Nitrate contamination in a shallow urban aquifer in East Ukraine: evidence from hydrochemical,stable isotopes of nitrate and land use analysis

A combined hydrochemical and stable isotope approach was used to investigate the origin of nitrate in the shallow unconfined groundwater of Kharkiv city, Eastern Ukraine. The contamination was investigated in the context of land use within the catchment area. The observed enrichment of sulfate, chloride and nitrate suggests significant groundwater contamination in the shallow urban aquifer, which is widely used as drinking water source for the urban population. Characteristic nitrate/chloride ratios as well as stable isotope ratios (N and O) of nitrate in the most contaminated springs confirmed that septic waste from leaky sewer systems was the main source of nitrate contamination in the groundwater. Nitrate contamination is linked to the type of land use and sewage treatment regime in the catchment area. It is also modulated by the regional hydrogeology, which determines the susceptibility of a given aquifer toward groundwater pollution. A more quantitative assessment of nitrate sources based on the nitrate isotope analysis alone is rather difficult. However, our study confirms that the combination of hydrochemical tracers, robust land-use analysis and nitrate stable isotope measurements represents a valuable approach to identify the origin of the nitrate contamination.     

Removal of Cr(VI) and phenol coupled with the reduction of sulfate by sulfate-reducing bacteria sludge

Biological treatment of industrial wastewater containing heavy metal and organic pollutant has attracted extensive attention. In this study, Cr(VI) reduction coupled with phenol degradation was investigated by the sulfate-reducing bacteria (SRB) sludge with addition of zero-valent iron (ZVI). The results showed that the SRB wet sludge (SWS) had a good bioactivity in the reduction of Cr(VI) only when the initial concentration of Cr(VI) was below 60 mg L^?1. The addition of ZVI significantly enhanced the bioactivity and reusability of SWS, and the reduction percentage of Cr(VI) achieved 98% after SWS was successively used for seven cycles. SWS coupled with ZVI showed a high activity in phenol degradation, with more than 94% phenol being degraded in each cycle. However, in the simultaneous removal of Cr(VI) and phenol, phenol degradation was inhibited due to the toxicity of Cr(VI) to phenol degrading microbes in SWS. On the other hand, reduction of sulfate and Cr(VI) was not affected by the presence of phenol, with more than 95% of sulfate and Cr(VI) being removed at the end of the 5th cycle. This study enriches our understanding on the applications of the SRB sludge in the removal of organic and inorganic contaminants in wastewater.     

Influence of retardation and acceleration of setting time on the efficiency of water defluoridation by calcined gypsum

Fluoride ion (F^?) removal technologies from water (defluoridation) suffer from cost and/or efficiency drawbacks. The hugely available low-cost calcined gypsum (plaster of paris) represents a material of choice, especially in the developing countries. Partially soluble calcined gypsum introduces Ca²⁺ and SO₄ ^2? into the water. In this work, the influence of tartaric acid, paracetamol, polyvinyl alcohol and Zn/Al layered double hydroxide additives (either retarders or accelerators) on defluoridation of water by calcined gypsum was studied. These additives act as retarders to the calcined gypsum setting and, hence, delay or disturb the crystallization of gypsum, offering the time for the crystallization of fluoro-compounds containing calcium, fluoride, phosphate and silicate. The more retarded the setting time, the more the Ca²⁺ is introduced in the solution, and hence, the more efficient the defluoridation process. The values of ΔG ⁰ are negative for all additives, indicating the spontaneity of the fluoride removal process. The results of X-ray diffraction, Fourier transform infrared and scanning electron microscopy of the produced gypsum supported this interpretation.     

High- and low-Cr chromitite and dunite in a Tibetan ophiolite: evolution from mature subduction system to incipient forearc in the Neo-Tethyan Ocean

