Biomedical subjects

Thomas D Bucheli

Publications and source records attributed to Thomas D Bucheli.

11 recordsLinked to original sources

PubMed2006

Quantification of estrogenic mycotoxins at the ng/L level in aqueous environmental samples using deuterated internal standards.

Because of their pronounced estrogenicity, resorcyclic acid lactones (RALs) are of concern in aqueous environments even at the low ng/L level. Therefore, we developed an accurate, precise and sensitive HPLC-MS/MS method to detect these mycotoxins in different aqueous environmental samples. The compounds investigated included zearalenone (ZON), alpha- and beta-zearalenol, zearalanone as well as alpha- and beta-zearalanol. The use of isotope labelled internal standards (in this case deuterated RAL-analogues) ensured an accurate quantification of the target analytes, independent of matrix compounds interfering with the analytes during ionisation and analyte losses occurring during sample preparation. Sample enrichment was carried out by solid-phase extraction (SPE) using Supelclean Envi-18 cartridges. Absolute method recoveries for all analytes ranged from 95 to 108%, 70 to 102%, and 76 to 109%, method detection limits from 0.5 to 2.1 ng/L, 0.4 to 1.1 ng/L, and 0.8 to 12.4 ng/L and precision from 3 to 14%, 2 to 13% and 4 to 16% in drainage water, river water and wastewater treatment plant (WWTP) effluent, respectively. The method was applied to verify the emission of RALs from a Fusarium graminearum infested crop field into the drainage system. Zearalenone was present in drainage water in concentrations up to 30 ng/L. So far, none of the other five investigated compounds have been detected.

Analytic Sample Preparation Methods↗

PubMed2006

Two-dimensional gas chromatography coupled to triple quadrupole mass spectrometry for the unambiguous determination of atropisomeric polychlorinated biphenyls in environmental samples.

Two-dimensional gas chromatography coupled to triple quadrupole mass spectrometry (GC-GC-MS-MS) is presented as a robust, selective and sensitive method for the accurate quantification of enantiomeric fractions (EFs) of atropisomeric polychlorinated biphenyls (PCBs) in a range of environmental matrices. The method was subjected to a set of quality control and validation experiments. EF precision of the atropisomers 95, 149, 132, and 174 ranged from 0.7 to 1.4% in soil samples. Quantified amounts of these congeners in soil and compost samples (59<n<100) were on average within 3-26% of the numbers gathered with conventional (achiral) bench top GC-MS. However, significant deviations were observed between EFs obtained by GC-GC-MS-MS and those by GC-GC-MS, GC-MS-MS, and GC-MS. The method was successfully applied to a variety of sample types, such as soil, air, herring, human milk, and, for the first time, compost. EFs in soils are shown to vary with land use and correlations with soil pH were observed. EFs in compost samples were mostly close to, or racemic.

Biodegradation, Environmental↗

PubMed2005

Black carbon: the reverse of its dark side.

The emission of black carbon is known to cause major environmental problems. Black carbon particles contribute to global warming, carry carcinogenic compounds and cause serious health risks. Here, we show another side of the coin. We review evidence that black carbon may strongly reduce the risk posed by organic contaminants in sediments and soils. Extremely efficient sorption to black carbon pulls highly toxic polycyclic aromatic hydrocarbons, polychlorinated biphenyls, dioxins, polybrominated diphenylethers and pesticides into sediments and soils. This increased sorption is general, but strongest for planar (most toxic) compounds at environmentally relevant, low aqueous concentrations. Black carbon generally comprises about 9% of total organic carbon in aquatic sediments (median value of 300 sediments), and then may reduce uptake in organisms by up to two orders of magnitude. This implies that current environmental risk assessment systems for these contaminants may be unnecessarily safe.

Adsorption↗

PubMed2005

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.

Adsorption↗

PubMed2005

Persistent organic pollutants in source-separated compost and its feedstock materials--a review of field studies.

Composting and the application of compost to the soil follow the principle of recycling and sustainability. Compost can also have a positive effect on physical, chemical, and biological soil parameters. However, little is known about the origin, concentration, and transformation of persistent organic pollutants (POPs) in compost. We therefore compiled literature data on some priority POPs in compost and its main feedstock materials from more than 60 reports. Our data evaluation suggests the following findings. First, median concentrations of Sigma 16 polycyclic aromatic hydrocarbons (PAHs), Sigma 6 polychlorinated biphenyls (PCBs), and Sigma 17 polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) were higher in green waste (1803, 15.6 microg/kg dry wt., and 2.5 ng international toxicity equivalent [I-TEQ]/kg dry wt.) than in organic household waste (635, 14.6 microg/kg dry wt., and 2.2 ng I-TEQ/kg dry wt.) and kitchen waste (not available [NA], 14.9 microg/kg dry wt., 0.4 ng I-TEQ/kg dry wt.). The POP concentrations in foliage were up to 12 times higher than in other feedstock materials. Second, in contrast, compost from organic household waste and green waste contained similar amounts of Sigma 16 PAHs, Sigma 6 PCBs, and Sigma 17 PCDD/Fs (1915, 39.8 microg/kg dry wt., and 9.5 ng I-TEQ/kg dry wt., and 1715, 30.6 microg/kg dry wt., and 8.5 ng I-TEQ/kg dry wt., respectively). Third, concentrations of three-ring PAHs were reduced during the composting process, whereas five- to six-ring PAHs and Sigma 6 PCBs increased by roughly a factor of two due to mass reduction during composting. Sigma 17 PCDD/Fs had accumulated by up to a factor of 14. Fourth, urban feedstock and compost had higher POP concentrations than rural material. Fifth, the highest concentrations of POPs were usually observed in summer samples. Finally, median compost concentrations of POPs were greater by up to one order of magnitude than in arable soils, as the primary recipients of compost, but were well within the range of many urban soils. In conclusion, this work provides a basis for the further improvement of composting and for future risk assessments of compost application.

