Occurrence of coal and coal-derived particle-bound polycyclic aromatic hydrocarbons (PAHs) in a river floodplain soil

A PAH contaminated river floodplain soil was separated according to grain size and density. Coal and coal-derived particles from coal mining, coal industry and coal transportation activities were identified by organic petrographic analysis in our samples. Distinct concentrations of PAHs were found in different grain size and density fractions, however, similar distribution patterns of PAHs indicated similar sources. In addition, although light fractions had the mass fraction by weight of less than 5%, they contributed almost 75% of the total PAHs in the soil. PAH concentrations of all sub fractions showed positive correlation with their TOC contents. Altogether, coal and coal-derived particles that were abundant in light fractions could be the dominant geosorbents for PAHs in our samples.     

Relation between PAH and black carbon contents in size fractions of Norwegian harbor sediments

Distributions of total organic carbon (TOC), black carbon (BC), and polycyclic aromatic hydrocarbons (PAH) were investigated in different particle size fractions for four Norwegian harbor sediments. The total PAH (16-EPA) concentrations ranged from 2 to 113 mg/kg dry weight with the greatest fraction of PAH mass in the sand fraction for three of the four sediments. TOC contents ranged from 0.84% to 14.2% and BC contents from 0.085% to 1.7%. This corresponds to organic carbon (OC = TOC - BC) contents in the range of 0.81-14% and BC:TOC ratios of 1.3-18.1%. PAH isomer ratios suggested that the PAH in all four sediments were of pyrogenic origin. Furthermore, stronger correlations between PAH versus BC (r2 = 0.85) than versus OC (r2 = 0.15) were found. For all size fractions and bulk sediments, the PAH-to-BC ratios for the total PAHs were on average 6+/-3 mg PAH/g BC. These results suggest that PAH distributions were dominated by the presence of BC, rather than OC. As sorption to BC is much stronger than sorption to OC, this may result in significantly lower dissolved concentrations of PAH than expected on the basis of organic carbon partitioning alone.     

Effect of condensed organic matter on solvent extraction and aqueous leaching of polycyclic aromatic hydrocarbons in soils and sediments

The contents of nonhydrolyzable organic matter (NHC) and black carbon (BC) were measured in soils and sediments from the Pearl River Delta, South China. Polycyclic aromatic hydrocarbons (PAHs) were extracted respectively by Soxhlet and an accelerated solvent extraction device (ASE) using different solvents. In addition, sequential aqueous leaching at different temperatures was carried out. The PAH content extracted with the sequential three solvent ASE is two times higher than that using the Soxhlet extraction method. The relationship of the PAH content with the NHC content is very significant. The PAH concentrations measured at various temperature steps fit well to the Van't Hoff equation and the enthalpy was estimated. The investigation indicates that condensed organic matter such as kerogen carbon, aged organic matter, and BC is relevant for the extraction and distribution of native PAHs in the investigated field soils and sediments.     

Is black carbon a better predictor of polycyclic aromatic hydrocarbon distribution in soils than total organic carbon?

Black carbon (BC) and total organic carbon (TOC) were quantified in the surface soils of Switzerland (N = 105) and Delhi (N = 36), India, to examine their relationships with contents of polycyclic aromatic hydrocarbons (PAH). BC content in Swiss (background) soils (N = 104) varied from 0.41 to 4.75 mg/g (median: 1.13 mg/g) and constituted 1-9% (median: 3%) of TOC. Indian (urban) soils had similar BC concentrations (0.37-2.05 mg/g, median: 1.19 mg/g), with relatively higher BC/TOC (6-23%, median: 13%). Similar to TOC, BC showed significant positive correlation with lighter PAH, but no correlation with heavier PAH in Swiss soils. In contrast, heavier PAH were significantly correlated only with BC in Delhi soils. It seems that TOC governs the distribution of PAH in organic matter rich background soils, while the proximity to emission sources is reflected by BC-PAH association in urban soils.     

Polycyclic aromatic hydrocarbons, black carbon, and molecular markers in soils of Switzerland

