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Wildlife exposures to pest controlling substances have resulted in population declines of many predatory species during the past decades. Many pesticides were subsequently classified as persistent, bioaccumulative, and toxic (PBT) and banned on national or global scales. However, despite their risks for non-target vertebrate wildlife, PBT substances such as anticoagulant rodenticides (ARs) are still permitted for use in Europe and have shown to threaten raptors. Whereas risks of ARs are known, much less information is available on emerging agrochemicals such as currently used PPPs and medicinal products (MPs) in higher trophic level species. We expect that currently used PPPs are relatively mobile (vs. lipophilic) as a consequence of the PBT criteria and thus more likely to be present in aqueous matrices. We therefore analyzed blood of 204 raptor nestlings of three terrestrial (red kite, common buzzard, Montagu's harrier) and two aquatic species (white-tailed sea eagle, osprey) from Germany. In total, we detected ARs in 22.6% of the red kites and 8.6% of the buzzards, whereas no Montagu's harriers or aquatic species were exposed prior to sampling. ΣAR concentration tended to be higher in North Rhine-Westphalia (vs. North-Eastern Germany) where population density is higher and intense livestock farming more frequent. Among the 90 targeted and currently used PPPs, we detected six substances from which bromoxynil (14.2%) was most frequent. Especially Montagu's harrier (31%) and red kites (22.6%) were exposed and concentrations were higher in North Rhine-Westphalia as well. Among seven MPs, we detected ciprofloxacin (3.4%), which indicates that risk mitigation measures may be needed as resistance genes were already detected in wildlife from Germany. Taken together, our study demonstrates that raptors are exposed to various chemicals during an early life stage depending on their sampling location and underpins that red kites are at particular risk for multiple pesticide exposures in Germany., (© 2022. The Author(s).)

Anticoagulant rodenticides (ARs) are used globally to control rodent pest infestations in both urban and agricultural settings. It is well documented that non-target wildlife, including predatory birds, are at risk for secondary anticoagulant exposure and toxicosis through the prey they consume. However, there have been no large-scale studies of AR exposure in raptors in Ontario, Canada since new Health Canada legislation was implemented in 2013 in an attempt to limit exposure in non-target wildlife. Our objective was to measure levels of ARs in wild raptors in southern Ontario to assess their exposure. We collected liver samples from 133 raptors representing 17 species submitted to the Canadian Wildlife Health Cooperative (CWHC) in Ontario, Canada, between 2017 and 2019. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used to quantitatively assess the level of exposure to 14 first- and second-generation ARs. Detectable levels of one or more ARs were found in 82 of 133 (62%) tested raptors, representing 12 species. The most commonly detected ARs were bromadiolone (54/133), difethialone (40/133), and brodifacoum (33/133). Of AR-positive birds, 34/82 (42%) contained residues of multiple (> 1) anticoagulant compounds. Our results indicate that AR exposure is common in raptors living in southern Ontario, Canada. Our finding that brodifacoum, difethialone, and bromadiolone were observed alone or in combination with one another in the majority of our sampled raptors indicates that legislative changes in Canada may not be protecting non-target wildlife as intended., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Rodents infest urban environments, causing damage and acting as vectors for disease transmission. Currently, anticoagulants are the most widely used chemical rodenticides, and their extensive and widespread use can contaminate the environment. To ensure effectiveness and avoid accumulation of rodent baits in the environment, it is important to evaluate how long rodent baits maintain their palatability and efficacy. In rodent control programs, rodent baits are placed in locations such as sewers, but after a few days, baits appear altered, causing doubts about the control efficacy. For this reason, baits are replaced periodically, which increases costs and generation of chemical waste. The objective of this study was to evaluate the palatability and efficacy of commercial paraffin-type rodent bait blocks placed in sewers in São Paulo City over a period of 90 days. Bait blocks were placed in sewers and collected after 30, 60, and 90 days. Additionally, in a laboratory two-choice test, wild-caught urban Norway rats were offered 40-60 g of bait and an equal volume of standard rat pellets. The amount of bait and rat pellet consumed was registered, the palatability was calculated, and the efficacy was measured as the percentage mortality over 14 days. The results showed that, even when they had an altered appearance, bait blocks remained palatable to the rats and were effective after at least 90 days. Leaving bait blocks for longer periods could be an effective strategy for reducing costs and could help to ensure the control of urban rodents in an environmentally sustainable way.

