Effect of groundwater composition on arsenic detection by bacterial biosensors.

A luminescent bacterial biosensor was used to quantify bioavailable arsenic in artificial groundwater. Its light production above the background emission was proportional to the arsenite concentration in the toxicologically relevant range of 0 to 0.5 mu M. Effects of the inorganic solutes phosphate, Fe(II) and silicate on the biosensor signal were studied. Phosphate at a concentration of 0.25 g L-1 phosphate slightly stimulated the light emission, but much less than toxicologically relevant concentrations of the much stronger inducer arsenite. No effect of phosphate was oberved in the presence of arsenite. Freshly prepared sodium silicate solution at a concentration of 10 g L-1 Si reduced the arsenite-induced light production by roughly 37%, which can be explained by transient polymerization leading to sequestration of some arsenic. After three days of incubation, silicate did not have this effect anymore, probably because depolymerization occurred. In the presence of 0.4 g L-1 Fe(II), the arsenite-induced light emission was reduced by up to 90%, probably due to iron oxidation followed by arsenite adsorption on the less soluble Fe(III) possibly along with some oxidation to the stronger adsorbing As(V). Addition of 100 mu M EDTA was capable of releasing all arsenic from the precipitate and to transform it into the biologically measurable, dissolved state. The biosensor also proved valuable for monitoring the effectiveness of an arsenic removal procedure based on water filtration through a mixture of sand and iron granules.

Baseline nitrate concentration in groundwater of the Chalk in south Dorset, UK

Determining the degree of nitrate pollution in Chalk groundwater is difficult without a clear understanding of concentrations naturally present. In the UK, a general shortage of long-term records of nitrate concentrations in Chalk groundwater prevents a full quantification of baseline concentrations. This paper presents late nineteenth and early twentieth century data on nitrate concentrations in Chalk groundwater in south Dorset, UK and compares them with corresponding data for the last 25 years. The nitrate record is instructive in (1) providing an insight into the baseline nitrate concentration of groundwater; (2) defining the level of nitrate pollution in potable supplies from the Chalk aquifer; and (3) identifying the long-term variations in local nitrate concentrations. Over a period exceeding 100 years mean nitrate concentrations increased from 1.04 mg NO3-N l(-1) to 6.37 mg NO3-N l(-1). Anthropogenic modification of the local groundwater composition is not evident in the early nitrate record. Nitrate data throughout this early period reflect natural background concentrations of approximately I mg NO3-N l(-1) Intensified fertilser use and increased livestock numbers are suggested as the fundamental cause of the rise in nitrate concentrations. The implications of the nitrate record for regional hydrogeological processes are discussed. (C) 2003 Elsevier Science B.V. All rights reserved.

Anthropogenic impacts on mineral weathering: A statistical perspective

Correspondence Analysis was adopted as tool for investigating the statistical structure of hydrochemical and weathering datasets of groundwater samples, with the main purpose of identifying impacts on mineral weathering caused by anthropogenic activities, namely fertilizing of farmlands. The hydrochemical dataset comprised measured concentrations of major inorganic compounds dissolved in groundwater, namely bicarbonate, silica (usually by-products of chemical weathering), chloride, sulphate and nitrate (typically atmospheric plus anthropogenic inputs). The weathering dataset consisted of calculated mass transfers of minerals being dissolved in loess sediments of a region located in SW Hungary (Szigetvár area), namely Na-plagioclase, calcite and dolomite, and of pollution-related concentrations of sodium, magnesium and calcium. A first run of Correspondence Analysis described groundwater composition in the study area as a system of triple influence, where spots of domestic effluents-dominated chemistries are surrounded by areas with agriculture-dominated chemistries, both imprinted over large regions of weathering dominated chemistries. A second run revealed that nitrification of N-fertilizers is promoting mineral weathering by the nitric acid reaction (anthropogenic pathway), in concurrence with the retreating of weathering by carbonic acid (natural pathway). It also indicated that dolomite and calcite are being players in a dedolomitization process driven by dissolution of gypsum fertilizers and nitrification of N-fertilizers. © 2013 Elsevier Ltd.

