PAHs in high Arctic copepods Calanus hyperboreus following exposure of residues from in situ burning of oil spill.

In situ burning of marine oil spills reduces the total amount of oil in the environment, but a negative side effect may be the generation of environmentally hazardous polycyclic aromatic hydrocarbons (PAHs) that may pose a risk for bioaccumulation, particularly in organisms having a high lipid content. In this study uptake of PAHs from oil and burn residue were examined in the high arctic copepod Calanus hyperboreus. A major part of the low ring number petrogenic PAHs in the oil was removed during burning and relative higher concentrations of pyrogenic high ring number PAHs was found in the burn residue. This suggests that burning markedly reduces the general PAH exposure load. Furthermore, the pyrogenic PAHs generated during the burn were not bioconcentrated to quantifiable levels in the copepods. We conclude that in situ burning can mitigate the potential risk of PAH uptake for copepods and other pelagic organisms in the marine environment as the pyrogenic PAHs only pose low risk for uptake from the water by the copepods and other pelagic organisms.

The potential of VKORC1 polymorphisms in Mustelidae for evolving anticoagulant resistance through selection along the food chain.

In response to strong selection, new mutations can arise quickly and sweep through populations, particularly, if survival and reproduction depend on certain allele copies for adaptation to rapidly changing environments, like resistance against deadly diseases or strong toxins. Since the 1950s, resistance to anticoagulant rodenticides in several rodents has emerged through single nucleotide mutations in the vitamin-K-epoxid-reductase-complex-subunit-1 (VKORC1) gene, often located in its exon 3. Detection of high prevalence and concentrations of anticoagulant rodenticides in non-target vertebrates, including carnivorous Mustelidae, let us assume that secondary exposure by feeding on poisoned prey may also cause selection along the food chain and we hypothesized that VKORC1-based resistance might also have evolved in rodents' predators. Using newly-developed mustelid-specific primers for direct sequencing of genomic DNA, we studied VKORC1-DNA-polymorphisms in 115 mustelids of five species (Martes martes, M. foina, Mustela nivalis, M. erminea, M. putorius), obtained from northern Denmark, yielding six sites with nonsynonymous and several synonymous amino acid polymorphisms in exon 3. Comparison of these VKORC1-genotypes with hepatic rodenticide residues (obtained by HPLC combined with fluorescence or mass spectrometry) in 83 individuals (except M. martes), using generalized linear models, suggested that anticoagulant levels depended on species and specific polymorphisms. Although most VKORC-1 polymorphisms may present standing genetic variation, some are situated in resistance-mediating membrane parts of the VKORC1-encoded protein, and might be a result of selection due to exposure to anticoagulant poisons. Our new molecular markers might allow detecting indirect effects of anticoagulant rodenticides on rodent predator populations in the future.

Exposure of non-target small mammals to anticoagulant rodenticide during chemical rodent control operations.

The extensive use of anticoagulant rodenticides (ARs) results in widespread unintentional exposure of non-target rodents and secondary poisoning of predators despite regulatory measures to manage and reduce exposure risk. To elucidate on the potential vectoring of ARs into surrounding habitats by non-target small mammals, we determined bromadiolone prevalence and concentrations in rodents and shrews near bait boxes during an experimental application of the poison for 2 weeks. Overall, bromadiolone was detected in 12.6% of all small rodents and insectivores. Less than 20 m from bait boxes, 48.6% of small mammals had detectable levels of bromadiolone. The prevalence of poisoned small mammals decreased with distance to bait boxes, but bromadiolone concentration in the rodenticide positive individuals did not. Poisoned small mammals were trapped up to 89 m from bait boxes. Bromadiolone concentrations in yellow-necked mice (Apodemus flavicollis) were higher than concentrations in bank vole (Myodes glareolus), field vole (Microtus agrestis), harvest mouse (Micromys minutus), and common shrew (Sorex araneus). Our field trials documents that chemical rodent control results in widespread exposure of non-target small mammals and that AR poisoned small mammals disperse away from bating sites to become available to predators and scavengers in large areas of the landscape. The results suggest that the unintentional secondary exposure of predators and scavengers is an unavoidable consequence of chemical rodent control outside buildings and infrastructures.

Biodegradation of marine oil spills in the Arctic with a Greenland perspective.