Anticoagulant rodenticides (ARs) have been used for decades for rodent control worldwide. Research on the exposure of the environment and accumulation of these active substances in biota has been focused on terrestrial food webs, but few data are available on the impact of ARs on aquatic systems and water organisms. To fill this gap, we analyzed liver samples of bream (Abramis brama) and co-located suspended particulate matter (SPM) from the German Environmental Specimen Bank (ESB). An appropriate method was developed for the determination of eight different ARs, including first- and second-generation ARs, in fish liver and SPM. Applying this method to bream liver samples from 17 and 18 sampling locations of the years 2011 and 2015, respectively, five ARs were found at levels above limits of quantifications (LOQs, 0.2 to 2 μg kg -1 ). For 2015, brodifacoum was detected in 88% of the samples with a maximum concentration of 12.5 μg kg -1 . Moreover, difenacoum, bromadiolone, difethialone, and flocoumafen were detected in some samples above LOQ. In contrast, no first generation AR was detected in the ESB samples. In SPM, only bromadiolone could be detected in 56% of the samples at levels up to 9.24 μg kg -1 . A temporal trend analysis of bream liver from two sampling locations over a period of up to 23 years revealed a significant trend for brodifacoum at one of the sampling locations.

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.

Raptor population growth is dynamic and trends vary across species and by location in the United States. For those species that are declining, it is important to identify potential causes including chemical contaminants. Sampling wild raptors is problematic due to their small population sizes and role as a top predator. Therefore, we obtained liver samples (n = 56) from carcasses of several raptor species, including common species like red-tailed hawks, red-shouldered hawks, barred owls, great horned owls, and osprey that arrived dead or were euthanized from a non-profit rehabilitation center in Charlotte, North Carolina. Raptors were found or collected in South Carolina, North Carolina, and Virginia, but most samples were located near the metropolitan region of Charlotte, NC. We analyzed livers for total mercury residue (mg/kg, dry weight) and five anti-coagulant rodenticides (μg/kg wet weight). Mercury was analyzed using a direct mercury analyzer approach and rodenticides were quantified by LC-MS. Mercury residues were high in piscivorous birds (15.09 mg/kg for osprey and 6.93 mg/kg for great blue herons, dry weight) and relatively high in red-shouldered hawks and one eastern screech owl tested. Six of our samples exceeded a health threshold of 1 mg/kg (wet weight) including three osprey and one each of great blue heron, red-shouldered hawk, and eastern screech owl. Brodifacoum was the only rodenticide consistently detected in our samples. Brodifacoum detections exceeded 75% in barred owls, great horned owls, and red-shouldered hawks. Sixty-nine percent of owl samples were within (or exceeded) a threshold of brodifacoum residue associated with a 10-20% risk of acute toxicity. Correlations between residues and human population density were not significant for either mercury or brodifacoum. Our data suggest that mercury residues for most raptors were not of significant concern with the exception of osprey and possibly red-shouldered hawks. Rodenticide exposures associated with a risk of acute toxicity appear to be common and warrant further investigation.

The occurrence of 10 commonly used anticoagulant rodenticides in centrifuged sludge of 27 wastewater treatment plants was evaluated using solid-liquid extraction (SLE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Activated carbon, alumina, and Florisil cartridges with methanol/dichloromethane as eluting solvents were tested in combination with primary-secondary amine (PSA) to optimize an efficient sample cleanup. PSA in combination with Florisil was the best methodology to extract anticoagulant rodenticides in sludge providing recoveries between 42 ± 0.5 and 100 ± 2 %. Warfarin, bromadiolone, ferulenol, and coumachlor were the most ubiquitous compounds in sludge at concentrations up to 84.2 ng g(-1) for the latter. Coumatetralyl, dicoumarol, and brodifacoum were detected sporadically at levels between 6.1 and 17.4 ng g(-1). On the contrary, acenocoumarol, difenacoum, and flocoumafen were not detected in any sample. Finally, we estimated the amount of anticoagulant rodenticides discharged via sludge in order to determine the potential impact to agricultural soil according to different sludge usage practices in the region investigated. This study demonstrates that anticoagulant rodenticides are accumulated in sludge during activated sludge treatment and that the application of sludge as fertilizers may pose a future environmental risk, if not controlled.

