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.     

Variability in invasion risk for ballast water exchange on the Scotian Shelf of eastern Canada

A semi-quantitative risk assessment model for dispersion of ballast water organisms in shelf seas is applied to the Scotian Shelf region of eastern Canada. The ballast water exchange process is simulated as the dispersion of tracer released into the surface layer of an ocean circulation model of the region. Circulation model variability is driven by wind stress from a cyclical year of forcing representing climatological storminess. Dispersion metrics related to invasion risk are developed and incorporated into a risk equation that computes the relative overall risk of invasion for ballast water exchange segments along vessel tracks crossing the shelf. Three hundred and sixty dispersion simulations are done for each segment of each of six tracks. Because the flow fields represent climatological variability in shelf circulation, the application of the risk assessment model captures the expected variability in invasion risk. Model results indicate that more than an order of magnitude variation in risk can exist along a given vessel track, and that tracks with offshelf segments provide a lower risk option compared to onshelf tracks. The model provides quantitative guidance to regulators regarding what is an acceptable trip diversion and can aid in numerous other management decisions.     

Preliminary model of nitrogen loads from southern bluefin tuna aquaculture

Farming of wild tuna in coastal areas is a relatively new aquaculture industry and little is known about the magnitude of nutrient discharges to the environment. In this work we present a preliminary model of nitrogen loads from southern bluefin tuna (Thunnus maccoyii) aquaculture in lower Spencer Gulf, South Australia. The model was developed based on feed inputs, estimates of fish metabolism and environmental data. Two pens were monitored over a full grow-out season to determine nitrogen sedimentation fluxes, remineralization at the sediment-water interface and accumulation in the sediments. The model suggests that the high metabolic rates of tuna lead to low retention of nitrogen in fish tissues (7-12% of feed inputs) and high environmental losses (260-502kg Ntonne(-1) growth). Considering Australian annual production of 4380tonnes over initial stocked biomass, total loads can reach 1137tonnes N per year, 86-92% lost as dissolved wastes. The nature of wastes suggests low localized impacts at current stocking densities and holding periods.     

Carbon isotopes and iodine concentrations in a Mississippi River delta core recording land use, sediment transport, and dam building in the river's drainage basin

Sedimentary material from coastal and nearshore areas in the Mississippi Delta region are comprised of different organic carbon sources with diverse ages that require isotopic and elemental records for resolving the various sources of plant residues. Carbon isotopic ((13)C, (14)C) values were used to differentiate contributions from plants using the C3, C4, and/or CAM (crassulacean acid metabolism) carbon fixation pathways., and iodine concentrations indicated that wetland plant residues are a significant source of organic carbon in a sediment core from the Mississippi River delta region collected at a 60 m water depth. This sediment core had been extensively described in Oktay et al. [Oktay, S.D., Santschi, P.H., Moran, J.E., Sharma, P., 2000. The (129)Iodine Bomb Pulse Recorded in Mississippi River delta Sediments: Results from Isotopes of I, Pu, Cs, Pb, and C. Geochim. Cosmochim. Acta 64 (6), 989-996.] and significantly, includes unique features that had not previously been seen in the marine environment. These special features include a plutonium isotopic close-in fallout record that indicates a purely terrestrial source for these sediment particles and the elements associated with it, and a distinct iodine isotopic peak (as well as peaks for plutonium and cesium isotopes) that indicate little bioturbation in this core. Our carbon isotopic and iodine data can thus be compared to published records of changes in drainage basin land use, river hydrology, and hydrodynamic sorting of suspended particles to elucidate if these changes are reflected in nearshore sediments. This comparison suggests a significant contribution for organic carbon (OC) from C4 plants to these sediments during the 1950's to early 1960's. Relative older carbon isotopes, and episodically high iodine concentrations (up to 34 ppm) were observed during this time period that (1) indicate sediment deposition that is coincident with the times of major hydrological changes induced from dam and levee building in both the upper and lower reaches of the Mississippi River drainage basin, and (2) suggest episodic organic carbon deposition from wetland plant residues.     