New economic developments in the Arctic, such as shipping and oil exploitation, bring along unprecedented risks of marine oil spills. Microorganisms have played a central role in degrading and reducing the impact of the spilled oil during past oil disasters. However, in the Arctic, and in particular in its pristine areas, the self-cleaning capacity and biodegradation potential of the natural microbial communities have yet to be uncovered. This review compiles and investigates the current knowledge with respect to environmental parameters and biochemical constraints that control oil biodegradation in the Arctic. Hereby, seawaters off Greenland are considered as a case study. Key factors for biodegradation include the bioavailability of hydrocarbons, the presence of hydrocarbon-degrading bacteria and the availability of nutrients. We show how these key factors may be influenced by the physical oceanographic conditions in seawaters off Greenland and other environmental parameters including low temperature, sea ice, sunlight regime, suspended sediment plumes and phytoplankton blooms that characterize the Arctic. Based on the acquired insights, a first qualitative assessment of the biodegradation potential in seawaters off Greenland is presented. In addition to the most apparent Arctic characteristics, such as low temperature and sea ice, the impact of typical Arctic features such as the oligotrophic environment, poor microbial adaptation to hydrocarbon degradation, mixing of stratified water masses, and massive phytoplankton blooms and suspended sediment plumes merit to be topics of future investigation.

Bacterial community succession and degradation patterns of hydrocarbons in seawater at low temperature.

The risk of oil spills in cold marine environments is expected to increase in response to trans-Arctic shipping and as Arctic oil reserves get exploited. Marine hydrocarbon-degrading microbes can reduce the impact of spilled hydrocarbons, but their degradation capabilities at low temperature are yet to be uncovered. We combined DNA amplicon sequencing and chemometrics to investigate the effect of decreasing temperature (0-15 °C) on the succession and function of hydrocarbon-degrading bacteria in seawater. The bacterial community and degradation patterns were investigated at time points when a similar amount of hydrocarbons was mineralised at the different temperatures. This allowed decomposing the effect of temperature into a main component related to the reduced microbial activity at low temperature and a secondary effect. The reduced microbial activity at low temperature delayed the microbial community succession and degradation rates. The secondary effect of temperature was most pronounced at 0 °C, where (1) degradation of the least water-soluble n-alkanes (>C12) was suppressed in contrast to a relative stronger degradation of the most water-soluble n-alkanes (

Release of PAHs and heavy metals in coastal environments linked to leisure boats.

Leisure boats are responsible for elevated levels of heavy metals and PAHs in sediments in- and near marinas and natural harbours. As these compounds are released directly into the water column they also pose a threat to organisms in the pelagic environment. Passive samplers were deployed during peak and post tourist season in the water column of natural harbours, leisure boat waterways and small marinas to measure the dissolved fraction of PAHs and metal ions. Differences between seasons indicative of leisure boat activities were found as PAH composition differed between peak and post season for natural harbours and waterways, where heavier PAHs increased during peak season. During peak season, metal samplers were covered by biofouling, which likely affected the uptake. Post season metal concentrations differ between locations, with concentrations exceeding quality standards at near mainland locations where boats are maintained, compared to the sites in the archipelago.

Exposure of stone marten (Martes foina) and polecat (Mustela putorius) to anticoagulant rodenticides: Effects of regulatory restrictions of rodenticide use.

When anticoagulant rodenticides (ARs) are used to control rodent populations there is also a widespread secondary exposure of non-target predators to ARs. To reduce secondary exposure, regulatory restrictions in AR usage were tightened in Denmark in 2011. The restrictions included the cessation of AR use for plant protection and any use away from buildings, as well as limitations in private consumers' access to ARs. To quantify and evaluate the efficiency of the regulatory measures to reduce secondary exposure, we analysed ARs in liver tissue from 40 stone martens (Martes foina) and 40 polecats (Mustela putorius) collected before and 31 stone martens and 29 polecats collected after the restrictions were imposed. No declines in the prevalence ARs were detected following the regulatory restrictions in either stone marten (Before: 98%, After: 100%) or polecat (Before: 93%, After: 97%). The total AR concentration was higher in stone martens than in polecats in both sampling periods. Between the two sampling periods, the total AR concentrations in the mustelids increased (P<0.001). The increase was significant for stone marten (Before: 419ng/g ww, After: 1116ng/g ww, P<0.001), but not for polecat (Before: 170ng/g ww, After: 339ng/g ww). Overall, the total AR concentration was positively correlated to the urban area and the area used for Christmas tree production in which ARs were regularly used before 2011. The regulatory restrictions in AR usage did not reduce exposure of non-target stone martens and polecats. The temporal and spatial patterns of AR concentrations in predators indicate that chemical rodent control in and around buildings is the dominant source for the exposure of non-target predators in intensively human-dominated landscapes in Denmark. The results suggest that non-chemical methods for rodents control at buildings are necessary to prevent widespread secondary AR exposure of predators in human modified landscapes.

