Estimation of southern resident killer whale exposure to exhaust emissions from whale-watching vessels and potential adverse health effects and toxicity thresholds

Southern resident killer whales in British Columbia and Washington are exposed to heavy vessel traffic. This study investigates their exposure to exhaust gases from whale-watching vessels by using a simple dispersion model incorporating data on whale and vessel behavior, atmospheric conditions, and output of airborne pollutants from the whale-watching fleet based on emissions data from regulatory agencies.Our findings suggest that current whale-watching guidelines are usually effective in limiting pollutant exposure to levels at or just below those at which measurable adverse health effects would be expected in killer whales. However, safe pollutant levels are exceeded under worst-case conditions and certain average-case conditions. To reduce killer whale exposure to exhaust we recommend: vessels position on the downwind side of whales, a maximum of 20 whale-watching vessels should be within 800 m at any given time, viewing periods should be limited, and current whale-watch guidelines and laws should be enforced.     

Contaminants in cetaceans from UK waters: status as assessed within the Cetacean Strandings Investigation Programme from 1990 to 2008

Since 1990, tissue samples from UK-stranded and -bycaught cetaceans have been available for study of contaminant burdens. These have been used to study spatial and temporal trends in concentrations in UK waters, and to investigate potential associations between contaminants and health status. We describe the current status of cetaceans (primarily harbour porpoises, Phocoena phocoena) in UK waters in relation to pollution. Concentrations of BDEs, HBCD, and the organochlorine pesticides are declining. In contrast, concentrations of CBs have plateaued following earlier reductions due to regulation of use, and further reductions are likely to take decades. Blubber PCB concentrations are still at toxicologically significant levels in many harbour porpoises and regularly occur at even higher levels in bottlenose dolphins and killer whales due to their higher trophic level in marine food chains. Further reductions in PCB inputs into the marine environment are needed to mitigate risk from PCB exposure in these species.     

Isotopic composition and concentration of Pb in suspended particulate matter of the Irish Sea reveals distribution and sources

The isotopic composition and concentration of Pb was measured in suspended particulate matter of the Irish Sea. Aerosol, surficial and pre-industrial sediment was also analysed to provide information on sources terms. Concentrations of Pb in suspended sediments were lower than previously reported which presumably reflects the international effort to reduce Pb inputs to the environment. Lead concentrations were highest in Liverpool Bay and lowest in the western Irish Sea. A significant negative relationship between Pb and salinity suggests that present inputs and the resuspension of relict lead associated with particles in areas significantly affected by freshwater discharges are the predominant sources of Pb to the Irish Sea. The isotopic composition of Pb in the stratified region of the western Irish Sea demonstrates that atmospheric sources are also significant to this region, which is consistent with current knowledge on the hydrography. Pb isotopic ratios show that water entering the Irish Sea through St George's Channel is significantly influenced by anthropogenic inputs prior to additional contamination by direct inputs to the Irish Sea.     

Dibenzofurans a greater global pollutant than dioxins ? : Evidence from analyses of open ocean killer whale

Three specimens of killer whales (Orcinus orca), an open ocean carnivore, were analysed for extremely toxic polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) to understand their long-range distribution patterns. Several PCDF congeners, including the highly toxic 2,3,7,8-tetra- and 2,3,4,7,8-penta-CDFs were identified in the blubber of those specimens. The PCDF isomeric pattern in killer whale is more complex than the reported patterns in humans and birds, indicating the weaker metabolic potency of killer whales for these toxic compounds. High levels of PCBs (about 400 mg kg⁻¹) have also been detected in those specimens. The 2,3,7,8-substituted PCDF congeners identified in commercial PCBs were also found in killer whale, indicating PCBs as the possible source. Isomer-specific and trace level determinations of PCDD in killer whale, revealed no detectable quantities. The detection of comparatively high levels ( > 300 ng kg⁻¹) of PCDFs and undetection of PCDDs in open ocean killer whales suggest that PCDFs are more ubiquitous than PCDDs.     