Second-generation anticoagulant rodenticides are widely reported to contaminate and poison nontarget wildlife, primarily predatory birds and mammals. Exposure pathways, however, have not been well defined. Here, we examined potential movement of rodenticides from deployment of bait to exposure of small mammals and other biota. At two adjacent working farms, we placed baits containing either brodifacoum or bromadiolone. We monitored movement of those compounds to the surrounding environment by collecting small mammals, birds, and invertebrates. Similar collections were made at a third agricultural setting without active bait deployment, but located among intensive livestock production and regular rodenticide use by farmers. Livers and whole invertebrate samples were analyzed for rodenticides using a sensitive LC-MSMS method. Norway rats (Rattus norvegicus) from both baited and non-baited farms had residues of brodifacoum or bromadiolone, implicating rats as an important exposure pathway to wildlife. Among 35 analyzed nontarget small mammals, a single vole had high hepatic residues (18.6 μ/g), providing some indication of a small mammal pathway. One song sparrow (Melospiza melodia) sample from a baited farm contained 0.073 μg/g of brodifacoum in liver, while 0.39 μg/g of diphacinone was measured in a pool of carrion beetles (Dermestes spp.) from the non-baited farm area, implicating avian and invertebrate components in exposure pathways. Regurgitated pellets of barn owl (Tyto alba) selected randomly from baited farms contained no detectable rodenticide residues, while 90% of owl pellets collected from a variety of farms, and selected for the presence of rat fur, contained detectable anticoagulant residues. We recorded behavior of a captive sample of a representative songbird, the house sparrow (Passer domesticus); they readily entered bait stations and fed on (unloaded) bait.

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.

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.

Baits containing brodifacoum rodenticide were aerially applied to eradicate invasive black rats from Palmyra Atoll, an important biodiversity center. Bait application must be sufficient to be effective, while minimizing environmental hazards by not exceeding designated label rates, prompting our bait density assessments for two aerial drops. With few physical or human resources on this remote, uninhabited atoll, assessments were particularly challenging, requiring observations within 30 min of aerial application to avoid bait loss to rats, crabs, or elements. We estimated bait density using quadrat sampling within 13 terrestrial sampling areas. We also sampled 10 tidal flat areas to assess inadvertent bait scatter into marine aquatic environments. Of particular value for challenging sampling circumstances, our quadrats had to be lightweight and durable, which we addressed by using widely available PVC hoops ("Hula Hoops"), the size of which was ideal for sampling purposes. At 77.5 and 78.7 kg/ha, overall bait densities were very near to the target densities of 80 and 75 kg/ha, respectively. However, considerable variability in bait densities existed among sampled areas, 8.6-178.2 and 31.4-129.5 kg/ha for the respective drops, respectively. Environmental, human, and equipment factors likely accounted for this variability. Tidal flat sampling revealed variable bait scatter into aquatic environments, from 0-46.3 kg/ha across the two drops. No differences were found in average bait densities among 1-, 4-, and 7-m distances from high tide lines. Our methods might broadly assist bait density (and other) surveys under challenging circumstances.

The detection of 4-hydroxycoumarin rodenticides in poisoned domestic animals requires a highly sensitive method as tissue and serum levels of anticoagulants may be very low owing to rapid elimination, metabolism or post-mortem degradation. Thin-layer chromatography (TLC) and reversed-phase high-performance liquid chromatography (RP-HPLC) with fluorescence detection were used to identify the anticoagulants in spiked tissues and in suspicious samples. The analysis of ten suspicious samples highlighted the limitations of both methods. Only the three samples of baits were found positive by TLC whereas one of the five anticoagulants was detected in eight samples by RP-HPLC with fluorescence detection. Therefore, RP-HPLC with fluorescence detection proved to be the more sensitive method for detecting low levels of 4-hydroxycoumarins in blood serum, liver and ingesta, whereas TLC is usually sufficient for analysing baits.