Anoxic nitrification: Evidence from Humber Estuary sediments (UK)

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.     

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.     

Hydrochemical characteristics and the effects of irrigation on groundwater quality in Harran Plain,GAP Project,Turkey

Improper design, faulty planning, mismanagement and incorrect operation of irrigation schemes are the principle reasons for the deterioration of groundwater quality in a large number of countries, in particular in semi-arid and arid regions. The aim of this study is to determine the dimensions of groundwater quality after surface irrigation was begun in the semi-arid Harran Plain. Physical and chemical parameters of the groundwater including pH, temperature, electrical conductivity (EC), sodium, potassium, calcium, magnesium, chloride, bicarbonate, sulphate, nitrate, nitrite, ammonium, total phosphorus, total organic carbon and turbidity were determined monthly during the 2006 water year. The quality of the groundwater in the study area was assessed hydrochemically in order to determine its suitability for human consumption and agricultural purposes. In the general plain, the EC values measured were considerably above the guide level of 650 μS/cm, while nitrate in particular was found in almost all groundwater samples to be significantly above the maximum admissible concentration of 50 mg/l for the quality of water intended for human consumption as per the international and national standards. Total hardness reveals that a majority of the groundwater samples fall in the very hard water category. Interpretation of analytical data shows that Ca–HCO₃ and Ca–SO₄ are the dominant hydrochemical facies in the study area.     

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.     

Multivariate analysis of heavy metal contents of sediments from Gumusler creek, Nigde, Turkey

In this study, heavy metal contents of samples from Gumusler creek in Turkey were studied and the metal contamination characteristics were investigated. In this respect, considering the pollutant sites in the area, systematic sediment samples were collected in a zone starting from the manifestation part of the water to the entrance of the Karasu creek in Gumusler town. Samples were taken from lower section of the river bed at 30 stations along Gumusler creek, 13 km in length and their heavy metal contents were analyzed with XRF Spectrometer. Correlation coefficients, element coefitic coefficient correlation, dendogram hierarchical cluster, model summary and Annova analysis statistical methods were applied to data. Strong positive correlations were determined for some elements which are believed to have possibly the same origin. In addition, mineralizations in the area are thought to cause variation in metal contents. Results of chemical analysis show that soil limit values and clark values were exceeded. The heavy metal accumulation in the creek is believed to be derived from non-operated Sb-Hg-W and Fe quarries.     

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.     

Vulnerability and fate of a coastal sand dune complex,Rosetta-Idku,northwestern Nile Delta,Egypt

Types, distribution, and origin of recent sand dunes between Rosetta and Idku, in the western sector of the Nile Delta, Egypt were investigated. Sand samples from the dunes, beach, and seafloor were studied for grain size distribution and mineralogical composition. It has been found that most of the dunes in the study area have been subjected to deterioration and removal due to the construction of buildings and the International Coastal Highway. The remnant constitutes a damaged belt of foredunes that extends from El Bouseily village to the west of Idku town. The dune’s origin is interpreted to be the result of coastal drifting and the subsequent transport of sediments of the former Canopic Nile branch eastward by the predominant longshore current and by aeolian processes. The blown sand grains accumulated to form a belt of coastal sand dunes of original longitudinal and crescentic forms. Urbanization of the coast has severely altered the landscape. The study area is considered vulnerable to the impacts of climate change and the expected rise in sea level. The outcome of potential sea level rise is serious; erosion problems are expected to be exacerbated and vast areas from land and property would be lost. Thus, protection and preservation the remaining dunes in the study area are vital requirements for shore protection.     

A comparative study of four vulnerability mapping methods in a detritic aquifer under mediterranean climatic conditions

This paper presents the results of a comparative study relating to the application of four vulnerability mapping methods, GOD, AVI, DRASTIC and SINTACS, in a pilot detritic aquifer situated in NW Morocco, known as the Martil–Alila aquifer. The principal objective of this work is to determine the most suitable such methods for this aquifer type within a Mediterranean context, and to show the effect of the rainfall variations that are characteristic of the Mediterranean climate on the degree of vulnerability. The methods applied distinguish five classes of vulnerability, these being irregularly divided up in space, with the division varying according to the method in question. The vulnerability maps obtained by the different methods strongly suggest that the eastern half of the aquifer is more vulnerable to contamination than the western half, for all hydrological situations. The effect of climatic conditions on the degree of vulnerability is well represented by the DRASTIC, according to which the aquifer is moderately to strongly vulnerable during humid hydrological years and weakly to moderately vulnerable during dry ones. For the other methods, this climatic effect is limited to the area occupied by the two predominant classes (“High” and “Low” for GOD and “High” and “Moderate” for SINTACS) while it is null for AVI. In conclusion, DRASTIC appears the most suitable for mapping the vulnerability to contamination of Mediterranean coastal detritic aquifers such as the Martil–Alila aquifer.     

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.