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.     

Delineation of groundwater protection zones by the backward particle tracking method: theoretical background and GIS-based stochastic analysis

The backward particle tracking method, an effective and powerful tool that can be used to delineate groundwater protection zones, is presented. The theoretical background and insights on the applicability of this method are provided. Moreover, the present work enriches the backward particle tracking method with an uncertainty analysis concerning the porosity values, applying a Monte Carlo (MC) approach, coupled with the use of geographical information systems (GIS). As an application example, a wellfield in the Komotini area, Greece, is investigated. The present study may serve as a potential guideline for wellfield delineation, particularly in areas like Greece where lack of data related to the hydrogeological system is often a problem.     

Geomorphic changes in Ras Al-Subiyah area,Kuwait

The Ras Al-Subiyah area is considered one of the most promising areas in Kuwait for future development. This development will include a new town called Subiyah and its associated infrastructure. This area is also being considered as the location for connection between Boubyan Island, which is now undergoing major development and the Kuwait mainland. The present study investigates the geomorphology of the Ras Al-Sabiyah area in the northern sector of Kuwait. The study area is generally flat, and it is located west of the Jal Az-Zor escarpment. It is bordered on the east by the Khor Al-Sabiyah tidal channel and on the south by Kuwait Bay. The area receives sediments from several sources; currently the most important are aeolian sediments and the deposition of mud delivered through the Khor Al-Sabiyah from the Iraqi marshes. The study area has been subjected to severe environmental changes due to the Gulf wars and the drainage of Iraqi marshes and the associated artificial changes in fluvial system. Twenty-two surface sediments were collected from the Ras Al-Subiyah area. Samples were collected to include the main geomorphologic characteristic features of the study area. Field observations and remote sensing images from 1990 and 2001 were used to produce an updated geomorphologic map for the Ras Al-Subiyah and a map showing geomorphic changes between 1990 and 2001. Grain size of the surface sediment ranges from gravel to medium sand. In general, grain size statistical analysis indicates that most of the areas are composed of two or more classes of sands transported and deposited from different sources including aeolian, sabkhas, river and the bays. The variability in the grain size statistical parameters may be attributed to the complexity of surface morphology as well as the diversity in the type of depositional environment in the Ras Al-Subiyah area. The total area subjected to change during the 12-year period (1990–2001) is about 32 km² as calculated using GIS techniques.     

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.     

Doline probability map using logistic regression and GIS technology in the central Ebro Basin (Spain)

In the surroundings of Zaragoza, karstification processes are especially intense in covered karst areas where fluvial terraces lie directly on Tertiary evaporites. Since the beginning of Quaternary, these processes have lead to the development of collapse and subsidence dolines with a wide range of sizes, which have significant economic impacts. To reduce economic impact and increase safety, a regional analysis of this phenomenon is needed for spatial management. Therefore, a probability map of dolines was developed using logistic regression and geographic information system (GIS) techniques. This paper covers the selection of input data, manipulation of data using the GIS technology, and the use of logistic regression to generate a doline probability map. The primary variable in the doline development in this area is geomorphology, represented by the location of endorheic areas and different terrace levels. Secondary variables are the presence of irrigation and the water table gradient.     

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.     

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.     

Suitability analysis for sand and gravel extraction site location in the context of a sustainable development in the surroundings of Zaragoza (Spain)

Zaragoza city is located in the central Ebro Basin, in the Iberian Peninsula. The fluvial terraces formed by the Ebro River present a valuable resource of sand and gravel deposits. However, taking advantage of these available resources implies conflicts with other land use interests like urban and industrial development as well as agricultural use, which has also traditionally occupied the alluvial terraces. These deposits represent a substantial groundwater resource that should be preserved for future generations. The development of spatial decision support systems (SDSS) has greatly assisted efforts for solving land-use conflicts. These systems combine the benefits of geographic information systems (GIS) and decision support methodologies and are therefore suitable to manage sustainable development of urban areas. In this contribution, an extraction suitability map taking into consideration a variety of environmental criteria is created with the help of a SDSS. The method used is the analytical hierarchy process which is integrated in ArcGIS. Areas most suitable to sand and gravel extraction are located in the high terraces, and in those terraces covered by pediments where the thickness of resource is relatively high. These areas are far from valuable natural areas, outside areas most vulnerable to groundwater contamination, and beneath soils with poor irrigation characteristics.     

Quick-look assessments to identify optimal CO2 EOR storage sites

A newly developed, multistage quick-look methodology allows for the efficient screening of an unmanageably large number of reservoirs to generate a workable set of sites that closely match the requirements for optimal CO₂ enhanced oil recovery (EOR) storage. The objective of the study is to quickly identify miscible CO₂ EOR candidates in areas that contain thousands of reservoirs and to estimate additional oil recovery and sequestration capacities of selected top options through dimensionless modeling and reservoir characterization. Quick-look assessments indicate that the CO₂ EOR resource potential along the US Gulf Coast is 4.7 billion barrels, and CO₂ sequestration capacity is 2.6 billion metric tons. In the first stage, oil reservoirs are screened and ranked in terms of technical and practical feasibility for miscible CO₂ EOR. The second stage provides quick estimates of CO₂ EOR potential and sequestration capacities. In the third stage, a dimensionless group model is applied to a selected set of sites to improve the estimates of oil recovery and storage potential using appropriate inputs for rock and fluid properties, disregarding reservoir architecture and sweep design. The fourth stage validates and refines the results by simulating flow in a model that describes the internal architecture and fluid distribution in the reservoir. The stated approach both saves time and allows more resources to be applied to the best candidate sites.     

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.