The microstructures, major- and trace-element compositions of minerals and electron backscattered diffraction (EBSD) maps of high- and low-Cr# [spinel Cr# = Cr³⁺/(Cr³⁺ + Al³⁺)] chromitites and dunites from the Zedang ophiolite in the Yarlung Zangbo Suture (South Tibet) have been used to reveal their genesis and the related geodynamic processes in the Neo-Tethyan Ocean. The high-Cr# (0.77–0.80) chromitites (with or without diopside exsolution) have chromite compositions consistent with initial crystallization by interaction between boninitic magmas, harzburgite and reaction-produced magmas in a shallow, mature mantle wedge. Some high-Cr# chromitites show crystal-plastic deformation and grain growth on previous chromite relics that have exsolved needles of diopside. These features are similar to those of the Luobusa high-Cr# chromitites, possibly recycled from the deep upper mantle in a mature subduction system. In contrast, mineralogical, chemical and EBSD features of the Zedang low-Cr# (0.49–0.67) chromitites and dunites and the silicate inclusions in chromite indicate that they formed by rapid interaction between forearc basaltic magmas (MORB-like but with rare subduction input) and the Zedang harzburgites in a dynamically extended, incipient forearc lithosphere. The evidence implies that the high-Cr# chromitites were produced or emplaced in an earlier mature arc (possibly Jurassic), while the low-Cr# associations formed in an incipient forearc during the initiation of a new episode of Neo-Tethyan subduction at ~130–120 Ma. This two-episode subduction model can provide a new explanation for the coexistence of high- and low-Cr# chromitites in the same volume of ophiolitic mantle.     

Seasonal effects on geophysical–geotechnical relationships and their implications for electrical resistivity tomography monitoring of slopes

Current assessments of slope stability rely on point sensors, the results of which are often difficult to interpret, have relatively high costs and do not provide large-area coverage. A new system is under development, based on integrated geophysical–geotechnical sensors to monitor groundwater conditions via electrical resistivity tomography. So that this system can provide end users with reliable information, it is essential that the relationships between resistivity, shear strength, suction and water content are fully resolved, particularly where soils undergo significant cycles of drying and wetting, with associated soil fabric changes. This paper presents a study to establish these relationships for a remoulded clay taken from a test site in Northumberland, UK. A rigorous testing programme has been undertaken, integrating the results of multi-scalar laboratory and field experiments, comparing two-point and four-point resistivity testing methods. Shear strength and water content were investigated using standard methods, whilst a soil water retention curve was derived using a WP4 dewpoint potentiometer. To simulate seasonal effects, drying and wetting cycles were imposed on prepared soil specimens. Results indicated an inverse power relationship between resistivity and water content with limited hysteresis between drying and wetting cycles. Soil resistivity at lower water contents was, however, observed to increase with ongoing seasonal cycling. Linear hysteretic relationships were established between undrained shear strength and water content, principally affected by two mechanisms: soil fabric deterioration and soil suction loss between drying and wetting events. These trends were supported by images obtained from scanning electron microscopy.     

Discovery of Iapetognathus fauna from far western New South Wales: towards a more precisely defined Cambrian–Ordovician boundary in Australia

Conodont species Iapetognathus fluctivagus and Iapetonudus ibexensis are documented for the first time from Australia. The former is the primary marker internationally defining the base of the Ordovician, and the latter is also a distinctive species previously recorded only from the base of the Ordovician in North America. Both species were recovered from a single sample in the Kandie Tank Limestone of the Kayrunnera Group, located about 50 km west of White Cliffs in far western New South Wales. Other species recovered from this sample include Prooneotodus spp., Cordylodus lindstromi, Cordylodus proavus, Hirsutodontus simplex, Teridontus nakamurai and Variabiloconus sp. Recognition of the Iapetognathus fluctivagus Biozone in the Kandie Tank Limestone supports its correlation with the Green Point section (Global Stratigraphic Section and Point for the base of the Ordovician) in western Newfoundland and the Lawson Cove section of Utah (Auxiliary Stratigraphic Section and Point), as well as sections in Asia and South America. Review of other sections in Australia and elsewhere spanning the Cambrian–Ordovician boundary confirms that, in the absence of I. fluctivagus, the presence of C. lindstromi is a good proxy for this level.     

Characteristics of black shale in the Upper Ordovician Wufeng and lower Silurian Longmaxi formations in the Sichuan Basin and its periphery,China

Geochemical and mineralogical analyses, in addition to isothermal adsorption experiments on field samples, are used to characterise the sedimentary environments, reservoirs and adsorbed gas of the Upper Ordovician Wufeng–lower Silurian Longmaxi formations in the Sichuan Basin and its peripheral areas. The sedimentary environment of the Wufeng and the lower part of Longmaxi formations is a deep-water shelf with five different lithologies identified: siliceous shale, black shale, siltstone, biolithite limestone and bentonite. The black shale in the Wufeng and the lower part of Longmaxi formations is 50 m thick, with an average organic carbon content (TOC) of 3.81 wt% and a maturity (Ro) of 1.62%. Quartz comprises 54.94 vol% of the shale and positively correlates with the TOC. Micropores in the black shale include intergranular pores, intragranular pores, organic matter pores and microfractures. Among these pores, spaces between clay sheets and organic molecules represent a favourable storage space for the accumulation and preservation of oil and gas. The Langmuir volume parameter ranges between 1.52 and 3.01 cm³/g, with an average value of 2.33 cm³/g. The presence of organic matter pores and pores between clay sheets in the black shale is the main and controlling factor for accumulated gas.     

