Concentrations and patterns of organic contaminants in Atlantic white-sided dolphins (Lagenorhynchus acutus) from Irish and Scottish coastal waters

Chlorobiphenyls (CBs) and organochlorine pesticides (OCPs) have been determined in the blubber of 17 Atlantic white-sided dolphins stranded at Killala Bay, Co Mayo, Ireland and five from the Scottish coast. The concentrations of the contaminants measured range from 773 to 63,400 microg kg(-1) for sigmaCB and from 160 to 54,600 microg kg(-1) for sigmaDDT. The concentrations of the CBs and OCPs is highly dependent on the age, sex, reproductive state and nutritional condition of the animals in addition to the intake via the food web. Principal Components Analysis (PCA) has been used to study the variation of chemical patterns (data ratioed to CB 153). Immature animals (< 6 years), mature males and primogravid females, and lactating females could be distinguished on the basis of their contaminant patterns. This paper describes the different processes of bioaccumulation and metabolism of organochlorine contaminants (OCs) in this species.     

Organochlorine compounds in common dolphins (Delphinus delphis) from the Atlantic and Mediterranean waters of Spain

Blubber of free-ranging common dolphins (Delphinus delphis) from the northwestern coast of Spain (Atlantic), sampled in 1984 and 1996, and of common dolphins entangled in fishing nets in the southwestern Mediterranean, sampled during 1992 1994, was analysed for organochlorine pollutants. In the Atlantic, concentration of all pollutants was significantly higher in males than in females. The overall tPCB/tDDT ratio in this area was 3.35, which indicates a predominance of industrial inputs over those associated with agriculture. Individuals sampled in 1996 showed significantly lower DDT concentrations but a higher ppDDE/tDDT ratio than those sampled in 1984, which reflects the aging of the environmental load. In the same period, tPCB concentration remained constant and, as a consequence, the tPCB/tDDT ratio more than doubled. In the Mediterranean, the reduced sample size of adult individuals precluded proper statistical investigation of sex-related variation. The overall tPCB/tDDT ratio was 1.12, suggesting a higher contribution of pollutants of agricultural origin. Individuals had significantly higher levels of all DDT forms and a higher ppDDE/tDDT ratio than their counterparts from the Atlantic, but similar PCB concentrations. However, the relative frequency of the different congeners in relation to the total PCB load was different in the two areas. This indicates that the two populations do not mix, at least in the short- or medium-term. Organochlorine levels in both areas are at the mid to low end of the range of concentrations detected in other common dolphin populations and in that of other Delphinidae species from the same region. Although the impact of the organochlorine concentrations on the common dolphin populations surveyed cannot be assessed, it is considered unlikely that they have played a significant role in the decline that the species has suffered in recent decades in the western Mediterranean.     

Trace elements in striped dolphins (Stenella coeruleoalba) from the western Mediterranean

Tissues obtained from Stenella coeruleoalba stranded along the Spanish and Italian Mediterranean coasts from 1987 to 1994 were analysed for cadmium (Cd), copper (Cu), mercury (Hg), selenium (Se) and zinc (Zn). The age, length and weight of the dolphins were recorded. Hg levels were also assayed in skin biopsies from dolphins of the same species in the waters off northeastern Spain and in the Tyrrhenian and Ligurian Seas. Levels of all elements differed in muscle of stranded dolphins from the two areas. Hg was higher in tissues from animals stranded on the Italian coasts and in skin biopsies obtained in the Tyrrhenian and Ligurian Seas, than in the respective Spanish samples. This is probably related to Hg pollution from the natural weathering of cinnabar ores in central Italy. Se and Cd levels had similar accumulation patterns to those of Hg. Accumulation of Hg and Se is explained by the existence of a detoxification pathway involving both elements, however the reason for the similar Cd trend is unclear. Geographical differences in the accumulation pattern of these elements may reflect the existence of two different populations of Stenella coeruleoalba in the western Mediterranean.     