Polycyclic aromatic hydrocarbons (PAH) were analysed in 23 soil samples (0–10 cm layer) from the Swiss soil monitoring network (NABO) together with total organic carbon (TOC) and black carbon (BC) concentration, as well as some PAH source diagnostic ratios and molecular markers. The concentrations of the sum of 16 EPA priority PAHs ranged from 50 to 619 μg/kg dw. Concentrations increased from arable, permanent and pasture grassland, forest, to urban soils and were 21–89% lower than median numbers reported in the literature for similar Swiss and European soils. NABO soils contained BC in concentrations from 0.4 to 1.8 mg/g dw, except for two sites with markedly higher levels. These numbers corresponded to 1–6% of TOC and were comparable to the limited published BC data in soil and sediments obtained with comparable analytical methods. The various PAH ratios and molecular markers pointed to a domination of pyrogenically formed PAHs in Swiss soils. In concert, the gathered data suggest the following major findings: (1) gas phase PAHs (naphthalene to fluorene) were long-range transported, cold-condensated at higher altitudes, and approaching equilibrium with soil organic matter (OM); (2) (partially) particle-bound PAHs (phenanthrene to benzo[ghi]perylene) were mostly deposited regionally in urban areas, and not equilibrated with soil OM; (3) Diesel combustion appeared to be a major emission source of PAH and BC in urban areas; and (4) wood combustion might have contributed significantly to PAH burdens in some soils of remote/alpine (forest) sites.     

Persistent organic pollutants in soil density fractions: distribution and sorption strength

The sorption strength of persistent organic pollutants in soils may vary among different soil organic matter (SOM) pools. We hypothesized that polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were unevenly distributed and had different soil organic carbon (SOC)-water partition coefficients (K(OC)) among soil density fractions. We determined the concentrations and K(OC) values of 20 PAHs and 12 PCBs in bulk samples and three density fractions (light, <2.0, medium, 2.0-2.4, and heavy, >2.4 g cm(-3)) of 11 urban topsoils (0-5 cm) from Bayreuth, Germany. The K(OC) values were determined using sequential extraction with methanol-water mixtures (35% and 65% methanol) at 60 degrees C. The sum of 20 PAH concentrations in bulk soil ranged 0.4-186 mg kg(-1), and that of 12 PCB concentrations 1.2-158 microg kg(-1). The concentrations of all PAHs and PCBs decreased in the order light>medium>heavy fraction. When normalized to the SOC concentrations, PAH concentrations were significantly higher in the heavy than in the other density fractions. The K(OC) values of the PAHs in density fractions were 3-20 times higher than those of the PCBs with similar octanol-water partition coefficients (K(OW)). The K(OC) values of individual PAHs and PCBs varied up to a factor of 1000 among the studied soils and density fractions. The K(OC) values of 5- and 6-ring PAHs tended to be highest in the heavy fraction, coinciding with their enrichment in this fraction. For the other PAHs and all PCBs, the K(OC) values did not differ among the density fractions. Thus, there is no relationship between sorption strength and distribution among density fractions, indicating that density fractionation is not a suitable tool to distinguish among differently reactive PAH and PCB pools in soils.     

Black carbon (BC) in urban and surrounding rural soils of Beijing, China: spatial distribution and relationship with polycyclic aromatic hydrocarbons (PAHs)

The concentrations of black carbon (BC), total organic carbon (TOC) and polycyclic aromatic hydrocarbons (PAHs) have been determined in soils from urban and rural areas of Beijing. The rural area can be divided into plain and mountainous areas which are close to and relatively far from the urban area, respectively. Concentration of BC (5.83 ± 3.05 mg g⁻¹) and BC/TOC concentration ratio (0.37 ± 0.15) in Beijing’s urban soil are high compared with that in world background soils and rural soils of Beijing, suggesting the urban environment to be an essential source and sink of BC. Concentration of BC in the urban area decreases from the inner city to exterior areas, which correlates with the urbanization history of Beijing and infers accumulation of BC in old urban soils. Black carbon in Beijing soils mainly comes from fossil fuel combustion, especially traffic emission. Median PAH concentration in the urban area (502 ng g⁻¹) is one order of magnitude higher than that in the rural plain (148 ng g⁻¹) and mountainous area (146 ng g⁻¹) where PAHs are supposed to mainly come from atmospheric deposition from the urban area. Concentrations of BC correlate significantly with those of PAHs (p < 0.01, except naphthalene) in the urban area and with those of heavier 4-, 5- and 6- ring PAHs (p < 0.01) in the adjacent rural plain area, while there is no significant correlation with any PAH in the farther rural mountainous area.     

The lack of microbial degradation of polycyclic aromatic hydrocarbons from coal-rich soils

Analytical techniques used to assess the environmental risk of contamination from polycyclic aromatic hydrocarbons (PAHs) typically consider only abiotic sample parameters. Supercritical fluid extraction and sorption enthalpy experiments previously suggested slow desorption rates for PAH compounds in two coal-contaminated floodplain soils. In this study, the actual PAH availability for aerobic soil microorganisms was tested in two series of soil-slurry experiments. The experimental conditions supported microbial degradation of phenanthrene if it was weakly sorbed onto silica gel. Native coals and coal-derived particles in two soils effectively acted as very strong sorbents and prevented microbial PAH degradation. The long history of PAH exposure and degree of coal contamination apparently had no influence on the capability of the microbial soil community to overcome constraints of PAH availability. Within the context of the experimental conditions and the compounds chosen, our results confirm that coal-bound PAHs are not bioavailable and hence of low environmental concern.     

