Spatial and temporal analysis of second-generation anticoagulant rodenticide residues in polecats (Mustela putorius) from throughout their range in Britain, 1992-1999

Polecats (Mustela putorius) in Britain are currently expanding their range eastwards from Wales to reoccupy central and eastern areas of England. Second-generation anticoagulant rodenticides (SGARs), to which polecats are exposed by eating contaminated prey, are used more extensively in these central and eastern regions, leading to fears of increased exposure, and possible resultant mortality. We measured bromadiolone, difenacoum, flocoumafen and brodifacoum concentrations in the livers of 50 polecats from areas that included newly recolonised habitats and found that at least one SGAR was detected in the livers of 13 out of 37 (35.1%) male and 5 out of 13 (38.5%) female polecats. Difenacoum and bromadiolone were detected most frequently. We then combined these data with measurements on another 50 individuals from earlier studies to create a dataset for 100 polecats collected throughout the 1990s from across the whole of their current range. Using this dataset, we determined if there was any evidence that contamination in polecats had increased during the 1990s and whether animals from England were more contaminated than those from Wales, as might be expected given regional differences in the patterns of SGAR use. Overall, 31 of the 100 polecats analysed to date contained SGAR residues. The incidence was a little higher (40%) in animals that died between January and June and this probably better reflects the overall proportion of animals that are sub-lethally exposed. There was no statistically significant change during the 1990s in the proportion of polecats exposed to SGARs nor any evidence that greater use of SGARs in England resulted in more contamination of polecats. Contrary to expectation, the proportion of animals that contained difenacoum was marginally higher in Wales than elsewhere.     

Rodenticides in British barn owls

Out of 145 Barn Owls found dead through accidents (66%), starvation (32%), shooting (2%) and poisoning (<1%), 10% contained residues of rodenticides, difenacoum or brodifacoum, in their livers. Difenacoum was in the range 0.005-0.106 microg g(-1) fresh weight, and brodifacoum was in the range 0.019-0.515 microg g(-1). Minimum levels of detection were about 0.005 microg g(-1) for both chemicals. Mice fed for 1 day on food containing difenacoum and brodifacoum died after 2-11 days. Within these mice residues were present at greater concentration in the liver than in the rest of the carcass. The mean mass of residue in a whole 35g mouse was estimated at 10.17 microg (range 4.73-20.65 microg) for difenacoum and 15.36 microg (range 8.07-26.55) for brodifacoum. Such poisoned mice were fed to Barn Owls for successive periods of 1, 3 and 6 days. All six owls fed on difenacoum-dosed mice survived all three treatments, in which up to an estimated 101.7 microg of difenacoum was consumed, and the coagulation times of their blood returned to near normal in less than 5-23 days. Four of the six owls fed on brodifacoum-dosed mice died 6-17 days after the 1-day treatment, but the survivors also survived the 3-day and 6-day treatments. Those that died had each eaten 3 mice, with a combined weight of about 105g and a total brodifacoum content of about 46.07 microg, which was equivalent to a dose of 0.150-0.182 mg kg(-1) of owl body weight. After death these owls had 0.63-1.25 micro g(-1) of brodifacoum in their livers. Blood from the survivors would not coagulate at 9 days post-treatment, but did so at 16 days in one bird and between 38 and 78 days in the other. It is concluded that: (1) Barn Owls in Britain are now widely exposed to second-generation rodenticides; (2) not all owls exposed to these chemicals are likely to receive a lethal dose; (3) brodifacoum is more toxic to owls than difenacoum; and (4) while there is yet no evidence that rodenticides have had any appreciable effect on Barn Owl populations in Britain, further monitoring of residue levels and population trends in desirable.     

