Trends of perfluorochemicals in Greenland ringed seals and polar bears: Indications of shifts to decreasing trends

Time-series of perfluorinated alkylated substances (PFASs) in East Greenland polar bears and East and West Greenland ringed seals were updated in order to deduce whether a response to the major reduction in perfluoroalkyl production in the early 2000s had occurred. Previous studies had documented an exponential increase of perfluorooctane sulphonate (PFOS) in liver tissue from both species. In the present study, PFOS was still the far most dominant compound constituting 92% (West Greenland ringed seals), 88% (East Greenland ringed seals) and 85% (East Greenland polar bears). The PFOS concentrations increased up to 2006 with doubling times of approximately 6 years for the ringed seal populations and 14 years in case of polar bears. Since then a rapid decrease has occurred with clearing half-lives of approximately 1, 2 and 4 years, respectively. In polar bears perfluorohexane sulphonate (PFHxS) and perfluorooctane sulphonamide (PFOSA) also showed decreasing trends in recent years as do perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA). For the West Greenland ringed seal population perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), PFDA and PFUnA peaked in the mid 2000s, whereas PFNA, PFDA and PFUnA in the East Greenland population have been stable or increasing in recent years. The peak of PFASs in Greenland ringed seals and polar bears occurred at a later time than in Canadian seals and polar bears and considerably later than observed in seal species from more southern latitudes. We suggest that this could be explained by the distance to emission hot-spots and differences in long-range transport to the Arctic.     

Remote SO2 Mass Flux Measurements Using COSPEC

During the intensive Nanticoke Environmental Field Study of May/June 1978, three Barringer Correlation Spectrometers (COSPEC) were employed to obtain remote sensing estimates of sulfur dioxide emissions from a coal fired hydroelectric generating station. The results from about one hundred half-hourly sampling periods shows that the COSPEC derived estimate is within 7% of those computed by the utility. The sources of the variance in the COSPEC flux estimate are examined and sampling recommendations regarding the use of COSPEC for this purpose are made.     

Handling intensity and the short- and long-term survival of elephant seals: addressing and quantifying research effects on wild animals

This study addresses the consequences of repeated human handling on the survival of an endangered phocid, the southern elephant seal and the implications for wildlife research. Southern elephant seal pups were repeatedly handled during the first six weeks of their lives. The possibility that such anthropogenic research may have altered the very parameters that were being investigated is a topical and relevant study area that we address here. Our results show that there were no measurable effects on pups that were repeatedly handled and subjected to invasive research methods with respect to survivorship in the short term (the 24-day nursing period) nor in the long term (the first year of life and beyond) and hence fitness one year after handling. In support of this conclusion we were unable to detect any significant differences in the survival rates of the most intensively handled seals and the least intensively handled seals.     

Quality assured measurements of animal building emissions: gas concentrations

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), methane (CH4), nonmethane hydrocarbons (NMHC), particulate matter <10 microm in diameter, and total suspended particulate from swine and poultry production buildings in the United States. This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with > or =10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH3, H2S, CO2, CH4, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Studies of toxaphene in technical standard and extracts of background air samples (Point Petre, Ontario) using multidimensional gas chromatography-electron capture detection (MDGC-ECD)

MDGC-ECD procedures have been used to provide insight into the compositional complexity of some of the specific peaks or clusters observed in the gas chromatographic analysis of a technical toxaphene standard, with reference to individual toxaphene congeners (Parlar # components) that are flow commercially available. These investigations have focussed initially upon those peaks and clusters recently identified (Shoeib. M., Brice, K.A., Hoff, R., 1999. Chemosphere 39, 849-871) as dominant constituents of background ambient air. Multiple electron-capturing components have been found to be present in all the species studied: the available individual toxaphene congeners have been matched against these components where possible. In similar fashion, the responses obtained in equivalent gas chromatographic elution windows from the analysis of typical processed air sample extracts have been investigated, with the results showing clear differences relative to the patterns found in the technical toxaphene standard. In most cases, the air sample shows reduced complexity with fewer components present in the cluster. Also, the presence of interfering responses (due to PCBs and other organochlorines) is quite apparent and significant, showing that major problems and errors could arise when using single-column GC-ECD procedures for quantitation of toxaphene in environmental samples. The presence of certain of the Parlar species in the air samples has been confirmed and in most cases these represent the dominant toxaphene component found in the targeted cluster. Furthermore, the persistence of certain congeners in the atmospheric samples appears to be strongly dependent upon chemical structure, since the congeners in question possess an alternating exo-endo chlorine substitution pattern around the six-membered ring in the bornane skeleton. Such persistence is probably the result of lower metabolization of toxaphene residues in soils, water and sediments leading to a similar pattern in the atmosphere following volatilization.     