Reconstruction of contaminant trends in a salt wedge estuary with sediment cores dated using a multiple proxy approach

The Taunton River is a partially mixed tidal estuary in southeastern Massachusetts (USA) which has received significant contaminant inputs, yet little information exists on the history of discharge and the subsequent fate of these contaminants. Three sediment cores taken along a transect were analyzed, reconstructing the spatial and temporal trends of pollution in the estuary. A combination of radiometric dating, contaminant markers, and storm layers from major hurricanes were used to establish age models and sedimentation rates. Age estimates obtained from the different dating methods compared well, establishing an accurate history of contaminant release to the estuary. Polycyclic aromatic hydrocarbons (PAHs) were present in one core at depths corresponding to the early 1860s, earlier than previously established dates of introduction. Temporal and spatial trends of Cr, Cu, Hg and Pb indicated multiple sources of varying input to the river. Polychlorinated biphenyls (PCBs) were present in each of the cores from the 1930s onward, with elevated levels still present in surficial sediments at several sites. A unique organic compound, Topanol, which was produced locally was used as a tracer to track contaminant transport in the river. Tracer data indicates that contaminants are still being transported and deposited to surficial sediments at high concentrations well after their discharge. This reconstruction demonstrates the utility of using multiple dating proxies where often the sole use of radiometric dating techniques is not an option and provides insights into the fate of contaminants discharged decades ago but continue to represent environmental risks.     

Nitrogen isotopes in the recent solar wind from the analysis of Genesis targets: Evidence for large scale isotope heterogeneity in the early solar system

We have analyzed nitrogen, neon and argon abundances and isotopic ratios in target material exposed in space for 27 months to solar wind (SW) irradiation during the Genesis mission. SW ions were extracted by sequential UV (193 nm) laser ablation of gold-plated material, purified separately in a dedicated line, and analyzed by gas source static mass spectrometry. We analyzed gold-covered stainless steel pieces from the Concentrator, a device that concentrated SW ions by a factor of up to 50. Despite extensive terrestrial N contamination, we could identify a non-terrestrial, ¹⁵N-depleted nitrogen end-member that points to a 40% depletion of ¹⁵N in solar-wind N relative to inner planets and meteorites, and define a composition for the present-day Sun (¹⁵N/¹⁴N = [2.26 ± 0.67] × 10⁻³, 2σ), which is indistinguishable from that of Jupiter’s atmosphere. These results indicate that the isotopic composition of nitrogen in the outer convective zone of the Sun has not changed through time, and is representative of the protosolar nebula. Large ¹⁵N enrichments due to e.g., irradiation, low temperature isotopic exchange, or contributions from ¹⁵N-rich presolar components, are therefore required to account for inner planet values.     

Crustal sulfur is required to form magmatic Ni–Cu sulfide deposits: evidence from chalcophile element signatures of Siberian and Deccan Trap basalts

