Statistical uncertainty in hazardous terrestrial concentrations estimated with aquatic ecotoxicity data

Since chemicals’ ecotoxic effects depend for most soil species on the dissolved concentration in pore water, the equilibrium partitioning (EP) method is generally used to estimate hazardous concentrations (HC50) in the soil from aquatic toxicity tests. The present study analyzes the statistical uncertainty in terrestrial HC50s derived by the EP-method. For 47 organic chemicals, we compared freshwater HC50s derived from standard aquatic ecotoxicity tests with porewater HC50s derived from terrestrial ecotoxicity tests. Statistical uncertainty in the HC50s due to limited species sample size and in organic carbon–water partitioning coefficients due to predictive error was treated with probability distributions propagated by Monte Carlo simulations. Particularly for specifically acting chemicals, it is very important to base the HC50 on a representative sample of species, composed of both target and non-target species. For most chemical groups, porewater HC50 values were approximately a factor of 3 higher than freshwater HC50 values. The ratio of the porewater HC50/freshwater HC50 was typically 3.0 for narcotic chemicals (2.8 for nonpolar and 3.4 for polar narcotics), 0.8 for reactive chemicals, 2.9 for neurotoxic chemicals (4.3 for AChE agents and 0.1 for the cyclodiene type), and 2.5 for herbicides–fungicides. However, the statistical uncertainty associated with this ratio was large (typically 2.3 orders of magnitude). For 81% of the organic chemicals studied, there was no statistical difference between the hazardous concentration of aquatic and terrestrial species. We conclude that possible systematic deviations between the HC50s of aquatic and terrestrial species appear to be less prominent than the overall statistical uncertainty.     

High prevalence of infections and pathological changes in burbot (Lota lota) from a polluted lake (Lake Mjøsa,Norway)

The aim of the present study was to investigate whether exposure to high levels of persistent organic pollutants (POPs) affected a fish population in Lake Mjøsa. Lake Mjøsa is known to be contaminated by polybrominated diphenyl ethers (PBDEs), a subgroup of brominated flame retardants from local industrial activities. Fish from Lake Losna, a less contaminated lake located close to Lake Mjøsa, was used as reference (control).The sampling of burbot (Lota lota) was carried out between 2005 and 2008. Hepatic levels of POPs were analysed in burbot from the two lakes, and the fish were examined for bacterial- and parasite infection and histopathological changes. The levels of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs), and PBDEs were about 10, 15 and 300 times higher in fish from Lake Mjøsa compared to fish from Lake Losna. Mycobacterium salmoniphilum was present in 7% and 35% of the fish from Lake Losna and Lake Mjøsa respectively. Significantly higher number of external and visceral macroscopic lesions, histopathological diffuse changes and granulomas were seen in fish from Lake Mjøsa compared to Lake Losna. Furthermore the parasite infection was higher and the hepatic lipid content was significantly lower in burbot from Lake Mjøsa. The results of the present study suggest that the high level of contamination in Lake Mjøsa could have a negative impact on the health status of wild fish inhabiting the lake.     

Sulfur recirculation for increased electricity production in Waste-to-Energy plants

Sulfur recirculation is a new technology for reducing boiler corrosion and dioxin formation. It was demonstrated in full-scale tests at a Waste to Energy plant in Göteborg (Sweden) during nearly two months of operation. Sulfur was recirculated as sulfuric acid from the flue gas cleaning back to the boiler, thus creating a sulfur loop.The new technology was evaluated by extensive measurement campaigns during operation under normal conditions (reference case) and operation with sulfur recirculation. The chlorine content of both fly ash and boiler ash decreased and the sulfur content increased during the sulfur recirculation tests. The deposit growth and the particle concentration decreased with sulfur recirculation and the dioxin concentration (I-TEQ) of the flue gas was reduced by approximately 25%. Sulfuric acid dew point measurements showed that the sulfuric acid dosage did not lead to elevated SO₃ concentrations, which may otherwise induce low temperature corrosion.In the sulfur recirculation corrosion probe exposures, the corrosion rate decreased for all tested materials (16Mo3, Sanicro 28 and Inconel 625) and material temperatures (450 °C and 525 °C) compared to the reference exposure. The corrosion rates were reduced by 60–90%. Sulfur recirculation prevented the formation of transition metal chlorides at the metal/oxide interface, formation of chromate and reduced the presence of zinc in the corrosion products. Furthermore, measured corrosion rates at 525 °C with sulfur recirculation in operation were similar or lower compared to those measured at 450 °C material temperature in reference conditions, which corresponds to normal operation at normal steam temperatures. This implies that sulfur recirculation allows for higher steam data and electricity production without increasing corrosion.     

Spatial and temporal trends of metals and arsenic in German freshwater compartments

Cadmium, lead, mercury, copper, nickel, zinc, and arsenic were analyzed in suspended particulate matter (SPM), zebra mussels, and bream sampled yearly under the program of the German Environmental Specimen Bank (ESB) in the rivers Rhine, Elbe, Danube, Saar, Mulde, and Saale and in Lake Belau. Temporal and spatial trends were analyzed, correlations between metal levels in different specimen types assessed, and sampling sites ranked according to their metal levels by calculating a Multi-Metal Index (MMI) for every specimen type and site. SPM: Highest metal loads were detected in Mulde, Saale, and Elbe right downstream of the Saale confluence. In the Elbe, metal loads in SPM were mostly highest in the upper and middle section of the river while in Rhine and Saar concentrations increased downstream. Temporal trends since 2005 were detected only at three sites. Zebra mussel: MMIs were highest in the tidal section of the Elbe and the lower Rhine and lowest in Lake Belau and the upper Danube. Different temporal trends were detected since the early 1990s depending on site and metal. Bream: As, Pb, Cu, and Hg were analyzed in muscle tissue and Pb, Cd, Cu, and Zn in liver. For both tissues, MMIs were highest in Mulde and Saale and the lower and middle Elbe. Since the early 1990s, Hg, Pb, and Cu decreased in bream muscle at many sites while As increased at 6 of the 17 sites. The findings indicate that Hg, Pb, and Cu have obviously decreased in many freshwater ecosystems in recent years, whereas As and Ni levels have increased at several sites. Metal levels and temporal trends mostly differed between the specimen types under investigation and only few correlations between specimen types were detected. This underlines the importance of including different components of an ecosystem when assessing its environmental quality.     