Accumulation of anticoagulant rodenticides in a non-target insectivore, the European hedgehog (Erinaceus europaeus)

Studies on exposure of non-targets to anticoagulant rodenticides have largely focussed on predatory birds and mammals; insectivores have rarely been studied. We investigated the exposure of 120 European hedgehogs (Erinaceus europaeus) from throughout Britain to first- and second-generation anticoagulant rodenticides (FGARs and SGARs) using high performance liquid chromatography coupled with fluorescence detection (HPLC) and liquid-chromatography mass spectrometry (LCMS). The proportion of hedgehogs with liver SGAR concentrations detected by HPLC was 3-13% per compound, 23% overall. LCMS identified much higher prevalence for difenacoum and bromadiolone, mainly because of greater ability to detect low-level contamination. The overall proportion of hedgehogs with LCMS-detected residues was 57.5% (SGARs alone) and 66.7% (FGARs and SGARs combined); 27 (22.5%) hedgehogs contained >1 rodenticide. Exposure of insectivores and predators to anticoagulant rodenticides appears to be similar. The greater sensitivity of LCMS suggests that hitherto exposure of non-targets is likely to have been under-estimated using HPLC techniques.     

Simultaneous determination of seven anticoagulant rodenticides in agricultural products by gel permeation chromatography and liquid chromatography–tandem mass spectrometry

A sensitive and reliable method for the simultaneous determination of hydroxycoumarin-type (brodifacoum, bromadiolone, coumatetralyl, and warfarin) and indandione-type (chlorophacinone, diphacinone, and pindone) rodenticides in agricultural products by gel permeation chromatography (GPC) and liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed. The procedure involved extraction of the rodenticides from samples with acetone, followed by liquid–liquid partitioning with hexane/ethyl acetate (1:1, v/v) and 10% sodium chloride aqueous solution, then cleanup using GPC, and finally, analysis using LC–MS/MS. High recoveries from the GPC column were obtained for all rodenticides tested using a mobile phase of acetone/cyclohexane/triethylamine (400:1600:1, v/v/v). An ODS column, which contains low levels of metal impurities, gave satisfactory peak shapes for both hydroxycoumarin- and indandione-type rodenticides in the LC–MS/MS separation. The average recoveries of rodenticides from eight agricultural foods (apple, eggplant, cabbage, orange, potato, tomato, brown rice, and soybean) fortified at 0.0005–0.001 mg/kg ranged from 76 to 116%, except for bromadiolone in orange (53%) and diphacinone in soybean (54%), and the relative standard deviations ranged from 1 to 16%. The proposed method effectively removed interfering components, such as pigments and lipids, and showed high selectivity. In addition, the matrix effects were negligible for most of the rodenticide/food combinations. The results suggest that the proposed method is reliable and suitable for determining hydroxycoumarin- and indandione-type rodenticides in agricultural products.     

Rise and fall of endrin usage in Washington State fruit orchards: effects on wildlife

A study of the effects of endrin on wildlife was conducted from 1981 to 1983 in fruit orchards in central Washington State. The single post-harvest application of endrin as a rodenticide resulted in both acute and chronic toxicity to a variety of avian species. Of 194 birds found dead, brains of 125 were analysed; endrin toxicosis accounted for > 24% of the total and 37% of those analysed. Most mortality occurred soon after application, but several raptors died during the spring and summer. Most wildlife sampled in the orchard system contained residues of endrin. There was no evidence that endrin depressed reproductive success. Use of endrin abruptly declined during this study and its use is currently limited to emergency situations. Wildlife mortality from endrin also decreased; only six endrin-related mortalities were detected the last year of the study and there have been no reports of die-offs since the study ended.     

Does small mammal prey guild affect the exposure of predators to anticoagulant rodenticides?

Ireland has a restricted small mammal prey guild but still includes species most likely to consume anticoagulant rodenticide (AR) baits. This may enhance secondary exposure of predators to ARs. We compared liver AR residues in foxes (Vulpes vulpes) in Northern Ireland (NI) with those in foxes from Great Britain which has a more diverse prey guild but similar agricultural use of ARs. Liver ARs were detected in 84% of NI foxes, more than in a comparable sample of foxes from Scotland and similar to that of suspected AR poisoned animals from England and Wales. High exposure in NI foxes is probably due to greater predation of commensal rodents and non-target species most likely to take AR baits, and may also partly reflect greater exposure to highly persistent brodifacoum and flocoumafen. High exposure is likely to enhance risk and Ireland may be a sentinel for potential effects on predator populations.     

