Sulfur Concentration in Geochemical Reference Materials by Solution Inductively Coupled Plasma‐Mass Spectrometry

With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials.     

Bioremediation of dry olive-mill residue removes inhibition of growth induced by this waste in tomato plants

The disposal of dry olive-mill residue, the waste product from olive oil production, is a serious environmental issue. Dry olive-mill residue, being rich in organic and inorganic nutrients, could be used as fertilizer; however, it contains phenolic compounds that can inhibit plant growth. In order to clarify whether bioremediation of this waste could be a valuable strategy for its reuse, the effect of aqueous extract of dry olive-mill residue, untreated or bioremediated by the saprobe fungi Coriolopsis rigida and Penicillium chrysogenum-10, has been analyzed in relation to some physiological parameters of tomato plants. The data show that aqueous dry olive-mill residue significantly reduces the biomass of roots and shoots. In particular, it causes a dramatic reduction in root length, area, and volume as well as in the number of root tips. At an early stage, aqueous dry olive-mill residue also reduces the content of chlorophyll a and b and the efficiency of PS II. The inhibition of growth seems to be due to the increase in phenolic compounds that induce oxidative stress. Interestingly, when plants are treated with aqueous dry olive-mill residue bioremediated by saprobe fungi a decrease in phenolic content and an alleviation of oxidative stress occur. In conclusion, the results show that bioremediation of aqueous dry olive-mill residue is a useful tool to remove most of the inhibiting effects of this waste on plant growth.     

Effect of the injection of pure oxygen into a membrane bioreactor on the elimination of bisphenol A

The effect of the injection of pure oxygen instead of air in a membrane bioreactor for the elimination of bisphenol A is investigated. A dynamic experiment was developed in a pilot plant where the aerobic reactor was continuously spiked with 1 mg L^?1 of bisphenol A. Air was injected for 10 days and then pure oxygen was injected for another 10 days. The bisphenol A concentration was determined in aqueous phases and activated sludge using simple and sensitive analytical methods based on different extraction procedures and liquid chromatography tandem mass spectrometry analysis. Enzymatic activity was also determined and toxicity tests were performed to discard that the spiked bisphenol A concentration could negatively affect the microorganisms in the bioreactor and, thus, the membrane bioreactor performance. The effluent bisphenol A concentration increased up to 0.26 mg L^?1 after 4 days in the air injection treatment, and up to 0.48 mg L^?1 after only 12 h in the oxygen injection treatment. In both cases, this was followed by a decrease in concentration despite the continuous spiking of bisphenol A into the bioreactor. In presence of pure oxygen, bisphenol A concentration reached background levels (below the limit of quantification) after 5 days. In contrast, when using air a total of 10 days were required to reach background levels. The injection of pure oxygen instead of air is an important innovation in wastewater treatment, allowing permanent elimination of organic contaminants, avoiding their return to the environment and ensuring the safety of water.     

Linear system techniques applied to the Fuenmayor Karst Spring, Huesca (Spain)

Black box identification techniques are very useful tools to study the relationship between rainfall and the discharge of karst aquifers. Autocorrelation, cross-correlation, cross-spectral, impulse response identification (Wiener–Hopf and error minimization methods) and parametric identification of transfer functions techniques have been used by different authors. A review of these techniques has been realized to assess the possibilities and limitations. The reviewed techniques are applied to a time rainfall–discharge series of Fuenmayor karst spring, (southern central Pyrenees, Spain) to establish the relative quality of the obtained models. The quality is evaluated with the Nash–Sutcliffe model efficiency coefficient. In addition, effective rainfall has been used to improve the performance of every model. The whitening technique has been used in the cross-correlation technique with good results. The studied spring shows a Fontestorbes type behavior. The linearity of the system has been analyzed by the coherence function. Fuenmayor has an acceptable linear response, except for high frequency events. The parametric identification provides the best efficiency value E = 0.8164 and provides a proper transfer function, with five parameters (one zero, two poles, the gain and the delay). The prediction power of this transfer function is validated with another time series, with an efficiency value of E = 0.7904.     