Comparison of two methods for the determination of total organic halogen (TOX) in receiving waters

Two methods for the determination of total organic halogen (TOX), orginating from bleaching of pulp, in receiving waters have been compared. One of the methods (AC/MC) is based on adsorption of the halogenated matter onto an activated carbon sorbent. The halogen is determined by a microcoulometric technique after combustion of the carbon. The other method (XAD/PT) uses an XAD resin as sorbent and the determination of the halogen is carried out by potentiometric titration after a schöniger combustion of the resin eluate.Both methods showed good performance for samples consisting of spent bleach liquors diluted with distilled, fresh and brackish water. The repeatability was very good with a relative standard deviation less than a few per cent. The detection limit of the AC/MC method is about 0.1 μmol/1 and for the XAD/PT method about ten times higher. The AC/MC method gave in most cases 10–20% higher TOX concentrations compared to the XAD/PT method.     

Potential correlation between perfluorinated acids and liver morphology in East Greenland polar bears (Ursus maritimus)

In this study, residual concentrations of chlorpyrifos (CPF) were determined in feed (40) and fodder (25) samples collected from various locations of Tarai region of Uttarakhand. For extracting residues, liquid–liquid partition followed by alumina column clean up was used and the detection and quantification of residues was undertaken with the help of high-performance liquid chromatography using C18 column and diode array detector at 220?nm. Of the total 40 feed samples analyzed, 7 (17.5%) samples were found positive for CPF with the mean residual concentration of 0.058?µg?g^?1; while out of 25 fodder samples, CPF residues were detected in a single (4%) sample with residual concentration of 0.39?µg?g^?1. However, none of the feed or fodder samples contained CPF residues above the prescribed limit.     

Testosterone concentrations and male genital organ morphology in Greenland sledge dogs (Canis familiaris) dietary exposed to organohalogen contaminants

This study investigated whether low-level, long-term in utero and post-natal exposure to organohalogen pollutants disrupts male reproductive organ morphology and testosterone production in Greenland sledge dogs (Canis familiaris), as a model of Arctic top predators feeding on marine mammals. Six male dogs were followed for 1 year and testosterone concentrations, testes/baculum morphology and baculum bone mineral density (BMD) was determined. Three males were exposed to organohalogenated contaminants (OHCs) in utero through maternal dietary intake of minke whale blubber (Balaenoptera acutorostrata), with a post-weaning ∑OHC intake of 10.4–11.7 µg kg^?1 day^?1 resulting in an adipose tissue range of ∑OHC 4518–5729 ng (g lw)^?1 after 1 year. Three control males were exposed to very low concentrations of OHCs through pork fat. No significant differences were seen in plasma testosterone concentrations, baculum weight, BMD, and testicular length in the six male dogs (control, n = 3 and exposed, n = 3) measured at 3, 5, 7, 9, and 12 months of age. Testicular weights were significantly lower in the exposed group (p = 0.015, n = 2). Although this study had a limited number of animals, it was observed that in utero and the following 12 months of chronic exposure to a complex mixture of contaminants in the form of naturally accumulated OHCs does not affects testosterone levels, but possibly affects testicular weights in sledge dogs.     

Liver and renal lesions in mercury-contaminated narwhals (Monodon monoceros) from North West Greenland

Narwhals (Monodon monoceros) from North West Greenland are known to bioaccumulate mercury (Hg) in tissues and internal organs. This is postulated to be a health concern and therefore studies were undertaken to conduct a screening study of Hg concentrations and histopathology of liver and renal tissues in a total of 12 specimens. The sample consisted of two sub-adults (one male, one female) and 10 adult (six males, four females) collected in Qaanaaq (Thule) 2010. In liver, Hg mean ± SD was 11.88 ± 10.47 μg/g ww (range: 0.39?31.8 μg/g ww) while the concentrations in kidneys were 1.85 ± 1.20 μg/g ww (range: 0.41?4.03 μg/g ww). There was no marked difference in Hg concentrations between males and females while sub-adults had significantly lower concentrations. The histological examinations of renal tissue showed glomerular capillary dilatation and basement membrane thickening, dilatation, and hyalinization of Bowman's space/capsule and tubular lesions with hyaline casts accompanied by interstitial fibrosis in the kidneys. In liver tissue, portal cell infiltrates and fibrosis, bile duct proliferation, lipid-filled Ito cells, and steatosis were found. There was no marked difference in histological prevalence between males and females and in Hg concentrations in individuals with or without lesions. Four of seven renal lesions and one liver lesion were found in the two sub-adult whales. Based upon these findings, as well as the nature of the lesions, evidence suggests that histopathological alterations were a result of age but that Hg might be an aggravating co-factor in development of renal lesions in particular.