Biogeochemistry of an Amazonian podzol-ferralsol soil system with white kaolin

The podzol-ferralsol soil systems, which cover great areas of Amazonia and other equatorial regions, are frequently associated with kaolin deposits and store and export large amounts of carbon. Although natural organic matter (NOM) plays a key role in their dynamics, little is known about their biogeochemistry. In order to assess the specific role of dissolved organic matter (DOM) on NOM storage in deep horizons and to determine possible relationships between kaolin formation and DOM properties, we studied the groundwater composition of a typical podzol-ferralsol soil catena from the Alto Rio Negro region, Brazil. Groundwater was sampled using tension-free lysimeters placed according to soil morphology. DOC, E-H, p(H), and dissolved Si, Al3+, Fe2+, and Fe3+ were analyzed for all samples and values are given in a database. Quantification of other dissolved ions, small carboxylic acids and SUVA(254) index and acid-base microtitration was achieved on selected samples. Part of the DOM produced by the hydromorphic podzols is directly exported to the blackwater streams; another part percolates at greater depth, and more than 90% of it adsorbs in the Bh-Bhs horizons, allowing carbon storage at depth. Humic substances are preferentially adsorbed with regard to small carboxylic compounds. With regard to kaolin genesis, kaolinite precipitation is favored by Al release from NOM mineralization within the Bh-Bhs and kaolin bleaching is ensured by iron reduction due to acidity and relatively low E-H. Fe2+ mobility can be related to small E-H variations and enhanced by the significant concentration of small carboxylic acids. The long-term result of these processes is the thickening of the kaolin, and it can be inferred that kaolin is likely to occur where active, giant podzols are close to a slope gradient sufficient enough to lower the deep water table.

Effects of Resources Exploitation on Water Quality: case studies in Salt Water Intrusion and Acid Mine Drainage

Throughout the world, pressures on water resources are increasing, mainly as a result of human activity. Because of their accessibility, groundwater and surface water are the most used reservoirs. The evaluation of the water quality requires the identification of the interconnections among the water reservoirs, natural landscape features, human activities and aquatic health. This study focuses on the estimation of the water pollution linked to two different environmental issues: salt water intrusion and acid mine drainage related to the exploitation of natural resources. Effects of salt water intrusion occurring in the shallow aquifer north of Ravenna (Italy) was analysed through the study of ion- exchange occurring in the area and its variance throughout the year, applying a depth-specific sampling method. In the study area were identified ion exchange, calcite and dolomite precipitation, and gypsum dissolution and sulphate reduction as the main processes controlling the groundwater composition. High concentrations of arsenic detected only at specific depth indicate its connexion with the organic matter. Acid mine drainage effects related to the tin extraction in the Bolivian Altiplano was studied, on water and sediment matrix. Water contamination results strictly dependent on the seasonal variation, on pH and redox conditions. During the dry season the strong evaporation and scarce water flow lead to low pH values, high concentrations of heavy metals in surface waters and precipitation of secondary minerals along the river, which could be released in oxidizing conditions as demonstrated through the sequential extraction analysis. The increase of the water flow during the wet season lead to an increase of pH values and a decrease in heavy metal concentrations, due to dilution effect and, as e.g. for the iron, to precipitation.

Caracterização química e isotópica das águas subterrâneas da bacia hidrográfica do Rio Almonda

Relatório de estágio de mestrado, Geologia Aplicada (Hidrogeologia), Universidade de Lisboa, Faculdade de Ciências, 2016

Effect of pH and temperature on the carbonate promoted dissolution of sodium meta-autunite

Release of uranium from Na-autunite, an artificial mineral created as a result of polyphosphate injection in the subsurface at the DOE Hanford Site, takes place during slow dissolution of the mineral structure. Stability information of the uranyl-phosphate phases is limited to conditions involving pH, temperature, and a few aqueous organic materials. The carbonate ion, which creates very strong complexes with uranium, is the predominant ion in the groundwater composition. The polyphosphate technology with the formation of autunite was identified as the most feasible remediation strategy to sequester uranium in contaminated groundwater and soil in situ. The objectives of the experimental work were (i) to quantify the effect of bicarbonate on the stability of synthetic sodium meta-autunite created as a result of uranium stabilization through polyphosphate injection, (ii) calculate the kinetic rate law parameters of the uranium release from Na-autunite during dissolution, and (iii) to compare the process parameters with those obtained for natural calcium meta-autunite. Experiments were conducted using SPTF apparatus, which consists of syringe pumps for controlling flow rate, Teflon reactors and a heating/cooling system. 0.25 grams of synthetic Na-autunite was placed in the reactor and buffer solutions with varying bicarbonate concentrations (0.0005 to 0.003 M) at different pH (6 - 11) were pumped through the reactors. Experiments were conducted at four different temperatures in the range of 5 - 60oC. It was concluded that the rate of release of uranium from synthetic Na-autunite is directly correlated to the bicarbonate concentration. The rate of release of uranium increased from 1.90 x 10-12 at pH 6 to 2.64 x 10-10 (mol m-2 s-1) at pH 11 at 23oC over the bicarbonate concentration range tested. The activation energy values were invariant with the change in the bicarbonate concentration; however, pH is shown to influence the activation energy values. Uranyl hydroxides and uranyl carbonates complexes helped accelerate the dissolution of autunite mineral.