Potential eutrophication assessment in rivers; relationship between produced and exported loads

In contrast with biological processes in lacustrine environments, the physical characteristics of river waters greatly complicate the relationship between nutrient input and primary productivity. In this paper a new approach to quantify this relationship is developed, linking land use within the watershed to the bioavailability of nutrients in the receiving waters. It estimates by two different ways an enrichment index derived from N/P ratios. A load model links land-use within the watershed area to nutrient export, and allows the estimation of the potential enrichment index from the ratio of calculated annual exports of nitrogen and phosphorus. This index value correlates well with the real enrichment index representing the annual mean value of the corresponding measured ratios in running waters. The latter index can then be related to nutrient availability expressed by chl-a and the algal growth potential. This model, established from 7 sampling stations on the Yamaska-North river, allowed assessment of nutrient bioavailability in the river water as a function of hydrological (low or high water flow) as well as of seasonal (summer or winter) events.     

Mo marine geochemistry and reconstruction of ancient ocean redox states

Molybdenum(Mo) proxies, including bulk concentration and isotopic composition, have been increasingly used to reconstruct ancient ocean redox states. This study systematically reviews Mo cycles and their accompanying isotopic fractionations in modern ocean as well as their application in paleo-ocean redox reconstruction. Our review indicates that Mo enrichment in sediments mainly records the adsorption of Fe-Mn oxides/hydroxides and chemical bonding of H2 S. Thus, Mo enrichment in anoxic sediments generally reflects the presence of H2 S in the water column or pore waters. In addition to the effect of euxinia, sedimentary Mo enrichment is related to the size of the oceanic Mo reservoir. Given these primary mechanisms for oceanic Mo cycling, Mo abundance data and Mo/TOC ratios acquired from euxinic sediments in geological times show that fluctuations of the oceanic Mo reservoir are well correlated with oxygenation of the atmosphere and oceans and suggest that oxygenation occurred in phases. Mo proxies suggest that Mo isotopes in strongly euxinic sediments reflect the contemporaneous Mo isotopic composition of seawater, but other processes such as iron-manganese(Fe-Mn) adsorption and weak euxinia can result in different fractionations. Diagenesis may complicate Mo enrichment and its isotopic fractionation in sediments. With appropriate constraints on the Mo isotopic composition of seawater and various outputs, a Mo isotope mass-balance model can quantitatively reconstruct global redox conditions over geological history. In summary, Mo proxies can be effectively used to reconstruct oceanic redox conditions on various timescales due to their sensitivity to both local and global marine redox conditions. However, given the complexity of geochemical processes, particularly the effects of diagenesis, further work is required to apply Mo proxies to ancient oceans.     

The origin of ocean island basalt end-member compositions: trace element and isotopic constraints

Ocean island basalt (OIB) suites display a wide diversity of major element, trace element, and isotopic compositions. The incompatible trace element and isotopic ratios of OIB reflect considerable heterogeneity in the mantle source regions. In addition to the distinctive Sr, Nd and Pb isotopic signatures of the HIMU, EMI and EMII OIB end-members, differences in incompatible trace element ratios among these end-members are of great help in identifying the nature and origin of their sources. Examination of trace element and isotopic constraints for the three OIB end-members suggests a relatively simple model for their origin. The dominant component in all OIB is ancient recycled basaltic oceanic crust which has been processed through a subduction zone, and which carries the trace element and isotopic signature of a dehydration residue (enrichment in HFSE relative to LILE and LREE, low Rb/Sr, but high U/Pb and Th/Pb ratios leading to the development of radiogenic Pb isotope compositions). HIMU OIB are derived from such a source, with little contamination from other components. Both the EMI and EMII OIB end-members are also dominantly derived from this source, but they contain significant proportions (up to 5–10%) of sedimentary components derived from the continental crust. In the case of EMI OIB, ancient pelagic sediment with high LILE/HFSE, LREE/HFSE, Ba/Th and Ba/La ratios, and low U/Pb ratios, is the contaminant. EMII OIB are also contaminated by a sedimentary component, in the form of ancient terrigenous sediment with high LILE/HFSE and LREE/HFSE ratios, but lacking relative Ba enrichment, and with higher U/Pb and Rb/Sr ratios. A model whereby the source for all OIB is ancient (1–2 Ga old) subducted oceanic crust ± entrained sediment (pelagic and/or terrigenous) is therefore consistent with the trace element and isotopic data. Although subducted oceanic lithosphere will accumulate and be dominantly concentrated within the mesosphere boundary layer, forming the source for hot-spots, such material may also become convectively dispersed within the depleted upper mantle as blobs or streaks, giving rise to small-scale chemical heterogeneities in the upper mantle.     

