Fe sorption onto nontronite (NAu-2)

The sorption of ferrous iron to a clay mineral, nontronite (NAu-2, a ferruginous smectite), was investigated under strictly anoxic conditions as a function of pH (3-10), Fe²⁺ concentration (0.01-50 mM), equilibration time (1-35 days), and ionic strength (0.01-0.5 M NaClO₄). The surface properties of NAu-2 were independently characterized to determine its fixed charge and amphoteric site density in order to interpret the Fe²⁺ sorption data. Fe²⁺ sorption to NAu-2 was strongly dependent on pH and ionic strength, reflecting the coupled effects of Fe²⁺ sorption through ion exchange and surface complexation reactions. Fe²⁺ sorption to NAu-2 increased with increasing pH from pH 2.5 to 4.5, remained constant from pH 4.5 to 7.0, increased again with further increase of pH from pH 7.0 to 8.5, and reached a maximum above pH 8.5. The Fe²⁺ sorption below pH 7.0 increased with decreasing ionic strength. The differences of Fe²⁺ sorption at different ionic strengths, however, diminished with increasing equilibration time. The Fe²⁺ sorption from pH 4.5 to 7.0 increased with increasing equilibration time up to 35 days and showed stronger kinetic behavior in higher ionic strength solutions. The kinetic uptake of Fe²⁺ onto NAu-2 is consistent with a surface precipitation mechanism although our measurements were not able to identify secondary precipitates. An equilibrium model that integrates ion exchange, surface complexation and aqueous speciation reactions reasonably well describes the Fe²⁺ sorption data as a function of pH, ionic strength, and Fe²⁺ concentration measured at 24 h of equilibration. Model calculations show that the species Fe(OH)⁺ was required to describe Fe²⁺ sorption above pH 8.0 satisfactorily. Overall, this study demonstrated that Fe²⁺ sorption to NAu-2 is affected by complex equilibrium and kinetic processes, likely caused by surface precipitation reactions.     

Multivariate analysis of contamination in the mining district of Linares (Jaén, Spain)

Historically, a significant level of mining activity has taken place in the batholite-related metalogenic enclave of Linares (Jaén province, Spain), associated with Pb–Ag, Cu, Zn and Fe sulphides and Ba sulphate mineralization, though mining here has now been abandoned. Additionally, the area features a significant amount of urban, industrial and agricultural activities. These considerations, taken together, explain the need to assess the levels of concentration of trace elements and to determine their relationship with geogenic and anthropogenic factors. For geochemical characterisation of the soil, the region has been divided into 126 grid squares with an area of 1 km². For each grid square, 32 trace elements have been analysed. Elemental concentrations of Cu, Pb, Zn, As and Mn have been included in statistical analyses. According to the reference levels established by the Regional Government (Junta de Andalucía), soils in a large part of the study area require amendment applications. The comparison of the mean content for each grid square with the reference levels reveals a significant degree of contamination of the soil by Cu (719 mg kg⁻¹), Pb (22,964 mg kg⁻¹) and As (100 mg kg⁻¹) in those grid squares affected by metallurgic activities. By means of factor analysis, four scores have been identified which together account for 80% of the variance observed. The first score is highly correlated with the logarithms of the variables Fe, Th, La, Ti, Al, Na, K, Zr, Y, Nb, Be and Sc. It is a “natural” factor that indicates the type of soil matrix (fundamentally granites and, to a lesser degree, Triassic materials). The second score shows high correlation with the logarithms of the variables Mo, Cu, Pb, Zn, Ag, Co, Mn, As, Cd, Sb, Ba, W and Sn, and is the “metallization” factor related to the mineralization that has been exploited. The third score is mainly determined by the logarithms of the variables Sr, Ca and Mg. This is a “natural” factor that indicates a type of carbonate soil matrix (Miocene). Finally, the fourth factor groups the logarithms of the variables Ni, V and Cr, elements that are associated with the combustion of fossil fuels. Analysis of the patterns of each of the factors identified enabled achieving a global characterisation of the study area. Cluster analysis of the observations showed there to be five clusters relating to the grid squares, differentiated by lithologies and degrees of contamination. These clusters are used to determine the background of granite and to calculate the anomalous load.     

Vernacular heritage and evolving environmental policy in Australia: Lessons from the Murray–Darling Outreach Project

The interface between environmentalism and neoliberalism in industrialised nations is dynamic and evolving with each of these significant socio-political movements exerting influence on the other. In the context of Australian environmental policy, ideas of heritage, sense of place and belonging are increasingly invoked to support the current policy emphasis on the role of regional communities for realising goals for land and water conservation and environmental restoration. To explore the broader meaning and consequences of these developments, we focus on the manner in which ideas of heritage are employed and evoked within the Murray–Darling Outreach Project, a collaboration between the Murray–Darling Basin Commission, a key natural resource management agency, and the National Museum of Australia. The Murray–Darling Outreach Project has the aim of increasing community involvement in local environmental issues by promoting ideas of vernacular heritage.     

