In this study we explore the use of fish otoliths (‘earbones’) as a tool for detecting exposure to heavy metals in sediments. Because otoliths are metabolically inert and incorporate chemical impurities during growth, they can potentially provide a more permanent record of pollutant exposure history in aquatic environments than soft tissues. To validate this technique we cultured embryos of a native Australian fish, the common Galaxias (Galaxias maculatus), in the laboratory on sediments spiked with copper in a concentration gradient. Our aims were to test whether exposure to copper contaminated sediments is recorded in the otoliths of embryos and determine over what range in concentrations we can detect differences in exposure. We found elevated copper levels in otoliths of embryos exposed to high copper concentrations in sediments, suggesting that otoliths can be used as a tool to track a history of exposure to elevated copper levels in the environment.

Maternal hair and blood were investigated as biomarkers for prenatal methylmercury (MeHg) exposure among seventeen mothers recruited at parturition in Wanshan, Guizhou Province, China, where rice ingestion was the primary MeHg exposure pathway and atmospheric mercury (Hg) levels were elevated. For all three trimesters (n = 51), hair total Hg (THg) and MeHg concentrations ranged from 0.27 to 4.9 μg/g (median: 0.96 μg/g) and 0.077 to 2.3 μg/g (median: 0.43 μg/g), respectively, while blood THg levels ranged from 1.7 to 11 μg/L (median: 3.0 μg/L, n = 17). Despite adequate hair washing procedures, median %MeHg (of THg) was 37% (range: 14–89%, n = 51), indicating exogenous inorganic Hg(II) contamination or incorporation of elemental Hg (Hgo) into the hair shaft were important. Rice MeHg levels (n = 17) were highly correlated with blood THg (r2 = 0.66) compared to hair MeHg (r2 = 0.31) (when variables were log10-transformed), suggesting blood THg was a more preferable biomarker for prenatal MeHg exposure within this population.

Covalent coupling to natural humic constituents comprises an important transformation pathway for anilinic pollutants in the environment. We systematically investigated the reactions of chlorine substituted anilines with catechol and syringic acid in horseradish peroxidase (HRP) catalyzed systems. It was demonstrated that although nucleophilic addition was the mechanism of covalent bonding to both catechol and syringic acid, chloroanilines coupled to the 2 humic constituents via slightly different pathways. 1,4-addition and 1,2-addition are involved to catechol and syringic acid, respectively. 1,4-addition showed empirical 2nd order kinetics and this pathway seemed to be more permanent than 1,2-addition. Stability experiments demonstrated that cross-coupling products with syringic acid could be easily released in acidic conditions. However, cross-coupling with catechol was relatively stable at similar conditions. Thus, the environmental behavior and bioavailability of the coupling products should be carefully assessed.

Mercury (Hg) is a pervasive contaminant that can adversely affect predatory wildlife. Bird eggs provide insights into breeding females' Hg burdens, and are easily collected and archived. We present data on Hg trends in herring gull (Larus argentatus) eggs from five sites in Atlantic Canada from 1972 to 2008. We found a significant decrease in Hg at Manawagonish Island, New Brunswick and Île du Corossol, Quebec, but after correcting Hg for dietary shifts using stable isotopes (δ15N), these trends disappeared. Decreasing temporal trends of stable isotopes in gull eggs were observed at four sites, suggesting shifts in gull diets. At Gull Island, Newfoundland, diet-adjusted Hg increased from 1977 to 1992, dropped sharply between 1992 and 1996, and rose again from 1996 to 2008. After adjusting Hg trends for dietary shifts of herring gulls, it appears that environmental Hg in coastal ecosystems has remained relatively constant at most sites in Atlantic Canada over the last 36 years.

Hexabromocyclododecanes (HBCDs) has just been listed into Stockholm Convention as a persistent organic pollutant recently. This paper studied the HBCDs in 79 wild fish from high mountain lakes and rivers of the Tibetan Plateau. The ∑HBCDs in fish muscles ranged from non detectable levels to 13.7 ng/g lipid weight (lw) (mean value of 2.12 ng/g lw) with a high detection frequency of 65.8%. α-HBCD dominated among the isomers and accounted for 78.2% of the total burden. Concentrations of ∑HBCDs in the fish were significantly correlated with the lipid content. A decreasing trend was observed between α-HBCD and trophic level. Positive correlation was also noted between the HBCD levels in fish from lakes and the annual precipitation, and this implied the long-range atmospheric transport of HBCDs to the Tibet Plateau. This was the first work to widely explore HBCDs contamination in the aquatic ecosystems of the Tibetan Plateau.