Strontium isotopic identification of water-rock interaction and ground water mixing

87Sr/86Sr ratios of ground waters in the Bighorn and Laramie basins' carbonate and carbonate-cemented aquifer systems, Wyoming, United States, reflect the distinctive strontium isotope signatures of the minerals in their respective aquifers. Well water samples from the Madison Aquifer (Bighorn Basin) have strontium isotopic ratios that match their carbonate host rocks. Casper Aquifer ground waters (Laramie Basin) have strontium isotopic ratios that differ from the bulk host rock; however, stepwise leaching of Casper Sandstone indicates that most of the strontium in Casper Aquifer ground waters is acquired from preferential dissolution of carbonate cement. Strontium isotope data from both Bighorn and Laramie basins, along with dye tracing experiments in the Bighorn Basin and tritium data from the Laramie Basin, suggest that waters in carbonate or carbonate-cemented aquifers acquire their strontium isotope composition very quickly--on the order of decades. Strontium isotopes were also used successfully to verify previously identified mixed Redbeds-Casper ground waters in the Laramie Basin. The strontium isotopic compositions of ground waters near Precambrian outcrops also suggest previously unrecognized mixing between Casper and Precambrian aquifers. These results demonstrate the utility of strontium isotopic ratio data in identifying ground water sources and aquifer interactions.     

Severity of killer whale behavioral responses to ship noise: A dose–response study

Critical habitats of at-risk populations of northeast Pacific “resident” killer whales can be heavily trafficked by large ships, with transits occurring on average once every hour in busy shipping lanes. We modeled behavioral responses of killer whales to ship transits during 35 “natural experiments” as a dose–response function of estimated received noise levels in both broadband and audiogram-weighted terms. Interpreting effects is contingent on a subjective and seemingly arbitrary decision about severity threshold indicating a response. Subtle responses were observed around broadband received levels of 130 dB re 1 μPa (rms); more severe responses are hypothesized to occur at received levels beyond 150 dB re 1 μPa, where our study lacked data. Avoidance responses are expected to carry minor energetic costs in terms of increased energy expenditure, but future research must assess the potential for reduced prey acquisition, and potential population consequences, under these noise levels.     

Effects of age, sex and reproductive status on persistent organic pollutant concentrations in “Southern Resident” killer whales

“Southern Resident” killer whales (Orcinus orca) that comprise three fish-eating “pods” (J, K and L) were listed as “endangered” in the US and Canada following a 20% population decline between 1996 and 2001. Blubber biopsy samples from Southern Resident juveniles had statistically higher concentrations of certain persistent organic pollutants than were found for adults. Most Southern Resident killer whales, including the four juveniles, exceeded the health-effects threshold for total PCBs in marine mammal blubber. Maternal transfer of contaminants to the juveniles during rapid development of their biological systems may put these young whales at greater risk than adults for adverse health effects (e.g., immune and endocrine system dysfunction). Pollutant ratios and field observations established that two of the pods (K- and L-pod) travel to California to forage. Nitrogen stable isotope values, supported by field observations, indicated possible changes in the diet of L-pod over the last decade.     

