorochemicals in sediments by the aquatic oligochaete Lumbriculus variegatus

Bioaccumulation of perfluoroalkyl sulfonates, perfluorocarboxylates, and 2-(N-ethylperfluorooctane sulfonamido) acetic acid (N-EtFOSAA) from laboratory-spiked and contaminated field sediments was assessed using the freshwater oligochaete, Lumbriculus variegatus. Semistatic batch experiments were conducted to monitor the biological uptake of these perfluorochemicals (PFCs) over 56 days. The elimination of PFCs was measured as the loss of PFCs in L. variegatus exposed to PFC-spiked sediment for 28 days and then transferred to clean sediment. The resultant data suggest that PFCs in sediments are readily bioavailable and that bioaccumulation from sediments does not continually increase with increasing perfluorocarbon chain length. Perfluorooctane sulfonate (PFOS) and perfluorononanoate were the most bioaccumulative PFCs, as measured by laboratory-based estimated steady-state biota sediment accumulation factors (BSAFs) and BSAFs measured using contaminated field sediments. Elimination rate constants for perfluoroalkyl sulfonates and perfluorocaroboxylates were generally smaller than those previously measured for other organic contaminants. Last, a PFOS precursor, N-EtFOSAA, accumulated in the worm tissues and appeared to undergo biotransformation to PFOS and other PFOS precursors. This suggests that N-EtFOSAA, which has been detected in sediments and sludge often at levels exceeding PFOS, may contribute to the bioaccumulation of PFOS in aquatic organisms.     

Extensive sorption of organic compounds to black carbon, coal, and kerogen in sediments and soils: mechanisms and consequences for distribution, bioaccumulation, and biodegradation

Evidence is accumulating that sorption of organic chemicals to soils and sediments can be described by "dual-mode sorption": absorption in amorphous organic matter (AOM) and adsorption to carbonaceous materials such as black carbon (BC), coal, and kerogen, collectively termed "carbonaceous geosorbents" (CG). Median BC contents as a fraction of total organic carbon are 9% for sediments (number of sediments, n approximately 300) and 4% for soils (n = 90). Adsorption of organic compounds to CG is nonlinear and generally exceeds absorption in AOM by a factor of 10-100. Sorption to CG is particularly extensive for organic compounds that can attain a more planar molecular configuration. The CG adsorption domain probably consists of surface sites and nanopores. In this review it is shown that nonlinear sorption to CG can completely dominate total sorption at low aqueous concentrations (<10(-6) of maximum solid solubility). Therefore, the presence of CG can explain (i) sorption to soils and sediments being up to 2 orders of magnitude higher than expected on the basis of sorption to AOM only (i.e., "AOM equilibrium partitioning"), (ii) low and variable biota to sediment accumulation factors, and (iii) limited potential for microbial degradation. On the basis of these consequences of sorption to CG, it is advocated that the use of generic organic carbon-water distribution coefficients in the risk assessment of organic compounds is not warranted and that bioremediation endpoints could be evaluated on the basis of freely dissolved concentrations instead of total concentrations in sediment/soil.     

Relations between environmental black carbon sorption and geochemical sorbent characteristics

Pyrogenic carbon particles in sediments (soot and charcoal, collectively termed "black carbon" or BC) appear to be efficient sorbents of many hydrophobic organic compounds, so they may play an important role in the fate and toxicity of these substances. To properly model toxicant sorption behavior, it is important to (i) quantify the magnitude of the role of BC in sorption and (ii) elucidate which geochemical BC characteristics determine the strength of environmental BC sorption. Sorption isotherms of d10-phenanthrene (d10-PHE) were determined over a wide concentration range (0.0003-20 microg/L), for five sediments with widely varying characteristics. From the sorption isotherms, we determined Freundlich coefficients of environmental BC sorption, K(F,BCenv. These varied from 10(4.7) to 10(5.5). From the data, it could be deduced that BC was responsible for 49-85% of the total d10-PHE sorption at a concentration of 1 ng/L. At higher concentrations, the importance of BC for the sorption process diminished to <20% at 1 microg/L and 0-1% at 1 mg/L. There were no significant relationships between BC sorption strength and the tested geochemical BC characteristics [the fraction of small (<38 microm) BC particles, the BC resistance to high-temperature oxidation, the fraction of biomass-derived BC, the native polycyclic aromatic hydrocarbon and total organic carbon contents]. Because of the limited variation in BC sorption strength with widely varying BC characteristics, the presented BC sorption coefficients may putatively be used as generic starting points for environmental modeling purposes.     