Process models for ore formation in magmatic Ni–Cu–platinum group element (PGE) sulfide systems require that S saturation is achieved in a mafic–ultramafic magma. Traditional models explain the achievement of S saturation or sulfide saturation either by the addition of crustal S, by the felsification of the magma by crustal contamination, or by mixing between primitive and evolved magmas. Which process matters most is important to industry-oriented exploration models where crustal S sources are believed to be encouraging features of a metallotect. Studies of the Siberian Trap flood basalts at Noril’sk have demonstrated that chalcophile element depletion is linked to assimilation of silica-rich crust, but it is less clear whether this contaminant contained an appreciable amount of S. At Noril’sk, the Ni–Cu–PGE sulfide deposits are associated with subvolcanic intrusions that were emplaced into Permian and Carboniferous sedimentary sequences rich in shales, marlstones, and evaporites. Similar to the Siberian Trap basalts, the Deccan Trap contains a volumetrically important suite of crustally contaminated tholeiitic basalts. We present new PGE data for samples from a stratigraphic sequence of basalts from the southern Deccan province. Two of the formations in this sequence (the Bushe and Poladpur Formations) have geochemical signatures indicative of a wide degree of crustal contamination of a magma type that gave rise to the stratigraphically higher Ambenali Formation (a product of transitional midocean ridge basalt magmatism). There are no known deposits or occurrences of Ni–Cu–PGE sulfides associated with subvolcanic intrusions in the Deccan province. Despite the fact that the Bushe Formation exhibits a stronger crustal contamination signature than the most contaminated Siberian Trap basalt formations, and the Poladpur lavas are also strongly crustally contaminated, the Bushe and Poladpur basalts are undepleted in Ni, Cu, or PGE. This indicates that the contaminated Deccan Trap lavas did not achieve S saturation. This, in turn, places constraints on the potential of the Deccan Trap in southern India to host significant magmatic sulfide deposits. Conversely, this observation also indicates that an S-rich crustal contaminant is required for the genesis of magmatic Ni–Cu–PGE sulfide deposits.     

Numerical estimation of effective diffusion coefficients for charged porous materials based on micro-scale analyses

In order to describe diffusive transport of solutes through a porous material, estimation of effective diffusion coefficients is required. It has been shown theoretically that in the case of uncharged porous materials the effective diffusion coefficient of solutes is a function of the pore morphology of the material and can be described by the tortuosity (tensor) (Bear, 1988 [1]). Given detailed information of the pore geometry at the micro-scale the tortuosity of different materials can be accurately estimated using homogenization procedures. However, many engineering materials (e.g., clays and shales) are characterized by electrical surface charges on particles of the porous material which strongly affect the (diffusive) transport properties of ions. For these type of materials, estimation of effective diffusion coefficients have been mostly based on phenomenological equations with no link to underlying micro-scale properties of these charged materials although a few recent studies have used alternative methods to obtain the diffusion parameters (Jougnot et al., 2009; Pivonka et al., 2009; Revil and Linde, 2006 2, 3 and 4). In this paper we employ a recently proposed up-scaled Poisson–Nernst–Planck type of equation (PNP) and its micro-scale counterpart to estimate effective ion diffusion coefficients in thin charged membranes. We investigate a variety of different pore geometries together with different surface charges on particles. Here, we show that independent of the charges on particles, a (generalized) tortuosity factor can be identified as function of the pore morphology only using the new PNP model. On the other hand, all electro-static interactions of ions and charges on particles can consistently be captured by the ratio of average concentration to effective intrinsic concentration in the macroscopic PNP equations. Using this formulation allows to consistently take into account electrochemical interactions of ions and charges on particles and so excludes any ambiguity generally encountered in phenomenological equations.     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:

P–V–T equations of state of MgO and thermodynamics

A simplest equation within the framework of the Mie-Grüneisen–Einstein approach is considered. Pressure estimation values are presented that are derived by conventional arithmetic and algebraic calculations as a function of temperature and volume. The equation under consideration complies with the Mie-Grüneisen–Debye model at high temperature. Different versions of an equation of state (EoS) of MgO proposed by Speziale et al. (J Geophys Res 106B:515–528, 2001) as a pressure standard at high temperatures are subject to analyses. In the literature, at least four versions of Speziale et al. EoS of MgO are discussed; the discrepancy between them reaching a few GPa at T > 2,000 K and P > 100 GPa. Our analyses of these equations suggest that the volume dependence of the Debye temperature is accepted arbitrarily and does not agree with the definition of the Grüneisen parameter, γ = −(∂lnΘ/∂lnV) _T . Pressure as a function of temperature and volume in the Mie-Grüneisen–Einstein approach or the Gao pressure calculator can be used to estimate true pressure at compression x = V/V ₀ < 1 with the Speziale et al. EoS of MgO.