PAH desorption from river floodplain soils using supercritical fluid extraction

Sequential supercritical fluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (ρ < 2 g cm⁻³), and <63 μm fractions were studied for PAHs' desorption kinetics. Desorption data were successfully described using a two-site model. Desorption rate constants were one order of magnitude lower than those of “slow” and “very slow” desorption rates from other studies. This suggests very slow and extremely slow desorption. Estimated time scales releasing 99% of total extractable contaminants ranged from decades for 2-4-ring PAHs and hundreds of years for 5-6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.     

Characterization of carbonaceous combustion residues: II. Nonpolar organic compounds

Aromatic and aliphatic fractions of black carbon (BC) solvent extracts were examined by gas chromatography/mass spectrometry to determine how differences in broad chemical and physical features are correlated with the load, composition, "extractability" and bioavailability of organic compounds. Diesel soot, urban dust and chimney soot had concentrations of n-alkanes >20 microg/g and of carcinogenic polycyclic aromatic hydrocarbons (PAHs)>8 microg/g. These high levels of solvent-extractable compounds were interpreted as resulting from combustion at temperatures below optimum values for BC formation. PAH concentrations normalized to the amount of soot carbon in chimney soot were close to values for diesel soot. However, the high proportion of polar amorphous organic matter in chimney soot suggests a higher bioavailability for associated PAHs. Carbon black, vegetation fire residues, and straw and wood charcoals had only residual concentrations of n-alkanes (<9 microg/g) and PAHs (<0.2 microg/g). PAH distributions were mostly unspecific, while the overall signature of the aliphatic fraction varied with BC origin. Molecular markers among plant-derived BC included steroid and sesquiterpenoid hydrocarbons. Molecular fingerprints suggest that compounds associated with fossil BC might be more refractory than those associated with plant-derived BC.     

The Emergence of Black Carbon as a Super-Sorbent in Environmental Chemistry: The End of Octanol?

The distribution of aromatic contaminants between environmental solids and water solution reflects both absorption by the organic matrix (organic carbon, OC) and adsorption to black carbon (BC). In many instances, adsorption to BC dominates the interaction between aromatic contaminants and environmental solids. This holds especially true for the pyrogenically produced PAHs and PCDD/Fs, but also for the industrially produced PCBs and PCNs. In the future, research will need to surface-normalize the adsorption onto BC surfaces. One of the key questions to be addressed is the relative distribution and availability of contaminants associated with OC and BC fractions in environmental solids.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

PAHs in background soils from Western Europe: influence of atmospheric deposition and soil organic matter

The levels and distribution of polynuclear aromatic hydrocarbons (PAHs) were determined in soil samples from background locations in the UK and Norway, to investigate their spatial distribution and the controlling environmental factors. Concentrations ranged between 42 and 11200 microg kg(-1) (geometric mean 640 microg kg(-1)) and 8.6 and 1050 microg kg(-1) (150 microg kg(-1)) dry weight in the UK and Norwegian soil, respectively. Proximity to sources and locations susceptible to high atmospheric depositional inputs resulted in higher concentrations. Statistically significant relationships were observed between PAH and total organic carbon (TOC) in the Norwegian samples. High molecular weight PAHs correlated with black carbon (BC) in UK-woodland soil. These observations support the hypothesis that TOC plays an important role in the retention of PAHs in soil and that PAHs are often combined with BC during combustion emissions. PAHs with 4 and more rings comprised approximately 90% of total PAHs in the UK soil, but only 50% in the Norwegian soil. The mixture of PAHs implied that fractionation occurred during long-range atmospheric transport and deposition. The lighter PAHs with lower K(ow) values more readily reached the most remote sites. The heavier PAHs with higher K(ow) values remained in closer proximity to sources.     

Historical record of black carbon in urban soils and its environmental implications

Energy use in urbanization has fundamentally changed the pattern and fluxes of carbon cycling, which has global and local environmental impacts. Here we have investigated organic carbon (OC) and black carbon (BC) in six soil profiles from two contrast zones in an ancient city (Nanjing) in China. BC in soils was widely variable, from 0.22 to 32.19 g kg⁻¹. Its average concentration in an ancient residential area (Zone 1) was, 0.91 g kg⁻¹, whereas in Zone 2, an industrial and commercial area, the figure was 8.62 g kg⁻¹. The ratio of BC/OC ranged from 0.06 to 1.29 in soil profiles, with an average of 0.29. The vertical distribution of BC in soil is suggested to reflect the history of BC formation from burning of biomass and/or fossil fuel. BC in the surface layer of soils was mainly from traffic emission (especially from diesel vehicles). In contrast, in cultural layers BC was formed from historical coal use. The contents of BC and the ratio of BC/OC may reflect different human activities and pollution sources in the contrasting urban zones. In addition, the significant correlation of heavy metals (Cu, Pb, and Zn) with BC contents in some culture layers suggests the sorption of the metals by BC or their coexistence resulted from the coal-involved smelting.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K_oc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.     