Can the nitrogenous composition of xylem sap be used to assess salinity stress in Casuarina glauca?

It is predicted that dryland salinity will affect up to 17 Mha of the Australian landscape by 2050, and therefore, monitoring the health of tree plantings and remnant native vegetation in saline areas is increasingly important. Casuarina glauca Sieber ex Spreng. has considerable salinity tolerance and is commonly planted in areas with a shallow, saline water table. To evaluate the potential of using the nitrogenous composition of xylem sap to assess salinity stress in C. glauca, the responses of trees grown with various soil salinities in a greenhouse were compared with those of trees growing in field plots with different water table depths and groundwater salinities. In the greenhouse, increasing soil salinity led to increased allocation of nitrogen (N) to proline and arginine in both stem and root xylem sap, with coincident decreases in citrulline and asparagine. Although the field plots were ranked as increasingly saline-based on ground water salinity and depth-only the allocation of N to citrulline differed significantly between the field plots. Within each plot, temporal variation in the composition of the xylem sap was related to rainfall, rainfall infiltration and soil salinity. Periods of low rainfall and infiltration and higher soil salinity corresponded with increased allocation of N to proline and arginine in the xylem sap. The allocation of N to citrulline and asparagine increased following rainfall events where rain was calculated to have infiltrated sufficiently to decrease soil salinity. The relationship between nitrogenous composition of the xylem sap of C. glauca and soil salinity indicates that the analysis of xylem sap is an effective method for assessing changes in salinity stress in trees at a particular site over time. However, the composition of the xylem sap proved less useful as a comparative index of salinity stress in trees growing at different sites.

Effect of soil composition and dissolved organic matter on pesticide sorption

The effect of the solid and dissolved organic matter fractions, mineral composition and ionic strength of the soil solution on the sorption behaviour of pesticides were studied. A number of soils, chosen so as to have different clay mineral and organic carbon content, were used to study the sorption of the pesticides atrazine (6-chloro-N-2-ethyl-N-4-isopropyl-1,3,5-triazine-2,4-diamine), 2,4-D ((2,4-dichlorophenoxy) acetic acid), isoproturon (3-(4-isopropylphenyl)1,1-dimethylurea) and paraquat (1,1'-dimethyl-4,4'-bipyridinium) in the presence of low and high levels of dissolved organic carbon and different background electrolytes. The sorption behaviour of atrazine, isoproturon and paraquat was dominated by the solid state soil components and the presence of dissolved organic matter had little effect. The sorption of 2,4-D was slightly affected by the soluble organic matter in the soil. However, this effect may be due to competition for adsorption sites between the pesticide and the soluble organic matter rather than due to a positive interaction between the pesticide and the soluble fraction of soil organic matter. It is concluded that the major factor governing the sorption of these pesticides is the solid state organic fraction with the clay mineral content also making a significant contribution. The dissolved organic carbon fraction of the total organic carbon in the soil and the ionic strength of the soil solution appear to have little or no effect on the sorption/transport characteristics of these pesticides over the range of concentrations studied. (C) 2002 Elsevier Science B.V. All rights reserved.