Transforming students into digital academics: a challenge at both the individual and the institutional level.

BACKGROUND: Little is known of students' Information and Communication Technology (ICT) readiness in a learning context. Information about students' capabilities and resources is an important prerequisite for designing meaningful teaching and learning activities that engage and motivate students. To learn about health science students' usage of digital equipment, familiarity with software, online behavior and communication with the university, we have conducted a survey focusing on these areas. METHODS: A digital questionnaire was sent to 9134 health science students, of whom 1165 responded (12.8%). RESULTS: Almost all students owned a laptop (98.3%) and a smartphone (86.5%) and used these for internet access. The students were most familiar with typical office programs like word processing and spread sheets. Students used social media in their private lives but to a lesser extent in relation to their studies; they also experienced that their teachers made limited use of these media. The most commonly used tool for working with fellow students was email (80%) and for communication, SMS (47.6%). An age difference was found in relation to the way students communicated with each other. The mean age of chat users was 23.8 (Standard deviation 3.7) years, SMS users, 25 (Standard deviation 4.2) years and email users, 27.9 (Standard deviation 6.5) years. Over half of the students (53.4%) found that the degree of ICT incorporated in the teaching and learning activities was insufficient to provide them with the skills necessary in their future profession. CONCLUSIONS: Although a large percentage of the students had access to the internet, reported familiarity with basic software and used online services in their private lives, they were unfamiliar with the software and services they were expected to use in their studies. The students experienced that teachers did not use internet resources, which apparently influenced their perception of the importance of, and thereby their usage of, these services. The way the younger students communicate differs from the way communication takes place at the university, and it is recommended that the institutions should look into how they can meet the students in ways they are familiar with.

Endocrine-disrupting effects of compounds in Danish streams.

Effluents from municipal wastewater-treatment plants and scattered dwellings, as well as runoff from agricultural fields, are sources of endocrine-disrupting compounds (EDCs) in the aquatic environment. The present study investigated the correlation between the occurrence of EDCs in nine Danish streams using passive samplers (polar organic integrative samplers and silicone membranes) and determined their possible biological effects as assessed by mammal cell cultures and the mussel (Unio tumidus). The passive samplers and mussels were exposed simultaneously at the study sites. The extracts from the passive samplers were used to measure the concentrations of EDCs and the biological effects on the estrogen (ER), androgen (AR), and aryl hydrocarbon (AhR)-receptor transactivation. Male mussels were investigated for biomarkers of endocrine effects, such as the levels of vitellogenin-like proteins measured as alkali-labile phosphate (ALP). EDC concentrations, hormone-receptor transactivation (ER, AR, AhR), and level of ALP were greater downstream of wastewater-treatment plants compared with upstream sites and sites supposed to be relatively nonimpacted by wastewater. Furthermore, there was a significant positive correlation between in vitro AhR transactivation and frequency of ALP of male mussels. We conclude that wastewater effluent is an important source of endocrine-disrupting effects in the aquatic environment and that the combination of biological effect measurements and chemical analyses based on passive sampling is useful in the assessment of the ecological state of the aquatic environment.

High exposure rates of anticoagulant rodenticides in predatory bird species in intensively managed landscapes in Denmark.