Benzofurans↗

PubMed2005

Distribution of PCNs, PCBs, and other POPs together with soot and other organic matter in the marine environment of the Grenlandsfjords, Norway.

The apparently dissolved concentration of polychlorinated naphthalenes (PCNs) and three planar polychlorinated biphenyls (pPCBs) were sampled and analysed in the water column of a marine fjord system. We also measured how much of these persistent organic pollutants (POPs) were associated with suspended particles. The field observations showed that an unexpectedly high portion of the pollutants were particle-associated. The factor of deviation from model predictions had positive linear regression on the soot carbon:particulate organic carbon ratio of the particles, and on estimates of the soot-water distribution coefficient for the PCNs. The spatial distribution of surface sediment concentrations of PCNs and polycyclic aromatic hydrocarbons (PAH) were found to consistently follow the sediment content of soot (f(SC)) to a larger extent than the bulk organic matter (f(OC)). There were no systematic differences in the strength of correlation of sediments concentrations of other POPs, i.e. octachlorostyrene and organochlorine pesticides with sediment concentration to f(SC) and f(OC). Mechanisms possible of generating these types of observations, e.g. adsorption to soot carbon in the marine particle, are discussed.

Animals↗

PubMed2005

Testing common sediment-porewater distribution models for their ability to predict dissolved concentrations of POPs in The Grenlandsfjords, Norway.

This study compares in situ observed porewater concentration of persistent organic pollutants (POPs) with predictions by common solid-water phase distribution models. Bottom sediments were sampled in The Grenlandsfjords, Norway, and the interstitial porewater was isolated from the solids by centrifugation and filtration. Both phases were analysed for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F), polycyclic aromatic hydrocarbons (PAH), and organic carbon. Based on the sediments' solid phase content of POPs, organic carbon, and soot carbon, we used the organic matter partitioning (OMP), and also the soot and organic matter partitioning (SOMP) model to estimate the porewater concentration. The OMP model gave better agreement to observations than the SOMP model for both PCDD/Fs and PAHs. The observed concentration of the PCDD/Fs in the sediments' porewater was much higher than in the deep water of the fjord. The logarithm of the organic matter-water partitioning coefficent (log K(OC)) in the porewater had positive linear regression on the logarithm of the octanol-water partitioning coefficient (log K(OW)). The slope of the regression model was indistinguishable from 1, except for the PAHs as a group which had a slope less than 1. This contrasts to previous studies undertaken in The Grenlandsfjords water column, where the slopes were higher than 1 for PCDD/Fs, and the K(OC) were much higher than the K(OW). One explanation may be that the influence of POPs adsorption to soots decrease because competitive sorption by other compounds in the sediment are higher than in the water column. This indicates that the sorption isotherms for these POPs need better understanding in order to be applicable in both the water column and the porewater.

Algorithms↗

PubMed2005

Correlation of PCDD/F and PCB concentrations in soil samples from the Swiss soil monitoring network (NABO) to specific parameters of the observation sites.

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) were determined in 23 soil samples collected at reference sites of the Swiss national soil monitoring network (NABO). Total PCDD/F and PCB concentrations are well correlated and proportional (R2=0.720). The total PCDD/F levels were between 72 and 703 ng/kg corresponding to 1.1-11 ng I-TEQ/kg, total PCB concentrations (sum of seven congeners IUPAC no. 28, 52, 101, 118, 138, 153, and 180) were from 1.1 to 12 microg/kg. In all samples, the PCDD/F and PCB concentrations were in the range of background levels for these contaminants in Central Europe. Ninteen samples revealed PCDD/F levels below the guide value of 5 ng I-TEQ/kg set by the Swiss ordinance relating to impacts on the soil (OIS); concentrations for the remaining four samples were below the trigger value (20 ng I-TEQ/kg). All PCB concentrations were below the guide value of 100 microg/kg. The elevated PCDD/F and PCB levels in some of the samples originating from forested sites could be attributed to the scavenging effect of forest canopies for semivolatile organic compounds. This interpretation could be substantiated by the observed distortion of the congener and homolog patterns of PCDD/F and PCB which is characteristic for forested sites.

Benzofurans↗

PubMed2004

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 microg/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.

Carbon↗

PubMed2003

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.

Adsorption↗

PubMed2002

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.

Adsorption↗