Thomas D. Bucheli

Evaluation of a protocol for the quantification of black carbon in sediments

Formation of highly condensed black carbon (BC) from vegetation fires and wood fuel combustion presumably transfers otherwise rapidly cycling carbon from the atmosphere-biosphere cycle into a much slower cycling geological form. Recently reported BC fractions of total organic carbon (TOC) in surficial marine sediments span a wide range (2-90%), leaving it presently unclear whether this variation reflects natural processes or is largely due to method differences. In order to elucidate the importance of BC to carbon burial the specificity of applied methods needs to be constrained. Here the operating range and applicability of a commonly used chemothermal oxidation (CTO) method is evaluated using putative BC standards, potentially interfering substances, and natural matrix standards. Test results confirm the applicability of the method to marine sediments. Integrity tests with model substrates suggest applicability to low-carbon soils but only with a lower specificity to seawater particulate matter. The BC content of marine sediment samples in a set of studies employing the CTO method proved to be consistent with associated geochemical information. The radiocarbon content of the BC isolate in an environmental matrix standard was shown to be similar to the radiocarbon signature of pyrogenic polycyclic aromatic hydrocarbons (PAHs), here serving as molecular markers of combustion (fraction modern fM of BC was 0.065 ± 0.014 and of PAHs 0.056 ± 0.020), while being clearly distinct from the radiocarbon content of the bulk TOC (fM = 0.61 ± 0.08). Urgent questions such as the global accumulation rate of black carbon in soils and sediments may prove approachable with the chemothermal oxidation technique of BC quantification.

Soot sorption of non-ortho and ortho substituted PCBs.

Field-observations of distribution coefficients well above expectations from bulk organic-matter partitioning for several chlorinated aromatic compound classes have lead to the hypothesis that enhanced affinity to soot may not be limited to polycyclic aromatic hydrocarbons but may extend as a significant process for a wider range of hydrophobic organic compounds. This suggestion was here tested in soot-column sorption experiments with a series of ortho- and non-ortho substituted polychlorinated biphenyls (PCBs), using diesel particulate matter (NIST standard reference material SRM-1650) as model soot sorbent. For congeners of similar hydrophobicity, considerably higher affinities toward the soot sorbent were observed for the non-ortho substituted PCBs. Mono- to tetra-ortho substituted PCBs exhibited log-based soot-water distribution coefficients (K(sc)) from 5.25 to 5.51 l/kg(sc) at solute concentrations corresponding to 1-13 microg/l. In contrast, biphenyl, mono- and dichloro- non-ortho substituted PCBs yielded logK(sc) values between 5.09 and 6.35 l/kg(sc). These results are 20-50, and 75-110 times higher, respectively, than the corresponding K(ow)-predicted K(oc) numbers. This strong interaction with soot, particularly of non-ortho substituted PCBs, may fundamentally affect their environmental distribution and bioavailable exposure.

Soot-water distribution coefficients for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polybrominated diphenylethers determined with the soot cosolvency-column method.

For many types of hydrophobic compounds, sorption non-linearity and solid-water distributions in the field well above expectations from organic matter partitioning models have lead to the proposition that strong adsorption to soot surfaces may not be limited to polycyclic aromatic hydrocarbons but may extend as a significant process for many aromatic compound classes. Here, the soot-water distribution coefficients (Ksc) were determined with the soot cosolvency-column method for homolog series of five polychlorinated dibenzo-p-dioxins (PCDDs), five polychlorinated dibenzofurans (PCDFs) and for two polybrominated diphenylethers (PBDEs). All compounds exhibited significantly stronger association with soot carbon than expected from estimates of their bulk organic-carbon normalized partition coefficients (Koc). The Ksc/Koc ratios (at aqueous concentrations of around 0.1-1 microg/l) were for PCDDs (up to tetrachlorination) 19-130 (median 25), for PCDFs (also up to tetrachlorination) 150-490 (median 300), and for both the tetra- and pentabrominated PBDEs a factor of 60. The particularly strong soot sorption for the PCDFs is of similar enhancement factors as previously elucidated for polycyclic aromatic hydrocarbons. Compound-class specific correlations between log Ksc and octanol-water partition coefficients (log Kow) were significant for both PCDDs and PCDFs (and with R2 > 98%). These may prove useful for anticipating variable fractions of dissolved exposures between different environmental regimes and putative remediation objects.

Temporal and spatial variability of enantiomeric fractions (EFs) of chiral organochlorines in relation to soil properties

PurposeThe scope of this article was to investigate the spatial and temporal variability of enantiomeric fractions (EFs) of persistent organic pollutants (POPs) in soil compared to the uncertainty of the analytical data.Materials and methodsSoil samples were taken with high spatial resolution at two sites in Czech Republic in 2008 to investigate variability on a small spatial scale. In addition, composite soil samples were taken from ten sites in 2005 and 2008 to investigate temporal variations. All samples were analysed for a suite of soil properties as well as concentrations and EFs of polychlorinated biphenyl (PCB) -95, PCB-132 and PCB-149; α-hexachlorocyclohexane (HCH); o,p′-dichlorodiphenyltrichloroethane (DDT); and o,p′-dichlorodiphenyldichloroethane (DDD).Results and discussionMedian EFs of PCB-95 and PCB-149, α-HCH, o,p′-DDT and o,p′-DDD did not change significantly on the sites sampled in 2005 and again in 2008, while PCB-132 changed from EFu2009=u20090.38 to EFu2009=u20090.53. The sampling methodology is therefore very important, and composite samples will not be the best option if enantioselective degradation processes are investigated. Non-racemic EFs of POPs in the subsampled sites in 2008 were correlated to soil parameters, such as total organic carbon (TOC), total nitrogen and humic acids. These parameters are site specific and might vary on a small scale. This can explain why certain soil parameters are reported as significantly correlated with non-racemic EFs of chiral POPs in some studies, but not always in other similar studies.ConclusionsWhile composite samples may still represent the overall prevailing EF range, they are not ideally suited to study enantiomeric degradation processes, which are taking place at a relative small scale, depending on the heterogeneity of soil parameters such as TOC, total organic nitrogen (TON) and humic acids.