Toxaphene in minke whales (Balaenoptera acutorostrata) from the North Atlantic

Toxaphene contamination of minke whales (Balaenoptera acutorostrata) from North Atlantic waters was examined for the first time. Total toxaphene and SigmaCHB (sum of 11 chlorobornanes) concentrations in blubber samples ranged from 170+/-110 and 41+/-39 ng/g lipid weight (l.w.) for female minke whales from southeastern Greenland to 5800+/-4100 and 1100+/-780 ng/g l.w. for males from the North Sea, respectively. Very large variations in toxaphene concentrations among sampling areas were observed suggesting a spatial segregation of minke whales. However, much of the apparent geographical discrimination was explained by the seasonal fluctuation of animal fat mass. Patterns of CHBs in males revealed that recalcitrant CHBs were in higher proportions in animals from the more easterly areas than in animals from the more westerly areas. This trend may be influenced by the predominance of the US, over the European, input of toxaphene to North Atlantic waters.     

Organohalogen compounds and their metabolites in the blood of Japanese amberjack (Seriola quinqueradiata) and scalloped hammerhead shark (Sphyrna lewini) from Japanese coastal waters

Information on accumulation of polychlorinated biphenyl metabolites (OH-PCBs) and hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in the blood of marine fish is limited. The present study, we determined the residue levels and patterns of PCBs, OH-PCBs, PBDEs, OH-PBDEs and methoxylated PBDEs (MeO-PBDEs) in the blood collected from scalloped hammerhead shark (Sphyrna lewini) and Japanese amberjack (Seriola quinqueradiata), species of predatory fish at Japanese coastal waters. The predominant homologues found in Japanese amberjacks were mono- and di-chlorinated OH-PCBs, and scalloped hammerhead sharks were octa-chlorinated OH-PCBs. The predominant OH-PCB isomers were lower-chlorinated OH-PCBs such as 6OH-CB2 and 2'OH-CB9 in Japanese amberjacks. This result suggests that exposure of Japanese amberjacks to lower-chlorinated OH-PCBs might be from the ambient aquatic environment. In scalloped hammerhead sharks, 4,4'diOH-CB202, 4OH-CB201 and 4OH-CB146 were the predominant isomers accounting for approximately 60% of the total OH-PCBs. The predominant MeO-PBDE isomers were 6MeO-BDE47 followed by 2'MeO-BDE68 in both species. As for OH-PBDE isomers, 6OH-BDE47 was predominant followed by 2'OH-BDE68 in Japanese amberjacks and scalloped hammerhead sharks. Residue levels of ΣMeO-PBDEs and ΣOH-PBDEs showed a significant positive correlation (p=0.029). This result suggests that MeO-PBDEs and OH-PBDEs share a common source or a metabolic pathway in fishes. Characteristic differences found in the profiles of OH-PCBs and OH-PBDEs in Japanese amberjack and scalloped hammerhead shark show the need for further studies on the differences in exposure profiles, metabolic capacities and toxic effects in fish.     

In situ measurement of isoprene in the marine air and surface seawater from the western North Pacific

Isoprene (2-methyl-1,3-butadiene) was measured on board of R/V Mirai for eight air samples and 14 seawater samples collected in the western North Pacific during ACE-Asia campaign (from 18 to 26 May 2001). The measurements were conducted in situ using a cryo-focus/gas chromatography/mass spectrometry (Cryo/GC/MS). Concentrations of isoprene ranged from 7.2 to 110 parts-per-trillion (pptv) in the marine air, and ranged from below 12 to 94 pmol l⁻¹ in the seawater. Based on these results, sea-to-air fluxes of isoprene were calculated to be 184 and 300 nmol m⁻² day⁻¹ for two samples, and the upper limits of the fluxes were also calculated to be from 32 to 300 nmol m⁻² day⁻¹. Atmospheric isoprene concentrations cannot be explained only by the flux from the seawater. Thus, the concentrations of isoprene in the marine air in western North Pacific should be significantly affected by terrestrial vegetational emission and subsequent long-range atmospheric transport of isoprene.     

