Anthropogenic influence on trace element geochemistry of healing mud (peloid) from Makirina Cove (Croatia)

Due to their balneotherapeutic features, the organic-rich sediments in Makirina Cove are an important source of healing mud. An environmental geochemistry approach using normalization techniques was applied to evaluate the anthropogenic contribution of trace metals to sediments used as healing mud. Sediment geochemistry was found to be associated with land-use change and storm events, as well as with proximity of a road with heavy traffic in the summer months. Local valley topography preferentially channels lithogenic and pollutant transport to the cove. Concentrations and distribution of trace metals indicate lithogenic (Ni, Cr, Co) and anthropogenic (Pb, Cu, Zn and Se) contributions to the sediments. The calculation of enrichment factors indicates a moderate (EFs between 2–3.5) input of anthropogenic Cu and Pb in surficial sediments to a depth of 10 cm. Patients using the Makirina Cove sediments as healing mud could be to some extent exposed to enhanced uptake of metals from anthropogenic sources via dermal contact.     

Mineralogy and geochemistry of the Texeo Cu–Co mine site (NW Spain): screening tools for environmental assessment

The Cu–Co–Ni Texeo mine has been the most important source of Cu in NW Spain since Roman times and now, approximately 40,000 m³ of wastes from mine and metallurgical operations, containing average concentrations of 9,263 mg kg⁻¹ Cu, 1,100 mg kg⁻¹ As, 549 mg kg⁻¹ Co, and 840 mg kg⁻¹ Ni, remain on-site. Since the cessation of the activity, the abandoned works, facilities and waste piles have been posing a threat to the environment, derived from the release of toxic elements. In order to assess the potential environmental pollution caused by the mining operations, a sequential sampling strategy was undertaken in wastes, soil, surface and groundwater, and sediments. First, screening field tools were used to identify hotspots, before defining formal sampling strategies; so, in the areas where anomalies were detected in a first sampling stage, a second detailed sampling campaign was undertaken. Metal concentrations in the soils are highly above the local background, reaching up to 9,921 mg kg⁻¹ Cu, 1,373 mg kg⁻¹ As, 685 mg kg⁻¹ Co, and 1,040 mg kg⁻¹ Ni, among others. Copper concentrations downstream of the mine works reach values up to 1,869 μg l⁻¹ and 240 mg kg⁻¹ in surface water and stream sediments, respectively. Computer-based risk assessment for the site gives a carcinogenic risk associated with the presence of As in surface waters and soils, and a health risk for long exposures; so, trigger levels of these elements are high enough to warrant further investigation.     

A new method of estimating the ratio between in situ rock stresses and tectonics based on empirical and probabilistic analyses

This paper describes a new procedure for assessing the ratio between in situ stresses in rock masses by means of K (K = σ_H / σ_v, being σ_H and σ_v principal stress) and tectonics for purposes of engineering geology and rock mechanics. The method combines the use of the logic decision tree and the empirical relationship between the Tectonic Stress Index, TSI, and a series of K in situ values obtained from an extensive database. The decision tree considers geological and geophysical factors affecting stress magnitudes both on the regional and local scale. The TSI index is defined by geological and geomechanical parameters. The method proposed provides an assessment of the magnitude of horizontal stresses of tectonic origin. Results for several regions of Europe are presented and the possible applications of the procedure are discussed.     

Crystallization of authigenic carbonates in mud volcanoes at Lake Baikal

This paper presents data on authigenic siderite first found in surface sediments from mud volcanoes in the Central (K-2) and Southern (Malen’kii) basins of Lake Baikal. Ca is the predominant cation, which substitutes Fe in the crystalline lattice of siderite. The enrichment of the carbonates in the ¹³C isotope (from +3.3 to +6.8‰ for the Malen’kii volcano and from +17.7 to +21.9‰ for K-2) results from the crystallization of the carbonates during methane generation via the bacterial destruction of organic matter (acetate). The overall depletion of the carbonates in ¹⁸O is mainly inherited from the isotopic composition of Baikal water.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

Low-pressure,water-assisted anatexis of basic dykes in a contact metamorphic aureole,Fuerteventura (Canary Islands): oxygen isotope evidence for a meteoric fluid origin

