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Mass mortalities of honey bees occurred in France in the 1990s coincident with the introduction of two agricultural insecticides, imidacloprid and fipronil. Imidacloprid, a neonicotinoid, was widely blamed, but the differential potency of imidacloprid and fipronil has been unclear because of uncertainty over their capacity to bioaccumulate during sustained exposure to trace dietary residues and, thereby, cause time-reinforced toxicity (TRT). We experimentally quantified the toxicity of fipronil and imidacloprid to honey bees and incorporated the observed mortality rates into a demographic simulation of a honey bee colony in an environmentally realistic scenario. Additionally, we evaluated two bioassays from new international guidance for agrochemical regulation, which aim to detect TRT. Finally, we used analytical chemistry (GC-MS) to test for bioaccumulation of fipronil. We found in demographic simulations that only fipronil produced mass mortality in honey bees. In the bioassays, only fipronil caused TRT. GC-MS analysis revealed that virtually all of the fipronil ingested by a honey bee in a single meal was present 6 d later, which suggests that bioaccumulation is the basis of TRT in sustained dietary exposures. We therefore postulate that fipronil, not imidacloprid, caused the mass mortalities of honey bees in France during the 1990s because it is lethal to honey bees in even trace doses due to its capacity to bioaccumulate and generate TRT. Our results provide evidence that recently proposed laboratory bioassays can discriminate harmful bioaccumulative substances and, thereby, address evident shortcomings in a regulatory system that had formerly approved fipronil for agricultural use.

BACKGROUND Concentrations of the neonicotinoid insecticides clothianidin, thiamethoxam and imidacloprid were determined in honey collected in Spring 2013 from a variety of locations in England. The honey was produced before the moratorium in the EU on the use of neonicotinoids in pollinator-attractive crops became effective. RESULTS Neither imidacloprid nor its metabolites were detected in any honey samples. Concentrations of clothianidin ranged from

BACKGROUND Concentrations of the neonicotinoid insecticides clothianidin, thiamethoxam and imidacloprid were determined in arable soils from a variety of locations in England. RESULTS In soil samples taken from the central area of fields, concentrations of clothianidin ranged from 0.02 to 13.6 µg kg−1. Thiamethoxam concentrations were between

Recent theorizing on corruption is split between two approaches: corruption is described as a collective action or principal-agent problem. Insights from political science and geography suggest that these theories are not as bifurcated as some of the literature indicates, as their explanatory power is shaped by place-specific factors. This article draws on observations of administrative and community responses to decentralization policy in Papua New Guinea. Despite efforts of policy makers to institutionalize principal-agent theory inspired systems of government, we argue that state-society relations have meant that the potential for corruption is a part of a collective action problem in some places and a principal-agent problem in others. The applicability of these theories is determined by the degree of alignment between cultural and social values and administrative norms, which have been shaped by historic, political and economic factors. We call for a more nuanced understanding – one that better accounts for spatial difference – of the applicability of these theories beyond the scale of the nation-state.

Chemical markers are increasingly used to investigate consumption of baits used to deliver vaccines, toxicants, and contraceptives. We evaluated whether ethyl-iophenoxic acid (Et-IPA) and propyl-iophenoxic acid (Pr-IPA) can be used as long-lasting systemic bait markers for wild boar (Sus scrofa). We presented captive wild boar with baits treated with either Et-IPA or Pr-IPA at 5 mg/kg (low dose), 10 mg/kg (medium dose), and 20 mg/kg (high dose) of body weight. We collected serum from each boar at 5 time points: 5 days, 3 weeks, 6 weeks, 11 weeks, and 39 weeks following ingestion of iophenoxic acid–treated baits. We detected both Et-IPA and Pr-IPA for ≥39 weeks after ingestion. Throughout the trial, the Et-IPA we found in serum was proportional to the amount eaten. At each time point, animals in the high-dose group had significantly more Et-IPA than animals in the low-dose group. We concluded that both compounds can be used as long-lasting markers in wild boar and that Et-IPA can also be employed ...

An analytical method employing clean up by high-performance gel permeation chromatography (HPGPC) and solid-phase extraction (SPE) on Florisil cartridges was developed to determine residues of eleven imidazole and triazole ergosterol-biosynthesis-inhibiting (EBI) fungicides in honeybee samples. Detection was by means of gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The method was validated by fortifying control samples at levels of 0.01 and 0.05 micro g/bee. Mean recoveries for each analyte except imazalil were between 79 and 99% with relative standard deviations of 12.3% or less. Mean recoveries of imazalil were 51% at 0.01 micro g/bee and 81% at 0.05 micro g/bee. Limits of detection for the analytes investigated ranged from 0.005 to 0.001 micro g/bee.