Methylsulfonyl PCB and DDE metabolites and their enantioselective gas chromatographic separation in human adipose tissues, seal blubber and pelican muscle

In the present investigation, eleven human adipose tissue samples, two seal blubber samples and two pelican muscles samples were analyzed with regard to their concentrations of PCB parent compounds as well as to the respective chiral methylsulfonyl metabolites 3-MeSO2-CB 91, 4-MeSO2-CB 91, 3-MeSO2-CB 95, 4-MeSO2-CB 95, 3-MeSO2-CB 149, 4-MeSO2-CB 149, 3-MeSO2-CB 132, 4-MeSO2-CB 132, 3-MeSO2-CB 174, and 4-MeSO2-CB 174 and the achiral metabolites 3-MeSO2-CB 49, 4-MeSO2-CB 49, 3-MeSO2-CB 101, 4-MeSO2-CB 101, 3-MeSO2-CB 110, 4-MeSO2-CB 110 and 3-MeSO2-DDE. In order to verify enantioselective transformation processes and to compare the different enzymatic transformation pathways in birds and mammals, the enantioselective excesses of the chiral PCB-metabolites were determined by enantioselective gas chromatography with electron capture and mass spectrometric detection using modified cyclodextrin phases, including heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/OV1701 (1:1) for the parent PCBs and heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/SE52 (1:4) for the metabolites, respectively.     

Non-target screening of extractable and non-extractable organic xenobiotics in riverine sediments of Ems and Mulde Rivers, Germany

Subaquatic sediment samples derived form Elbe and Mulde Rivers, Germany, were analyzed for extractable and non-extractable anthropogenic organic compounds by a non-target screening approach. Applied methodologies were gas chromatography-mass spectrometry, dispersion extraction and degradation procedures, particularly alkaline and acidic hydrolysis, boron tribromide treatment, ruthenium tetroxide oxidation as well as pyrolysis and TMAH (tetramethylammonium hydroxide)-thermochemolysis. Numerous compounds were identified, including halogenated benzenes, anisoles, styrenes, alkanes, diphenylmethane derivates, anilines, phenols and diphenyl ethers. The results were interpreted with respect to compound specific modes of incorporation as well as to potential sources (e.g. municipal, agricultural, industrial). Extractable and non-extractable fractions differed significantly with respect to their qualitative and quantitative composition. For example, quantities in the extractable and non-extractable fractions of chlorinated benzenes differed up to factor 50. Among other significant results, the investigation revealed hints for a dependence of the mode of incorporation of chlorinated benzenes on their substitution pattern.     

Tree species effect on the redistribution of soil metals

Phytostabilization of metals using trees is often promoted although the influence of different tree species on the mobilization of metals is not yet clear. Soil and biomass were sampled 33 years after planting four tree species (Quercus robur, Fraxinus excelsior, Acer pseudoplatanus, Populus 'Robusta') in a plot experiment on dredged sediment. Poplar took up high amounts of Cd and Zn and this was associated with increased Cd and Zn concentrations in the upper soil layer. The other species contained normal concentrations of Cd, Cu, Cr, Pb and Zn in their tissues. Oak acidified the soil more than the other species and caused a decrease in the concentration of metals in the upper soil layer. The pH under poplar was lower than expected and associated with high carbon concentrations in the top soil. This might be assigned to retardation of the litter decomposition due to elevated Cd and Zn concentrations in the litter.     

Phytoextraction of metals from soils: how far from practice?

For most trace elements, the technique of phytoextraction needs significant improvements to become practically feasible. Calculations for Cd revealed that the amount of Cd taken up by Thlaspi caerulescens or Salix spp. needs at least to be the double of the present amount to slightly decrease the Cd concentration in the upper 0.5m of the soil within a period of 10 years. Additionally, metals taken up by the plants might pose an important risk. Alternatives as bioavailable contaminant stripping and phytostabilization might be more appropriate.     

Spatial distribution and internal metal concentrations of terrestrial arthropods in a moderately contaminated lowland floodplain along the Rhine River

Soil metal concentrations, inundation characteristics and abundances of 14 arthropod taxa were investigated in a moderately contaminated lowland floodplain along the Rhine River and compared to the hinterland. Internal metal concentrations were determined for the orders of Coleoptera (beetles) and Araneida (spiders) and were related to soil concentrations. The floodplain was characterized by larger arthropod abundance than the hinterland, in spite of recurrent inundations and higher soil metal concentrations. Most arthropod taxa showed increasing abundance with decreasing distance to the river channel and increasing average inundation duration. For Cd, Cu, Pb and Zn, significant relations were found between arthropod concentrations and concentrations in soil. Significant relations were few but positive, indicating that increasing soil concentrations result in increasing body burdens in arthropods. For arthropod-eating vertebrates, these results might imply that larger prey availability in the floodplain coincides with higher metal concentrations in prey, possibly leading to increased exposure to metal contamination.