Occurrence,elimination, and risk of anticoagulant rodenticides and drugs during wastewater treatment

Anticoagulants are biocides widely used as pest control agents in agriculture, urban infrastructures, and domestic applications for the control of rodents. Other anticoagulants such as warfarin and acenocoumarol are also used as drugs against thrombosis. After use, anticoagulants are discharged to sewage grids and enter wastewater treatment plants (WWTPs). Our hypothesis is that WWTP effluents can be a source of anticoagulants to receiving waters and that these can affect aquatic organisms and other nontarget species. Therefore, the objective of the present study was to determine the occurrence of 11 anticoagulants in WWTPs receiving urban and agricultural wastewaters. Warfarin was the most ubiquitous compound detected in influent waters and was partially eliminated during the activated sludge treatment, and low nanograms per liter concentration were found in the effluents. Other detected compounds were coumatetralyl, ferulenol, acenocoumarol, flocoumafen, brodifacoum, bromadiolone, and difenacoum at concentrations of 0.86–87.0 ng L^?1. Considering water volumes of each WWTP, daily emissions were estimated to be 0.02 to 21.8 g day^?1, and thus, WWTPs contribute to the loads of anticoagulants to receiving waters. However, low aquatic toxicity was observed using Daphnia magna as a model aquatic organism.     

Oil residues in Baltic sediment,mussel and fish. II. Study of the Finnish Archipelago 1979–1981

Aliphatic hydrocarbons and non-polar aromatic compounds have been analyzed after a spill of grude oil at Baltic Sea 1979 from drifting weathered oil glumps, sediment and sediment trap samples and bivalves at five areas of the Finnish Archipelago Sea. $\text{Mytilus}$ and flounder muscles and flounder livers were analyzed 1980 and 1981 from three of the previous five areas. The glumps were shown to be weathered grude oil. Sediment trap samples on the visibly contaminated area contained higher amounts of oil residues and in different ratios than the bottom sediments at the same areas. Extra local aliphatic hydrocarbon pollution was detected from the sediment traps at the reference area. Bivalves contained high amount of oil residues at visibly polluted but in some visibly non-polluted areas also 1979. Any significant decontamination was not detected at summer 1979 but next year the $\text{Mytilus}$ samples contained only traces if any and 1981 no detectable levels of aromatic oil residues. Aliphatic hydrocarbon residues in flounders showed no regional differences and no significant change of levels between 1980 and 1981. In contrary, the aromatic oil residues decreased to the non-detectable level in flounder muscles and to a significantly lower level in flouder livers 1981 related to 1980. Linear correlations of the analysis results are discussed.     

Effectiveness of rodenticides for managing invasive roof rats and native deer mice in orchards

Roof rats (Rattus rattus) and deer mice (Peromyscus maniculatus) are occasional pests of nut and tree fruit orchards throughout California and in many other parts of the USA and beyond. In general, the most practical and cost-effective control method for rodents in many agricultural environments is the use of rodenticides (toxic baits), but little or no information exists on the efficacy of current rodenticides in controlling roof rats and deer mice in orchards. Therefore, our goals were to develop an index of rodent activity to monitor efficacy of rodenticides and to subsequently test the efficacy of three California Department of Food and Agriculture rodenticide baits (0.005 % chlorophacinone treated oats, 0.005 % diphacinone treated oats, and 0.005 % diphacinone wax block) to determine their utility for controlling roof rats and deer mice in agricultural orchards. We determined that a general index using the number of roof rat photos taken at a minimum of a 5-min interval was strongly correlated to the minimum number known estimate of roof rats; this approach was used to monitor roof rat and deer mouse populations pre- and post-treatment. Of the baits tested, the 0.005 % diphacinone treated oats was most effective for both species; 0.005 % chlorophacinone grain was completely ineffective against roof rats. Our use of elevated bait stations proved effective at providing bait to target species and should substantially limit access to rodenticides by many non-target species.     

