Second generation anticoagulant rodenticides in predatory birds: Probabilistic characterisation of toxic liver concentrations and implications for predatory bird populations in Canada

Second-generation anticoagulant rodenticides (SGARs) are widely used to control rodent pests but exposure and poisonings occur in non-target species, such as birds of prey. Liver residues are often analysed to detect exposure in birds found dead but their use to assess toxicity of SGARs is problematic. We analysed published data on hepatic rodenticide residues and associated symptoms of anticoagulant poisoning from 270 birds of prey using logistic regression to estimate the probability of toxicosis associated with different liver SGAR residues. We also evaluated exposure to SGARs on a national level in Canada by analysing 196 livers from great horned owls (Bubo virginianus) and red-tailed hawks (Buteo jamaicensis) found dead at locations across the country. Analysis of a broader sample of raptor species from Quebec also helped define the taxonomic breadth of contamination. Calculated probability curves suggest significant species differences in sensitivity to SGARs and significant likelihood of toxicosis below previously suggested concentrations of concern (<0.1mg/kg). Analysis of birds from Quebec showed that a broad range of raptor species are exposed to SGARs, indicating that generalised terrestrial food chains could be contaminated in the vicinity of the sampled areas. Of the two species for which we had samples from across Canada, great horned owls are exposed to SGARs to a greater extent than red-tailed hawks and the liver residue levels were also higher. Using our probability estimates of effect, we estimate that a minimum of 11% of the sampled great horned owl population is at risk of being directly killed by SGARs. This is the first time the potential mortality impact of SGARs on a raptor population has been estimated.     

Perfluoroalkyl carboxylates and sulfonates and precursors in relation to dietary source tracers in the eggs of four species of gulls (Larids) from breeding sites spanning Atlantic to Pacific Canada

In the present study, we identified and examined the spatial trends, sources and dietary relationships of bioaccumulative perfluorinated sulfonate (PFSA; C(6), C(8), and C(10) chain lengths) and carboxylate (PFCA; C(6) to C(15) chain lengths) contaminants, as well as precursor compounds including several perfluorinated sulfonamides, and fluorotelomer acids and alcohols, in individual eggs (collected in 2008) from four gull species [glaucous-winged (Larus glaucescens), California (Larus californicus), ring-billed (Larus delawarensis) and herring (Larus argentatus) gulls] from 15 marine and freshwater colony sites in provinces across Canada. The pattern of PFSAs was dominated by perfluorooctane sulfonate (PFOS; >89% of ΣPFSA concentration) regardless of egg collection location. The highest ΣPFSA concentrations were found in the eggs collected in the urbanized areas in the Great Lakes and the St. Lawrence River area [Big Chicken Island 308 ng/g ww, Toronto Harbour 486 ng/g ww, and Ile Deslauriers (HG) 299 ng/g ww]. Also, eggs from all freshwater colony sites had higher ΣPFSA concentrations, which were significant (p<0.05) in many cases, compared to the marine sites with the exception of the Sable Island colony in Atlantic Canada off the coast of Nova Scotia. C(6) to C(15) chain length PFCAs were detected in the eggs, although the pattern was variable among the 15 sites, where PFUnA and PFTrA dominated the pattern for most colonies. Like the ΣPFSA, the highest concentrations of ΣPFCA were found in the eggs from Big Chicken Island, Toronto Harbour, Ile Deslauriers (HG), and Sable Island, although not all freshwater sites had higher concentrations compared to marine sites. Dietary tracers [δ(15)N and δ(13)C stable isotopes (SIs)] revealed that PFSA and PFCA exposure is colony dependent. SI signatures suggested that gulls from most marine colony sites were exposed to PFCs via marine prey. The exception was the Mandarte Island colony in Pacific British Columbia, where PFSA and PFCA exposure appeared to be via terrestrial and/or freshwater prey consumption. The same was true for the freshwater sites where egg SIs suggested both aquatic and terrestrial prey consumption as the source for PFC exposure depending on the colony. Both aquatic (marine and freshwater) and terrestrial prey are likely sources of PFC exposure to gulls but exposure scenarios are colony-specific.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Fate of bisphenol A during treatment with the litter-decomposing fungi Stropharia rugosoannulata and Stropharia coronilla

Bisphenol A is an endocrine disrupting compound, which is ubiquitous in the environment due to its wide use in plastic and resin production. Seven day old cultures of the litter-decomposing fungus Stropharia coronilla removed the estrogenic activity of bisphenol A (BPA) rapidly and enduringly. Treatment of BPA with purified neutral manganese peroxidase (MnP) from this fungus also resulted in 100% reduction of estrogenic activity, as analyzed using a bioluminescent yeast assay, and in the formation of polymeric compounds. In cultures of Stropharia rugosoannulata, estrogenic activity also quickly disappeared but temporarily re-emerged in the further course of cultivation. LC-MS analysis of the extracted estrogenic culture liquid revealed [M−H]⁻ ions with m/z values of 219 and 235. We hypothesize that these compounds are ring fission products of BPA, which still exhibit one intact hydroxyphenyl group to interact with estrogen receptors displayed by the yeast.     