Modeling decreased food chain accumulation of PAHs due to strong sorption to carbonaceous materials and metabolic transformation

The predictive power of bioaccumulation models may be limited when they do not accountfor strong sorption of organic contaminants to carbonaceous materials (CM) such as black carbon, and when they do not include metabolic transformation. We tested a food web accumulation model, including sorption to CM, on data from a model ecosystem experiment with historically contaminated sediment. In combination with measured CM contents of the sediment, the model gave good fits for the biota that are known not to metabolize PAHs (macrophytes, periphyton, floating algal biomass). The same model was applied to invertebrates and fish but now with optimization of their metabolic transformation rates (k(m)). For fish, these rates correlated empirically with log K(OW): Log k(m) = -0.8 log K(OW) + 4.5 (r2 adj = 0.73). For invertebrates, log k(m) did not correlate with logK(OW). Sensitivity analysis revealed that the model output is highly sensitive to sediment CM content and sorption parameters, moderately sensitive to metabolic transformation rates, and slightly sensitive to lipid fraction of the organism and diet-related parameters. It is concluded that CM-inclusive models yield a better assessment of accumulation than models without sorption to CM. Furthermore, inclusion of CM in a model enables metabolic transformation rates to be calculated from the remaining overestimation in the model results when compared to measured data.     

Sorption of phenanthrene to environmental black carbon in sediment with and without organic matter and native sorbates

Strong sorption to soot- and charcoal-like material (collectively termed black carbon or BC) in soils and sediments is possibly the reason for recent observations of elevated geosorbent-water distribution ratios, slow desorption, limited uptake, and restricted bioremediation. We evaluated the role of environmental BC in the sorption of phenanthrene (PHE) to a polluted lake sediment from a Rhine River sedimentation area. Sorption isotherms were determined over a wide concentration range (0.0005-6 microg/ L) for the original sediment (with organic matter or OM, native sorbates, and BC), sediment from which we had stripped > 90% of the native sorbates (only OM and BC), and sediment combusted at 375 degrees C (only BC). The sorption isotherms of the original and stripped sediments were almost linear (Freundlich coefficient or n(F) > 0.9), whereas the isotherm of the BC remaining after the sediment combustion was highly nonlinear (n(F) = 0.54). At low concentrations (ng/L range), PHE sorption to BC in the combusted sediment was found to exceed the total PHE sorption in the original and stripped sediments. This implies that it may not be possible to use a BC-water sorption coefficient measured in combusted sediment to estimate total sorption to the original sediment. This "intrinsic" BC-water sorption coefficient after combustion was calculated to be 9 times larger than the "environmental" one in the untreated sediment. Competition between the added PHE and the native PAHs and/or OM may explain this difference. It appears that, at low aqueous PHE concentrations (ng/L and below), BC is the most important geosorbent constituent with respect to sorption. At higher concentrations (microg/L), BC sorption sites become saturated and BC sorption is overwhelmed by sorption to the other OM constituents. Because sorption is a central process affecting contaminant behavior and ecotoxicity, understanding this process can strongly contribute to risk assessment and fate modeling.     

Evidence for very tight sequestration of BTEX compounds in manufactured gas plant soils based on selective supercritical fluid extraction and soil/water partitioning

Benzene, toluene, ethylbenzene, o-, m-, and p-xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs) were extracted from eight manufactured gas plant (MGP) soils from sites that had been abandoned for several decades. Supercritical fluid extraction (SFE) with pure carbon dioxide demonstrated the presence of BTEX compounds that were highly sequestered in both coal gas and oil gas MGP soils and soots. Benzene was generally the slowest compound to extract from all samples and was even more difficult to extract than most two- to five-ring PAHs found on the same samples. Since the solubility of benzene in carbon dioxide is 2-5 orders of magnitude higher than the solubilities of PAHs, these results demonstrate that benzene was more tightly sequestered than toluene, ethylbenzene, xylenes, or the multi-ring PAHs. Additional evidence for very tight binding was based on the fact that BTEX concentrations determined using either SFE or with methylene chloride sonication were much higher than those obtained by the U.S. EPA purge-and-trap method, especially for benzene (whose concentration was underestimated by as much as 1000-fold by the EPA method). However, soil/water desorption showed little benzene mobility, and Kd values for benzene were 1-2 orders of magnitude higher than those calculated based on literature sorption K(OC) values. These results indicate that environmentally relevant concentrations of benzene may be better represented by mild extraction methods than by methods capable of extracting tightly bound benzene.     

