Laurie K. Wilson

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.

Reproductive success and chlorinated hydrocarbon contamination of resident great blue herons (Ardea herodias) from coastal British Columbia, Canada, 1977 to 2000

Over the period 1977-2000, eggs of Pacific great blue heron (Ardea herodias fannini) were collected from 23 colonies along the southern coast of British Columbia, Canada, and analyzed for persistent organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs). Concentrations of OC pesticides in eggs declined sharply in the late 1970s, after which there were minimal changes. The sums of PCB congeners were not reduced appreciably during the 1980s and 1990s, but Aroclor 1260 concentrations suggested a sharp decline in PCB contamination of eggs in the late 1970s, similar to that shown for OC pesticides. Eggs collected along or near the Fraser River delta showed higher levels of most pesticides compared to other monitored colonies. Although the delta lands support a long-standing agricultural economy, the primary factors influencing OC levels in the delta colonies were thought to be driven by estuarine processes. We suggest two possible influencing factors were: 1) a greater rate of bioaccumulation in the estuary due to the deposition of particulates collected over a vast area encompassed by the Fraser River watershed; or 2) a higher rate of biomagnification in the estuary due to species differences at lower trophic levels of the heron food chain. Eggs from urban colonies contained higher levels of PCBs. The congener pattern was not clearly different from that observed in less contaminated eggs from rural and pulp mill-influenced colonies, except that colonies in Vancouver had greater proportions of PCB-66, suggesting a local source of Aroclor 1242. Productivity in the coastal heron colonies was highly variable over the period of study, with 71% of recorded colony-wide reproductive failures occurring in colonies near pulp mills. However, the predominant factors influencing reproductive success were probably disturbance by humans and bald eagles, combined with loss and degradation of nesting habitat, and not sublethal toxicity.

Monitoring Temporal and Spatial Trends in Polychlorinated Dibenzo-p-dioxins (PCDDs) and Dibenzofurans (PCDFs) in Eggs of Great Blue Heron (Ardea herodias) on the Coast of British Columbia, Canada, 1983–1998

Abstract Eggs from 21 resident great blue heron (Ardea herodias) rookeries were monitored from 1983 to 1998 along the coast of British Columbia, Canada, for contamination with polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs). Dominant congeners (1,2,3,7,8-PnCDD, 1,2,3,6,7,8-HxCDD, 2,3,7,8-TCDD, 2,3,7,8-TCDF, 1,2,3,7,8,9-HxCDD and 2,3,4,7,8-PnCDF) fell markedly in the early 1990s after pulp mills changed from molecular chlorine bleaching to alternative bleaching technologies, and the use of chlorophenolic wood preservatives and anti-sapstains was severely restricted. Strong positive linear regressions between prey fish and heron egg contaminant levels suggested that local dietary uptake was an important route of exposure for herons. Toxic equivalent concentrations (TEQs) sufficient to produce embryotoxicity in great blue heron chicks were measured in eggs from 1985 to 1991 at some colonies. Despite reduction in PCDD/Fs, estimated TEQs remained elevated throughout the 1980s at some urban colonies due to contributions from PCBs.

Chlorinated hydrocarbons in livers of American mink (Mustela vison) and river otter (Lutra canadensis) from the Columbia and Fraser River Basins, 1990-1992