Technical, financial and location criteria for the design of land application system treatment

Conventional water treatments when downsized to cover the demands of small and scattered populations are costly and ineffective. In fact, many small towns cannot afford the high average treatment costs nor provide the skill and complex management requirements. Even when these facilities are available, waste water might not be properly treated. Land application system treatments (LAST) have been shown to be preferable on the basis of their technical effectiveness and financial viability. The recently approved Spanish regulations (RDL 1620/2007, pp 50369–50661) represent an opportunity for the implementation of well-designed LASTs. This paper presents an assessment methodology for the design of LASTs by combining technical, financial and location criteria. The method is applied to the design of LASTs to cover the water disposal demand of twelve municipalities located within the protected natural landscape, and surrounding areas of ‘El Rebollar’, Salamanca, Spain.     

Building a 3D geomodel for water resources management: case study in the Regional Park of the lower courses of Manzanares and Jarama Rivers (Madrid, Spain)

Water resources management of protected sites requires a powerful tool to analyze the process and changes that are occurring in the environment. This paper describes a 3D geomodel design of the Jarama River Detrital Aquifer located in Madrid (Spain). That hydrogeological unit is included in the “Parque Regional de los Cursos Bajos de los Ríos Manzanares y Jarama” (Regional Park of the Lower Courses of Manzanares and Jarama Rivers). The goal of this work is to define a method by which a three-dimensional (3D) model can be created with hydrogeologic geometry real of main aquifer, to accomplish an adequate management of the groundwater resources. All data used in this study were integrated in a geographic database: geological and hydrogeological information, geological map (1:25,000), eleven cross-sections, piezometric maps and a digital elevation model. The constructed 3D model of the Jarama Aquifer shows geometric features and spatial distribution and variations of geologic units. Thus, the 3D model allows the assessment of volumes of each unit, the depth and thickness variations of the main aquifer, and the spatial and temporal variations of water tables. From the 3D model, the most suitable areas (in terms of groundwater protection) for managed recharge and mining works have been identified.     

Mercury colonial footprint in Darién Gulf sediments,Colombia

The mercury (Hg) deposition history in the Darién Gulf is reconstructed from three sediment cores spanning up to 1,000 years. Knowledge on the contribution to global Hg budget from the Caribbean is limited. Patterns of water circulation, sediment deposition rates, cataclysmic atmospheric inputs, and post-depositional migration have been considered in Hg trapping in the seabed. The sediment delivery rates to the coastal zone over the Late Holocene have increased from 0.2 to 1 cm year^?1 owing to anthropogenic influence. This alteration took the form of geological effects, like coastal morphology change, that played a major role in Hg downcore signal preservation. Natural background Hg levels in Southern Caribbean sediments (77.0 μg kg^?1) are up to three times higher than preindustrial signals at other latitudes, because of volcanic contributions from the Pacific ring of fire. Enrichment factors rose from 0.9 to 1.5 (70.1–113.5 μg kg^?1) within profiles related to Hg usage since Spanish colonial times between the calendar years 1550 and 1811.     

3D modeling and monitoring of karst system as a base for its evaluation and utilization: a case study from eastern Serbia