Organohalogen pollutants in herring from the northern Baltic Sea: concentrations, congener profiles and explanatory factors

Organohalogen contaminants were investigated in Baltic herring caught from three catchment areas in the Baltic Sea, off the coasts of Finland. Pools of both small and large herring were analysed for polychlorinated biphenyls (PCB), dibenzo-p-dioxins, dibenzofurans, naphthalenes, camphenes (toxaphene), polybrominated diphenyl ethers and the pesticide DDT and its metabolites. PCB concentrations per fresh weight in small herring were at the same level in all catchment areas, i.e. the Bothnian Bay, the Bothnian Sea and the Gulf of Finland, revealing no hot spots and reflecting most likely long term emissions and atmospheric deposition. Differences in the levels and/or congener profiles of other contaminants between catchment areas may be explained by point sources. Similar concentrations in small and large herring in the Gulf of Finland were possibly due to their common nutrition. In the other areas, differences between small and large herring most likely reflected their different food sources.     

Understanding the contributions of anthropogenic and biogenic sources to CO enhancements and outflow observed over North America and the western Atlantic Ocean by TES and MOPITT

We investigate the effects of anthropogenic and biogenic sources on tropospheric CO enhancements and outflow over North America and the Atlantic during July–August 2006, the 3rd warmest summer on record. The analysis is performed using the 3D Regional chEmical trAnsport Model (REAM), satellite data from TES on the Aura satellite, MOPITT on the Terra satellite and surface monitor data from the SEARCH network. The satellite measurements of CO provide insight into the location of regional CO enhancements along with the ability to resolve vertical features. Satellite and surface monitor data are used to compare with REAM, illustrating model's ability to reproduce observed CO concentrations. The REAM model used in this study features CO emissions reduced by 50% from the 1999 EPA NEI and biogenic VOC emissions scaled by EPA-observed isoprene concentrations (20% reduction). The REAM simulations show large variations in surface CO, lower tropospheric CO and column CO, which are also observed by the surface observations and satellite data. Over the US, during July–August 2006, the model estimates monthly CO production from anthropogenic sources (5.3 and 5.1 Tg CO) is generally larger than biogenic sources (4.3 and 3.5 Tg CO). However, the model shows that for very warm days, biogenic sources produce as much CO as anthropogenic sources, a result of increased biogenic production due to warmer temperatures. The satellite data show CO outflow occurs along the East Coast of the US and Canada in July and is more broadly distributed over the Atlantic in August. REAM results show the longitudinally exported CO enhancements from anthropogenic sources (3.3 and 3.9 Tg CO) are larger than biogenic sources (2.8 and 2.7 Tg CO) along the eastern boundary of REAM for July–August 2006. We show that when compared with the impacts of both sources on increasing tropospheric CO exports, the relative impacts in August are greater than in July because of preferable outflow transport.     

Bioaccumulation of persistent organic pollutants in female common dolphins (Delphinus delphis) and harbour porpoises (Phocoena phocoena) from western European seas: geographical trends, causal factors and effects on reproduction and mortality

Concentrations of polychlorinated biphenyls (PCBs) in blubber of female common dolphins and harbour porpoises from the Atlantic coast of Europe were frequently above the threshold at which effects on reproduction could be expected, in 40% and 47% of cases respectively. This rose to 74% for porpoises from the southern North Sea. PCB concentrations were also high in southern North Sea fish. The average pregnancy rate recorded in porpoises (42%) in the study area was lower than in the western Atlantic but that in common dolphins (25%) was similar to that of the western Atlantic population. Porpoises that died from disease or parasitic infection had higher concentrations of persistent organic pollutants (POPs) than animals dying from other causes. Few of the common dolphins sampled had died from disease or parasitic infection. POP profiles in common dolphin blubber were related to individual feeding history while those in porpoises were more strongly related to condition.     

Levels and patterns of persistent organochlorines in minke whale (Balaenoptera acutorostrata) stocks from the North Atlantic and European Arctic

