Elemental dispersion and stable isotope fractionation during reactive fluid-flow and fluid immiscibility in the Bufa del Diente aureole,NE-Mexico: evidence from radiographies and Li,B, Sr,Nd, and Pb isotope systematics

The 31.6±0.3 Ma old Bufa del Diente alkali-syenite (NE Mexico) intruded a sequence of Cretaceous limestones with intercalated sub-horizontal chert layers. The cherts acted as aquifers that facilitated transport of brines and pegmatitic melts within the shallow-level (<1 kbar) contact-metamorphic aureole. Fluid-driven reactions between chert and marble wallrock, and the influx of late melts and various fluids gave rise to distinct chemical and isotopic signatures within the aquifer and across the zones of infiltration and fluid-driven reaction. Aqueous brines of magmatic origin produced thick wollastonite mantles around the chert layers. Wollastonite formation occurred at the expense of limestone and chert and generated CO₂. This CO₂-induced fluid unmixing into an aqueous brine and a low-density CO₂-rich fluid, which was lost to the overlying marble where it oxidized organic matter and caused ¹³C and ¹⁸O shifts in a zone some 5–10 cm wide. After wollastonite formation, the chert aquifers were locally intruded by pegmatite veins carrying alkali feldspar, quartz, aegirine-augite, eudialyte, zircon, and apatite. Aqueous fluids that exsolved during crystallization of the pegmatite veins escaped along late cross-fractures and migrated along the inner and outer borders of the wollastonite margins. Chemical dispersion patterns of U, Al, Na + K, P, S, Fe, and REE across the chert-to-marble boundary and its metasomatic rims are shown by autoradiography and neutron-induced radiography. Scavenging of cations at mineralogical contacts and cation transport into the marbles occurred only on the mm to cm scale. Isotopic data for Pb and Sr across a simple metachert-marble boundary and for Pb, Sr, Nd, B, and Li across a metachert-pegmatite-marble sequence demonstrate the following: (1) The Pb and Sr isotopic signature of early fluids was buffered by the carbonate wallrock. Only late fluids, shielded from wallrock interaction by a wollastonite mantle, variably preserved a memory of their initial magmatic signature. (2) Since the Nd isotope signature of marble and chert is bound to calcite and clay minerals, systematic shifts to unradiogenic Nd in marble reflect loss of carbonate-bound Nd as the wollastonite margin is approached. Nd in the wollastonite margin is dominated by Nd originally bound to clay minerals. The later emplacement of the pegmatite, which carried the Nd isotope signature of its alkali-syenite source, had little effect on the Nd isotopic composition of the wollastonite rim. (3) Although the Li and B isotopic compositions reflect the alkali-syenite source, they are also affected by isotopic fractionation and partitioning between melt, fluid, and solids.Editorial responsibility J. Hoefs     

Ammonium loss and nitrogen isotopic fractionation in biotite as a function of metamorphic grade in metapelites from western Maine, USA

Ammonium fixed in micas of metamorphic rocks is a sensitive indicator both of organic-inorganic interactions during diagenesis as well as of the devolatilization history and fluid/rock interaction during metamorphism. In this study, a collection of geochemically well-characterized biotite separates from a series of graphite-bearing Paleozoic greenschist- to upper amphibolite-facies metapelites, western Maine, USA, were analyzed for ammonium nitrogen () contents and isotopic composition (δ¹⁵N_NH4) using the HF-digestion distillation technique followed by the EA-IRMS technique. Biotite separates, sampled from 9 individual metamorphic zones, contain 3000 to 100 ppm with a wide range in δ¹⁵N from +1.6‰ to +9.1‰. Average contents in biotite show a distinct decrease from about 2750 ppm for the lowest metamorphic grade (∼500 °C) down to 218 ppm for the highest metamorphic grade (∼685 °C). Decreasing abundances in are inversely correlated in a linear fashion with increasing K⁺ in biotite as a function of metamorphic grade and are interpreted as a devolatilization effect. Despite expected increasing δ¹⁵N_NH4 values in biotite with nitrogen loss, a significant decrease from the Garnet Zones to the Staurolite Zones was found, followed by an increase to the Sillimanite Zones. This pattern for δ¹⁵N_NH4 values in biotite inversely correlates with Mg/(Mg + Fe) ratios in biotite and is discussed in the framework of isotopic fractionation due to different exchange processes between or , reflecting devolatilization history and redox conditions during metamorphism.     

