Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax)

In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.     

The changing state of contamination in the Lagoon of Venice. Part 1: organic pollutants

The Lagoon of Venice is a transitional environment suffering from industrial, urban and agricultural impact. Recently the mechanical clam fishing, preventing a regular deposition of sediments has made sampling of cores suitable for radiodating very problematic. Therefore, in this study, in order to assess temporal and spatial trends of contamination, the same sampling scheme was repeated three times over a 12-year period. The concentrations of PCBs, PAHs and organochlorine pesticides were measured in the uppermost 5 cm of sediments collected in 25 sites in the central portion of the lagoon during three campaigns conducted in 1987, 1993 and 1998. Analytical results, validated statistically, indicated that, while PCB and pesticide concentrations tend to decrease during the considered period of time, PAH do not, showing that the input rate of these compounds to the lagoon environment is still important. A spatial trend of pollution was also found in the lagoon for PCBs and pesticides, which decrease from the sources, namely the industrial zone and the mouths of rivers, to areas closer to the sea: a reduction up to 80% and 90%, respectively, was monitored. PAH contamination, originating chiefly from incomplete combustion of fossil fuels, as inferred from ratios of congeners, was mainly located around the historical center of Venice, where most of the boat traffic is concentrated and has an increasing trend.     

Influence of pre-treatment step on PAHs analyses in contaminated soils

There is no specific standardization for the pre-treatment of a soil sample for PAHs analyses. The ISO/FDIS 14507 method for soil quality gives a guidance for sample pre-treatment before measurement of organic contaminants in soil. It refers to cryogenic crushing which is not so easy to carry out. So, analysts lead to develop in house methods which can be very different from a laboratory to another and can involve deviations in the pollution quantification. This study has explored different ways of drying, grinding and sieving in order to determine the influence of the soil sample handling on the measured pollutant concentration. It appears that the influence of pre-treatment depends on the soil nature and on the PAHs distribution. As a conclusion, it is advised "light" drying ways like air drying or drying at 40 degrees C in a drying oven instead of more "drastic" ways (freeze-drying, cryogenic crushing) which can induce some losses. Crushing and sieving are also recommended for more reproducible measures.     

In-field measurements of PCDD/F emissions from domestic heating appliances for solid fuels

Within this project the emissions into the atmosphere of polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) of 30 domestic heating appliances in Austrian households were tested. The appliances were single stoves (kitchen stove, continuous burning stove and tiled stove) and central heating boilers for solid fuels up to a nominal heat input of 50 kW. A main objective of this survey was to determine the PCDD/F emissions of domestic heating units under routine conditions. Therefore, the habitual combustion conditions used by the operators were not influenced. The original fuels and lightning supports were used and the operation of the units was carried out by the householders according to their usual practice. The data obtained were used to calculate in-field PCDD/F-emission factors. Most of the appliances have shown PCDD/F emissions within a concentration range of 0.01-0.3 ng TEQ/MJ. Modern fan-assisted wood heating boilers with afterburning and units for continuously burning of wood chips and wood pellets had the lowest emissions. High emissions were caused by unsuitable heating habits such as combustion of wastes and inappropriate operation of the appliances. There were only small differences between single stoves and central heating boilers or between wood and coal-fired appliances. The emission factors calculated are higher than those cited in literature, which are mainly derived from trials on test stands under laboratory conditions.     

Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments using delta13C and 14C measurements