Concentrations of the neonicotinoid insecticides clothianidin, thiamethoxam and imidacloprid were determined in honey collected in Spring 2013 from a variety of locations in England. The honey was produced before the moratorium in the EU on the use of neonicotinoids in pollinator-attractive crops became effective.Neither imidacloprid nor its metabolites were detected in any honey samples. Concentrations of clothianidin ranged from0.02 to 0.82 µg kg(-1) , and thiamethoxam concentrations were between0.01 and 0.79 µg kg(-1) .Neonicotinoid concentrations were below those likely to cause any chronic mortality. The concentrations detected should provide a useful baseline against which the effectiveness of the moratorium in reducing exposure of honeybees can be measured. © 2016 Society of Chemical Industry.

This study describes a generic biological screening assay designed to detect anticoagulant rodenticides based on their inhibitory action on the vitamin K epoxide reductase protein complex, resulting in an accumulation of under-carboxylated prothrombin or proteins induced by vitamin K antagonism (PIVKA-II). A combined cell culture/ELISA assay was optimized to measure PIVKA-II production by the human hepatoma HepG2 cell line cultured in the presence of anticoagulant rodenticides. The specificity and sensitivity of the assay was validated using 41 grain extracts containing representative concentrations of rodenticide or appropriate nonrodenticide control compounds. In all cases, PIVKA-II produced by HepG2 cells in response to grain extracts spiked with rodenticides was detected by ELISA, while PIVKA-II was not detected in supernatants collected from cells exposed to nonrodenticide controls. This represents a novel, class-specific biological assay for the detection of anticoagulant rodenticides present in contaminated grain.

Solid-phase micro extraction (SPME) coupled with GC enables rapid and simple analysis of organophosphorus pesticides in a range of complex matrices. Investigations were made into the extraction efficiencies from water of six organophosphorus insecticides (methamidophos, omethoate, dimethoate, parathion methyl, malathion, and parathion ethyl) showing a wide range of polarities. Three SPME fibres coated with different stationary phases, polydimethylsiloxane, polyacrylate, and carbowax-divinylbenzene (CW-DVB), were investigated. Water was spiked with the pesticides at concentrations from 1 to 0.01 µg mL-1, and the solutions used for optimization of the procedure. The CW-DVB fibre, with a 65 µm coating, gave the best performance. The optimized experimental conditions were sample volume 10 mL at 20°C, equilibration time 16 min, pH 5, and presence of 10% w/v NaCl. SPME analyses were performed on solutions obtained by equilibrating aqueous pesticide solutions with six certified soils with various physico-chemical characteristics. SPME data were also assessed by comparison with analyses performed by using conventional solid-phase extraction. Results indicate the suitability of SPME for analysis of pesticides in environmental water samples.

Globally threatened Sarus cranes Grus antigon are resident at Keoladeo National Park World Heritage site and the surrounding area near Bharatpur, Western Rajasthan, India. In winter, they are joined by c. 200 wintering common cranes Grus grus. On 23 November 2000, 15 Sarus cranes and three common cranes were found dead in a field adjacent to the park, where wheat seed had been sown the previous day. Chemical analyses of seed samples from the field and the cranes' alimentary tract contents identified residues of the organophosphate insecticide monocrotophos. Monocrotophos concentrations of 0.8 and 1.8 ppm were found in wheat samples, and 0.2-0.74 ppm (x=0.33) in the alimentary tract contents of five of the seven cranes examined. No other organophosphate or organochlorine pesticides were detected. We conclude that the cranes died from monocrotophos poisoning after eating treated seed. We discuss similar incidents of avian mortality, and recommend that measures be taken to reduce these.

Concentrations of the neonicotinoid insecticides clothianidin, thiamethoxam and imidacloprid were determined in arable soils from a variety of locations in England.In soil samples taken from the central area of fields, concentrations of clothianidin ranged from 0.02 to 13.6 µg kg(-1) . Thiamethoxam concentrations were between0.02 and 1.50 µg kg(-1) , and imidacloprid concentrations between0.09 and 10.7 µg kg(-1) . Concentrations of clothianidin and thiamethoxam were lower in soil samples taken from the edges of fields than from the centres of fields, but this difference was less pronounced for imidacloprid.This work gives a clear indication of the levels of neonicotinoids in arable soils after typical use of these compounds as seed dressings in the United Kingdom. There was evidence that imidacloprid was more persistent in the soils studied than clothianidin and thiamethoxam. As clothianidin and thiamethoxam have largely superseded imidacloprid in the United Kingdom, neonicotinoid levels were lower than suggested by predictions based on imidacloprid alone.

