History of crustal growth and recycling at the Pacific convergent margin of South America at latitudes 29°–36° S revealed by a U–Pb and Lu–Hf isotope study of detrital zircon from late Paleozoic accretionary systems

Detrital zircon provides a powerful archive of continental growth and recycling processes. We have tested this by a combined laser ablation ICP-MS U–Pb and Lu–Hf analysis of homogeneous growth domains in detrital zircon from late Paleozoic coastal accretionary systems in central Chile and the collisional Guarguaráz Complex in W Argentina. Because detritus from a large part of W Gondwana is present here, the data delineate the crustal evolution of southern South America at its Paleopacific margin, consistent with known data in the source regions.Zircon in the Guarguaráz Complex mainly displays an U–Pb age cluster at 0.93–1.46 Ga, similar to zircon in sediments of the adjacent allochthonous Cuyania Terrane. By contrast, zircon from the coastal accretionary systems shows a mixed provenance: Age clusters at 363–722 Ma are typical for zircon grown during the Braziliano, Pampean, Famatinian and post-Famatinian orogenic episodes east of Cuyania. An age spectrum at 1.00–1.39 Ga is interpreted as a mixture of zircon from Cuyania and several sources further east. Minor age clusters between 1.46 and 3.20 Ga suggest recycling of material from cratons within W Gondwana.The youngest age cluster (294–346 Ma) in the coastal accretionary prisms reflects a so far unknown local magmatic event, also represented by rhyolite and leucogranite pebbles. It sets time marks for the accretion history: Maximum depositional ages of most accreted metasediments are Middle to Upper Carboniferous. A change of the accretion mode occurred before 308 Ma, when also a concomitant retrowedge basin formed.Initial Hf-isotope compositions reveal at least three juvenile crust-forming periods in southern South America characterised by three major periods of juvenile magma production at 2.7–3.4 Ga, 1.9–2.3 Ga and 0.8–1.5 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf of Mesoproterozoic zircon from the coastal accretionary systems is consistent with extensive crustal recycling and addition of some juvenile, mantle-derived magma, while that of zircon from the Guarguaráz Complex has a largely juvenile crustal signature. Zircon with Pampean, Famatinian and Braziliano ages (< 660 Ma) originated from recycled crust of variable age, which is, however, mainly Mesoproterozoic. By contrast, the Carboniferous magmatic event shows less variable and more radiogenic ¹⁷⁶Hf/¹⁷⁷Hf, pointing to a mean early Neoproterozoic crustal residence. This zircon is unlikely to have crystallized from melts of metasediments of the accretionary systems, but probably derived from a more juvenile crust in their backstop system.     

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.     

Using ALSM to map sinkholes in the urbanized covered karst of Pinellas County,Florida—1, methodological considerations

Comparison of a database of interpreted sinkholes made using airborne laser swath mapping (ALSM) with databases of sinkholes made from interpretation of aerial photographs reveals substantial disagreement. The discrepancies involve the location, number, areas, and circularity of interpreted sinkholes. Methodological factors that contribute to the discrepancies include blockage of ALSM laser returns in thick vegetation, multi-path reflections, and misrepresentation of the true extent of sinkholes. Comparison of two ALSM-derived databases made (1) independently from versus (2) in combination with earlier air photo analysis in undeveloped regions had the following result: one-fourth of the sinkholes interpreted by using the composite method were missed by the independent analysis, and one-third of the sinkholes that were interpreted from the independent analysis were not interpreted as sinkholes using the composite method. Subjective interpretation leads to a high level of uncertainty such that the results of the remote sensing studies are suspect, if not invalid.     

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.     

Use of sinkhole and specific capacity distributions to assess vertical gradients in a karst aquifer

The carbonate-rock aquifer in the Great Valley, West Virginia, USA, was evaluated using a database of 687 sinkholes and 350 specific capacity tests to assess structural, lithologic, and topographic influences on the groundwater flow system. The enhanced permeability of the aquifer is characterized in part by the many sinkholes, springs, and solutionally enlarged fractures throughout the valley. Yet, vertical components of subsurface flow in this highly heterogeneous aquifer are currently not well understood. To address this problem, this study examines the apparent relation between geologic features of the aquifer and two spatial indices of enhanced permeability attributed to aquifer karstification: (1) the distribution of sinkholes and (2) the occurrence of wells with relatively high specific capacity. Statistical results indicate that sinkholes (funnel and collapse) occur primarily along cleavage and bedding planes parallel to subparallel to strike where lateral or downward vertical gradients are highest. Conversely, high specific capacity values are common along prominent joints perpendicular or oblique to strike. The similarity of the latter distribution to that of springs suggests these fractures are areas of upward-convergent flow. These differences between sinkhole and high specific capacity distributions suggest vertical flow components are primarily controlled by the orientation of geologic structure and associated subsurface fracturing.     

GIS-based colour composites and overlays to delineate heavy metal contamination zones in the shallow alluvial aquifers, Ankaleshwar industrial estate, south Gujarat, India

In an attempt to delineate heavy metal contamination precincts and to evaluate the extent and degree of toxic levels, besides their possible sources, 38 water samples from Ankaleshwar Industrial Estate, south Gujarat, India were analyzed. By clutching geochemical analyses and GIS-based colour composites areas depicting anomalously high concentration of heavy metals (Mo, Zn, Pb, Ni, Co, Cd, etc.) in the groundwater were revealed. The multicomponent overlays in grey-scale facilitated in identifying situates of heavy metal ‘hot spots’, and lateral protuberances of the contamination plume around defile stretch of the main stream Amla Khadi flowing through the area. The multiple pollution plumes emerging from other parts of the area further coincide with effluent laden streams and small channels indicating industrial establishments as major sources of groundwater contamination. Influent nature of the streams, accelerated infiltration process, high mass influx and shallow groundwater table are the factors conducive for easy access of heavy metals to the phreatic aquifers affecting over 20 km² area. On the basis of P/U ratios (concentration of metals in polluted water to unpolluted water), geogenic and anthropogenic sources have been identified. Very high levels of technogenic elements present in the ground water raise concerns about possible migration into food crops, as the area is an important horticultural locale and is highly cultivated.     

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.     

Georadiochemical evidence to weathering of mining residues of the Mansfeld mining district,Germany

Mining heaps are used as archives for the investigation of weathering processes. Aim of this work was to investigate the different weathering behavior of heap materials derived from Kupferschiefer mining with respect to environmental hazard. For this purpose, Kupferschiefer and slag material of two heaps of different age were examined regarding to the radionuclide distribution and geochemical composition. By measuring of the local dose rate, performing digital autoradiography and gamma spectrometry the radiological load of the heaps and the heap materials was determined. The geochemical characterization of the samples was performed by XRF, ICP–OES and ICP–MS. The results show a clear higher radionuclide load of the younger slag heap. A depletion of chalcophile and lithophile elements in the older slag was determined. Apart from a homogeneous radionuclide distribution, considerable radionuclide enrichments in fossil fragments could be proven. The results reveal a different weathering behavior of slag material in comparison to the Kupferschiefer depending on the chemical binding of the elements on organic and inorganic species. Natural organic matter as well as apatite in Kupferschiefer act as retention barrier for some metals.     

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.