Migmatites produced by low-pressure anatexis of basic dykes are found in a contact metamorphic aureole around a pyroxenite–gabbro intrusion (PX2), on Fuerteventura. Dykes outside and inside the aureole record interaction with meteoric water, with low or negative δ¹⁸O whole-rock values (+0.2 to −3.4‰), decreasing towards the contact. Recrystallised plagioclase, diopside, biotite and oxides, from within the aureole, show a similar evolution with lowest δ¹⁸O values (−2.8, −4.2, −4.4 and −7.6‰, respectively) in the migmatite zone, close to the intrusion. Relict clinopyroxene phenocrysts preserved in all dykes, retain typically magmatic δ¹⁸O values up to the anatectic zone, where the values are lower and more heterogeneous. Low δ¹⁸O values, decreasing towards the intrusion, can be ascribed to the advection of meteoric water during magma emplacement, with increasing fluid/rock ratios (higher dyke intensities towards the intrusion acting as fluid-pathways) and higher temperatures promoting increasing exchange during recrystallisation. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Shear strength characterization of municipal solid waste at the Suzhou landfill, China

The current practice of slope stability analysis for a municipal solid waste (MSW) landfill usually overlooks the dependence of waste properties on the fill age or embedment depth. Changes in shear strength of MSW as a function of fill age were investigated by performing field and laboratory studies on the Suzhou landfill in China. The field study included sampling from five boreholes advanced to the bottom of the landfill, cone penetration tests and monitoring of pore fluid pressures. Twenty-six borehole samples representative of different fill ages (0 to 13 years) were used to perform drained triaxial compression tests. The field and laboratory study showed that the waste body in the landfill can be sub-divided into several strata corresponding to different ranges of fill age. Each of the waste strata has individual composition and shear strength characteristics. The triaxial test results showed that the MSW samples exhibited a strain-hardening and contractive behavior. As the fill age of the waste increased from 1.7 years to 11 years, the cohesion mobilized at a strain level of 10% was found to decrease from 23.3 kPa to 0 kPa, and the mobilized friction angle at the same strain level increasing from 9.9° to 26°. For a confinement stress level greater than 50 kPa, the shear strength of the recently-placed MSW seemed to be lower than that of the older MSW. This behavior was consistent with the cone penetration test results. The field measurement of pore pressures revealed a perched leachate mound above an intermediate cover of soils and a substantial leachate mound near the bottom of the landfill. The measurements of shear strength properties and pore pressures were utilized to assess the slope stability of the Suzhou landfill.     

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from −2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ³⁰Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ³⁰Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO₂ precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo (α_pre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ³⁰Si value from roots to stem, including larger ratio of dissolved H₄SiO₄ to precipitated SiO₂ in roots than in stem. There is a positive correlation between the δ³⁰Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor (α_bam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO₂ contents and δ³⁰Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ³⁰Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ³⁰Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.     

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.     

Biotite weathering and nutrient uptake by ectomycorrhizal fungus, Suillus tomentosus, in liquid-culture experiments

Ectomycorrhiza-forming fungi (EMF) alter the nutrient-acquisition capabilities of vascular plants, and may play an important role in mineral weathering and the partitioning of products of weathering in soils under nutrient-limited conditions. In this study, we isolated the weathering function of Suillus tomentosus in liquid-cultures with biotite micas incubated at room temperature. We hypothesized that the fungus would accelerate weathering by hyphal attachment to biotite surfaces and transmission of nutrient cations via direct exchange into the fungal biomass. We combined a mass-balance approach with scanning electron microscopy (SEM) and atomic force microscopy (AFM) to estimate weathering rates and study dissolution features on biotite surfaces. Weathering of biotite flakes was about 2-3 orders of magnitude faster in shaken liquid-cultures with fungus compared to shaken controls without fungus, but with added inorganic acids. Adding fungus in nonshaken cultures caused a higher dissolution rate than in inorganic pH controls without fungus, but it was not significantly faster than organic pH controls without fungus. The K⁺, Mg²⁺ and Fe²⁺ from biotite were preferentially partitioned into fungal biomass in the shaken cultures, while in the nonshaken cultures, K⁺ and Mg²⁺ was lost from biomass and Fe²⁺ bioaccumulated much less. Fungal hyphae attached to biotite surfaces, but no significant surface changes were detected by SEM. When cultures were shaken, the AFM images of basal planes appeared to be rougher and had abundant dissolution channels, but such channel development was minor in nonshaken conditions. Even under shaken conditions the channels only accounted for only 1/100 of the total dissolution rate of 2.7 × 10⁻¹⁰ mol of biotite m⁻² s⁻¹. The results suggest that fungal weathering predominantly occurred not by attachment and direct transfer of nutrients via hyphae, but because of the acidification of the bulk liquid by organic acids, fungal respiration (CO₂), and complexation of cations which accelerated dissolution of biotite. Results further suggest that both carbohydrate source (abundant here) and a host with which nutrients are exchanged (missing here) may be required for EMF to exert an important weathering effect in soils. Unsaturated conditions and physical dispersal of nutrient-rich minerals in soils may also confer a benefit for hyphal growth and attachment, and promote the attachment-mediated weathering which has been observed elsewhere on soil mineral surfaces.