Partitioning of polycyclic aromatic hydrocarbons between water and particles compared to bioaccumulation in mussels: a harbour case

Water and particles from three sites located in Halifax Harbour, near and further away from combined municipal sewage effluents (CMSE) were analysed for parental and alkylated polycyclic aromatic hydrocarbons (par and alkPAH). Bioavailability of PAH was compared for inter-tidal mussels collected at the same sites in April and November. The PAH fingerprint determined over 9 sampling times covering a period of 19 months differed more between phases (water and particles) and seasons, than between sites. In the spring, more alkPAH associated with diesel and gasoline were detected in the soluble phase, along with more bioaccumulation of alkPAH in inter-tidal mussels. A broader number of parPAH were detected in mussels collected in the fall. The mean sum of dissolved alkPAH concentrations was higher in water at the site closer to raw CMSE than at the other two sites and particles of that site. However, lowest bioconcentration factors (BCF) were determined in mussels of this more contaminated site. Similar biota-particle accumulation factors (BPAF) were determined for parPAH in mussels from the three sites, all lower than the BCF of alkPAH. The study indicates that sewage treatment plants will reduce the amount of parPAH especially larger than fluoranthene and pyrene from being deposited in the harbour; that alk naphthalenes and fluorenes present in water will continue to be discharged; that the disturbance of sediments can make particle-bound PAH available to mussels.     

Exhumation during crustal folding in the Namche-Barwa syntaxis

Geological observation in the eastern end of the Himalaya shows that the Asia/India Suture is folded. Metamorphic rocks derived from India occur structurally below the suture, in the core of a regional antiform. Isotopic and fission track dating establish cooling-exhumation of rocks from c.30 km depth within the last 4 Myr. We argue that exhumation is caused by ～ 10 mm yr^-1 erosion coeval with crustal scale folding.     

Adsorption of Copper, Nickel, and Cadmium on Goethite in the Presence of Organic Ligands

Adsorption of copper, cadmium and nickel at low concentrations on goethite was studied in the presence of the simple organic ligands oxalate, salicylate, and pyromellitate. The experimental metal adsorption behavior was compared to calculations with a surface complexation model to evaluate the most important interactions. Oxalate mostly decreased Cu and Ni adsorption at high pH-values by competition between solution and surface complexation but had no effect on Cd adsorption. Cu adsorption in the presence of oxalate below pH 6 could best be described by defining a ternary complex of type A (surface-metal-ligand). Salicylate had only minor effects on metal adsorption. The adsorption of Cu in the presence of salicylate above pH 5 could be explained by a ternary complex of type A. Pyromellitate increased the adsorption of Cu and Cd in the acidic pH-range, likely by formation of ternary surface complexes of type B (surface-ligand-metal).     

α-Emitting mineral inclusions in apatite, their effect on (U-Th)/He ages, and how to reduce it

U-Th rich mineral inclusions in apatite are often held responsible for erroneously old (U-Th)/He ages, because they produce “parentless” He. Three aspects associated with this problem are discussed here. First, simple dimensional considerations indicate that for small mineral inclusions, the parentless helium problem might not be as serious as generally thought. For example, a mineral inclusion that is 10% the length, width and height of its host apatite needs to be a thousand times more concentrated in U and Th to produce an equal amount of He. Therefore, single isolated inclusions smaller than a few μm are unlikely to contribute significant helium. For larger or more abundant inclusions, the parentless helium problem can be solved by dissolution of the apatite and its inclusions in hot HF. Second, besides creating parentless helium, inclusions also complicate α-ejection corrections. Mathematical exploration of this latter problem for spherical geometries reveals that for randomly distributed inclusions, the probability distribution of single-grain ages is predicted to have a sharp mode at the mean age, with tails towards younger and older ages. Multiple-grain measurements will yield accurate and precise age estimates if 10 or more randomly distributed α-emitting mineral inclusions are present in a sample. Third, thermal modeling indicates that mineral inclusions have a non-trivial but minor (<5 °C) effect on the closure temperature. These predictions were tested on apatites from rapidly cooled migmatites of Naxos (Greece) which contain abundant U-rich zircon inclusions. Thirty-seven samples were subjected to two kinds of treatment. The “pooled” age (i.e., the synthetic multi-grain age computed from a number of single-grain analyses) of four inclusion-free samples (13 apatites), prepared in HNO₃ is 10.9 Ma, close to apatite and zircon fission-track ages from the same rock. (U-Th)/He ages of 14 inclusion-bearing samples dissolved in HNO₃ range between 9 and 45 Ma, with a pooled age of 22.6 Ma. The ages of 19 HF-treated samples range between 5 and 16 Ma, with 10 of 14 single-grain samples between 9 and 13 Ma and a pooled age of 10.9 Ma. These observations agree with the theoretical predictions and support the addition of HF-treated apatite (U-Th)/He dating to the thermochronological toolbox.     

