Persistent organic pollutants and stable isotopes in biopsy samples (2004/2006) from Southern Resident killer whales

“Southern Resident” killer whales include three “pods” (J, K and L) that reside primarily in Puget Sound/Georgia Basin during the spring, summer and fall. This population was listed as “endangered” in the US and Canada following a 20% decline between 1996 and 2001. The current study, using blubber/epidermis biopsy samples, contributes contemporary information about potential factors (i.e., levels of pollutants or changes in diet) that could adversely affect Southern Residents. Carbon and nitrogen stable isotopes indicated J- and L-pod consumed prey from similar trophic levels in 2004/2006 and also showed no evidence for a large shift in the trophic level of prey consumed by L-pod between 1996 and 2004/2006. ∑PCBs decreased for Southern Residents biopsied in 2004/2006 compared to 1993–1995. Surprisingly, however, a three-year-old male whale (J39) had the highest concentrations of ∑PBDEs, ∑HCHs and HCB. POP ratio differences between J- and L-pod suggested that they occupy different ranges in winter.     

Biological influences on modern sulfates: Textures and composition of gypsum deposits from Guerrero Negro,Baja California Sur,Mexico

Gypsum (CaSO₄·2H₂O) deposits from a range of sedimentary environments at Guerrero Negro, Baja California Sur, Mexico were investigated for microscale texture and composition in order to differentiate features formed under substantial microbial influence from those for which microbial effects were relatively minor or absent. Gypsum deposits were classified according to their sedimentary environment, textures, crystal habit, brine composition and other geochemical factors. The environments studied included subaqueous sediments in anchialine pools and in solar salterns, as well as subsurface sediments of mudflats and saltpans. Gypsum that developed in the apparent absence of biofilms included crystals precipitated in the water column and subsedimentary discs that precipitated from phreatic brines. Subsedimentary gypsum developed in sabkha environments exhibited a sinuous microtexture and poikilitically enclosed detrital particles. Water column precipitates had euhedral prismatic habits and extensive penetrative twinning. Gypsum deposits influenced by biofilms included bottom nucleated crusts and gypsolites developing in anchialine pools and saltern ponds. Gypsum precipitating within benthic biofilms, and in biofilms within subaerial sediment surfaces provided compelling evidence of biological influences on crystal textures and habits. This evidence included irregular, high relief surface textures, accessory minerals (S°, Ca-carbonate, Sr/Ca-sulfate and Mg-hydroxide) and distinctive crystal habits such as equant forms and crystals having distorted prism faces.     

Sampling and Characterizing Rare Earth Elements in Groundwater in Deep-Lying Fractures in Granitoids Under In Situ High-Pressure and Low-Redox Conditions

Several countries are preparing to dispose of radioactive nuclear waste deep underground in crystalline rock. This type of bedrock is commonly extensively fractured and consequently carries groundwater that serves as a medium for transporting metals and radionuclides. A group of metals of particular interest in this context is the rare earth elements (REEs), because they are analogues of actinides contained within radioactive waste and are tracers of hydrological pathways and geochemical processes. Concentrations of REEs are commonly low in these groundwaters, leading to values below detection limits of standard monitoring methods, particularly for the heavy REEs. We present a new technical set-up for monitoring REEs (and other trace metals) in groundwater in fractured crystalline rock. The technique consists of passing the fracture groundwater, commonly under high pressure and containing reduced chemical species, through a device that maintains the physicochemical character of the groundwater. Within the device, diffusive gradient in thin-film (DGT) discs are installed in triplicate. With this set-up, we studied REEs in groundwater in fractures at depths of approximately ?144, ?280, and ?450 m in granitoids in the Äspö Hard Rock Laboratory in southern Sweden. The entire REE suite was detected (concentrations down to 0.1 ng L^?1) and was differently fractionated among the groundwaters. The shallowest groundwater, composed of dilute modern Baltic Sea water, was enriched in the heavy REEs, whereas the deeper groundwaters, dominated by old saline water, were depleted in the heavy REEs. Deployment periods varying from 1 to 4 weeks delivered similar REE concentrations, indicating stability and reproducibility of the experimental set-up. The study finds that 1 week of deployment may be enough. However, if the overall setting and construction allow for longer deployment times, 2–3 weeks will be optimal in terms of reaching reliable REE concentrations well above the detection limit while maintaining the performance of the DGT samplers.     

Effects of carbon dioxide on deep-sea harpacticoids revisited

As part of the evaluation of the environmental impact of sequestering carbon dioxide in the deep ocean, we exposed the sediment-dwelling fauna at a station in Monterey Submarine Canyon (36.378°N, 122.676°W, 3262 m) to carbon dioxide-rich seawater and found that most of the harpacticoid copepods were killed. In an expanded, follow-on experiment on the continental rise nearby (36.709°N, 123.523°W, 3607 m), not only did harpacticoids survive exposure to carbon dioxide-rich seawater, but we found no evidence from seven additional metrics that the harpacticoids had been affected. We infer that during the second experiment the harpacticoids were not exposed to a stressful dose. During the second experiment, carbon dioxide-rich seawater appears to have been produced more slowly than in the first, probably because of differences in the near-bottom flow regimes. We conclude that local physical circumstances can substantially influence the results of experiments of this type and will complicate the evaluation of the environmental consequences of deep-ocean carbon dioxide sequestration.     