Few techniques exist to measure the biodegradation of recalcitrant organic compounds such as chlorinated hydrocarbons (CHC) in situ, yet predictions of biodegradation rates are needed for assessing monitored natural attenuation. Traditional techniques measuring O2, CO2, or chemical concentrations (in situ respiration, metabolite and soil air monitoring) may not be sufficiently sensitive to estimate biodegradation rates for these compounds. This study combined isotopic measurements (14C and delta13C of CO2 and delta13C of CHCs) in conjunction with traditional methods to assess in situ biodegradation of perchloroethylene (PCE) and its metabolites in PCE-contaminated vadose zone sediments. CHC, ethene, ethane, methane, O2, and CO2 concentrations were measured over 56 days using gas chromatography (GC). delta13C of PCE, trichloroethylene (TCE) and cis-1,2-dichloroethylene (DCE), delta13C and 14C of vadose zone CO2 and sediment organic matter, and delta13C, 14C, and deltaD of methane were measured using a GC-isotope ratio mass spectrometer or accelerator mass spectrometer. PCE metabolites accounted for 0.2% to 18% of CHC concentration suggesting limited reductive dechlorination. Metabolites TCE and DCE were significantly enriched in (13)C with respect to PCE indicating metabolite biodegradation. Average delta13C-CO2 in source area wells (-23.5 per thousand) was significantly lower compared to background wells (-18.4 per thousand) indicating CHC mineralization. Calculated CHC mineralization rates were 0.003 to 0.01 mg DCE/kg soil/day based on lower 14C values of CO2 in the contaminated wells (63% to 107% modern carbon (pMC)) relative to the control well (117 pMC). Approximately 74% of the methane was calculated to be derived from in situ CHC biodegradation based on the 14C measurement of methane (29 pMC). 14C-CO2 analyses was a sensitive measurement for quantifying in situ recalcitrant organic compound mineralization in vadose zone sediments for which limited methodological tools exist.     

Isotopic characterisation of lead in contaminated soils from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria

Soil samples from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria contained very high concentrations of cadmium, lead and zinc (up to 140, 4900 and 5900 mg kg(-1), respectively). A roadside soil in a relatively uncontaminated area also contained high concentrations of the same metals (24, 1550 and 1870 mg kg(-1), respectively) indicating that the transport of ores could be a source of contamination. Even though the lead isotope ratios in all the samples fell within a very narrow range (for example, 1.186-1.195 for (206)Pb/(207)Pb), the samples could be differentiated into three distinct groups: ores ((206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.1874-1.1884 and 2.4755-2.4807, respectively), current deposition (1.1864 and 2.4704-2.4711, respectively) and local background (1.1927-1.1951 and 2.4772-2.4809, respectively). Although most of the current deposition has its origin in the ores used at the smelter, up to 12% could be from other sources such as petrol lead.     

Oil spill in the Rio de la Plata estuary, Argentina: 2-hydrocarbon disappearance rates in sediments and soils

The 6-month assessment of the oil spill impact in the Rio de la Plata described in the preceding paper [Colombo, J.C., Barreda, A., Bilos, C., Cappelletti, N., Demichelis, S., Lombardi, P., Migoya, M.C., Skorupka, C., Suarez, G., 2004. Oil spill in the Rio de la Plata estuary, Argentina: 1 - biogeochemical assessment of waters, sediments, soils and biota. Environmental Pollution] was followed by a 13- and 42-month campaigns to evaluate the progress of hydrocarbon decay. Average sediment hydrocarbon concentrations in each sampling include high variability (85-260%) due to contrasting site conditions, but reflect a significant overall decrease after 3 years of the spill: 17 +/- 27, 18 +/- 39 to 0.54 +/- 1.4 microg g(-1) for aliphatics; 0.44 +/- 0.49, 0.99 +/- 1.6 to 0.04 +/- 0.03 microg g(-1) for aromatics at 6, 13 and 42 months, respectively. Average soil hydrocarbon levels are 100-1000 times higher and less variable (61-169%) than sediment values, but display a clear attenuation: 3678 +/- 2369, 1880 +/- 1141 to 6.0 +/- 10 microg g(-1) for aliphatics and 38 +/- 26, 49 +/- 32 to 0.06 +/- 0.04 microg g(-1) for aromatics. Hydrocarbon concentrations modeled to first-order rate equations yield average rate constants of total loss (biotic+abiotic) twice as higher in soils (k = 0.18-0.19 month(-1)) relative to sediments (0.08-0.10 month(-1)). Individual aliphatic rate constants decrease with increasing molecular weight from 0.21 +/- 0.07 month(-1) for isoprenoids and n-C27, similar to hopanes (0.10 +/- 0.05 month(-1)). Aromatics disappearance rates were more homogeneous with higher values for methylated relative to unsubstituted species (0.17 +/- 0.05 vs. 0.12 +/- 0.05 months(-1)). Continued hydrocarbon inputs, either from biogenic (algal n-C15,17; vascular plant n-C27,29) or combustion related sources (fluoranthene and pyrene), appear to contribute to reduced disappearance rate. According to the different loss rates, hydrocarbons showed clear compositional changes from 6-13 to 42 months. Aliphatics disappearance rates and compositional changes support an essentially microbiologically-mediated recovery of coastal sediments to pre-spill conditions in a 3-4 year period. The lower rates and more subtle compositional changes deduced for aromatic components, suggest a stronger incidence of physical removal processes.     