Electrodynamic Disaggregation: Does it Affect Apatite Fission-Track and (U-Th)/He Analyses?

Apatite fission-track and (U-Th)/He analyses require the liberation of intact idiomorphic apatite grains from rock samples. While routinely being carried out by mechanical methods, electrodynamic disaggregation (ED) offers an alternative approach. The high-voltage discharges produced during the ED process create localised temperature peaks (10000 K) along a narrow plasma channel. In apatite, such high temperatures could potentially reduce the length of fission tracks, which start to anneal at temperatures > 60 °C, and could also enhance He diffusion, which becomes significant at 30–40 °C over geological time scales. A comparison of fission-track analyses and (U-Th)/He ages of apatites prepared both by mechanical (jaw crusher, disk mill) and ED processing provides a way of determining whether heating during the latter method has any significant effect. Apatites from three samples of different geological settings (an orthogneiss from Madagascar, the Fish Canyon Tuff, and a muscovite-gneiss from Greece) yielded statistically identical track length distributions compared to samples prepared mechanically. Additionally, (U-Th)/He ages of apatites from a leucogranite from Morocco prepared by both methods were indistinguishable. These first results indicated that during electrodynamic disaggregation apatite crystals were not heated enough to partially anneal the fission tracks or induce significant diffusive loss of He.     

A linear Boltzmann equation to model wave scattering in the marginal ice zone

We present a linear Boltzmann equation to model wave scattering in the Marginal Ice Zone (the region of ocean which consists of broken ice floes). The equation is derived by two methods, the first based on Meylan et al. [Meylan, M.H., Squire, V.A., Fox, C., 1997. Towards realism in modeling ocean wave behavior in marginal ice zones. J. Geophys. Res. 102 (C10), 22981–22991] and second based on Masson and LeBlond [Masson, D., LeBlond, P., 1989. Spectral evolution of wind-generated surface gravity waves in a dispersed ice field. J. Fluid Mech. 202, 111–136]. This linear Boltzmann equation, we believe, is more suitable than the equation presented in Masson and LeBlond [Masson, D., LeBlond, P., 1989. Spectral evolution of wind-generated surface gravity waves in a dispersed ice field. J. Fluid Mech. 202, 111–136] because of its simpler form, because it is a differential rather than difference equation and because it does not depend on any assumptions about the ice floe geometry. However, the linear Boltzmann equation presented here is equivalent to the equation in Masson and LeBlond [Masson, D., LeBlond, P., 1989. Spectral evolution of wind-generated surface gravity waves in a dispersed ice field. J. Fluid Mech. 202, 111–136] since it is derived from their equation. Furthermore, the linear Boltzmann equation is also derived independently using the argument in Meylan et al. [Meylan, M.H., Squire, V.A., Fox, C., 1997. Towards realism in modeling ocean wave behavior in marginal ice zones. J. Geophys. Res. 102 (C10), 22981–22991]. We also present details of how the scattering kernel in the linear Boltzmann equation is found from the scattering by an individual ice floe and show how the linear Boltzmann equation can be solved straightforwardly in certain cases.     