Particulate matter fluxes in the southern and central Kara Sea compared to sediments: Bulk fluxes, amino acids, stable carbon and nitrogen isotopes, sterols and fatty acids

The Kara Sea is one of the arctic marginal seas strongly influenced by fresh water and river suspension. The highly seasonal discharge by the two major rivers Yenisei and Ob induces seasonal changes in hydrography, sea surface temperature, ice cover, primary production and sedimentation. In order to obtain a seasonal pattern of sedimentation in the Kara Sea, sediment traps were deployed near the river mouth of the Yenisei (Yen) as well as in the central Kara Sea (Kara) within the framework of the German–Russian project “Siberian River run-off; SIRRO”. Two and a half years of time-series flux data were obtained between September 2000 and April 2003 and were analyzed for bulk components, amino acids, stable carbon and nitrogen isotopes as well as sterols and fatty acids.Sediment trap data show that much of the annual deposition occurred under ice cover, possibly enhanced by zooplanktonic activity and sediment resuspension. An early bloom of ice-associated algae in April/May occurred in the polynya area and may have been very important to sustain the life cycles of higher organisms after the light limitation of the winter months due to no/low insolation and ice cover. The strong river input dominated the months June–August in the southern part of the Kara Sea. The central Kara Sea had a much shorter productive period starting in August and was less affected by the river plumes. Despite different time-scales of sampling and trapping biases, total annual fluxes from traps were in the same order of magnitude as accumulation rates in surface sediments. Terrestrial organic carbon accumulation decreased from 10.7 to 0.3 g C m⁻² a⁻¹ from the riverine source to the central Kara Sea. Parallel to this, preservation of marine organic matter decreased from 10% to 2% of primary productivity which was probably related to decreasing rates of sedimentation.     

Effects of spring warming and mixing duration on diatom deposition in deep Tiefer See,NE Germany

Monitoring during three meteorologically different spring seasons in 2012, 2013, and 2014 revealed that temperature increase in spring, which influences spring lake mixing duration, markedly affected nutrient availability and diatom deposition in a sediment trap close to the bottom of deep Tiefer See, NE Germany. Deposition of Stephanodiscus taxa and small Cyclotella taxa was much higher after late ice out and a deep, short lake mixing period in spring 2013, compared to that after gradual warming and lengthy lake mixing periods in spring 2012 and 2014, when only brief or marginal ice cover occurred. Availability of dissolved Si and P was 33 and 20 % higher, respectively, in 2013 compared to 2014. The observed relation between high (low) diatom deposition and short (lengthy) mixing duration in spring was applied to varved sediments deposited between AD 1924 and 2008. Low detrital Si content in trapped material and a sediment core enabled use of µXRF-counts of Si as a proxy for diatom silica. The spring mixing duration for 1951–2008 was derived from FLake-model calculations. The spring warming duration related to lake mixing was approximated from air temperatures for 1924–2008 using the dates when daily mean air temperature exceeded 5 °C (start) and 10 °C (end). Diatom silica deposition showed a significant (p < 0.0001) inverse linear relationship with the modeled spring mixing duration (R² = 0.36) and the spring warming duration (R² = 0.28). In both cases, the relationship is strengthened when data from the period of low diatom production (1987–2005) is excluded (R² = 0.59 and R² = 0.35). Part of this low diatom production is related to external nutrient supply that favored growth of cyanobacteria at the expense of diatoms. This approach shows that diatom Si deposition was strongly influenced by the availability of light and nutrients, related to the duration of lake mixing and warming in spring, during most of the studied period. The remaining unexplained variability, however, indicates that additional factors influence Si deposition. Further tests in other deep, temperate lakes are necessary to verify if this relation is a common feature and consequently, if diatom Si can be used as a proxy for spring mixing duration in such lakes.     

