Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

Modeling on adsorption–desorption of trace metals to suspended particle matter in the Changjiang Estuary

The uptake and release of trace metals (Cu, Ni, Zn, Cd, and Co) in estuaries are studied using river and sea end-member waters and suspended particulate matter (SPM) collected from the Changjiang Estuary, China. The kinetics of adsorption and desorption were studied in terms of environmental factors (pH, SPM loading, and salinity) and metal concentrations. The uptake of the metals studied onto SPM occurred mostly within 10 h and reached an asymptotic value within 40 h in the Changjiang Estuary. As low pH river water flows into the high pH seawater and the water become more alkaline as it approaches to the seaside of estuary, metals adsorb more on SPM in higher pH water, thus, particulate phase transport of metal become increasingly important in the seaward side of the estuary. The percentage of adsorption recovery and the distribution coefficients for trace metals remained to be relatively invariable and a significant reduction only occurred in very high concentrations of metals (>0.1 mg L⁻¹). The general effect of salinity on metal behavior was to decrease the degree of adsorption of Cu, Zn, Cd, Co, and Ni onto SPM but to increase their adsorption equilibrium pH. The adsorption–desorption kinetics of trace metals were further investigated using Kurbatov adsorption model. The model appears to be most useful for the metals showing the conservative behavior during mixing of river and seawater in the estuary. Our work demonstrates that dissolved concentration of trace metals in estuary can be modeled based on the metal concentration in SPM, pH and salinity using a Kurbatov adsorption model assuming the natural SPM as a simple surfaced molecule.     

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.     

Phosphorus transport in shallow groundwater in peri-urban Kampala, Uganda: results from field and laboratory measurements

To understand Phosphorus (P) sources and transport processes in the subsurface in Bwaise III Parish, Kampala, P attenuation and adsorption capacities of soils were studied in situ and from laboratory measurements. Relationships between sorption parameters and soil matrix properties, rates and mechanism of the adsorption process and soil P fractions were also investigated. P was generally higher in the wet than the dry season, but for both seasons, the maximum was 5 mgP/l. P transport mechanisms appeared to be a combination of adsorption, precipitation, leaching from the soil media and by colloids with the latter two playing an important role in the wet season. The sorption process comprised two phases with the first stage rate constants being about fourfold those of the second stage. The Langmuir isotherm described the sorption data well (R ² ≥ 0.95) with the second soil layer exhibiting the highest sorption maximum (C _max) (average value 0.6 ± 0.17 mgP/gDW). The best prediction of C _max had organic carbon, Ca, available P and soil pH. Residual P consisting mostly of organics was the main fraction in all the layers followed by inorganic HCl-P and NaOH-P in the top and middle layers, respectively. Loosely bound P (NH₄Cl-P) was the least fraction (<0.4% of total P) in all layers indicating the high binding capacity of P by the soils. The study results suggest that P dynamics is related to Ca, Fe and organic carbon content of the soils.     

Determining effective wellbore permeability from a field pressure test: a numerical analysis of detection limits

We propose a simple pressure test that can be used in the field to determine the effective permeability of existing wellbores. Such tests are motivated by the need to understand and quantify leakage risks associated with geological storage of CO₂ in mature sedimentary basins. If CO₂ is injected into a deep geological formation, and the resulting CO₂ plume encounters a wellbore, leakage may occur through various pathways in the “disturbed zone” surrounding the well casing. The effective permeability of this composite zone, on the outside of the well casing, is an important parameter for models of leakage. However, the data that exist on this key parameter do not exist in the open literature, and therefore specific field tests need to be done in order to reduce the uncertainty inherent in the leakage estimates. The test designed and analyzed herein is designed to measure effective wellbore permeability within a low-permeability caprock, bounded above and below by permeable reservoirs, by pressurizing the reservoir below and measuring the response in the reservoir above. Alternatively, a modified test can be performed within the caprock without directly contacting the reservoirs above and below. We use numerical simulation to relate pressure response to effective well permeability and then evaluate the range of detection of the effective permeability based on instrument measurement error and limits on fracture pressure. These results can guide field experiments associated with site characterization and leakage analysis.     

The landslides threatening Tasova town (Central Anatolia, Turkey) and their environmental impacts

There exist a number of landslides along the north Anatolian fault zone (NAFZ) between Tasova and Alparslan in Amasya province in Turkey. These landslides extending over an area of 2.5 × 6.0 km are triggered by steepening of slopes due to undercutting by the Yesilirmak River and groundwater fluctuations. The landslides have affected 30 buildings in the western part of Tasova. In this study, in order to investigate the engineering geological characteristics of the landslides and their environmental impacts, representative samples from geological units were collected and a total of six boreholes were drilled. Plastic pipes were installed into the boreholes to measure the groundwater fluctuations and to determine the position of the sliding surface. For a two-year monitoring period, using a GPS linked to a fixed station system, the magnitude of the movements ranged between 11.7 and 17.6 cm at the toe of landslide. The landslides that occurred in the study area were in the form of retrogressive circular and multiple circular failures. The factor of safety along a number of cross-sections calculated by the limit-equilibrium method of analysis is 0.96 in static condition. After further analyses, construction of a toe buttress with surface drainage may be suggested as a remedial measure to minimize the effects of these landslides.     

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.     

Sediment salt-load in the St Lucia Estuary during the severe drought of 2002–2006

The purpose of this study was to determine whether there was a sufficiently high residual salt load in the dry sediments of the St Lucia Estuary to cause salinity problems should it later fill up with either freshwater or seawater. The estuary lakes have suffered the effects of a severe drought since 2002 with the result that many areas were dry, and the salinity of the residual water varied between 4 psu and up to five times that of seawater. Measurements of the salts content in the sediments to a depth of 20 cm showed that more than 2 million tonnes of salt was held in this layer of the sediment in 2006. Recent management of the estuary (since 1970) has ensured that the mouth was not artificially opened. This was to prevent the inflow of seawater, with its salts, that would otherwise enter while the drought was in place. The results of the sediment salinity data showed that if the drought had been broken and the lake area filled with rain and river water, the resulting salinity would be about 6 psu. In March 2007, Cyclone Gamede in the Indian Ocean off the east coast of South Africa produced a wave climate at sea that resulted in the mouth breaching; thus introducing an estimated 12 million tonnes of salts. The high salinity in the system resulting from this breach is expected to have an adverse effect on the ecology of the system, whereas the residual salinity in the sediments would not have caused an environmental problem. If the estuary and lake system were to fill completely with seawater, the residual salts together with seawater will raise the salinity to an initial value higher than 40 psu, which will have the effect of suppressing much of the important submerged vegetation that is vital for sustaining juvenile fish in the system. Many of the large fauna will also suffer from a shortage of freshwater.