Semi‐analytical solution to one‐dimensional consolidation for unsaturated soils with semi‐permeable drainage boundary under time‐dependent loading

This paper presents semi‐analytical solutions to Fredlund and Hasan's one‐dimensional consolidation of unsaturated soils with semi‐permeable drainage boundary under time‐dependent loadings. Two variables are introduced to transform two coupled governing equations of pore‐water and pore‐air pressures into an equivalent set of partial differential equations, which are easily solved by the Laplace transform. The pore‐water pressure, pore‐air pressure and settlement are obtained in the Laplace domain. Crump's method is adopted to perform the inverse Laplace transform in order to obtain semi‐analytical solutions in time domain. It is shown that the present solutions are more general and have a good agreement with the existing solutions from literatures. Furthermore, the current solutions can also be degenerated into conventional solutions to one‐dimensional consolidation of unsaturated soils with homogeneous boundaries. Finally, several numerical examples are provided to illustrate consolidation behavior of unsaturated soils under four types of time‐dependent loadings, including instantaneous loading, ramp loading, exponential loading and sinusoidal loading. Parametric studies are illustrated by variations of pore‐air pressure, pore‐water pressure and settlement at different values of the ratio of air–water permeability coefficient, depth and loading parameters. Copyright © 2017 John Wiley & Sons, Ltd.     

Tracing subsurface migration of contaminants from an abandoned municipal landfill

This paper aims at determining of inorganic leachate contamination for a capped unsanitary landfill in the absence of hydrogeological data. The 2D geoelectrical resistivity imaging, soil physicochemical characterization, and surface water analysis were used to determine contamination load and extent of selective heavy metal contamination underneath the landfill. The positions of the contaminated subsoil and groundwater were successfully delineated in terms of low resistivity leachate plumes of <10 Ωm. Leachate migration towards the reach of Kelang River could be clearly identified from the resistivity results and elevated concentrations of Fe in the river downslope toe of the site. Concentration of Fe, Mn, Ca, Na, K, Mg, Cu, Cr, Co, Ni, Zn, and Pb was measured for the subsoil samples collected at the downslope (BKD), upslope (BKU), and the soil-waste interface (BKI), of the landfill. The concentration levels obtained for most of the analyzed heavy metals significantly exceed the normal range in typical municipal solid waste landfill sites. The measured heavy metal contamination load in the subsoil is in the following order Fe ? Mn > Zn > Pb > Cr > Cu. Taking into consideration poor physical and chemical characteristics of the local soil, these metals first seem to be attenuated naturally at near surface then remobilize unavoidably due to the soil acidic environment (pH 4.2-6.18) which in turn, may allow an easy washing of these metals in contact with the shallow groundwater table during the periodic fluctuation of the Kelang River. These heavy metals are believed to have originated from hazardous industrial waste that might have been illegally dumped at the site.     

Geochemical characterization of surface water and spring water in SE Kashmir Valley,western Himalaya: Implications to water–rock interaction

Water samples from precipitation, glacier melt, snow melt, glacial lake, streams and karst springs were collected across SE of Kashmir Valley, to understand the hydrogeochemical processes governing the evolution of the water in a natural and non-industrial area of western Himalayas. The time series data on solute chemistry suggest that the hydrochemical processes controlling the chemistry of spring waters is more complex than the surface water. This is attributed to more time available for infiltrating water to interact with the diverse host lithology. Total dissolved solids (TDS), in general, increases with decrease in altitude. However, high TDS of some streams at higher altitudes and low TDS of some springs at lower altitudes indicated contribution of high TDS waters from glacial lakes and low TDS waters from streams, respectively. The results show that some karst springs are recharged by surface water; Achabalnag by the Bringi stream and Andernag and Martandnag by the Liddar stream. Calcite dissolution, dedolomitization and silicate weathering were found to be the main processes controlling the chemistry of the spring waters and calcite dissolution as the dominant process in controlling the chemistry of the surface waters. The spring waters were undersaturated with respect to calcite and dolomite in most of the seasons except in November, which is attributed to the replenishment of the CO₂ by recharging waters during most of the seasons.