We investigated chlorinated hydrocarbon contaminants in aquatic mustelid species on the Fraser and Columbia Rivers of northwestern North America. Carcasses of river otter (Lutra canadensis) (N=24) and mink (Mustela vison) (N=34) were obtained from commercial trappers during the winters of 1990–91 and 1991–92. Pooled liver samples were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), including non-ortho congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Most samples contained detectable concentrations of DDE, PCBs, although there was substantial variability in patterns and trends among neighboring samples. Concentrations of DDE were in some mink and several otter samples from the lower Columbia River elevated (to 4700 μg/kg wet weight); excluding one mink sample from the Wenatchee area, mean DDE levels generally decreased between 1978–79 and 1990–92. PCBs were present in all samples. PCB concentrations in otter livers collected from the lower Columbia were ten-fold lower than measured a decade previously; nevertheless, a sample taken near Portland had a mean concentration of 1500 μg/kg, within a range of concentrations associated with reproductive effects in captive mink. Concentrations of 2,3,7,8-TCDD and TCDF were generally below detection limits, except for one otter collected near a pulp mill at Castlegar, on the upper Columbia, with 11 ng TCDD/kg in liver. Elevated concentrations of higher chlorinated PCDD/Fs, probably resulting from use of chlorophenolic wood preservatives, were found in both species; one otter sample from the lower Columbia had 2200 ng OCDD/kg. International TCDD toxic equivalent levels in mink (31 ng/kg) and otter (93 ng/kg) from the lower Columbia River approached toxicity thresholds for effects on reproduction in ranch mink.

Bald eagle mortality and chlorinated hydrocarbon contaminants in livers from British Columbia, Canada, 1989-1994.

Between 1989 and 1994, we obtained 278 carcasses of bald eagles (Haliaeetus leucocephalus) found dead or dying in British Columbia, Canada. All specimens were necropsied and the cause of death determined wherever possible. Livers from a subset of 75 birds were analyzed for polychlorinated biphenyl (PCB) and organochlorine (OC) pesticide residues. A further subset of 19 eagles found dead around the Strait of Georgia, an area of known pulp mill pollution, in summer, and therefore presumably resident birds, were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) and non-ortho PCBs. Liver concentrations ranged from less than 1 to 190 mg/kg for DDE, and up to 72 mg/kg for total PCBs. Concentrations of other OCs were generally less than 1 mg/kg, with the exception of chlordane-related compounds which were occasionally over 2 mg/kg. All birds analyzed for PCDDs and PCDFs contained detectable concentrations of the major 2,3,7,8-substituted isomers. Some birds were very contaminated; one eagle found near a kraft pulp mill site in 1990 contained: 400 ng/kg 2,3,7,8-TCDD, 1400 ng/kg 1,2,3,7,8-PnCDD and 4400 ng/kg 1,2,3,6,7,8-HxCDD. Birds with higher PCB and dichlorodiphenyldichloroethane (DDE) concentrations appeared to weigh less, and there was a significant negative relationship between both PCBs and DDE and numeric scoring of body condition, reflecting the well known process of starvation-induced mobilization of body lipids and contaminants. Birds with higher 2,3,7,8-TCDD concentrations tended to have unusually low concentrations of 2,3,7,8-TCDF, interpreted to indicate hepatic cytochrome P4501A-type induction by TCDD and subsequent metabolism of TCDF.

Secondary poisoning of birds of prey by the organophosphorus insecticide, phorate

As a part of a monitoring study, five dead or debilitated bald eagles (Haliaeetus leucocephalus) and a red-tailed hawk (Buteo jamaicensis) from the Fraser River Delta of British Columbia (BC), Canada tested positive for residues of the organophosphorus insecticide, phorate. The first group of three birds was found during January and February 1992, from which two eagles were confirmed to have been poisoned by phorate. The second poisonings took place from December 1993 to March 1994, when three eagles and a hawk were confirmed as phorate poisoned. The brain and plasma cholinesterase results are presented along with data on chemical residue analyses of ingesta. Granular phorate, used in the area to control pests on potatoes and other root crops, appears to have a prolonged half-life similar to carbofuran and fensulfothion, two other granular insecticides associated with secondary mortality of raptors in the Fraser Delta. The soil persistence of phorate combined with a high acute toxicity poses a risk to waterfowl which are attracted to flooded fields in the autumn and winter and, thus, to raptors scavenging on dead waterfowl. The manufacturer has voluntarily withdrawn phorate, marketed as Thimet 15G, from the BC market as a result of the evidence presented here