Morphometric and hypsometric analysis in the Tierra Nueva Basin,San Luis Potosí, México

In areas with long periods of drought, it is essential to implement strategies to manage the available water resource. Tierra Nueva Basin is affected by this situation, consequently the farm production and livestock holdings are affected and the people don’t have access to enough water. In this paper, we propose an integrative methodology based on mathematical tools such as hypsometric and morphometric analysis applying geographic information systems. The proposal is strengthened with the aggregation of geological-structural, morphometrical, hypsometrical parameters and climatological information through a precipitation analysis provided by the National Water Commission from 1962 to 2010. According to the available data and the results obtained through the implemented proposal, an acceptable level of reliability is inferred allowing to determine areas structurally suitable for the use of surface water and its uptake. The methodology that we propose facilitates and simplifies the processes of searching and exploring locations suitable for surface water capture in arid and semi-arid zones, identifying in a qualitative and quantitative manner the optimal zone. For the case study, test-and-validation of the methodology the Tierra Nueva Basin in San Luis Potosí, México was selected. Tierra Nueva is a semi-arid site where “La Muñeca” dam is located. The results obtained in this work confirm the location of the “La Muñeca” dam as one of the most suitable areas for water collection. The methodology that we propose is a useful tool for the studies of water capturing purposes in arid and semi-arid zones.     

Fluxes of amino acids and hexosamines to the deep South China Sea

Settling particles collected by sediment traps deployed between 1987 and 1999 in the northern, central and southwestern South China Sea (SCS) were analysed to study seasonal, interannual and spatial variations in the composition and flux of labile particulate matter. Results were combined with remote-sensing and surface-sediment data in order to describe the factors controlling the preservation of organic matter en route from the upper ocean to the seafloor. Organic carbon, amino acid and hexosamine fluxes generally follow the fluxes of total particulate matter, with maxima during the SW and NE monsoon periods. During non-El Niño conditions spectral amino acid distributions show that degradation of organic matter in the water column decreases as the flux rates increase. This is suggested to be the combined result of enhanced primary productivity, greater input of lithogenics serving as ballast to increase settling rates, and sorption of labile components to clay minerals. During El Niño conditions, in contrast, the degree of organic matter degradation is at very high and comparable levels at all trap sites. Flux component seasonality is strongly reduced except for the coastal upwelling areas, particularly off central Vietnam, which show significantly higher fluxes of organic carbon and lithogenic matter as compared to the open SCS. This suggests that the fluxes are affected by lateral advection of reworked organic matter from riverine sources or resuspended sediments from the nearby shelf/slope. Comparison of the measured organic carbon fluxes in 1200 m depth with those accumulating in surface sediments results in a more than 80% loss of organic matter before final burial in the sediments. The degree of organic matter preservation in the surface sediments of the deep SCS is distinctly lower than in other monsoonal oceans. This may be due to varying lithogenic input and almost complete dissolution of protective biogenic mineral matrices at greater water depth.     

Climatic and limnological changes at Lake Karakul (Tajikistan) during the last ~29 cal ka

We present results of analyses on a sediment core from Lake Karakul, located in the eastern Pamir Mountains, Tajikistan. The core spans the last ~29 cal ka. We investigated and assessed processes internal and external to the lake to infer changes in past moisture availability. Among the variables used to infer lake-external processes, high values of grain-size end-member (EM) 3 (wide grain-size distribution that reflects fluvial input) and high Sr/Rb and Zr/Rb ratios (coinciding with coarse grain sizes), are indicative of moister conditions. High values in EM1, EM2 (peaks of small grain sizes that reflect long-distance dust transport or fine, glacially derived clastic input) and TiO₂ (terrigenous input) are thought to reflect greater influence of dry air masses, most likely of Westerly origin. High input of dust from distant sources, beginning before the Last Glacial Maximum (LGM) and continuing to the late glacial, reflects the influence of dry Westerlies, whereas peaks in fluvial input suggest increased moisture availability. The early to early-middle Holocene is characterised by coarse mean grain sizes, indicating constant, high fluvial input and moister conditions in the region. A steady increase in terrigenous dust and a decrease in fluvial input from 6.6 cal ka BP onwards points to the Westerlies as the predominant atmospheric circulation through to present, and marks a return to drier and even arid conditions in the area. Proxies for productivity (TOC, TOC/TN, TOC _Br ), redox potential (Fe/Mn) and changes in the endogenic carbonate precipitation (TIC, δ¹⁸O _Carb ) indicate changes within the lake. Low productivity characterised the lake from the late Pleistocene until 6.6 cal ka BP, and increased rapidly afterwards. Lake level remained low until the LGM, but water depth increased to a maximum during the late glacial and remained high into the early Holocene. Subsequently, the water level decreased to its present stage. Today the lake system is mainly climatically controlled, but the depositional regime is also driven by internal limnogeological processes.     