Comet Grains: Their IR Emission and Their Relation to ISm Grains

Comets and the chondritic porous interplanetary dust particles (CP IDPs) that they shed in their comae are reservoirs of primitive solar nebula materials. The high porosity and fragility of cometary grains and CP IDPs, and anomalously high deuterium contents of highly fragile, pyroxene-rich Cluster IDPs imply these aggregate particles contain significant abundances of grains from the interstellar medium (ISM). IR spectra of comets (3–40 μm) reveal the presence of a warm (near-IR) featureless emission modeled by amorphous carbon grains. Broad andnarrow resonances near 10 and 20 microns are modeled by warm chondritic (50% Feand 50% Mg) amorphous silicates and cooler Mg-rich crystalline silicate minerals, respectively. Cometary amorphous silicates resonances are well matched by IRspectra of CP IDPs dominated by GEMS (0.1 μm silicate spherules) that are thought to be the interstellar Fe-bearing amorphous silicates produced in AGB stars. Acid-etched ultramicrotomed CP IDP samples, however, show that both the carbon phase (amorphous and aliphatic) and the Mg-rich amorphous silicate phase in GEMS are not optically absorbing. Rather, it is Fe and FeS nanoparticles embedded in the GEMS that makes the CP IDPs dark. Therefore, CP IDPs suggest significant processing has occurred in the ISM. ISM processing probably includes in He⁺ ion bombardment in supernovae shocks. Laboratory experiments show He⁺ ion bombardment amorphizes crystalline silicates, increases porosity, and reduces Fe into nanoparticles. Cometary crystalline silicate resonances are well matched by IR spectra of laboratory submicron Mg-rich olivine crystals and pyroxene crystals. Discovery of a Mg-pure olivine crystal in a Cluster IDP with isotopically anomalous oxygen indicates that a small fraction of crystalline silicates may have survived their journey from AGB stars through the ISM to the early solar nebula. The ISM does not have enough crystalline silicates (<5%), however, to account for the deduced abundance of crystalline silicates in comet dust. An insufficient source of ISMMg-rich crystals leads to the inference that most Mg-rich crystals in comets are primitive grains processed in the early solar nebula prior to their incorporation into comets. Mg-rich crystals may condense in the hot (～1450 K), inner zones of the early solar nebula and then travel large radial distances out to the comet-forming zone. On the other hand, Mg-rich silicate crystals may be ISM amorphous silicates annealed at ～1000 K and radially distributed out to the comet-forming zone or annealed in nebular shocks at ～5-10 AU. Determining the relative abundance of amorphous and crystalline silicatesin comets probes the relative contributions of ISM grains and primitive grains to small, icy bodies in the solar system. The life cycle of dust from its stardust origins through the ISM to its incorporation into comets is discussed.     

Use of composite data sets for source-tracking enterococci in the water column and shoreline interstitial waters on Pensacola Beach, Florida

Sources of Enterococcus faecalis isolates from Pensacola Beach, FL. were identified using a library-based approach by applying the statistical method of average similarity to single and composite data sets generated from separate analyses. Data sets included antibiotic resistance analysis (ARA), rep-fingerprints, and fatty acid methyl ester (FAME) profiles. Use of a composite data set composed of ARA and rep-fingerprints, added to the confidence of the identifications. The addition of FAME data to composite data sets did not add to the confidence of identifications. Source identification was performed to better understand risk associated with higher densities of enterococci found in swash zone interstitial water (SZIW) as compared to adjacent bathing water on Pensacola Beach, FL. The "swash zone" is that area of the beach continually washed over by waves. As the potential sources of enterococci were limited in this environment, only two library units, sea gull and human, were constructed. Identification of the beach isolates using a composite data set indicated a sea gull origin. The clonality of the beach isolates suggested that the beach environment selects certain subspecies of E. faecalis.     

Altering intertidal sediment topography: effects on biodiversity and ecosystem functioning

Sedimentary marine systems are often highly productive and perform important nutrient regeneration functions as they efficiently decompose organic material. In recent years the role of habitat effects and of species composition in ecosystem functioning has become of interest. Estuarine environments are frequently subject to considerable anthropogenic pressures whilst supporting a variety of habitats ranging from well sorted soft muds through biogenically stable sediments to highly mobile coarse sands. There is therefore considerable spatial complexity in habitat type and faunal composition. This study set out to observe the effects of altering the topographical habitat features of an estuarine mudflat on a range of porewater nutrient concentrations (NH₄⁺, NO₃⁻, NO₂⁻, PO₄³⁻ and SiO) collected from four depths (3, 5, 9, and 12 cm) and on faunal composition. Two treatments (Shelled Nets and Net Controls) were used to alter the topography from simple mud to a mussel shell crumble and were compared to un-manipulated Control areas. Sediment granulometry and organic matter content analyses alongside biological traits analysis of the fauna were also conducted.
Differences were observed in porewater nutrient concentrations between the Control and both netted treatments at 5 cm depth only; the species diversity and abundance were also different in the netted treatments compared to the Controls, although no difference between the two manipulated treatments were observed. The changes in faunal composition were attributed solely to the altered topography and the observed nutrient changes were attributed to the faunal alteration rather than the topographical manipulation.