Regional variation in PCBs and organochlorine (OC) pesticide concentrations was examined using the blubber of 155 minke whales (Balaenoptera acutorostrata) sampled in seven regions in the North Atlantic and European Arctic, including western and southeastern Greenland, the Norwegian Sea, the North Sea and the Barents Sea. The levels and relative proportions of OCs were also used to examine the boundaries for North Atlantic minke whale stocks previously defined by the International Whaling Commission (IWC). Concentrations of major OC groups (sigmaPCB, 89.1-22 800 ng/g lipid; sigmaDDT, 65.3-6280 ng/g lipid; sigmaCHL, 33.3-2110 ng/g lipid) generally increased from west to east, while HCH concentrations (sigmaHCH, < 1-497 ng/g lipid) showed the opposite trend. Statistical comparison between six regions using sex-adjusted least squared mean concentrations showed that minke whales from the Barents Sea had significantly higher concentrations of EPCBs than those from the Vestfjorden/Lofoten, the North Sea, and west Svalbard, as well as significantly higher sigmaDDT concentrations compared to west Greenland animals. The differences in concentrations suggest that west and southeast Greenland minkes may represent one group of whales, which are distinct from both the Jan Mayen minkes and those from other IWC defined stocks in northern European waters. Principal components analysis using proportions of 71 PCB congeners and 20 OC pesticides (of total OCs) did not reveal any major differences among groups although minkes from the North Sea were distinguished from those from Greenland waters by higher loadings of more highly chlorinated PCBs and recalcitrant OC pesticides. The general similarity in mean levels of sigmaPCBs, sigmaDDT and sigmaCHL, as well as mean principal components analysis scores, among minkes sampled at Jan Mayen, Svalbard, Vestfjorden/Lofoten, the North Sea and the Barents Sea suggests that the whales are quite mobile and may feed in multiple areas within the northeastern Atlantic.     

Status and trends of terrestrial arthropod abundance and diversity in the North Atlantic region of the Arctic

Ambio - The Circumpolar Biodiversity Monitoring Programme (CBMP) provides an opportunity to improve our knowledge of Arctic arthropod diversity, but initial baseline studies are required to...     

Sources and mass fluxes of the main contaminants in a heavily polluted and modified river of the North China Plain

Many rivers in China and other newly industrialized countries have suffered from severe degradation of water quality in the context of rapid economic growth. An accounting method was developed to investigate the source and mass fluxes of the main contaminants in the Ziya River, a severely polluted and heavily modified river in a semiarid area of the North China Plain, where chemical oxygen demand (COD) and ammonia nitrogen (NH₄-N) were the most important indicators of pollution. The results showed that the urban sewage with high concentration of COD and NH₄-N dominated the streams, contributing to 80.7 % of the streamflow, 92.2 % of COD, and 94.5 % of NH₄-N. The concentrations of COD and NH₄-N in streams varied from 24.0–195.0 to 5.8–43.8 mg/L, respectively. Mass fluxes of COD and NH₄-N of all pathways were quantified. Much of the polluted water was diverted to irrigation, and some eventually flowed into the Bohai Sea. Installation of adequate wastewater treatment facilities and making strict discharge standards can help improve the water quality. Our findings imply that a simple accounting method provides an extremely well-documented example for load estimation and can be useful for intervention strategies in heavily polluted and modified rivers in newly industrialized countries.     

Organohalogen contamination in breeding glaucous gulls from the Norwegian Arctic: associations with basal metabolism and circulating thyroid hormones

Exposure to organohalogens in endotherms has been suggested to impose chemically induced stress by affecting functions related to maintenance energy requirements. Effects on basal metabolic rate (BMR) have been suggested to be, in part, mediated through interactions with the thyroid hormones (THs). We investigated the relationships between plasma concentrations of major organochlorines, PBDEs, hydroxylated (OH)- and methoxylated (MeO)-PBDEs and OH-PCBs, circulating TH levels and BMR in breeding glaucous gulls (Larus hyperboreus) from the Norwegian Arctic. Negative associations were found between BMR and concentrations of sigma PCB, Sigma DDT and particularly Sigma chlordane, which combined made up 91% of the total contaminant burden. Levels of THs (thyroxine and triiodothyronine) were not associated significantly with variation of BMR or concentrations of any of the compounds determined. The present study suggests that BMR may be altered in glaucous gulls exposed to high loadings of persistent contaminants in the Norwegian Arctic environment.     