Longevity of rodenticide bait pellets in a tropical environment following a rat eradication program

Invasive rodents (primarily Rattus spp.) are responsible for loss of biodiversity in island ecosystems worldwide. Large-scale rodenticide applications are typically used to eradicate rats and restore ecological communities. In tropical ecosystems, environmental conditions rapidly degrade baits and competition for baits by non-target animals can result in eradication failure. Our objective was to evaluate persistence of rodenticide baits during a rat eradication program on Palmyra Atoll; a remote tropical atoll with intense competition for resources by land crabs. Following aerial application, bait condition was monitored in four terrestrial environments and in the canopy foliage of coconut palms. Ten circular PVC hoops were fixed in place in each of Palmyra’s four primary terrestrial habitats and five rodenticide pellets were placed in each hoop. Five coconut palms were selected in three distinct regions of the atoll. One rodenticide pellet was placed on each of five palm fronds in each coconut palm. Fresh baits were placed in all monitoring locations after each broadcast bait application. Bait condition and survival was monitored for 7 days after the first bait application and 6 days after second application. Bait survival curves differed between applications at most monitoring sites, suggesting a decrease in overall rat activity as a result of rodenticide treatment. One terrestrial site showed near 100 % bait survival after both applications, likely due to low localized rat and crab densities. Median days to pellet disappearance were one and two days for the first and second application, respectively. Differences in survival curves were not detected in canopy sites between bait applications. Median days to pellet disappearance in canopy sites were 2 and 4 days for the first and second application, respectively. Frequent rainfall likely contributed to rapid degradation of bait pellets in coconut palm fronds.     

Study on the fluorescence characteristics of bromadiolone in aqueous and organized media and application in analysis

The fluorescence spectroscopic behavior of bromadiolone (anticoagulant rodenticide), a substituted 4-hydroxycoumarin derivative, was investigated in water and in organized media like micelles and cyclodextrins. A detailed study on various photophysical parameters like fluorescence intensity (I_F), quantum yield (), lifetime (τ) and steady state fluorescence anisotropy (r) of bromadiolone in aqueous and in organized media was carried out. Bromadiolone in aqueous solution was observed to be in an aggregated state, thereby showing weak emission due to self-quenching. Marked enhancement of fluorescence intensity was observed in organized media like micelles and β-cyclodextrin. A preliminary investigation has been done to find out whether this enhancement of fluorescence can be used to develop a sensitive analytical method for determination of bromadialone in aqueous media. A linear relationship between the fluorescence intensity and concentration of bromadiolone was observed in the range of 0.15–7.9 μg ml⁻¹ in cetyltrimethylammonium bromide (CTAB) and 0.5–26.4 μg ml⁻¹ in β-cyclodextrin medium. The lower detection limit was found to be 37 ng ml⁻¹ in presence of CTAB and 23 ng ml⁻¹ in β-cyclodextrin. Comparison with 4-hydroxycoumarin, an unsubstituted analogue, was made.     

Detection of herbicides in water bodies of the Samambaia River sub-basin in the Federal District and eastern Goiás

Abstract

The objective of this study was to identify and quantify herbicide residues in water samples of rain, cisterns, streams, ponds, springs, semi-artesian wells, dams and a river in the Rio Samambaia sub-basin in the Federal District and eastern Goiás. A total of 287 samples were collected from 20 farms in the sub-basin in the rainy (February, summer) and dry (August, winter) seasons in 2016. Aminomethylphosphonic acid (AMPA, a glyphosate metabolite), clethodim, chlorimuron-ethyl, diuron, fluazifop acid (a fluazifop-p-butyl metabolite and the active ingredient), haloxyfop acid (a haloxyfop-methyl metabolite and the active ingredient), imazamox, mesotrione, metsulfuron, nicosulfuron and pendimethalin were not identified in any water sample. In the rainy season, approximately 99% of the samples contained residues at least one of the evaluated herbicides; in the dry season (, 100% of the samples contained residues of at least one of the evaluated herbicides. When considering only detection frequency, metribuzin, atrazine, clomazone and haloxyfop-methyl were the main herbicides found in the water of the Samambaia River sub-basin. In turn, based on levels higher than the limit of quantification, the main compounds detected were atrazine, clomazone, haloxyfop-methyl and glyphosate. In both seasons, the highest relative concentrations of herbicides for the rainy and dry seasons were found in spring water, 25% and 56%, respectively, and dam water, 23% and 16%, respectively.     