Levels and distribution of chlorinated paraffins were studied in randomly taken house dust samples (<63 μm) from the greater area of Munich, Germany. Quantification of short- (SCCPs, C10–C13) and medium-chain chlorinated paraffins (MCCPs, C14–C16) were performed using gas chromatography electron capture negative ion mass spectrometry (GC–ECNI–MS). Concentrations of MCCPs in private household samples varied between 9 μg/g and 892 μg/g, and exceeded levels of SCCPs, which were in the range of 4–27 μg/g. Two dust samples from a public building contained up to 2050 μg/g SCCPs but no MCCPs. Among MCCPs, chlorinated tetradecanes were major components with a proportion of almost 50%. Among SCCPs, chlorinated dodecanes were usually present at higher concentrations than the congeners of any C10, C11, and C13 chains. The results indicate that particularly MCCPs may be present in relatively high concentrations in house dusts.

Freeze–thaw cycling may influence the chemistry, mineral stability and reaction rate during metal orthophosphate fixation. This study assessed the formation and stability of Cu-, Pb-, and Zn-phosphates in chemically simple laboratory systems during 240 freeze–thaw cycles (120 days) from +10 to −20 °C, using X-ray diffractometry. In single heavy metal systems, chloro- and hydroxy-pyromorphite (Pb5(PO4)3(Cl,OH)), sodalite (Na6Zn6(PO4)6·8H2O), chiral zincophosphate (Na12(Zn12P12O48)·12H2O), and copper phosphate hydrate (Cu3(PO4)2·3H2O) were the primary phosphate minerals that formed, and were typically stable during the experiment. Zinc and Cu-phosphate formation was reduced in multi heavy metal systems, and was substantially lower in abundance than chloropyromorphite. Successful Cu-, Pb- and Zn-phosphate formation can be expected in cold and freezing environments like the polar regions. However, field implementation of orthophosphate fixation needs to consider competing ion effects, concentration of the phosphate source, and the amount of free-water.

A new passive exchange meter (PEM) to measure inter-compartment fluxes of persistent organic pollutants (POPs) at the interface between soil and the atmosphere is described. The PEM uses labeled reference compounds (RC) added in-situ to vegetation litter deployed in open cylinders designed to trap the vertical downward export of the RCs while allowing free exchange of POPs between litter and air. Fluxes of native compounds (bulk deposition, volatilization and downward export) are quantitatively tracked. One scope of the PEM is to investigate the influence of biogeochemical controls on contaminant re-mobilization. The PEM performance was tested in a subtropical forest by comparing measurements under dense canopy and in a canopy gap; conditions in which deposition and turn-over of organic matter (OM) occur at different rates. Significant differences in fate processes were successfully detected. Surprisingly, mobilization by leaching of more hydrophobic compounds was higher under canopy, possibly as a result of canopy mediated enhancement of OM degradation.

Column experiments were conducted in undisturbed and in repacked soil columns at water contents close to saturation (85–96%) to investigate the transport and retention of functionalized 14C-labeled multi-walled carbon nanotubes (MWCNT) in two natural soils. Additionally, a field lysimeter experiment was performed to provide long-term information at a larger scale. In all experiments, no breakthrough of MWCNTs was detectable and more than 85% of the applied radioactivity was recovered in the soil profiles. The retention profiles exhibited a hyper-exponential shape with greater retention near the column or lysimeter inlet and were successfully simulated using a numerical model that accounted for depth-dependent retention. In conclusion, results indicated that the soils acted as a strong sink for MWCNTs. Little transport of MWCNTs is therefore likely to occur in the vadose zone, and this implies limited potential for groundwater contamination in the investigated soils.

This study derived Species Sensitivity Distributions (SSD), representing a cumulative stressor-response distribution based on single-species sensitivity data, for ozone exposure on natural vegetation. SSDs were constructed for three species groups, i.e. trees, annual grassland and perennial grassland species, using species-specific exposure–response data. The SSDs were applied in two ways. First, critical levels were calculated for each species group and compared to current critical levels for ozone exposure. Second, spatially explicit estimates of the potentially affected fraction of plant species in Northwestern Europe were calculated, based on ambient ozone concentrations. We found that the SSD-based critical levels were lower than for the current critical levels for ozone exposure, with conventional critical levels for ozone relating to 8–20% affected plant species. Our study shows that the SSD concept can be successfully applied to both derive critical ozone levels and estimate the potentially affected species fraction of plant communities along specific ozone gradients.