Enhanced ozone over western North America from biomass burning in Eurasia during April 2008 as seen in surface and profile observations

During April 2008, as part of the International Polar Year (IPY), a number of ground-based and aircraft campaigns were carried out in the North American Arctic region (e.g., ARCTAS, ARCPAC). The widespread presence during this period of biomass burning effluent, both gaseous and particulate, has been reported. Unusually high ozone readings for this time of year were recorded at surface ozone monitoring sites from northern Alaska to northern California. At Barrow, Alaska, the northernmost point in the United States, the highest April ozone readings recorded at the surface (hourly average values >55 ppbv) in 37 years of observation were measured on April 19, 2008. At Denali National Park in central Alaska, an hourly average of 79 ppbv was recorded during an 8-h period in which the average was over 75 ppbv, exceeding the ozone ambient air quality standard threshold value in the U.S. Elevated ozone (>60 ppbv) persisted almost continuously from April 19–23 at the monitoring site during this event. At a coastal site in northern California (Trinidad Head), hourly ozone readings were >50 ppbv almost continuously for a 35-h period from April 18–20. At several sites in northern California, located to the east of Trinidad Head, numerous occurrences of ozone readings exceeding 60 ppbv were recorded during April 2008. Ozone profiles from an extensive series of balloon soundings showed lower tropospheric features at ～1–6 km with enhanced ozone during the times of elevated ozone amounts at surface sites in western Canada and the U.S. Based on extensive trajectory calculations, biomass burning in regions of southern Russia was identified as the likely source of the observed ozone enhancements. Ancillary measurements of atmospheric constituents and optical properties (aerosol optical thickness) supported the presence of a burning plume at several locations. At two coastal sites (Trinidad Head and Vancouver Island), profiles of a large suite of gases were measured from airborne flask samples taken during probable encounters with burning plumes. These profiles aided in characterizing the vertical thickness of the plumes, as well as confirming that the plumes reaching the west coast of North America were associated with biomass burning events.     

Coarse particulate matter concentrations from residential outdoor sites associated with the North Carolina Asthma and Children's Environment Studies (NC-ACES)

Coarse particulate matter (PM${}_{10\text{-}2.5})$ concentration data from residential outdoor sites were collected using portable samplers as part of an exposure assessment for the North Carolina Asthma and Children's Environment Studies (NC-ACES). PM${}_{10\text{-}2.5}$ values were estimated using the differential between independent PM${}_{10}$ and PM${}_{2.5}$ collocated MiniVol measurements. Repeated daily 24-h integrated PM${}_{10}$ and PM${}_{2.5}$ residential outdoor monitoring was performed at a total of 26 homes during September 2003–June 2004 in the Research Triangle Park, NC area. This effort resulted in the collection of 73 total daily measurements. This assessment was conducted to provide data needed to investigate the association of exposures to coarse particle PM mass concentrations with observed human health effects. Potential instrument bias between the differential MiniVol methodology and a dichotomous sampler were investigated. Results indicated that minimal bias of PM${}_{10\text{-}2.5}$ mass concentration estimates (slope $=$ 0.8, intercept $=0.36\mathrm{\mu }$g m${}^{-3})$ existed between the dichotomous and differential MiniVol procedures. Residential outdoor PM${}_{10\text{-}2.5}$ mass concentrations were observed to be highly variable across measurement days and ranged from 1.1 to $12.6\mathrm{\mu }$g m${}^{-3}$ (mean of $5.4\mathrm{\mu }$g m${}^{-3})$. An average correlation coefficient of $r=0.75$ existed between residential outdoor PM${}_{10\text{-}2.5}$ mass concentrations and those obtained from the central ambient monitoring site. Temporal and spatial variability of PM${}_{10\text{-}2.5}$ mass concentrations during the study were observed and are described in this report.     

Organohalogen compounds in human breast milk from mothers living in Payatas and Malate, the Philippines: Levels, accumulation kinetics and infant health risk

Human breast milk samples (n = 33) from primipara and multipara mothers from Payatas a waste dump site, and Malate a reference site in the Phillipines were collected in 2004 and analyzed for eight organohalogen compounds, viz., PCBs, DDTs, CHLs, HCHs, HCB, TCPMe, PBDEs and HBCDs. DDTs and PCBs were predominant in all the samples. Overall mean concentrations of PBDEs found in our study were higher (7.5 ng/g lipid wt.) than those reported for Japan and many other Asian countries. Primipara mothers had significantly higher levels of DDTs, CHLs and HCHs than multipara mothers, but not PBDEs and HBCDs. A few individuals accumulated CHLs close to or even higher than the tolerable daily intake guidelines proposed by Health Canada.     

