Origin of nickel in water solution of the chalk aquifer in the north of France and influence of geochemical factors

In the north of France, high registers of nickel are sometimes recorded within the chalk aquifer. In a confined context, the presence of pyrite in the covering clays or in the marcasite nodules encrusted in the clay may constitute a natural source of trace metals. With an objective of sanitary control, the limits of chemical contents regulating the quality of water destined for human consumption have been lowered by the European Framework Directive in the field of water policy (2000/60/EC). As a result, nickel limits have been reduced from 50 to 20 μg/l. The analyses, carried out on three water catchment fields in our area of study, were centred on variable parameters (Eh, O₂(d), pH, Conductivity, T°), major elements (SO₄, NO₃) and metals (Fe, Ni, Mn, Co). The acquired data enabled us to identify from one hand, the conditions which are presented within the site, special thanks to the evolution of nitrate and iron contents and on the other hand, the natural origin (geological) of nickel for two of the three sites studied based essentially on the evaluation of the Nickel/Cobalt ratio. Thus, on the first site, the evolution of nickel content and nitrate content showed the influence of the phenomenon of denitrification on the re-mobilisation of the nickel. Whereas on the second site, a high variation of total iron content and oxygen dissolved in solution highlighted a particular phenomenon of oxidation of the pyrite through molecular oxygen. Finally, the correlation with the sulphates clearly showed behaviour of the nickel, once released, that was entirely dependent on the phenomenon of adsorption on the iron and manganese hydroxides.     

The surface of labradorite feldspar after acid hydrolysis

After reaction with a pH < 4, the surface of labradorite is extensively enriched in Si and H, and depleted in Al, Ca and Na relative to an unreacted crystal. However, the amount of hydrogen measured in the reacted surface is less than that predicted on the basis of exchange of hydrogen (or hydronium) ions for cations in the feldspar. By analogy with studies of silicate glass, this low concentration of hydrogen suggests that some silanol groups in the reacted surface repolymerize subsequent to ion-exchange and depolymerization reactions. The net result is a relatively porous, Si-rich leached layer which is amorphous to electron diffraction, and which allows rapid diffusion of unreactive solutes.

Both the surface area of the reacted feldspar and the porosity increase with acid hydrolysis. Modeling of nitrogen sorption onto the surface suggests that the pores have a nominal radius of 20–80 Å or less. This distribution of pore sizes resembles other acid-reacted silicate materials, such as glass, chrysotile and kaolinite. Although the mineral surface clearly becomes more porous during acid hydrolysis, the increase in powder area also does not coincide with an increase in the flux of dissolved Si from the powder. We thus attribute most of this increase in area to spallation of the silica-rich surface from the feldspar upon drying.     

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.     

Distribution and Trophic Importance of Anthropogenic Nitrogen in Narragansett Bay: An Assessment Using Stable Isotopes

Narragansett Bay has been heavily influenced by human activities for more than 200 years. In recent decades, it has been one of the more intensively fertilized estuaries in the USA, with most of the anthropogenic nutrient load originating from sewage treatment plants (STP). This will soon change as tertiary treatment upgrades reduce nitrogen (N) loads by about one third or more during the summer. Before these reductions take place, we sought to characterize the sewage N signature in primary (macroalgae) and secondary (the hard clam, Mercenaria mercenaria) producers in the bay using stable isotopes of N (δ¹⁵N) and carbon (δ¹³C). The δ¹⁵N signatures of the macroalgae show a clear gradient of approximately 4‰ from north to south, i.e., high to low point source loading. There is also evidence of a west to east gradient of heavy to light values of δ¹⁵N in the bay consistent with circulation patterns and residual flows. The Providence River Estuary, just north of Narragansett Bay proper, receives 85% of STP inputs to Narragansett Bay, and lower δ¹⁵N values in macroalgae there reflected preferential uptake of ¹⁴N in this heavily fertilized area. Differences in pH from N stimulated photosynthesis and related shifts in predominance of dissolved C species may control the observed δ¹³C signatures. Unlike the macroalgae, the clams were remarkably uniform in both δ¹⁵N (13.2 ± 0.54‰ SD) and δ¹³C (−16.76 ± 0.61‰ SD) throughout the bay, and the δ¹⁵N values were 2–5‰ heavier than in clams collected outside the bay. We suggest that this remarkable uniformity reflects a food source of anthropogenically heavy phytoplankton formed in the upper bay and supported by sewage derived N. We estimate that approximately half of the N in the clams throughout Narragansett Bay may be from anthropogenic sources.     

Sampling characteristics and biases of enclosure traps for sampling fishes in estuaries

We evaluated the sampling characteristics of enclosure traps in estuaries in southern California, USA. Using enclosure traps that sampled 0.25, 0.5, and 1-m² footprints, we found that enclosure trap size significantly affected estimates of fish density and the precision of these estimates. The highest estimates were produced by the 0.5-m² trap and the lowest by the 0.25-m² trap. Precision of the density estimates improved with increasing trap size, while the proportion of zero values in the data sets decreased and estimates of species richness increased. The largest trap was difficult to use in the field and often did not function properly; thus we concluded that intermediate enclosure trap sizes offered the best compromise between statistical and logistical considerations. By examination of burrows in sediment cores taken in fished out enclosure traps, we found no evidence to support the widely held view that burrow-dwelling fishes evaded capture by hiding in burrows. We also used mark-recapture techniques to estimate recovery efficiency in 0.43-m² enclosure traps. Recovery efficiency averaged 91% and did not differ significantly among estuaries or sampling stations within estuaries. Based on extensive netting within enclosure traps, we determined that in areas with dense fish populations (>90 fish 0.43-m⁻²), netting could be ceased after the first sweep that captured no fish with only a trivial effect on the estimate of density. In more sparsely populated areas, netting had to continue until 2–3 sweeps had captured no fish in order to obtain estimates of density that were within 90% of the actual values present. Overall, we found enclosure traps to be effective tools for sampling small, abundant fishes in shallow estuaries in southern California, but we recommend that care be taken when choosing trap size and sampling (netting) effort within traps in order to optimize their sampling characteristics.     