The extensive use of anticoagulant rodenticides (ARs) for rodent control has led to widespread secondary exposure in nontarget predatory wildlife species. We investigated exposure rates and concentrations of five ARs in liver samples from five raptors and six owls from Denmark. A total of 430 birds were analysed. ARs were detected in 84-100 % of individual birds within each species. Multiple AR exposure was detected in 73 % of all birds. Average number of substances detected in individual birds was 2.2 with no differences between owls and raptors. Difenacoum, bromadiolone, and brodifacoum were the most prevalent substances and occurred in the highest concentrations. Second-generation ARs made up 96 % of the summed AR burden. Among the six core species (sample size >30), summed AR concentrations were lower in rough-legged buzzard (Buteo lagopus) and long-eared owl (Asio otus) than in barn owl (Tyto alba), buzzard (B. buteo), kestrel (Falco tinnunculus), and tawny owl (Strix aluco). There was a strong tendency for seasonal variations in the summed AR concentration with levels being lowest during autumn, which is probably related to an influx of less-exposed migrating birds from northern Scandinavia during autumn. High hepatic AR residue concentrations (>100 ng/g wet weight), which have been associated with symptoms of rodenticide poisoning and increased mortality, were recorded high frequencies (12.9-37.4 %) in five of the six core species. The results suggest that the present use of ARs in Denmark, at least locally, may have adverse effects on reproduction and, ultimately, population status in some raptors and owls.

Concentrations of anticoagulant rodenticides in stoats Mustela erminea and weasels Mustela nivalis from Denmark.

Anticoagulant rodenticides are widely used to control rodent populations but they also pose a risk of secondary poisoning in non-target predators. Studies on anticoagulant rodenticide exposure of non-target species have mainly reported on frequency of occurrence. They have rarely analyzed variations in residue concentrations. We examine the occurrence and concentrations of five anticoagulant rodenticides in liver tissue from 61 stoats (Mustela erminea) and 69 weasels (Mustela nivalis) from Denmark. Anticoagulant rodenticides were detected in 97% of stoats and 95% of weasels. 79% of the animals had detectable levels of more than one substance. Difenacoum had the highest prevalence (82% in stoats and 88% in weasels) but bromadiolone was detected in the highest concentrations in both stoat (1.290 µg/g ww) and weasel (1.610 µg/g ww). Anticoagulant rodenticide concentrations were highest during autumn and winter and varied with sampling method. Anticoagulant rodenticide concentrations were higher in stoats and weasels with unknown cause of death than in specimens killed by physical trauma. There was a negative correlation between anticoagulant rodenticide concentrations and body condition. Our results suggest that chemical rodent control in Denmark results in an extensive exposure of non-target species and may adversely affect the fitness of some stoats and weasels.

Polychlorinated biphenyls, organochlorine pesticides and polycyclic aromatic hydrocarbons in a one-off global survey of bivalves.

During the Danish Galathea 3 expedition, bivalve samples were collected at the Faroe Islands, Greenland, Ghana, South Africa, Australia, Solomon Islands, New Zealand, Chile, US Virgin Islands, Boston, Newfoundland and Shetland Islands and analysed for organochlorines and PAHs. Concentration differences of up to three orders of magnitude were observed, with the highest concentrations at Boston harbour (SPCB 338 ng g(-1) dw, ΣSPAH 5966 ng g(-1) dw) and the Sydney estuary (ΣSPCB 282 ng g(-1) dw, SPAH 1453 ng g(-1) dw). Local impacts were also found for the Greenland capital Nuuk in terms of PCB and PAH levels, while other Greenland samples came closest to representing PAH background levels. Several locations had undetectable organochlorine levels, including Hobart and Chile, which had the lowest SPAH concentrations (<200 ng g(-1) dw). It was possible to group the stations according to their pyrogenic/petrogenic influence using Principal Component Analyses, and indications of petroleum sources were found at Nuuk.

SPE and HPLC/UV of resin acids in colophonium-containing products.

A new method, involving SPE and HPLC/UV diode-array detection (DAD), was developed for the quantification of colophonium components in different consumer products, such as cosmetics. Colophonium is a common cause of contact dermatitis since its components can oxidize into allergens on exposure to air. Three different resin acids were used as markers for native and oxidized colophonium, abietic acid (AbA), dehydroabietic acid (DeA), and 7-oxodehydroabietic acid (7-O-DeA). The SPE method, utilizing a mixed-mode hydrophobic and anion exchange retention mechanism, was shown to yield very clean extracts. The use of a urea-embedded C(12) HPLC stationary phase improved the separation of the resin acids compared to common C(18). Concentrations higher than 2 mg/g of both AbA and DeA were detected in wax strips. In this product also 7-O-DeA, a marker for oxidized colophonium, was detected at a level of 28 microg/g. The LODs were in the range of 7-19 microg/g and the LOQs 22-56 microg/g. The method is simple to use and can be applied on many types of technical products, not only cosmetics. For the first time, a method for technical products was developed, which separates AbA from pimaric acid.

