Aerobic methanotrophy at ancient marine methane seeps: A synthesis

The molecular fingerprints of the chemosynthesis based microbial communities at methane seeps tend to be extremely well preserved in authigenic carbonates. The key process at seeps is the anaerobic oxidation of methane (AOM), which is performed by consortia of methanotrophic archaea and sulphate reducing bacteria. Besides the occurrence of ¹³C depleted isoprenoids and n-alkyl chains derived from methanotrophic archaea and sulphate reducing bacteria, respectively, ¹³C depleted triterpenoids have been reported from a number of seep deposits. In order to evaluate the significance of these apparently non-AOM related molecular fossils, the biomarker inventories of one Campanian and two Miocene methane seep limestones are compared. These examples provide strong evidence that methane was not solely oxidized by an anaerobic process. Structural and carbon isotope data reveal that aerobic methanotrophy was common at some ancient methane seeps as well. The Miocene Marmorito limestone contains abundant 3β-methylated hopanoids (δ¹³C: −100‰). Most likely, 3β-methylated hopanepolyols, prevailing in aerobic methanotrophs, were the precursor lipids of these compounds. A series of isotopically depleted 4-methylated steranes (lanostanes; δ¹³C: −80‰ to −70‰) and similarly isotopically depleted 17β(H),21β(H)-32-hopanoic acid in the Miocene Pietralunga seep limestone also are derived probably from aerobic methanotrophs. Lanosterol, which is known to be produced by aerobic methanotrophs, is the most likely precursor of 4-methylated steranes. Less obvious is the origin of 8,14-secohexahydrobenzohopanes (δ¹³C: −110‰ to −107‰) in Late Cretaceous seep limestones. These hopanoids probably reflect early degradational products of precursor lipids locally produced by seep endemic aerobic methanotrophs.     

Soil contamination from urban and industrial activity: example of the mining district of Linares (southern Spain)

The Linares region (southern Spain) has been subjected to two important sources of pollution: the intensive mining works and the urban-industrial activity. To obtain a geochemical characterisation of the soil, 31 trace elements were analysed and 669 soil samples were collected. By means of clustering analysis, we identified groups of elements and grid squares in which relations could be established concerning soil lithology, urban and industrial activities and the degree of pollution impact; in addition, we were able to characterise the geochemical background of the study area. The multivariate study led us to identify four factors. Particularly important was factor 2, which represented the elements associated with mineral paragenesis (Cu, Pb, As, Co, Mn, Zn, Sn, Ba). This factor also contains elements related with an urban-industrial activity, such as Pb, Cu, Zn, As and Ba. Furthermore, we identified factor 4, associating Ni, V and Cr, and which is related to the use of fuels.     

Impact evaluation on groundwater of the infiltration of an urban wastewater geopurification system placed over a detrital aquifer in a semiarid region (Spain)

Over a period of 4 years and 4 months, the geopurification installations at Dehesas de Guadix (Granada, Spain) were monitored to determine the impact on soil and groundwater of the controlled discharge of urban wastewater, and also to identify the best indicators of the entry of the recharged water into the aquifer. The installations are located in an area where the climate is Mediterranean sub-arid, with an average precipitation of less than 287 mm/year, and a rate of evapotranspiration that is almost three times greater. The system was controlled by determining the balance of majority nutrients and boron in the soil and in the groundwater, both at the points affected directly by the wastewater discharge and at others. The quantity of mass discharged was relatively large (COD 14,656 g/m², NO₃ 85 g/m², NO₂ 4 g/m², NH₄ 2,425 g/m², PO₄ 1,143 g/m², K 1,531 g/m², B 63 g/m²). It was observed that the elimination of nutrients within the soil (COD 97.5%, PO₄ 94.4%, K 59.17%, N _total 18.8%, B 12.69%) was very efficient except for the nitrogen, which nevertheless did not reach the groundwater, as it was eliminated at deep levels of the unsaturated zone. Only 12.69% of the boron was removed, and appreciable, increasing amounts of this element did reach the groundwater. Unexpectedly, none of the majority nutrients behaved as a reliable indicator of the impact on groundwater; despite this, the boron and the bicarbonate did clearly reflect the arrival of the recharged water, and are proposed as the best indicators.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

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.     