Beljanica Mountain in eastern Serbia is a part of the Carpathian Balkan arch (northern Alpine branch). It covers an area of about 300 km² and consists mostly of Jurassic and Cretaceous limestones. Numerous surface karst features, long caves and several large karstic springs located in Beljanica’s piedmont along the contact of karstic and non-karstic rocks are all indicators of an intense karstification. Currently, the large karstic water reserves of Beljanica Mountain are not properly utilized because of their distance from main consumers, the objection by national water managers that the springs lack a stable and sufficient discharge particularly during recession periods. Due to its unpolluted and high quality water, the area is a great prospect for future water supply, and provides an opportunity for artificial regulation and for the design and implementation of specific tapping structures. This paper includes an analysis of the created 3D ArcGIS model of karst interior and its correlation with historical and newly collected data of spring discharges and groundwater physico-chemical characteristics. The results of karst aquifer monitoring (both quantitative and qualitative) are linked with the results of extensive field geological and speleological survey of the upper non-saturated part of the karst (such as sinkholes, pits and caves) and with the investigation of the permanently saturated deeper part of the aquifer (including the diving methods). The model of karst interior is based on the data from the 69 caves, 15 sinks and 1,682 dolines (sinkholes) surveyed. The total length of the karst channels network, calculated using the GIS model and presented in a 3D environment, is 647 km. The catchment areas of five major springs that drain the areas are estimated to range from only 7 km² (Malo Vrelo Spring) to 124 km² (Vrelo Mlave Spring). The groundwater exploitable reserves of Beljanica karst aquifer are estimated to be over 4 m³/s. The waters are low mineralized, unpolluted and have a great potential for water supply.     

Iron ore mining promotes iron enrichment in sediments of the Gualaxo do Norte River basin,Minas Gerais State,Brazil

The objective of the present study is to assess the influence of iron ore mining on Fe concentrations in fluvial sediments of the Gualaxo do Norte River basin (Minas Gerais State, Brazil). Initially background values were determined for Fe by means of the boxplot representation, the iterative 2σ technique and the calculated distribution function, using geochemical data obtained for alluvial terraces. Geochronologic analyses in carbonaceous materials attested for the proposed background values. After that, chemical analyses of active drainage sediments collected along the entire basin were carried out and a geochemical map of the study area was prepared. The mean background value for Fe is relatively high (8.2 wt %), when compared to the Fe concentration in the Earth’s crust (5.6 wt %). Such background value is strongly associated with the geological characteristics of the region. It was observed that most of the high Fe concentrations were detected in active sediments collected in the main river of the basin and not in its tributaries. This suggests that Fe enrichment is not only linked to the local geology but also to possible increase resulting from accidental leakage of iron ore mining tailings from containment dams and lakes upstream. It is suggested that measures that help stop or minimize such impact be adopted. The large capacity of Fe to adsorb and form complexes with toxic metals implicates in environmental hazards that may not be restricted only to the Gualaxo do Norte river basin, but may affect the other basins downstream.     

Magnetic susceptibility and electrical conductivity as a proxy for evaluating soil contaminated with arsenic,cadmium and lead in a metallurgical area in the San Luis Potosi State,Mexico

A total of 113 samples of waste and soil were collected from a site in the state of San Luis Potosi, Mexico, that was occupied for several years by the metallurgical industry. Specific magnetic susceptibility (MS), electrical conductivity (EC) and pH were determined, as well as the total and available concentrations of potentially toxic elements (PTEs) such as As, Cd, Cu, Fe, Pb and Zn, which may cause a health risk for humans, animals and ecosystems, and the concentrations of major ions in aqueous extracts of soils and wastes. The solid phases of the samples were also characterized. The results revealed that the soils and wastes exhibited elevated values of PTEs, MS and EC. For soils these values decreased with increasing distance from the waste storage sites. The MS values were elevated primarily due to the presence of Fe-oxyhydroxides, such as magnetite, hematite and goethite, which contain PTEs in their structure leading to a high correlation between the value of MS and the As, Cd, Fe and Pb contents (r = 0.57–0.91) as well as between the PTEs values (r = 0.68–0.92). The elevated EC values measured in the metallurgical wastes were the result of presence of the sulfate minerals of Ca, Mg and Fe. The pollution index, which indicates the levels of simultaneous toxicity from elements such as As, Cd and Pb, was determined, with extreme hazard zones corresponding to areas that exhibit high MS values (0.91 correlation). In conclusion, MS measurements can be used as an indirect indicator to evaluate the PTE contamination in metallurgical areas, and EC measurements can aid in the identification of pollution sources.