Biota--sediment accumulation factors for polychlorinated biphenyls, dibenzo-p-dioxins, and dibenzofurans in southern Lake Michigan lake trout (Salvelinus namaycush)

A set of high-quality, age-specific biota-sediment accumulation factors (BSAFs) for polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) have been determined from concentrations measured with high-resolution gas chromatography/high-resolution mass spectrometry, by use of the 13C isotopic dilution technique, in lake trout and surficial (0-2 cm) sediment samples from southern Lake Michigan. BSAFs ranged from <0.1 to 18 for PCBs and from <0.001 to 0.32 for PCDDs and PCDFs detected in the fish. PCBs with zero or one chlorine in an ortho position had smaller BSAFs than other PCBs. PCDDs and PCDFs with chlorines at the 2,3,7,8-positions had larger BSAFs than most other PCDDs and PCDFs. The fidelity of the relative bioaccumulation potential data between independent lake trout samples, within and among age classes, suggests that differences in slight rates of net metabolism in the food chain are important and contribute to the apparent differences in BSAFs, not only for PCDDs and PCDFs but also possibly for some PCBs. A complicating factor for non-ortho- and mono-ortho-PCBs is the uncertain contribution of enhanced affinity for black carbon (and possibly volatility) acting in concert with metabolism to reduce measured BSAFs for lake trout. On the basis of the association between chemicals with apparent slight rates of metabolism and measured dioxin-like toxicity, several PCDFs with similar measured BSAFs but unknown toxicity may be candidates for toxicity testing.     

Effect of sorbate planarity on environmental black carbon sorption

Soot and charcoal, collectively termed "black carbon" or BC, can exhibit extremely strong sorption of many hydrophobic organic compounds. In order to include BC sorption in fate models, it is important to know BC nanopore surface areas. In addition, it is useful to know for which compounds BC sorption can be expected to be important. By nitrogen adsorption measurements at ultralow pressures on sediment that was strongly enriched in BC by HF treatment and/or chemothermal oxidation at 375 degrees C, we found that environmental BC has nanoporosity in the <4-10 A size range. The nanopore surface area (<50 A) of BC in Lake Ketelmeer (The Netherlands) sediment was approximately 58 m2/g. We measured sorption isotherms over a wide concentration interval for four compounds with the same Kow (10(46+/-0.1): planar anthracene (ANT), phenanthrene (PHE), and 4-chlorobiphenyl (4-PCB) along with nonplanar 2,2'-dichlorobiphenyl (2,2'-PCB). The environmental BC sorption coefficients of these iso-Kow compounds decreased in the order ANT > PHE approximately 4-PCB > 2,2'-PCB and spanned a factor of 50-200, depending on concentration. Nonplanar 2,2'-PCB showed much more linear BC sorption (nF = 0.92) than the planar compounds (nF = 0.54-0.70). This shows that steric hindrance strongly attenuates BC-sorbate interactions for a nonplanar PCB. Thus, BC is more important for environmental sorption of planar compounds (>50% sorbed to BC in the nanogram per liter range) than for nonplanar ones (<10-20%). Using the measured BC nanopore surface area, a close agreement between modeled and measured BC sorption data could be found.     

Enhanced sorption of PAHs in natural-fire-impacted sediments from Oriole Lake, California

Surface sediment cores from Oriole Lake (CA) were analyzed for organic carbon (OC), black carbon (BC), and their δ(13)C isotope ratios. Sediments displayed high OC (20-25%) and increasing BC concentrations from ～0.40% (in 1800 C.E.) to ～0.60% dry weight (in 2000 C.E.). Petrographic analysis confirmed the presence of fire-derived carbonaceous particles/BC at ～2% of total OC. Natural fires were the most likely cause of both elevated polycyclic aromatic hydrocarbon (PAH) concentrations and enhanced sorption in Oriole Lake sediments prior to 1850, consistent with their tree-ring-based fire history. In contrast to other PAHs, retene and perylene displayed decreasing concentrations during periods with natural fires, questioning their use as fire tracers. The occurrence of natural fires, however, did not result in elevated concentrations of black carbon or chars in the sediments. Only the 1912-2007 sediment layer contained anthropogenic particles, such as soot BC. In this layer, combining OC absorption with adsorption to soot BC (using a Freundlich coefficient n = 0.7) explained the observed sorption well. In the older layers, n needed to be 0.3 and 0.5 to explain the enhanced sorption to the sediments, indicating the importance of natural chars/inertinites in sorbing PAHs. For phenanthrene, values of n differed significantly between sorption to natural chars (0.1-0.4) and sorption to anthropogenic black carbon (>0.5), suggesting it could serve as an in situ probe of sorbents.