生物壳体锶地球化学恢复盆地古水文——以泥河湾盆地为例

本文以著名的泥河湾盆地小渡口剖面28层为实例,通过有孔虫,介形虫,腹足类微体生物壳体87Sr/86Sr比值与盆地汇水区域Sr同位素地层分布特征对比分析以及生物壳体Sr/Ca国度的相关性,来重塑沉积盆地汇水来源变更,湖水变化等古水文要素,进而可以反演区域构造－气候变化,实例研究结果表明,生物壳体87Cr/86Sr 及Sr/Ca比值等地球化学方法是恢复盆地古水文条件的重要手段。     

Radiocarbon and δ13C Values Related to Ground-Water Recharge and Mixing

Ground-water levels in the Upper Floridan aquifer beneath the southeastern coast of South Carolina have undergone pumpage-induced declines approaching 20 ft below sea level at the southern end of Hilton Head Island. This scenario suggests the potential exists for the inducement of recharge to the Upper Floridan aquifer across the island, which could affect the quality of water being pumped by wells. However, low radiocarbon concentrations in ground-water samples (0.5 to 1.4 ± 0.1 PMC) indicate that most of the water is relict ground water reflecting prepumpage ground-water flow conditions in the Upper Floridan aquifer. The isotopic data indicate long residence times and water-chemistry evolution more characteristic of ground-water recharge occurring farther inland prior to the commencement of pumpage in the late 1800s. Radiocarbon concentrations (as Percent Modern Carbon) and stable carbon isotope ratios (as δ¹³C in dissolved inorganic carbon) determined during this study and reported in other studies on and around Hilton Head Island varied in a systematic manner. Heavier δ¹³C values (–2.8 to –1.6 per mil) in ground water beneath southern Hilton Head Island reflect ground-water discharge from prepumpage flowpaths originating over 100 miles away, hence a depletion in radiocarbon concentration with corrected ground-water ages no younger than 16,000 yrs BP. In contrast, lighter δ¹³C values (–13.9 to –8.67 per mil) beneath the northern part of the island indicate recent recharge as a result of water-level declines, and recharge in areas off the island that have not changed as a result of pumpage (evidenced by enrichment in radiocarbon with corrected ground-water ages no older than 4,000 yrs BP). This suggests that the δ¹³C composition of ground water in the Upper Floridan aquifer is a useful indicator of mixing between ground waters from different sources, and can be used to delineate recharge-discharge patterns. This approach may be applicable to other aquifers of highly evolved ground-water chemistry in regional carbonate aquifer systems that may be receiving recent recharge. Moreover, this approach could prove useful in delineating the contribution of recent water being captured by pumped wells as part of wellhead protection programs designed to assess aquifer vulnerability from surficial contaminant sources.     

D/H and O/O ratios of water in the crater lake at Kusatsu-Shirane volcano, Japan

The D/H and ¹⁸O/¹⁶O ratios of water in the active crater lake situated on the Kusatsu-Shirane volcano, Japan are about 20 and 6‰, respectively, higher than local meteoric water. The ratios show seasonal variations superimposed on a gradual change over nine years. The isotopic ratios started to increase in early 1990 and decrease in the spring of 1995. The seasonal variation which is high in winter and low in summer correlates with the temperature difference between lake water and ambient air. The large temperature difference in winter enhances the evaporation of lake water and produces the enriched isotopic ratios relative to the ratios in summer. The accumulation of snow and the decrease in the flux of meteoric water into the lake strengthens the winter-time isotopic enrichment. The enriched isotopic ratios of the lake water over a long time result from the addition of an end member with heavy isotopic ratios contained in a thermal fluid supplied to the lake. Considering the water balance in the lake, the isotopic ratios of the thermal fluid were found to be close to the lake water itself, suggesting the circulation of the lake water seeping through lake floor. Based on the correlation between Cl⁻concentration and the isotopic ratios, the contribution by the heavy end member was estimated to be 25–36% relative to the enrichment by evaporation. The heavy end member could be a liquid phase evolved from a parental fluid, which is a mixture of local meteoric water and a magmatic fluid as found in high-temperature volcanic gases.     