Identification of perfluoroalkyl acid sources in Swiss surface waters with the help of the artificial sweetener acesulfame

Anthropogenic perfluorinated compounds (PFCs), especially the perfluoroalkyl acids (PFAAs) are ubiquitously found in surface waters around the globe. Emissions from households, industries and also atmospheric transport/deposition are discussed as the possible sources. In this study, these sources are evaluated using Switzerland as the study area. Forty-four surface water locations in different rivers and an Alpine lake were investigated for 14 PFAAs, four precursors and acesulfame, an artificial sweetener used as a population marker. Concentrations of individual PFAAs were generally low, between 0.02 and 10 ng/L. Correlation analysis showed that some PFAAs concentrations correlated well with population and less with catchment area, indicating that emissions from population, i.e., from consumer products, is the most important source to surface waters in Switzerland. The correlation with the population marker acesulfame confirmed this observation but highlighted also a few elevated PFAA levels, some of which could be attributed to industrial emissions.     

Determination of PM₁₀ deposition based on antimony flux to selected urban surfaces

Deposition of PM(10) particles to several types of urban surfaces was investigated within this study. Antimony was chosen as a tracer element to calculate dry deposition velocities for PM(10), since antimony proved to be present almost exclusively in PM(10) particles in ambient urban air. During 18 months, eight sampling sites in Berlin and Karlsruhe, two cities in Germany, were operated. PM(10) concentrations and dry deposition were routinely sampled as two week averages. Additionally, leaf-samples were collected at three sites with tall vegetation. The obtained deposition velocities ranged from 0.8 to 1.3 cms(-1) at roadside sites and from 0.4 to 0.5 cms(-1) at the other sites. With reference to the whole canopy, additional deposition velocities of about 0.5 cms(-1) were obtained for leaf surfaces. As a consequence, it can be concluded that vegetation-covered areas beside streets show the highest potential to capture particles in urban areas.     

Antiradical activity of natural honeys and antifungal effect against Penicillium genera

The purpose of the study was to examine the antiradical activity of 11 natural honeys and to evaluate the antifungal properties of honey. Honey samples (10) were collected from different locations of Slovak Republic. Honeys were native to different plant species of Robinia pseudoacaccia, Brassica napus subs. napus, Castanea sativa Mill. Thymus serpyllum vulgaris and the other samples had multifloral origin. The low antiradical activitity in honey samples was determined. The best results were found in thyme honey from Rhodos (11.84 %) and Castanea honey from Nitra (10.61 %). The lowest antiradical activity was found in Acacia honey and determined to be 7.62 %. Statistically significant differences (P< 0.001) were found among thyme/Rhodos and Castanea/Nitra. The antifungal activities of honey samples were tested by 10 %, 25 % and 50 % (by mass per volume) concentration against fungi Penicillium crustosum, P. expansum, P. griseofulvum, P. raistrickii and P. verrucosum and by the agar well diffusion method. The solutions containing 10 % (by mass per volume) of honey did not have any effect on the growth of fungi. The strongest antifungal effect was shown by 50 % honey concentration against P. raistrickii.     

Hexachlorocyclohexane (HCH) as new Stockholm Convention POPs��a global perspective on the management of Lindane and its waste isomers

Purpose

Hexachlorocyclohexane (HCH) isomers (??-, ??- and ??- (Lindane)) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention, and therefore, the legacy of HCH and Lindane production became a contemporary topic of global relevance. This article wants to briefly summarise the outcomes of the Stockholm Convention process and make an estimation of the amount of HCH waste generated and dumped in the former Lindane/HCH-producing countries.

Results

In a preliminary assessment, the countries and the respective amount of HCH residues stored and deposited from Lindane production are estimated. Between 4 and 7 million tonnes of wastes of toxic, persistent and bioaccumulative residues (largely consisting of alpha- (approx. 80%) and beta-HCH) are estimated to have been produced and discarded around the globe during 60 years of Lindane production. For approximately 1.9 million tonnes, information is available regarding deposition. Countries are: Austria, Brazil, China, Czech Republic, France, Germany, Hungary, India, Italy, Japan, Macedonia, Nigeria, Poland, Romania, Slovakia, South Africa, Spain, Switzerland, Turkey, The Netherlands, UK, USA, and former USSR. The paper highlights the environmental relevance of deposited HCH wastes and the related POPs?? contaminated sites and provides suggestions for further steps to address the challenge of the legacy of HCH/Lindane production.

Conclusion

It can be expected that most locations where HCH waste was discarded/stockpiled are not secured and that critical environmental impacts are resulting from leaching and volatilisation. As parties to the Stockholm Convention are legally required to take action to stop further POPs pollution, identification and evaluation of such sites are necessary.     

Body metal concentrations and glycogen reserves in earthworms (Dendrobaena octaedra) from contaminated and uncontaminated forest soil

Stress originating from toxicants such as heavy metals can induce compensatory changes in the energy metabolism of organisms due to increased energy expenses associated with detoxification and excretion processes. These energy expenses may be reflected in the available energy reserves such as glycogen. In a field study the earthworm, Dendrobaena octaedra, was collected from polluted areas, and from unpolluted reference areas. If present in the environment, cadmium, lead and copper accumulated to high concentrations in D. octaedra. In contrast, other toxic metals such as aluminium, nickel and zinc appeared to be regulated and kept at low internal concentrations compared to soil concentrations. Lead, cadmium and copper accumulation did not correlate with glycogen reserves of individual worms. In contrast, aluminium, nickel and zinc were negatively correlated with glycogen reserves. These results suggest that coping with different metals in earthworms is associated with differential energy demands depending on the associated detoxification strategy.