Extreme <Superscript>15</Superscript>N Depletion in Seagrasses

Seagrass beds form an important part of the coastal ecosystem in many parts of the world but are very sensitive to anthropogenic nutrient increases. In the last decades, stable isotopes have been used as tracers of anthropogenic nutrient sources and to distinguish these impacts from natural environmental change, as well as in the identification of food sources in isotopic food web reconstruction. Thus, it is important to establish the extent of natural variations on the stable isotope composition of seagrass, validating their ability to act as both tracers of nutrients and food sources. Around the world, depending on the seagrass species and ecosystem, values of seagrass N normally vary from 0 to 8?‰ δ¹⁵N. In this study, highly unusual seagrass N isotope values were observed on the east coast of Qatar, with significant spatial variation over a scale of a few metres, and with δ¹⁵N values ranging from +2.95 to ?12.39?‰ within a single bay during March 2012. This pattern of variation was consistent over a period of a year although there was a seasonal effect on the seagrass δ¹⁵N values. Seagrass, water column and sediment nutrient profiles were not correlated with seagrass δ¹⁵N values and neither were longer-term indicators of nutrient limitation such as seagrass biomass and height. Sediment δ¹⁵N values were correlated with Halodule uninervis δ¹⁵N values and this, together with the small spatial scale of variation, suggest that localised sediment processes may be responsible for the extreme isotopic values. Consistent differences in sediment to plant ¹⁵N discrimination between seagrass species also suggest that species-specific nutrient uptake mechanisms contribute to the observed δ¹⁵N values. This study reports some of the most extreme, negative δ¹⁵N values ever noted for seagrass (as low as ?12.4?‰) and some of the most highly spatially variable (values varied over 15.4?‰ in a relatively small area of only 655 ha). These results are widely relevant, as they demonstrate the need for adequate spatial and temporal sampling when working with N stable isotopes to identify food sources in food web studies or as tracers of anthropogenic nutrients.     

Disposition and metabolism of 2,3,7,8-tetrachlorodibenzofuran (TCDF) in rainbow trout

In order to elucidate the metabolic fate of 2,3,7,8-tetrachlorodibenzofuran (TCDF) in fish and to thereby facilitate the assessment of the risks posed by this environmental toxin, we determined the whole body half-life, tissue distribution and metabolism of [³H TCDF in rainbow trout (Onchorynchus mykiss), treated orally. A whole body biphasic elimination pattern resulted in the excretion of 60% of the administered chemical during the first 3 days, after which a much slower elimination-rate (half-life = 14 days) was observed. Significant amounts of water-soluble metabolites were found in both bile and liver. Of the TCDF-derived radioactivity in bile, approximately 50% represented glucuronide conjugates, predominantly 4-hydroxy-2,3,7,8-TCDF: substantial amounts of the sulfate conjugate of this same metabolite were also present. Except at early time points, muscle contained the predominant fraction of TCDF-derived radioactivity, amounting to 25–65% of the total radioactivity present in the fish. More than 95% of the radioactivity present in muscle represented unmetabolized TCDF.     

Laboratory effects of microcosm size and the pesticide chlorpyrifos on benthic macroinvertebrate colonization of soft estuarine sediments

A 42-d flow-through experiment was conducted to evaluate the effects of the organo-phosphate pesticide, chlorpyrifos, and microcosm size (small: 144 cm²; large: 400 cm²) on benthic estuarine macroinvertebrate colonization. Nested central and perimeter (outside margin) cores were used to assess animal distribution within microcosms. Fine-grained, organically-rich (approximately 4.0% organic carbon and 20% dry wt) sediments were nominally fortified with chlorpyrifos controls, low (1.0) and high treatments (10.0 μg⁻¹ wet sediment). Large microcosms contained a significantly (p < 0.05) higher average taxa richness (10.9) than small microcosms (8.6) but small microcosms contained a significantly greater average animal density (295.8; numerical abundance adjusted to unit area) than large microcosms (120.5). Density of the polychaete, Neanthes succinea, the amphipod, Corophium acherusicum, and the barnacle, Balanus sp., was significantly greater in small microcosms but density of Ensis minor was significantly greater in large microcosms. In small and large microcosms, respectively, densities averaged significantly greater numbers in perimeter cores (e.g. 203.1 and 75.1) vs central cores (71.9 and 45.4). Average density decreased significantly with increasing chlorpyrifos concentration from controls (326.8), to low (123.8) and high (78.8) treatments. The density decrease was significantly related only to C. acherusicum whose densities decreased from controls (285.8) to low (88.5) and high (43.9) dosed microcosms. Application of an equilibrium partitioning model indicated that density of C. acherusicum was sensitive to an estimated interstitial water concentration of approximately 0.48 μg liter⁻¹. Non-metric multidimensional scaling ordination analyses provided important insights into response patterns not available through ANOVA procedures. A permutation procedure (ANOSIM) detected a significant size effect (p < 0.0001) and a significant effect between controls and low (p < 0.042) and high doses (p < 0.013) but not between low and high chlorpyrifos treatments (p < 0.465). A single species, C. ascherusicum, as in the ANOVA analyses, dominated contributions to community average percent dissimilarity in most combinations of microcosm size and chlorpyrifos treatment effects (range: 8.4–21.9%). Community structure differed significantly in several combinations of microcosm size, core position and chlorpyrifos treatment. Results confirm earlier work that intrinsic design factors influence benthic macroinvertebrate community structure and determine taxa available to pesticide exposure in microcosms.     

Enceladus' plume: Compositional evidence for a hot interior

The combined observations of Saturn's moon Enceladus by the Cassini CAPS, INMS and UVIS instruments detected water vapor geysers in which were present molecular nitrogen (N₂), carbon dioxide (CO₂), methane (CH₄), propane (C₃H₈), acetylene (C₂H₂), and several other species, together with all of the decomposition products of water. We propose that the presence of N₂ in the plume indicates thermal decomposition of ammonia, and hence high temperatures in the interior of the moon (e.g., 500 to 800 K). Such an environment also appears to be suitable for the production of methane (CH₄) from carbon monoxide (CO), or carbon dioxide (CO₂). The presence of C₂H₂ and C₃H₈ strongly suggest that catalytic reactions took place within a very hot environment. The internal environment of Enceladus is inferred to be or have been favorable for aqueous, catalytic chemistry. This permits the synthesis of many complex organic compounds that could be detected in future Cassini observations.