Supercritical fluid extraction (SFE) was evaluated for the extraction of organophosphate and carbamate insecticides in honeybees. Extracts were analyzed by gas chromatography (GC) with nitrogen−phosphorus detection or flame-photometric detection with confirmation by GC with ion-trap mass spectrometry. Samples were mixed with diatomaceous earth and optimal extraction conditions were: (1) CO2 density of 0.7 g/mL, (2) 60 °C, (3) 2 min equilibration time, (4) 40 mL of CO2, and (5) 1.6 mL/min flow rate. Analytes were trapped on octadecyl silane (ODS) and eluted with acetonitrile. No further cleanup was necessary and chromatographic interferences in SFE extracts were comparable to those in solvent extracts that had undergone extensive cleanup procedures. Recoveries from honeybees fortified at 1 and 0.1 μg/g were greater than 75% for all pesticides studied except omethoate. Samples containing residues were also extracted by SFE, and there was good quantitative agreement with results from analyses based on solve...

For the first time, it has been unequivocally shown that multiple-feed second-generation anticoagulant rodenticides were ineffective against a population of rats in N.W. Berkshire, UK because of an unusually high prevalence and high degree of resistance. Use of the non-anticoagulant rodenticide calciferol led to a substantial reduction in the population, although primary poisoning of small birds appeared to be greater than with anticoagulant baits. There was strong evidence that many of the surviving rats had developed an aversion towards calciferol-treated bait. A reduction in the degree of anticoagulant resistance in the population was evident after a period of 17 months without anticoagulant use. The long-term strategy to manage the resistant population should integrate non-anticoagulant and anticoagulant rodenticide use to take advantage of possible pleiotropic costs of resistance.

Resistance amongst rats to second-generation anticoagulants, notably difenacoum, has been recognised since the 1970s. Although initially considered to be of practical significance, doubts were subsequently expressed that the degree of resistance was sufficient to explain ineffective rodenticide treatments. Research published elsewhere demonstrated the overriding importance of poor poisoned bait consumption, caused by the influence of certain ecological factors on rat behaviour, in reducing the effectiveness of second-generation anticoagulant treatments on farms in southern England. In this paper we consider, however, the subtle effects of resistance to anticoagulants on treatment outcome. The prevalence of resistance was increased amongst survivors of treatments and bait consumption by resistant survivors was higher than amongst susceptible survivors. The overall prevalence and degree of resistance to second-generation anticoagulants does not, however, currently represent a practical problem. Nevertheless, selection favouring increased resistance remains a long-term threat to the effectiveness of both difenacoum and bromadiolone.

Iophenoxic acid (IPA), a marker used to investigate the feeding behaviour of bait-consuming animals has previously been indirectly determined by measuring protein-bound iodine levels in serum or plasma. For the first time a method is reported for the direct determination of IPA in biological fluids. IPA was determined in de-proteinized serum by high-performance liquid chromatography (HPLC) on a C18 column with a mobile phase of acetonitrile-water. Isocratic and gradient systems are described with limits of detection of 0.2 microgram/ml (isocratic) and 0.05 microgram/ml (gradient). Recoveries from fox serum were 85% at 0.5 microgram/ml, 95% at 5 micrograms/ml and 91% at 50 micrograms/ml.

Recent declines in the populations of three species of vultures in the Indian subcontinent are among the most rapid ever recorded in any bird species. Evidence from a previous study of one of these species, Gyps bengalensis, in the Punjab province of Pakistan, strongly implicates mortality caused by ingestion of residues of the veterinary non-steroidal anti-inflammatory drug diclofenac as the major cause of the decline. We show that a high proportion of Gyps bengalensis and G. indicus found dead or dying in a much larger area of India and Nepal also have residues of diclofenac and visceral gout, a post-mortem finding that is strongly associated with diclofenac contamination in both species. Hence, veterinary use of diclofenac is likely to have been the major cause of the rapid vulture population declines across the subcontinent.

A method was developed to detect the molluscicide metaldehyde in samples of stomach contents for forensic toxicology investigations. Gas chromatography−ion trap mass spectrometry in full-scan mode was used to identify and quantify metaldehyde. The limit of detection based on mass chromatograms for the m/z 89 ion was 3 μg/g. Mean recoveries from six different spiked samples were 74% at 25 μg/g and 94% at 500 μg/g. The relative standard deviation of six replicate determinations of a sample containing 632 μg/g metaldehyde was 7.3%. Keywords: Metaldehyde; molluscicide; stomach contents; toxicology; GC−MS