Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

Biomagnification of anthropogenic and naturally-produced organobrominated compounds in a marine food web from Sydney Harbour, Australia

Polybrominated diphenyl ethers (PBDEs) and naturally-produced organobrominated compounds, such as methoxylated PBDEs (MeO-PBDEs), have been scarcely studied in the Southern Hemisphere. Yet, sources of the latter group of compounds were found in Southern regions, specifically in Australia. The environmental distribution and biomagnification potential of organobrominated compounds were therefore investigated in a representative aquatic food chain (invertebrates and fish) from the Sydney Harbour, Australia. Mean PBDE concentrations ranged from 6.4 ng/g lipid weight (lw) in squid to 115 ng/g lw in flounder. BDE 47 was the dominant congener, followed by BDE 100. Mean levels of MeO-PBDEs (sum of congeners 2’-MeO-BDE 68 and 6-MeO-BDE 47) were as high as 110 ng/g lw in tailor, with a slight dominance of 2’-MeO-BDE 68. Polybrominated hexahydroxanthene derivates (PBHDs), another class of naturally-produced compounds, were found at variable concentrations and ranged from 4.7 ng/g lw in fanbelly and 146 ng/g lw in tailor. The tribrominated PBHD isomer dominated in the samples, except for luderick and squid. The lower levels of PBDEs found in luderick from the harbour compared to those obtained from the upper Parramatta River indicated a terrestrial (anthropogenic) origin of PBDEs, while the higher levels of MeO-PBDEs and PBHDs in the samples from the harbour confirmed the marine (natural) origin of these compounds. The highest trophic magnification factor (TMF) was found for sum PBDEs (3.9), while TMFs for sum MeO-PBDEs and sum PBHDs were 2.9 and 3.4, respectively. This suggests that biomagnification occurs in the studied aquatic food chain for anthropogenic brominated compounds, but also for the naturally-produced organobromines.     

Distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in soils from the East Antarctic coast

Concentrations of hexachlorobenzene (HCB), alpha-, beta- and gamma-hexachlorocyclohexane (HCH) isomers, 6 o,p'-and p,p'-isomers of DDT and 28 PCB congeners have been measured in eleven soil samples and one lichen collected on the Eastern coast of Antarctica from 5 Russian stations. For samples with low concentrations of PCBs (range 0.20-0.41 ng g(-1) dry weight) and pesticides (0.86-4.69 ng g(-1) and 0.11-1.22 ng g(-1) dry weight for HCHs and DDTs, respectively), atmospheric long-range transport from Africa, South America or Australia was suggested as the sole source of contamination. The profile of PCB congeners was dominated by the more volatile tri-, tetra- and penta-PCBs congeners, thus supporting long-range transport hypothesis. Four samples contained moderate levels of PCBs (range 1.98-6.94 ng g(-1) dry weight) and variable concentrations of pesticides (gamma-HCH, p,p'-DDT and o,p'-DDT being the main contaminants). For samples with high concentrations of PCBs (range 90.26-157.45 ng g(-1)) and high concentrations of pesticides, the presence of high molecular weight PCB congeners such as: 153, 180, 187, 170 etc, strongly suggest a local source (biotic) of PCBs rather than atmospheric transport. It is likely that on a local scale, biotic focussing of pollutants, due to bird activities (nesting and excrement) can cause high contamination levels and become more significant than contaminant input via abiotic pathways.     

Testing and Improving Temperature Thresholds for Snow and Rain Prediction in the Western United States

The phase of precipitation at the land surface is critical to determine the timing and amount of water available for hydrological and ecological systems. However, there are few techniques to directly observe the precipitation phase and many prediction tools apply a single temperature threshold (e.g., 0°C) to determine phase. In this paper, we asked two questions: (1) what is the accuracy of default and station optimized daily temperature thresholds for predicting precipitation phase and (2) what are the regions and conditions in which typical temperature‐based precipitation phase predictions are most suited. We developed a ground truth dataset of rain vs. snow using an expert decision‐making system based on precipitation, snow depth, and snow water equivalent observations. This dataset was used to evaluate the accuracy of three temperature‐threshold‐based techniques of phase classification. Optimizing the temperature threshold improved the prediction of precipitation phase by 34% compared to using 0°C threshold. Developing a temperature threshold based on station elevation improved the error by 12% compared with using the 0°C temperature threshold. We also found the probability of snow as a function of temperature differed among ecoregions, which suggests a varied response to future climate change. These results highlight a current weakness in our ability to predict the effects of regional warming that could have uneven impacts on water and ecological resources.     