A comparison of microplastic contamination in freshwater fish from natural and farmed sources

Contamination of aquatic systems mainly by urbanization and poor sanitation, deficient or lack of wastewater treatments, dumping of solid residues, and run off has led to the presence of particles, including manmade polymers, in tissues of many marine and freshwater species. In this study, the prevalence of microplastics (MPs) in freshwater fish from farmed and natural sources was investigated. Oreochromis niloticus from aquaculture farms in the Huila region in Colombia, and two local species (Prochilodus magdalenae and Pimelodus grosskopfii), naturally present in surface waters were sampled. Of the particles identified, fragments were the predominant type in the three tissue types (stomach, gill, and flesh) derived from farmed and natural fishes. MicroFT-IR spectroscopy was conducted on 208 randomly selected samples, with 22% of particles identified as MPs based on spectra with a match rate ≥ 70%. A total of 53% of identified particles corresponded to cellophane/cellulose, the most abundant particle found in all fish. Not all fish contained MPs: 44% of Oreochromis farmed fish contained MPs, while 75% of natural source fish contained MPs in any of its tissues. Overall, polyethylene terephthalate (PET), polyester (PES), and polyethylene (PE) were the prevalent MPs found in the freshwater fish. A broader variety of polymer types was observed in farmed fish. The edible flesh part of fish presented the lower prevalence of MPs compared to gill and stomach (gut), with gut displaying a higher frequency and diversity of MPs. This preliminary study suggests that the incidence and type of MPs varies in farmed verses natural fish sources as well as across different tissue types, with significantly less detected within the edible flesh tissues compared with stomach and gill tissues.

     

Organochlorine insecticide residues in birds and fish from the Transvaal, South Africa

Fatty extracts of wild birds and fishes were analysed for certain organochlorine insecticides. Nearly all samples contained residues of one or more of the insecticides.     

Effect of squalane on hexachlorobenzene (HCB) concentrations in tissues of mice

Abstract

Female mice were given 100 mg HCB/kg body weight i.p. and fed diets containing 0, 2.5, 5.0, and 7.5% of squalane. After 3 weeks samples of livar, blood and abdominal fat ware analysed for HCB as well as for squalane. HCB concentrations were significantly lowered as comoared to controls in all tissues and at all dietary concentrations of squalane to a maximum of about 36% in fat, 44% in liver and 47% in blood. The effect of squalane upon HCB concentrations was strongly dose depedent in abdominal fat. In contrast, no significant differences were seen with liver and blood between animals fed 5.0 or 7.5% of squalane. Squalane was detected in considerable amounts in the livers (50–100 ppm) but r.ct in abdominal fat (<1 ppm) of mice fed squalane.     

Pesticide residues in thermal mineral water in Greece

Eight different hot springs (SPA) in Greece were monitored over a one-year survey for priority pesticide residues. A specific and effective procedure including solid phase extraction in combination with HPLC and GC analytical methods were applied. Samples that were sensitive to nitrogen-phosphorus (NPD) and/or electron capture (ECD) detectors were analysed by capillary gas chromatography. From the twenty-six water samples, pesticide residues were detected in fourteen of them (54%) but no one exceeding the European Union Maximum Acceptable Concentration (MAC). Lindane (gamma-BHC) was the most frequently detected pesticide. It was found in nine samples (35%) in concentrations from < 0.005 to 0.01 microg/L. Other pesticides detected were phorate (in five samples), propachlor (in two samples) and chlorpyriphos ethyl (in three samples) but in concentrations far below the permissible levels.     