Space–time distribution of ancient and active alluvial karst subsidence: examples from the central Ebro Basin,Spain

Space and time variations of alluvial karst subsidence in the central Ebro Basin are analysed in trenches (paleodolines), aerial photographs (historical dolines) and field surveys (present-day active dolines). The measured subsidence rates, as well as a comparison between densities of paleodolines computed in randomly selected scan-lines and density of active dolines computed in maps, suggest that present-day subsidence in favourable areas is more intense than that of Pleistocene times. According to diachronic maps drawn from (a) different aerial photographs taken after 1946 and (b) field surveys on deformations in urbanized areas, subsidence behaved as a nearly steady process while the whole area was used for agriculture. In contrast, rapid changes (through periods of several tens of years) have occurred in urbanized areas, in which dolines expand their boundaries through small marginal collapses, shifting sharply their sinking centres to neighbouring sites. These rapid changes do not have an equivalent in observed paleodolines.     

Environmental risk evaluation of the use of mine spoils and treated sewage sludge in the ecological restoration of limestone quarries

The ecologic restoration criteria in areas degraded from extraction activities require making use of their mine spoils. These materials do not meet fertility conditions to guarantee restoration success and therefore, need the incorporation of organic amendments to obtain efficient substratum. Reducing the deficiencies in the organic material and restoration material nutrients with the contribution of treated sewage sludge is proposed in this work. This experiment was based on a controlled study using columns. The work was conducted with two mine spoils, both very rich in calcium carbonate. The first mineral, of poor quality, came from the formation of aggregates of crushed limestone (Z). The other residual material examined originated in limestone extraction, formed by the levels of interspersed non-limestone materials and the remains of stripped soils (D). Two treatments were undertaken (30,000 and 90,000 kg/ha of sewage sludge), in addition to a control treatment. The water contribution was carried out with a device that simulated either short-duration rain or a flooding irrigation system in order to cover the surface and then percolate through the soil. The collection of leached water took place 24 h after the applications. Different parameters of the leached water were determined, including pH, electrical conductivity, nitrate anions, ammonium, phosphates, sulphates and chlorides. The values obtained for each irrigation application are discussed, and the nitrate values obtained were very elevated.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mineral inclusions in diamonds from the Kelsey Lake Mine, Colorado, USA: Depleted Archean mantle beneath the Proterozoic Yavapai province

Thirty-four silicate and oxide inclusions large enough for in situ WDS electron microprobe analysis were exposed by grinding/polishing of 19 diamonds from the Kelsey Lake Mine in the Colorado-Wyoming State Line Kimberlite district. Eighteen olivines, seven Cr-pyropes, four Mg-chromites, and one orthopyroxene in 15 stones belong to the peridotite (P) suite and three garnets and one omphacite in three stones belong to the eclogite (E) suite. The fact that this suite is dominated by the peridotite population is in stark contrast to the other diamond suites studied in the State Line district (Sloan, George Creek), which are overwhelmingly eclogitic. Kelsey Lake olivine inclusions are magnesian (17 of 18 grains in 9 stones are in the range Fo 92.7-93.1), typical of harzburgitic P-suite stones worldwide, but unlike the more Fe-rich (lherzolitic) Sloan olivine suite. Mg-chromites (wt% MgO = 12.8-13.8; wt% Cr₂O₃ = 61.4-66.6) are in the lower MgO range of diamond inclusion chromites worldwide. Seven harzburgitic Cr-pyropes in five stones have moderately low calcium contents (wt% CaO = 3.3-4.3) but are very Cr-rich (wt% Cr₂O₃ = 9.7-16.7). A few stones have been analyzed by SIMS for carbon isotope composition and nitrogen abundance. One peridotitic stone is apparently homogeneous in carbon isotope composition (δ¹³C_PDB = −6.2‰) but with variable nitrogen abundance (1296-2550 ppm). Carbon isotopes in eclogitic stones range from “normal” for the upper mantle (δ¹³C_PDB = −5.5‰) to somewhat low (δ¹³C_PDB = −10.2‰), with little internal variation in individual stones (maximum difference is 3.6‰). Nitrogen contents (2-779 ppm) are lower than in the peridotitic stone, and are lower in cores than in rims. As, worldwide, harzburgite-suite diamonds have been shown to have formed in Archean time, we suggest that the Kelsey Lake diamond population was derived from a block of Archean lithosphere that, at the time of kimberlite eruption, existed beneath the Proterozoic Yavapai province. The mixed diamond inclusion populations from the State Line kimberlites appear to support models in which volumes of Wyoming Craton Archean mantle survive buried beneath Proterozoic continental crust. Such material may be mixed with eclogitic/lherzolitic regimes emplaced beneath or intermingled with the Archean rocks by Proterozoic subduction.     

Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.