An evaluation of septic tank effluent movement in soil and groundwater systems

Recent studies have shown that septic tank systems are a major source of groundwater pollution. Many public health workers feel that the most cri^cal aspect of the use of septic tanks as a means of sewage disposal is the contamination of private water wells with attendant human health hazards. In this study the movement and attenuation of septic tank effluents in a range of soil/overburden types and hydrogeological situations was investigated. The suitability of a number of chemical and biological tracer materials to monitor the movement of septic tank effluent constituents to groundwater sources was also examined. The investigation was divided into three separate but inteiTelated sections. In the first section of the study the movement of septic tank effluent from two soil treatment systems was investigated by direct measurements of soil nutrient concentrations and enteric bacterial numbers in the soil beneath and downgradient of the test systems. Two sites with different soil types and hydrogeological characteristics were used. The results indicated that the attenuation of the effluent in both of the treatment systems was incomplete. Migration of nitrate, ammonium, phosphate and fecal bacteria to a depth of 50 cm beneath the inverts of the distribution tiles was demonstrated on all sampling occasions. The lateral migration of the pollutants was less pronounced, although on occasions high nutrients levels and fecal bacterial numbers were detected at a lateral distance of 4.0 m downgradient of the test systems. There was evidence that the degree and extent of effluent migration was increased after periods of heavy or prolonged rainfall when the attenuating properties of the treatment systems were reduced as a result of saturation of the soil. The second part of the study examined the contamination of groundwaters downgradient of septic tank soil treatment systems. Three test sites were used in the investigation. The sites were chosen because of differences in the thicknesses and nature of the unsaturated zone available for effluent attenuation at each of the locations. A series of groundwater monitoring boreholes were installed downgradient of the test systems at each of the sites and these were sampled regularly to assess the efficiency of the overburden material in reducing the polluting potential of the wastewater. Effluent attenuation in the septic tank treatment systems was shown to be incomplete, resulting in chemical and microbiological contamination of the groundwaters downgradient of the systems. The nature and severity of groundwater contamination was dependent on the composition and thickness of the unsaturated zone and the extent of weathering in the underlying saturated bedrock. The movement of septic tank effluent through soil/overburdens to groundwater sources was investigated by adding a range of chemical and biological tracer materials to the three septic tank systems used in section two of the study. The results demonstrated that a single tracer type cannot be used to accurately monitor the movement of all effluent constituents through soils to groundwater. The combined use of lithium bromide and endospores of Bacillus globigii was found to give an accurate indication of the movement of both the chemical and biological effluent constituents.

Radiocarbon dating of modern groundwater: the role of the unsaturated zone

Biological and physical processes occurring in soils may lead to significant isotopic changes between the isotopic compositions of atmospheric CO2 and of soil CO2. Also, during water and gas transport from the soil surface to the water table, isotopic changes likely occur due to numerous physical processes such as gas production and diffusion, water advection, and gas-water-rock interactions. In most cases, these changes are not included in the correction models developed for groundwater dating, whereas they can significantly impact the calculation of the 14C age. We explore the role of these processes using: i) experimental data from two aquifer sites (Fontainebleau sands and Astian sands, France), ii) a distributed model to simulate the 14C activities of soil CO2, and iii) numerical simulations in order to highlight the role of the physical processes.¦The 13C content in soil CO2 showed seasonal variations and highlighted the competition between CO2 production and CO2 diffusion. Their respective contributions played a significant role in defining the isotopic composition of CO2 at the water table. On both study sites, variations of the 14C activity in soil CO2 reflect the competition between the fluxes of root derived-CO2 and organic matter derived-CO2. Since the nuclear weapon tests in the fifties and sixties, soil CO2 became significantly depleted in 14C compared to modern atmospheric CO2. Models that take into account this 14C depletion in soil CO2 for dating modern groundwater would lead to apparent younger 14C ages than models that only consider the 14C activity in atmospheric CO2. Moreover, since 2000-2005, the inverse effect is observed as soil CO2 is enriched in 14C compared to atmospheric CO2.¦Therefore, we conclude that the isotopic composition of CO2 at the water table have to be taken into account for the dating of modern groundwater. This requires a systematic sampling of soil CO2 and the measurement of its 13C and 14C contents. We used this information in a numerical simulation to calculate the evolution of isotopic composition of CO2 from the soil surface to the water table. This simulation integrated physical processes in the unsaturated zone (e.g. CO2 production and diffusion, water advection, etc.) and gas-water-rock interactions.

Open to closed system transition traced through the TDIC isotopic signature at the aquifer recharge stage, implications for groundwater 14C dating

14C dating models are limited when considering recent groundwater for which the carbon isotopic signature of the total dissolved inorganic carbon (TDIC) is mainly acquired in the unsaturated zone. Reducing the uncertainties of dating thus implies a better identification of the processes controlling the carbon isotopic composition of the TDIC during groundwater recharge. Geochemical interactions between gas, water and carbonates in the unsaturated zone were investigated for two aquifers (the carbonate-free Fontainebleau sands and carbonate-bearing Astian sands, France) in order to identify the respective roles of CO2 and carbonates on the carbon isotopic signatures of the TDIC; this analysis is usually approached using open or closed system terms. Under fully open system conditions, the seasonality of the 13C values in the soil CO2 can lead to important uncertainties regarding the so-called "initial 14C activity" used in 14C correction models. In a carbonate-bearing unsaturated zone such as in the Astian aquifer, we show that an approach based on fully open or closed system conditions is not appropriate. Although the chemical saturation between water and calcite occurs rapidly within the first metre of the unsaturated zone, the carbon isotopic contents (δ13C) of the CO2 and the TDIC evolve downward, impacted by the dissolution-precipitation of the carbonates. In this study, we propose a numerical approach to describe this evolution. The δ13C and the A 14C (radiocarbon activity) of the TDIC at the base of the carbonate-hearing unsaturated zone depends on (i) the δ13C and the A 14C of the TDIC in the soil determined by the soil CO2, (ii) the water's residence time in the unsaturated zone and (iii) the carbonate precipitation-dissolution fluxes. In this type of situation, the carbonate δ13C-A 14C evolutions indicate the presence of secondary calcite and permit the calculation of its accretion flux, equal to ~ 4.5 ± 0.5 x 10-9 mol grock-1 yr-1. More generally, for other sites under temperate climate and with similar properties to the Astian sands site, this approach allows for a reliable determination of the carbon isotopic composition at the base of the unsaturated zone as the indispensable "input function" data of the carbon cycle into the aquifer.