Spatial and Temporal Gradients of Triazines in the Baltic Sea off Poland

The herbicides atrazine, simazine and terbuthylazine (and the degradation product deethylatrazine) were analysed in two river-to-open-sea transects and two vertical (open-sea) profiles in the southern Baltic off Poland. Samples taken in September 1995 and April 1997 contained total triazine concentrations ranging from 7 to 31 and 4.5 to 13 ng/dm³, respectively. Concentrations of the individual compounds ranged from 0 to 8 ng/dm³. These are generally higher than levels reported, for example, in the North Sea. The largest surface concentrations were found close to the Vistula and Odra river mouths, endorsing river run-off as a primary source of the triazines. Temporal variability can be related to the late-spring and early-summer agricultural applications of the compounds. Variations in ratios between the individual triazines can be explained by usage patterns and differing residence times. Offshore vertical profiles indicate enrichment of the surface layer through atmospheric triazines inputs, highest concentrations above the halocline associated with colloidal organics and lowest concentrations in the bottom waters, probably as a result of particulate scavenging. The influence of the North Sea inflow to the Baltic is also discussed.     

Organohalogen and organotin compounds in killer whales mass-stranded in the Shiretoko Peninsula, Hokkaido, Japan

Blubber and liver samples were obtained for analysis of wide ranges of contaminants from killer whales (Orcinus orca) which were locked away in drifting sea ice on the coast of Rausu, the Shiretoko Peninsula in Eastern Hokkaido, Japan in February 2005. Among the organohalogen compounds analyzed, DDTs were the predominant contaminants with concentrations ranging from 28 to 220 microg/g on a lipid-weight basis followed by PCBs and other organochlorine pesticides. PBDEs levels were two or three orders of magnitude lower than those of PCBs and DDTs. 2,3,7,8-Tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) derived by WHO mammal-TEF in killer whales were in the range of 110-440 pgTEQ/g. Mono-ortho coplanar PCBs contributed to 75-98% of total TEQs, indicating coplanar PCBs are significant contaminants for risk assessment in this species. The fact that hepatic residue levels of butyltins (from 13 to 770 ng/g wet weight) were much higher than those of phenyltins may be reflecting extensive use of tributyltin as antifouling paint.     

Concentrations of PCBs,dieldrin and DDT residues in marine animals from Liverpool Bay

The levels of DDT residues, dieldrin and PCBs have been determined in the tissues of 15 species of marine animals from the Liverpool Bay area of the Irish Sea. In general, the concentrations of these compounds are somewhat lower than those reported earlier for fish from other British inshore areas, despite the fact that the Bay is subject to pollution, not only from the River Mersey, but also from extensive sewage sludge dumping. This difference may reflect recent controls on the use of these compounds.     

Hydrogen and oxygen isotope ratios in the waters of the Ngawha hydrothermal area,North Auckland