Organochlorinated contaminants in decapod crustaceans from the coasts of Brittany and Normandy (France)

The contamination and distribution of organochlorinated compounds were considered in three crustacean species (edible crab, Cancer pagurus; spider crab, Maja brachydactyla; velvet swimming crab, Necora puber) from five sites along the coasts of Brittany and Normandy (Western and North-Western France). PCBs (16 single congeners), pp'-DDE and HCB were measured in hepatopancreas, gonads and muscle: in all, 175 samples were analysed. The spider crab was the only species found in the five sampling sites, thus enabling comparison between areas. Specimens from Antifer were much more contaminated (summation operator 16 PCBs in hepatopancreas=2000-4000 ng g(-1) dry weight) than those from other sites (50-1000 ng g(-1) d.w.). Among all the three species, the spider crab appeared more contaminated by PCBs than the edible crab, by a factor 2-3, probably in relation with specific differences in their life cycle. There was no difference due to the gender of the species. Within the different analysed tissues, contamination levels increased from muscle to gonads and hepatopancreas in relation with the fat content. A very similar PCB composition was observed in all samples, PCB fingerprints being characterised by the relative importance of the more persistent PCB congeners: CB153, 138, 180, 187, and 118. Finally, these results were compared to recent food regulations first of maximum marker PCB intake and secondly of maximum dioxin-like PCB intake. By considering the muscle, all samples were far below the regulatory limits; for hepatopancreas and gonads, however, some samples were unfit for human consumption.     

Seasonal variation of levoglucosan in aerosols over the western North Pacific and its assessment as a biomass-burning tracer

Levoglucosan is considered as a useful molecular tracer of biomass-burning aerosols in the atmosphere. To characterize the seasonal variation of its concentrations over the Pacific Ocean and to assess its usefulness as a tracer after long-range transport, we investigated long-term variations of levoglucosan over Chichi-jima in the western North Pacific, from 2001 to 2004. Organic carbon (OC), elemental carbon (EC) and d-glucose were analyzed for comparison. The seasonal variation of levoglucosan concentrations showed a maximum in the winter, which is consistent with the enhanced Asian outflow to the Pacific indicated by backward air-mass trajectories. The concentration levels of levoglucosan estimated from global aerosol model outputs in the winter are, on average, comparable to the observed levels, suggesting that a considerable fraction of levoglucosan did not decompose during long-range transport from the Asian continent by westerly/northwesterly winds. This result is supported by comparable ratios of levoglucosan to EC in Chichi-jima and the East Asian coastal region. Conversely, the measured concentrations of levoglucosan in the summer were significantly lower than the modeled one. This implies a degradation of levoglucosan in the air masses that stagnated over the Pacific, although uncertainties in the model estimate may also be partly responsible for this discrepancy. One possible degradation pathway is oxidation by OH radicals; the contribution of acid-catalyzed reactions needs further investigation.     

Carbonyl sulphide in and over seawater: summer data from the northeast Atlantic Ocean

Carbonyl sulphide (COS) concentrations in air and dissolved in seawater were determined during a cruise in summer 1997 in the northeast Atlantic Ocean. Seawater characteristics and meteorological parameters were monitored. Dissolved COS concentrations throughout the entire cruise exhibited a strong diel cycle with maximum concentrations in late afternoon and minimum concentrations at sunrise. This is in good agreement with the theory that COS is photochemically produced from dissolved organic matter during the day and removed by hydrolysis. The overall mean concentration of dissolved COS was 23.6 pmol dm^-3; the daily mean varied according to water mass characteristics and was highest in upwelling areas owing to increased dissolved organic matter. Atmospheric COS concentrations, varying from about 450 to 800 pptv with an average value of 657 pptv, showed some dependency on air mass history and local COS flux from the sea surface. The exchange of COS between the ocean and the atmosphere depended on dissolved COS concentrations and wind speed. The daily integrated flux was always from the sea into the air, and the average was 1.3±0.8 g COS km^-2 d^-2. The collected data were used to test a mixed layer box model and a one-dimensional model, both describing the behaviour of COS in seawater. We found that the one-dimensional model simulates the data more closely, especially during the night.