Spatial and temporal trends in brominated flame retardants in seabirds from the Pacific coast of Canada

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) are bioaccumulative flame retardants. PBDEs increased in many ecosystems during the late 20th century, but recently have declined in some environments. To examine trends in the northern Pacific, we analysed PBDEs, HBCDD and carbon and nitrogen stable isotopes (δ13C and δ15N) to account for dietary effects in archived eggs of three seabird species from British Columbia, Canada, 1990-2011 (rhinoceros auklets, Cerorhinca monocerata; Leachs storm-petrels, Oceanodroma leucorhoa; ancient murrelets, Synthliboramphus antiquus, 2009 only). PBDEs increased until approximately 2000 and then decreased, while HBCDD increased exponentially throughout the examined period. No significant changes in dietary tracers were observed. HBCDD and ΣPBDE levels varied among species; ΣPBDE also varied among sites. Temporal changes in contaminant concentrations are unlikely to have been caused by dietary changes, and likely reflect the build-up followed by decreases associated with voluntary phase-outs and regulations implemented in North America to control PBDEs.

Fonofos poisons raptors and waterfowl several months after granular application

From 1994 to 1999 in the Lower Fraser Valley region of southwest Canada, fonofos (Dyfonate G) was recommended for control of introduced wireworm (Agriotes spp.) pests on potato and other root crops. As part of a wildlife-monitoring program, we collected 15 raptors, including 12 bald eagles (Haliaeetus leucocephalus), found dead or debilitated on or near agricultural lands with severely inhibited brain and/or plasma cholinesterase activity and fonofos residues in ingesta. Bird remains, in nine cases waterfowl, were identified in the ingesta samples. Another seven bald eagles had severe cholinesterase inhibition, but without evidence of fonofos residues. During two winters from 1996 to 1998, 420 ha of potato fields, half of which had been treated the previous spring with fonofos and the remainder untreated, were searched weekly for evidence of wildlife mortality. Search efficiency was assessed with placed duck carcasses. Waterfowl outnumbered other species in field-use counts and comprised the greatest proportion of birds found dead. We found 211 wildlife remains, most scavenged; 35 intact carcasses were suitable for postmortem examination and/or toxicology analyses. Cholinesterase activity was assayed in brains of 18 waterfowl, five of which had severely depressed activity (average inhibition 74%; range, 69-78%). The gastrointestinal tract of a mallard found in a field treated with granular product contained 49 microg/g fonofos residues, linking waterfowl mortality with labelled use of the product. These findings demonstrate the risk of both primary and secondary poisoning by anticholinesterase insecticides where wildlife make intensive use of farmed fields.

Brominated flame retardant trends in aquatic birds from the Salish Sea region of the west coast of North America, including a mini-review of recent trends in marine and estuarine birds

Polybrominated diphenyl ethers (PBDEs) increased in many matrices during the 1990s and early 2000s. Since voluntary restrictions and regulations on PBDEs were implemented in North America circa early 2000s, decreases in PBDEs have occurred in many of these same matrices. To examine temporal trends in the North Pacific, we retrospectively analysed PBDEs and eight non-PBDE flame retardants (FR) in eggs of two aquatic bird species, great blue herons, Ardea herodias, and double-crested cormorants, Phalacrocorax auritus, collected along the British Columbia coast, Canada from 1979 to 2012. Increasing PBDE concentrations were observed in both species followed by significant decreases post-2000 for all dominant congeners and ΣPBDE. Non-PBDE FRs were generally undetected in cormorant eggs, or detected at very low levels in heron eggs, except for hexabromocyclododecane (HBCDD). HBCDD, currently unregulated in North America, was not detected in early sampling years; however low concentrations were observed in both species in recent sampling years (2003-2012). Dietary tracers (δ(13)C and δ(15)N) did not change significantly over time, indicating that temporal changes in PBDEs are likely caused by implemented regulations. A comparison with recently published temporal trends of ΣPBDE in marine birds from North America and Europe is given.