The ratios of D/H and O¹⁸/O¹⁶ in natural waters from streams, boreholes, soda springs, hot pools, ponds and larger bodies of water in the Ngawha hydrothermal area were determined. The results are considered in relation to the isotopic changes known to occur in water subjected to evaporation. Where applicable chemical and other work was also considered. It is assumed that stream water isotope composition is the mean value for the isotopic composition of meteoric waters. Measurements on waters taken from boreholes drilled to 65 feet and 350 feet and from the other water sources mentioned, indicate that they were of meteoric origin as judged by stream isotope composition. The waters from the soda springs appeared to be isotopically the same as the stream water, a finding consistent with the absence of evaporative surface. These borehole waters were similar but slightly different in O¹⁸ due probably to exchange between rock and water. Heavy isotope enrichment of the ponds and larger bodies of water appeared to be due to non-equilibrium evaporation at ambient temperature. The hot pools in the Ngawha springs area proper were enriched in the heavier isotopes probably due to non-equilibrium evaporation at the usual hot pool temperature of about 40°C and also to exchange of O¹⁸ between water and rock. The water from a further borehole drilled to approximately 2,000 feet appeared also to be of meteoric origin but was changed in O¹⁸ content to an extent consistent with the assumption that oxygen isotope exchange with rock had taken place at approximately 230°C. The results are used to illustrate possibilities for the use of oxygen and hydrogen isotope measurements in hydrothermal investigations.     

The significance of imposex levels and TBT contamination in the red whelk, Neptunea antiqua (L.) from the offshore Irish Sea

The extent to which open seas and oceanic waters have been contaminated by TBT is unclear since most sampling programmes have concentrated on inshore areas, particularly near harbours. Accordingly, the red whelk, Neptunea antiqua L. (Mollusca: Prosobranchia), a sublittoral and dioecious prosobranch species, was selected to investigate the potential effects of TBT-induced imposex in the central western Irish Sea. The presence of imposex was noted in > 90% of all female whelks that were examined on a monthly basis over a 12-month period. However, the proliferation of the vas deferens was not considered severe enough to affect the reproductive capabilities of the population. Low concentrations of butyltins were detected in the soft tissues of all whelks examined, ranging from 0.009 to 0.112 microg g(-1) Sn dry wt There was no significant correlation between the documented imposex stages and total butyltin contamination, indicating that the species is not a reliable bioindicator species of the effects of this contaminant.     

D/H ratios in speleothem fluid inclusions: A guide to variations in the isotopic composition of meteoric precipitation?

D/H ratios of fluid inclusion waters extracted from²³⁰Th/²³⁴U-dated speleothems that were originally deposited under conditions of isotopic equilibrium should provide a direct estimate of the hydrogen isotopic composition of ancient meteoric waters. We present here D/H ratios for 47 fluid inclusion samples from thirteen speleothems deposited over the past 250,000 years at cave sites in Iowa, West Virginia, Kentucky and Missouri. At each site glacial-age waters are depleted in deuterium relative to those of interglacial age. The average interglacial/glacial shift in the hydrogen isotopic composition of meteoric precipitation over ice-free areas of east-central North America is estimated to be ?12‰. This shift is consistent with the present climatic models and can be explained in terms of the prevailing pattern of atmospheric circulation and an increased ocean-continent temperature gradient during glacial times which more than compensated for the increase in deuterium content of the world ocean.     

Particulate aluminium, iron and manganese chemistry at the deep Atlantic boundary layer

Scanning electron microscopy and instrumental neutron activation analyses of filtered suspended matter from the Atlantic Ocean show that particulate aluminium (Al_p) is a sensitive measure of bottom derived or resuspended material. The proportion of Al_p in suspended particulate matter (SPM) increases slightly between surface and intermediate depths but shows large and steady increases in deep waters with approach to the bottom.

Fe_p/Al_p andMn_p/Al_p ratios are always higher than the crustal ratios throughout the water column. We show that the processes which can explain such enrichments are different for particulate matter in surface waters (scavenging, incorporation in biogenic particles) than for resuspended material (precipitation from interstitial waters on surficial sediments).

Close to the Mid-Atlantic Ridge, the bottom suspended matter exhibits higher Fe_p/Al_p andMn_p/Al_p ratios than in abyssal plains. A ridge crest source must be invoked to explain the striking enrichment of Mn_p. This source could also explain the enrichment of Fe_p, although primarily because the resuspended flux is small in that region, one cannot exclude the contribution of particles from the mid-water column.