Hydraulic fracturing: a toxicological threat for groundwater and drinking-water?

This paper deals with the possible impact of hydraulic fracturing (fracking), employed in the exploitation of unconventional shale gas and tight gas reservoirs, on groundwater, which is the most important source of drinking-water in Germany and many other European countries. This assessment, which is part of an interdisciplinary study by a panel of neutral experts on the risks and environmental impact of hydraulic fracturing, is based mainly on data obtained from three ExxonMobil drilling sites in northern Germany. First, the basic technical aspects of fracking and its relevant water fluxes are explained. The type, purpose and fate of the constituents of the fracking fluids are discussed. The chemicals used in the fracking fluids are assessed with regard to their hazardous properties according to the Regulation (EC) No. 1272/2008 of the European Parliament and of the Council on the classification, labelling and packaging of substances and mixtures (CLP regulation) and the German “Water Hazard Classes”. Contamination of groundwater by ingredients of fracking fluids may occur from under ground or may result from above-ground accidents associated with the transport, storage and handling of hazardous substances used as additives in fracking fluids. The degree of groundwater contamination cannot be predicted in a general way. Therefore, different dilutions of the fracking fluid in groundwater are considered. It is shown that the concentrations of most ingredients resulting from a 1:10,000 up to 1:100,000 dilution of the fracking fluid in groundwater are below health-based reference values such as the limit values of the European Drinking Water Directive, the WHO Guideline Values for Drinking-water Quality, and other health-based guide values for drinking-water. Regarding the salinity of fracking fluids, a dilution of 1:1,000 is sufficient to reach concentrations which are acceptable for drinking-water. From the human-toxicological point of view, the constituents of flowback water are more problematic with respect to drinking-water produced from groundwater than those of the fracking fluids. The few reliable data which have become available, as well as hydrogeological considerations, point in the direction of considerable salt concentrations and toxic constituents, e.g., Hg, As, Pb, Zn, Cd, BTX, PAHs, or even radioactive elements. The identification and assessment of reaction products and metabolites, which are produced as a result of the fracking operation and the metabolic activity of microorganisms, are important topics for further research. The recommendations include the need for a better understanding of the environmental impact of fracking operations, especially with regard to the development of sustainable rules for planning, permission, performance and management of fracking, and for the monitoring of groundwater quality around fracked drilling sites.     

Investigation of the fate of nitrogen in Palaeozoic shales of the Central European Basin

Nitrogen geochemistry of Upper Carboniferous shales from the Central European Basin (CEB) was investigated by elemental analysis, stable isotope mass spectrometry and non-isothermal pyrolysis. Total N-contents of Namurian shales from four deep wells (4400–7000 m) in NE Germany ranged between 520 and 2680 ppm. Up to 90% of this nitrogen occurs as ammonium in minerals with δ¹⁵N values between + 1‰ and + 3.5‰. Low nitrogen contents (down to 460 ppm) and high δ¹⁵N values (up to + 5.6‰) in one well in the basin centre suggest a large-scale release of nitrogen associated with isotopic fractionation. Pyrolytic liberation of N₂ from pelagic Namurian A shales of NW and NE Germany occurred at significantly lower temperatures than from paralic Namurian B shales and terrestrial Westphalian samples. On-line isotope analysis of N₂ liberated between 400 and 1200 °C indicates the presence of precursor pools with different thermal stability and nitrogen isotopic composition.