Persistence of chlorpyrifos in a mineral and an organic soil

Chlorpyrifos (Lorsban emulsifiable concentrate) was applied at 3.4 kg AI/ha and incorporated into sand and muck soil contained in small field plots. Soil samples were taken at intervals over 2 yr. Radishes and carrots, seeded yearly, served as indicator crops for absorption of insecticide residues. Samples were extracted and analyzed, by gas-liquid chromatography, for chlorpyrifos, oxychlorpyrifos, and 3,5,6-trichloro-2-pyridinol. Chlorpyrifos residues declined rapidly, with 50% of the initial application remaining after 2 and 8 wk in sand and muck, respectively, and 4 and 9% after 1 yr. Pyridinol residues increased to 13 and 39% of the initial chlorpyrifos application in sand and muck after 1 and 8 wk, respectively, and declined thereafter. Oxychlorpyrifos was detected in the 2 soils at very low levels only in immediate posttreatment samples. In the first year of the study low levels (less than 0.1 ppm) of chlorpyrifos and the pyridinol were detected in radishes and carrots.     

PESTICIDE RESIDUES IN THERMAL MINERAL WATER IN GREECE

Eight different hot springs (SPA) in Greece were monitored over a one-year survey for priority pesticide residues. A specific and effective procedure including solid phase extraction in combination with HPLC and GC analytical methods were applied. Samples that were sensitive to nitrogen-phosphorus (NPD) and/or electron capture (ECD) detectors were analysed by capillary gas chromatography.

From the twenty-six water samples, pesticide residues were detected in fourteen of them (54%) but no one exceeding the European Union Maximum Acceptable Concentration (MAC).

Lindane (γ-BHC) was the most frequently detected pesticide. It was found in nine samples (35%) in concentrations from <0.005 to 0.01 μg/L. Other pesticides detected were phorate (in five samples), propachlor (in two samples) and chlorpyriphos ethyl (in three samples) but in concentrations far below the permissible levels.     

Distribution of mercury in the organs and tissues of five toothed-whale species of the Mediterranean

Mercury levels were determined in the tissues and organs (lung, liver, kidney, skin, muscle, bone) of five toothed-whales stranded along the Corsican coast between November 1993 and February 1996. The species taken into consideration were the bottlenose dolphin Tursiops truncatus, the common dolphin Delphinus delphis, the striped dolphin Stenella coeruleoalba, the pilot whale Globicephala melas and the Risso's dolphin Grampus griseus. The variation in mercury levels between the different tissues and organs (lung, liver, kidney, skin, muscle, bone) of the cetacean species are discussed as regards storage, biotransformation and elimination. In all cases, the liver appears to be the preferential organ for mercury accumulation (with concentrations as high as 4250 microg Hg/g dw and 3298 microg Hg/g in the livers of Tursiops truncatus and Grampus griseus, respectively). The kidney and lung are the next organs in terms of mercury uptake followed by the muscle, bone and skin. The stomach contents of Grampus griseus and D. delphis were determined and consisted of cephalopods for Grampus griseus, and of sardines Sardina pilchardus and mackerels Trachurus sp. for D. delphis. Cephalopods had higher mercury concentrations (25.4 microg Hg/g dw) than fish (ca 1 microg Hg/g). These contents represent only one meal and mercury levels found in livers may integrate mercury uptake having occurred during the whole life span of animals.     

Detection and occurrence of pentachlorophenol residues in chicken liver and fat

Abstract

A method for the detection of pentachlorophenol (PCP) residues in chicken liver and fat is presented. A detection limit of 0.002 mg/kg was achieved. Recoveries from liver and fat were in the range 82–88% and 95–97%, respectively.

Low level residues of PCP were found in all 1072 liver and 723 fat samples. These levels were <0.010 mg/kg in 92.7% of the fat and 75.6% of the livers. Only 0.75% of the liver samples had PCP levels>0.1 mg/kg. None of the more toxic impurities of PCP were detected in the chicken tissues.