Therapeutic effects of a restraint procedure on posttraumatic place learning in fimbria-fornix transected rats.

Restraint procedures have been shown to influence the neural processes in the brain (dendritic changes or changes in the expression of neurotrophines, etc.) as well as to alter the behavioural performance. While many report deleterious effects of this procedure in normal animals, there are also indications of positive effects in the context of brain injury. In order to address the issue from the perspective of functional posttraumatic recovery, we studied 6 experimental groups of rats--3 groups undergoing a fimbria-fornix transection, and 3 groups remaining neurally intact. Within the lesioned and intact groups, respectively, one group of animals was subjected to an 8-day long restraint procedure (2 h daily) that ended immediately prior to the infliction of trauma; another group was subjected to the same procedure starting immediately after the infliction of trauma; and one group was not subjected to the restraint procedure at all. After a brief period of postoperative pause, the animals were tested on their acquisition of an 8-arm radial maze based place learning task and the effects of the restraint procedure on the task acquisition were evaluated. The results show that within the neurally intact groups, the administration of this procedure had no effect at all. However, the lesioned groups that were subjected to the restraint procedure showed significantly improved acquisition of the studied task compared to the lesioned animals that did not undergo the restraint procedure. The improved task performance suggests a therapeutic effect of this manipulation on the functional recovery after a mechanical trauma.

Reverse quantitative structure-activity relationship for modelling the sorption of esfenvalerate to dissolved organic matter. A multivariate approach.

The sorption of the pyrethroid, esfenvalerate, to the dissolved and/or dispersed fraction of eight different natural humic compounds has been investigated. The dissolved organic matters (DOMs) included in this study originate from ground water, soil pore water, and surface waters. Sorption was modelled at DOM concentration levels where equilibrium partitioning of esfenvalerate between DOM and the aqueous bulk phase prevails. The inherent characteristics of the eight different humic materials, quantified in the preceding paper by Thomsen et al. (2002, this issue (PII: S0045-6535(02)00335-1)), have been used as explanatory variables for modelling this equilibrium partitioning. Using a reverse QSAR approach based on by projection-into-latent-structure regression (PLS-R) inherent sorbent properties determining for the sorption affinity of esfenvalerate to DOM were analysed. For all humic substances a decrease in the DOM-normalised equilibrium-partitioning coefficient, K(DOM), with increasing concentration of DOM was observed. Significant variations in K(DOM) values, as function of the inherent characteristics of the individual humic substances, were found at DOM concentrations of 75 and 100 ppm, respectively. The latter is a strong indication of variations in sorption mechanisms of esfenvalerate to DOM of varying inherent properties. Groupings in the principal property space quantifying DOMs may indicate that separate models are needed for quantifying the equilibrium partitioning to different classes of DOM.

Characterisation of humic materials of different origin: a multivariate approach for quantifying the latent properties of dissolved organic matter.

The inherent chemical properties of eight different dissolved organic matters (DOMs) originating from soil, surface and groundwater have been analysed. The samples consist of isolated fulvic acids (FA), humic acids (HA), and humic substances (HS), i.e. natural mixtures containing a humic and a fulvic fraction. The humic substances have been characterised by elemental analysis, size exclusion chromatography, E2/E3 and E4/E6 UV absorption ratios, and liquid-state 13C-NMR spectroscopy. The information contents of the different analytical methods have been investigated by pattern recognition, i.e. cluster analysis and principal component analysis (PCA). A comparative study of the information contents of DOM descriptors derived from different analytical methods is presented. Through extraction of information content of the individual analytical methods the inherent properties of DOM are quantified. Pattern recognition revealed significant quantitative differences in the inherent properties of DOM of different origin and type. PCA based on the NMR descriptors showed highest explained variance. However, all models showed low robustness due to the limited number of samples. The supervised pattern recognition, i.e. PCA, indicates a classification of DOMs into groups of similar properties by an increase in the number of samples. Furthermore that the number of groups may be higher and more continuously distributed than the conventional classification into fulvic acids, humic acids or humic substances.