Innovative aspects of environmental chemistry and technology regarding air,water, and soil pollution

Environmental Science and Pollution Research -     

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.     

Organic pollutants in compost and digestate. Part 1. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and molecular markers

In Europe, 9.3 x 10(6) t(dry weight (dw)) of compost and digestate are produced per year. Most of this is applied to agricultural land, which can lead to considerable inputs of organic pollutants, such as polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) to soil. This paper presents an inventory of the pollutant situation in source-separated composts, digestates and presswater in Switzerland by a detailed analysis of over 70 samples. PCB concentrations ( summation PCB 28, 52, 101, 118, 138, 153, 180) were significantly higher in urban (median: 30 microg kg(-1)dw, n = 52) than in rural samples (median: 14 microg kg(-1)dw, n = 16). Together with low concentrations in general, this points to aerial deposition on compost input material as the major contamination pathway. Enantiomeric fractions of atropisometric PCB were close to racemic. Median PAH concentration was 3010 microg kg(-1)dw( summation 15PAH, n = 69), and one quarter of the samples exhibited concentrations above the relevant Swiss guide value for compost (4000 microg kg(-1)dw). The levels were influenced by the treatment process (digestate > compost), the season of input material collection (spring-summer > winter > autumn), the particle size (coarse-grained > fine-grained), and maturity (mature > less mature). The main source of PAH in compost was pyrogenic, probably influenced mainly by liquid fossil fuel combustion and some asphalt abrasion, as suggested by multiple linear regression. This study, together with a companion paper reporting on other organic contaminates including emerging compound classes, provides a starting point for a better risk-benefit estimation of the application of compost and digestate to agricultural soil in Switzerland.     

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.     

Phytoestrogens and mycotoxins in Iowa streams: an examination of underinvestigated compounds in agricultural basins

This study provides the first broad-scale investigation on the spatial and temporal occurrence of phytoestrogens and mycotoxins in streams in the United States. Fifteen stream sites across Iowa were sampled five times throughout the 2008 growing season to capture a range of climatic and crop-growth conditions. Basin size upstream from sampling sites ranged from 7 km2 to > 836,000 km2. Atrazine (herbicide) also was measured in all samples as a frame-of-reference agriculturally derived contaminant. Target compounds were frequently detected in stream samples: atrazine (100%), formononetin (80%), equol (45%), deoxynivalenol (43%), daidzein (32%), biochanin A (23%), zearalenone (13%), and genistein (11%). The nearly ubiquitous detection of formononetin (isoflavone) suggests a widespread agricultural source, as one would expect with the intense row crop and livestock production present across Iowa. Conversely, the less spatially widespread detections of deoxynivalenol (mycotoxin) suggest a more variable source due to the required combination of proper host and proper temperature and moisture conditions necessary to promote Fusarium spp. infections. Although atrazine concentrations commonly exceeded 100 ng L(-1) (42/75 measurements), only deoxynivalenol (6/56 measurements) had concentrations that occasionally exceeded this level. Temporal patterns in concentrations varied substantially between atrazine, formononetin, and deoxynivalenol, as one would expect for contaminants with different source inputs and processes of formation and degradation. The greatest phytoestrogen and mycotoxin concentrations were observed during spring snowmelt conditions. Phytoestrogens and mycotoxins were detected at all sampling sites regardless of basin size. The ecotoxicological effects from long-term, low-level exposures to phytoestrogens and mycotoxins or complex chemicals mixtures including these compounds that commonly rake place in surface water are poorly understood and have yet to be systematically investigated in environmental studies.     

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.     

Testing the resistance of fullerenes to chemothermal oxidation used to isolate soots from environmental samples

We tested the resistance of five different fullerenes (C₆₀, C₇₀, C_76/78 mix, and C₈₄) to chemothermal oxidation at 375 °C (CTO-375), a method that has been used and tested for quantifying black carbon (BC) and CNTs in soils and sediments. C₆₀ survived CTO-375 the most (50%), while C₇₀ was the fullerene with the lowest survival rate (<1%). Standard additions of C₆₀ to soil and sediment reference materials yielded recoveries between 18 and 36%. Although lower than recoveries previously observed for soot and CNTs, these results demonstrate the capability of CTO-375 to partially isolate C₆₀ from solid environmental matrices. Standard additions of C₇₀, C_76/78, and C₈₄ yielded slightly higher survival rates when added to soil and sediment than in their pure form. These results indicate that the mineral matrices of these samples probably had a catalytic effect towards C₆₀ and a protective effect towards C₇₀, C_76/78, and C₈₄ during CTO-375.     

Contrasting temporal trends and relationships of total organic carbon, black carbon, and polycyclic aromatic hydrocarbons in rural low-altitude and remote high-altitude lakes

Historical records of total organic carbon (TOC), black carbon (BC), and polycyclic aromatic hydrocarbons (PAHs) were reconstructed in dated sediment cores from four nearby lakes in central Switzerland. In the sub-Alpine Lake Thun, located at 558 m a.s.l., the proximity to anthropogenic emission sources is reflected in higher input of BC and PAHs into sediments with fluxes only slightly decreasing during the last decades. PAH/BC ratios are relatively high and correlation between levels of total PAHs and BC is almost inexistent in Lake Thun, probably due to the presence of less condensed forms of the BC spectrum (char BC) that is underestimated with the chemothermal oxidation method applied in this study. The sediment profiles of TOC, BC, and PAHs are noticeably different in the mountain lakes located around 2000 m a.s.l. In Lake Engstlen, the PAH/BC ratios, as well as the correlation between PAHs and BC, point towards appreciable amounts of predominantly light soot particles. Light soot particles have higher mobility and can, therefore, be efficiently transported to this remote site. The proglacial Lake Oberaar is shown to be a receptor of BC and PAHs released by the fast melting adjacent glacier acting as a secondary source for these conservative species temporarily stored in the glacier ice. Finally, Lake Stein is in strong contrast to all other lakes. High flux of BC into Lake Stein, combined with constant temporal evolutions of BC and PAHs, and in particular BC/TOC ratios approaching 100% are all strong indications for a geogenic presence of graphite in its catchment area.     

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.