A lysimeter experiment to investigate the leaching of veterinary antibiotics through a clay soil and comparison with field data

Pharmaceuticals used in livestock production may be present in manure and slurry as the parent compound and/or metabolites. The environment may therefore be exposed to these substances due to the application of organic fertilisers to agricultural land or deposition by grazing livestock. For other groups of substances that are applied to land (e.g. pesticides), preferential flow in clay soils has been identified as an extremely important mechanism by which surface water pollution can occur. This lysimeter study was therefore performed to investigate the fate of three antibiotics from the sulphonamide, tetracycline and macrolide groups in a clay soil. Only sulphachloropyridazine was detected in leachate and soil analysis at the end of the experiment showed that almost no antibiotic residues remained. These data were analysed alongside field data for the same compounds to show that soil tillage which breaks the connectivity of macropores formed over the summer months, prior to slurry application, significantly reduces chemical mobility.     

Screening the wetland plant species Alisma plantago-aquatica, Carex rostrata and Phalaris arundinacea for innate tolerance to zinc and comparison with Eriophorum angustifolium and Festuca rubra Merlin

Several wetland plant species appear to have constitutive metal tolerance. In previous studies, populations from contaminated and non-contaminated sites of the wetland plants Typha latifolia, Phragmites australis, Glyceria fluitans and Eriophorum angustifolium were found to be tolerant to high concentrations of metals. This study screened three other species of wetland plants: Alisma plantago-aquatica, Carex rostrata and Phalaris arundinacea for innate tolerance to zinc. The degree of tolerance was compared to known zinc-tolerant E. angustifolium and Festuca rubra Merlin. It was found that A. plantago-aquatica and P. arundinacea did not posses innate tolerance to zinc, but that C. rostrata was able to tolerate elevated levels of zinc, at levels comparable to those tolerated by E. angustifolium and F. rubra Merlin. The findings support the theory that some wetland angiosperm species tend to be tolerant to exposure to high levels of metals, regardless of their origin.     

No evidence for a critical salinity threshold for growth and reproduction in the freshwater snail Physa acuta

The growth and reproduction of the freshwater snail Physa acuta (Gastropoda: Physidae) were measured at various salinity levels (growth: distilled water, 50, 100, 500, 1000 and 5000 microS/cm; reproduction: deionized water, 100, 500, 1000 and 3000 microS/cm) established using the artificial sea salt, Ocean Nature. This was done to examine the assumption that there is no direct effect of salinity on freshwater animals until a threshold, beyond which sub-lethal effects, such as reduction in growth and reproduction, will occur. Growth of P. acuta was maximal in terms of live and dry mass at salinity levels 500-1000 microS/cm. The number of eggs produced per snail per day was maximal between 100 and 1000 microS/cm. Results show that rather than a threshold response to salinity, small rises in salinity (from low levels) can produce increased growth and reproduction until a maximum is reached. Beyond this salinity, further increases result in a decrease in growth and reproduction. Studies on the growth of freshwater invertebrates and fish have generally shown a similar lack of a threshold response. The implications for assessing the effects of salinisation on freshwater organisms need to be further considered.