Preparation and Measurement of Cassiterite for Sn Isotope Analysis

Increased interest in the fractionation of Sn isotopes has led to the development of several techniques for preparing cassiterite (SnO₂, the primary ore of Sn) for isotopic analysis. Two distinct methods have been applied in recent isotopic studies of cassiterite: (a) reduction to tin metal with potassium cyanide (KCN) at high temperature (800 °C), with subsequent dissolution in HCl, and (b) reduction to a Sn solution with hydriodic acid (HI) at low temperature (100 °C). This study compares the effectiveness and accuracy of these two methods and contributes additional methodological details. The KCN method consistently yielded more Sn (> 70% in comparison with < 5%), does not appear to fractionate Sn isotopes at high temperatures over a 2‐hour period and produced consistent Sn isotope values at flux mass ratios of ≥ 4:1 (flux to mineral) with a minimum reduction time of 40 min. By means of a distillation experiment, it was demonstrated that HI could volatilise Sn, explaining the consistently low yields by this method. Furthermore, the distillation generated Sn vapour, which is up to 0.38‰ per mass unit different from the starting material, the largest induced Sn fractionation reported to date. Accordingly, the HI method is not recommended for cassiterite preparation for Sn isotopic analysis.     

Using computational intelligence techniques to model subglacial water systems

Measurements of water pressure beneath Trapridge Glacier, Yukon Territory, Canada show that the basal water system is highly heterogeneous. Three types of behaviour were recorded: pressure records which are strongly correlated, records which are strongly anticorrelated, and records which alternate between strong correlation and strong anticorrelation. We take the pressure in bore-holes that are connected to the evacuation route for basal water as the forcing, and the other pressures as the response to this forcing. Previous work (Murray and Clarke 1995) has shown that these relationships can be modelled using low-order nonlinear differential equations optimized by inversion. However, despite optimizing the model parameters we cannot be sure that the final model forms are themselves optimal. Computational intelligence techniques provide alternative methods for fitting models and are robust to missing or noisy data, applicable to non-smooth models, and attempt to derive optimal model forms as well as optimal model parameters. Four computational intelligence techniques have been used and the results compared with the more conventional mathematical model. These methods were genetic programming, artificial neural networks, fuzzy logic and self-organizing maps. We compare each technique and offer an evaluation of their suitability for modelling the pressure data. The evaluation criteria are threefold: (1) goodness of fit and an ability to predict subsequent data under different surface weather conditions; (2) interpretability, and the extent and significance of any new insights offered into the physics of the glacier; (3) computation time. The results suggest that the suitability of the computational intelligence techniques to model these data increases with the complexity of the system to be modelled.     

A strong temperature effect on U/Ca in planktonic foraminiferal carbonates

Three planktonic foraminiferal species Globigerina bulloides, Neogloboquadrina pachyderma (d), and Globorotalia inflata collected from core-tops spanning 35° to 65°N in the North Atlantic were used for U/Ca and Mg/Ca and foraminiferal shell weight analyses. Except for U/Ca in G. bulloides calcified under warm conditions (>∼13 °C), U/Ca ratios in all three studied species increase with decreasing latitude and show strong positive correlations with Mg/Ca ratios. A dissolution effect on planktonic U/Ca is suggested by decreased shell weight and U/Ca and Mg/Ca ratios for shells from very deep water depth (>4.4 km) along the latitudinal transect. G. bulloides from down core samples in the North Atlantic show low U/Ca ratios during the last glacial and high ratios during the Holocene, similar to the Mg/Ca evolution trend. In general, our data indicate that the U incorporation into planktonic foraminiferal carbonates is strongly influenced by calcification temperature, although U/Ca in G. bulloides may be affected by seawater carbonate ion concentration under warm conditions and/or other factors.     

Community Vulnerability to Tropical Cyclones: Cairns, 1996–2000

This paper is a partial discussion of a four-year study that investigated the vulnerability of the people living in the Cairns region to the tropical cyclone hazard. The longitudinal case study, focussing on the Cairns Northern Beaches area, was unique in that it included a social and societal `pre-cyclone impact' evaluation of various resident communities within the region, and then two consecutive `post-cyclone impact' studies. The primary research method supported an inductive qualitative approach to the collection and analysis of survey data. Some quantitative methods were invoked to support qualitative research findings. Survey data was collected in five separate questionnaire-based social surveys that were administered between 1996 and 2000. During the study, residents experiencedthe direct impact of two land-falling tropical cyclones. In addition to this, targeted andfocussed tropical cyclone awareness education was made increasingly available withinthe community. The social and demographic attributes that influence the individual'sperception of risk and contribute to our understanding of community vulnerability were examined and evaluated. Changes in the residents' attitudes, cyclone preparednessbehaviours and willingness to respond to cyclone warnings were monitored and measured. Analysis of early survey data indicated that community residents generally had some knowledge of cyclones but a limited understanding of cyclone processes and very little direct personal experience of the cyclone hazard. Individually and collectively, residents frequently demonstrated a biased perception of the risks associated with cyclones. The resident community was shown to be fragmented, with limited support being available to individual households. Initially, residents were found to be poorly prepared for cyclones and unlikely to respond to warnings appropriately. It appeared that, in the event of a land-falling tropical cyclone impacting the area, the community was highly vulnerable to unnecessary loss of property, livelihood and – in extreme circumstances – life. By 2000, Cairns community residents were somewhat better informed about cyclones and certainly more experienced. This paper provides some insight into how cyclone experience and education may synergisticly have contributed to a change in risk perceptions and a reduction in the vulnerability of Cairns residents to the tropical cyclone and storm surge hazards.