Concentrations, sources and spatial distribution of polycyclic aromatic hydrocarbons in soils from Beijing, Tianjin and surrounding areas, North China

The concentrations, profiles, sources and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) were determined in 40 surface soil samples collected from Beijing, Tianjin and surrounding areas, North China in 2007, and all sampling sites were far from industrial areas, roadsides and other pollution sources, and across a range of soil types in remote, rural villages and urban areas. The total concentrations of 16 PAHs ranged from 31.6 to 1475.0 ng/g, with an arithmetic average of 336.4 ng/g. The highest PAH concentrations were measured in urban soils, followed by rural village soils and soils from remote locations. The remote-rural village-urban PAH concentration gradient was related to population density, gross domestic product (GDP), long-range atmospheric transport and different types of land use. In addition, the PAH concentration was well correlated with the total organic carbon (TOC) concentration of the soil. The PAH profile suggested that coal combustion and biomass burning were primary PAH sources.     

Partitioning and source diagnostics of polycyclic aromatic hydrocarbons in rivers in Tianjin, China

Water, suspended particulate matter (SPM), and sediment samples were collected from ten rivers in Tianjin and analyzed for 16 polycyclic aromatic hydrocarbons (PAHs), dissolved organic carbon (DOC), particulate organic carbon (POC) in SPM and total organic carbon (TOC) in sediment. The behavior and fate of PAHs influenced by these parameters were examined. Generally, organic carbon was the primary factor controlling the behavior of the 16 PAH species. Partitioning of PAHs between SPM and water phase was studied, and K(OC) for some PAH species were found to be significantly higher than the predicted values. The source of PAHs contamination was diagnosed by using PAH isomer ratios. Coal combustion was identified to be a long-term and prevailing contamination source for sediment, while sewage/wastewater source could reasonably explain a short-term PAHs contamination of SPM.     

Low accessibility and chemical activity of PAHs restrict bioremediation and risk of exposure in a manufactured gas plant soil

Composting of manufactured gas plant soil by a commercial enterprise had removed most of its polycyclic aromatic hydrocarbons (PAHs), but concentrations remained above regulatory threshold levels. Several amendments and treatments were first tested to restart the PAH degradation, albeit with little success. The working hypothesis was then that PAHs were “stuck” due to strong sorption to black carbon. Accessibility was measured with cyclodextrin extractions and on average only 4% of the PAHs were accessible. Chemical activity of the PAHs was measured by equilibrium sampling, which confirmed a low exposure level. These results are consistent with strong sorption to black carbon (BC), which constituted 59% of the total organic carbon. Composting failed to remove the PAHs, but it succeeded to minimize PAH accessibility and chemical activity. This adds to accumulating evidence that current regulatory thresholds based on bulk concentrations are questionable and alternative approaches probing actual risk should be considered.     

The influence of Sarcocornia fruticosa on retention of PAHs in salt marsh sediments (Sado estuary, Portugal)

Depth concentration profiles of PAHs, organic carbon and dissolved oxygen in non-colonised sediments and sediments colonised by Sarcocornia fruticosa from Mitrena salt marsh (Sado, Portugal) were determined in November 2004 and April 2005. Belowground biomass and PAH levels in below and aboveground material were also determined. In both periods, colonised sediments were oxygenated until 15-cm, rich in organic carbon (max 4.4%) and presented much higher PAH concentrations (max. 7.1 microg g(-1)) than non-colonised sediments (max. 0.55 microg g(-1)). Rooting sediments contained the highest PAH concentrations. The five- and six-ring compounds accounted to 50-75% of the total PAHs in colonised sediments, while only to 30% in non-colonised sediments. The elevated concentrations of PAHs in colonised sediments may be attributed to the transfer of dissolved PAH compounds towards the roots as plant uptake water and subsequent sequestration onto organically rich particles. A phase-partitioning mechanism probably explains the higher retention of the heavier PAHs. In addition oxygenated conditions of the rooting sediments favour the degradation of the lighter PAHs and explain the elevated proportion of the heavier compounds. Below and aboveground materials presented lower PAH concentrations (0.18-0.38 microg g(-1)) than colonised sediments. Only 3- and 4-PAHs were quantified in aboveground material, reflecting either preferential translocation of lighter compounds from roots or atmospheric deposition.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the 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 charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain 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 enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association 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.