Evidence for mass-dependent isotopic fractionation of strontium in a glaciated granitic watershed

The stable isotope composition of strontium (expressed as δ^88/86Sr) may provide important constraints on the global exogenic strontium cycle. Here, we present δ^88/86Sr values and ⁸⁷Sr/⁸⁶Sr ratios for granitoid rocks, a 150 yr soil chronosequence formed from these rocks, surface waters and plants in a small glaciated watershed in the central Swiss Alps. Incipient chemical weathering in this young system, whether of inorganic or biological origin, has no resolvable effect on the ⁸⁷Sr/⁸⁶Sr ratios and δ^88/86Sr values of bulk soils, which remain indistinguishable from bedrock in terms of Sr isotopic composition. Although due in part to the chemical heterogeneity of the forefield, the lack of a resolvable difference between soil and bedrock isotopic composition indicates that these soils have thus far witnessed minimal net loss of Sr; a low degree of chemical weathering is also implied by bulk soil chemistry. The isotopic composition of Sr in streamwater is more radiogenic than median soil, reflecting the preferential weathering of biotite in the catchment; streamwater δ^88/86Sr values, however, are indistinguishable from bulk soil δ^88/86Sr values, implying that no resolvable fractionation of Sr isotopes takes place during release to the weathering flux in the Damma forefield. Analyses of plant tissue reveal that plants (Rhododendron and Vaccinium) preferentially assimilate the lighter isotopes of Sr such that their δ^88/86Sr values are significantly lower than those of the soils in which they grow. Additionally, δ^88/86Sr values of foliar and floral tissues are lower than those of roots, contrary to observations for Ca, for which Sr is often used as an analogue in weathering studies. We suggest that processes that discriminate against Sr in favour of Ca, due to the different nutritional requirement of plants for these two elements, are responsible for the observed contrast.     

Chondritic Mg isotope composition of the Earth

The processes of planetary accretion and differentiation have potentially been recorded as variations in the stable isotope ratios of the major elements between planetary objects. However, the magnitude of observed isotopic variations for several elements (Mg, Fe, Si) is at the limit of what current analytical precision and accuracy are able to resolve. Here, we present a comprehensive data set of Mg isotope ratios measured in ocean island and mid-ocean ridge basalts, peridotites and chondrites. The precision and accuracy were verified by isotopic standard addition for two samples, one carbonaceous chondrite (Murchison) and one continental flood basalt (BCR-1). In contrast with some previous studies, our data from terrestrial and chondritic materials have invariant Mg isotope ratios within the uncertainty of the method (0.1‰ for the ²⁶Mg/²⁴Mg ratio, 2SD). Although isotopic variations of less than about 0.1‰ could still be present, the data demonstrate that, at this level of uncertainty, the bulk silicate Earth and chondritic Mg reservoir have a homogeneous δ²⁶Mg = −0.23‰ (²⁶Mg/²⁴Mg ratio of the sample relative to the DSM3 standard set to zero by definition). This implies that neither planetary accretion processes nor partial mantle melting and subsequent shallow-level differentiation have fractionated Mg isotope ratios. These observations imply in particular that the formation of the Earth cannot stem from preferential sorting of chondrite constituents that would have been fractionated in their Mg isotope composition. It also implies that unlike oxygen isotopes, there was no zonation in Mg isotopes in the inner solar system.     

Palaeo-environmental and dietary analysis of intestinal contents of a mammoth calf (Yamal Peninsula,northwest Siberia)

Intestinal samples from the one-month-old Siberian mammoth calf ‘Lyuba’ were studied using light microscopy and ancient DNA to reconstruct its palaeo-environment and diet. The palynological record indicates a ‘mammoth steppe’. At least some pollen of arboreal taxa was reworked, and thus the presence of trees on the landscape is uncertain. In addition to visual comparison of 11 microfossil spectra, a PCA analysis contributed to diet reconstruction. This yielded two clusters: one of samples from the small intestine and the other of large-intestine samples, indicating compositional differences in food remains along the intestinal tract, possibly reflecting different episodes of ingestion. Based on observed morphological damage we conclude that the cyperaceous plant remains and some remains of dwarf willows were originally eaten by a mature mammoth, most likely Lyuba’s mother. The mammoth calf probably unintentionally swallowed well-preserved mosses and mineral particles while eating fecal material deposited on a soil surface covered with mosses. Coprophagy may have been a common habit for mammoths, and we therefore propose that fecal material should not be used to infer season of death of mammoths. DNA sequences of trnL and rbcL genes amplified from ancient DNA extracted from intestinal samples confirmed and supplemented plant identifications based on microfossils and macro-remains. Results from different extraction methods and barcoding markers complemented each other and show the value of longer protocols in addition to fast and commercially available extraction kits.