CH4/CO2 ratios indicate highly efficient methane oxidation by a pumice landfill cover-soil

Landfills that generate too little biogas for economic energy recovery can potentially offset methane (CH₄) emissions through biological oxidation by methanotrophic bacteria in cover soils. This study reports on the CH₄ oxidation efficiency of a 10-year old landfill cap comprising a volcanic pumice soil. Surface CH₄ and CO₂ fluxes were measured using field chambers during three sampling intervals over winter and summer. Methane fluxes were temporally and spatially variable (?0.36 to 3044 mg CH₄ m^?2 h^?1); but were at least 15 times lower than typical literature CH₄ fluxes reported for older landfills in 45 of the 46 chambers tested. Exposure of soil from this landfill cover to variable CH₄ fluxes in laboratory microcosms revealed a very strong correlation between CH₄ oxidation efficiency and CH₄/CO₂ ratios, confirming the utility of this relationship for approximating CH₄ oxidation efficiency. CH₄/CO₂ ratios were applied to gas concentrations from the surface flux chambers and indicated a mean CH₄ oxidation efficiency of 72%. To examine CH₄ oxidation with soil depth, we collected 10 soil depth profiles at random locations across the landfill. Seven profiles exhibited CH₄ removal rates of 70–100% at depths <60 cm, supporting the high oxidation rates observed in the chambers. Based on a conservative 70% CH₄ oxidation efficiency occurring at the site, this cover soil is clearly offsetting far greater CH₄ quantities than the 10% default value currently adopted by the IPCC.     

Persistent organochlorine pollutants in human serum of 50-65 years old women in the Flanders Environmental and Health Study (FLEHS). Part 2: Correlations among PCBs,PCDD/PCDFs and the use of predictive markers

In 1999, the FLEHS was set by the Flemish Ministry of Health, Belgium to assess pollutant concentrations and related health effect biomarkers in humans living in Flanders. Concentrations of selected organochlorine pesticides, polychlorinated biphenyls (PCB) and polychlorinated dibenzo-p-dioxins (PCDD) and furans (PCDF) were measured by gas chromatography-mass spectrometry and Chemical-Activated LUciferase gene eXpression (CALUX) bioassay in 47 serum pools of 200 women between 50 and 65 years living in two areas of Flanders. Correlation between TEQ values of different groups of compounds were computed in these pool results and it was found that total toxic equivalencies (TEQs) correlated well with the values of the groups of contributing compounds: mono-ortho PCBs (r = 0.77), non-ortho PCBs (r = 0.65) and PCDD/Fs (r = 0.88). The total TEQ was lower correlated to the CALUX-TEQ (r = 0.57). When calculating associations between those classes of compounds in the two studied regions separately, they were all higher correlated in the urban area compared to the more rural region. High correlation coefficients (r > 0.80) were also calculated between individual compounds and groups of compounds. It was suggested that in this studied background-exposed population, some compounds could be good predictors for a group: e.g. PCB 153 for indicator and total PCBs, PCB 118 for total PCB TEQ, PCB 156 for mono-ortho PCB-TEQs and total TEQ, 2,3,4,7,8-P5CDF for PCDD/F TEQs and total TEQs. This means that in pooled serum samples correlations between persistent organochlorine compounds are as strong as for individual POP measurements observed in earlier studies.     

Biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in harbour seals and harbour porpoises from the Southern North Sea

Harbour seals and harbour porpoises are top predator species from the North Sea, have long life spans and hence, are known to accumulate high levels of anthropogenic contaminants. To gain knowledge about the behaviour of naturally-produced compounds in these marine mammals, the biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) was assessed. The biomagnification of MeO-PBDEs (2′-MeO-BDE 68 and 6-MeO-BDE 47) was lower in harbour seals (all biomagnification factors (BMFs) < 1) compared to the same age–gender groups of the harbour porpoises (all BMFs > 1). This may indicate a better metabolic breakdown of MeO-PBDEs in harbour seals, as was previously suggested for polybrominated diphenyl ethers (PBDEs). In both predators, 6-MeO-BDE 47 had the highest concentrations (range: 45–483 ng/g lw and 2–38 ng/g lw for harbour porpoises and seals, respectively) compared to 2′-MeO-BDE 68 (range: 2–28 ng/g lw and 1–6 ng/g lw for harbour porpoises and seals, respectively). In general, the highest concentrations were found in juveniles, suggesting an increased biotransformation capacity with age or the influence of dilution by growth for both species. Here we show that naturally-produced brominated organic compounds can biomagnify and accumulate in North Sea top predators, although to a lesser extent than anthropogenic lipophilic contaminants, such as polychlorinated biphenyls (PCBs) or PBDEs.     

“An eye for an eye?”—on the generality of the intimidating quality of eyespots in a butterfly and a hawkmoth

Large eyespots on the wings of butterflies and moths have been ascribed generally intimidating qualities by creating a frightening image of a bird or mammal much larger than the insect bearing the eyespots. However, evidence for this anti-predator adaptation has been largely anecdotal and only recently were peacock butterflies, Inachis io, shown to effectively thwart attacks from blue tits, Parus caeruleus. Here, we test whether large eyespots on lepidopterans are generally effective in preventing attacks from small passerines and whether the size of insect or bird can influence the outcome of interactions. We staged experiments between the larger eyed hawkmoths, Smerinthus ocellatus, and the smaller peacock butterflies, I. io, and the larger great tits, Parus major, and the smaller blue tits, P. caeruleus. Survival differed substantially between the insect species with 21 of 24 peacock butterflies, but only 6 of 27 eyed hawkmoths, surviving attacks from the birds. Thus, surprisingly, the smaller prey survived to a higher extent, suggesting that factors other than insect size may be important. However, great tits were less easily intimidated by the insects’ eyespots and deimatic behaviour and consumed 16 of 26, but the blue tits only 8 of 25, of the butterflies and hawkmoths. Our results demonstrate that eyespots per se do not guarantee survival and that these two insects bearing equally large eyespots are not equally well protected against predation.