Groundwater quality comparison between rural farms and riparian wells in the western Amazon, Brazil

Groundwater quality of a riparian forest is compared to wells in surrounding rural areas at Urupá River basin. Groundwater types were calcium bicarbonated at left margin and sodium chloride at right, whereas riparian wells exhibited a combination of both (sodium bicarbonate). Groundwater was mostly solute-depleted with concentrations within permissible limits for human consumption, except for nitrate. Isotopic composition suggests that inorganic carbon in Urupá River is mostly supplied by runoff instead of riparian groundwater. Hence, large pasture areas in addition to narrow riparian forest width in this watershed may have an important contribution in the chemical composition of this river.

Tree species composition and environmental relationships in a Neotropical swamp forest in Southeastern Brazil

We examined the relationships between topography, soil properties and tree species composition in a Neotropical swamp forest in southeastern Brazil. Plots were sampled in the forest, encompassing three different soil ground water regimes along the topographical declivity. All non-climbing plant individuals with trunk height >1.3 m were sampled. A canonical correspondence analysis-CCA-of the species-environmental relationships grouped tree species according to drainage and chemical soil conditions. A total of 86 species were found, being 77 species in the inferior, 40 species in the intermediate and 35 species in the superior topographic section. Some species were among the 10 most abundant ones, both in the overall sampled area and in each topographical section, with alternation events occurring only with their abundance position. However, substantial differences in floristic composition between sections were detected in a fine spatial scale, due to higher number of species, diversity index (H′) and species unique (exclusives) in the inferior topographic section. These higher values can be attributed to its higher spatial heterogeneity that included better drained and seasonally waterlogged soils, higher soil fertility and lower acidity. The increase of the soil water saturation and the uniform conditions derived from the superficial water layer has led to a lower number of species and an increase on the palm trees abundance in the intermediate and superior sections. Our results showed that at a small spatial scale niche differentiation must be an important factor related to the increase of the local diversity. The wide distribution of the most abundant species in the studied area and the increase of local diversity corroborate the pattern of distribution of species in larger scales of swamp forests, in which the most abundant species repeat themselves in high densities in different remnants. However, the floristic composition of each remnant is strongly variable, contributing to the increase of regional diversity. © 2008 Springer Science+Business Media B.V.

Temporal and Spatial Variations of Ions, Isotopes and Agricultural Contaminants in Surface Waters and Groundwater of Nebraska's Rainwater Basin Wetland Region

The wetlands of south-central Nebraska’s Rainwater Basin region are considered of international importance as a habitat for millions of migratory birds, but are being endangered by agricultural practices. The Rainwater Basin extends across 17 counties and covers 4,000 square miles. The purpose of this study was to assemble baseline chemical data for several representative wetlands across the Rainwater Basin region, and determine the use of these chemical data for investigating groundwater recharge. Eight representative wetlands were chosen across the Rainwater Basin to monitor surface and groundwater chemistry. At each site, a shallow well and deep well were installed and sampled once in the summer of 2009 and again in the spring of 2010. Wetland surface water was sampled monthly from April, 2009 to May, 2010. Waters were analyzed for major ions, nutrients, pesticides and oxygen-18 and deuterium isotopes at the University of Nebraska Water Sciences Laboratory. Geochemical analysis of surface waters presents a range of temporal and spatial variations. Wetlands had variable water volumes, isotopic compositions, ion chemistries and agricultural contaminant levels throughout the year and, except for a few trends, theses variations cannot be predicted with certainty year-to-year or wetland-to-wetland. Isotopic compositions showed evaporation was a contributor to water loss, and thus, did impact water chemistry. Surface water nitrate concentrations ranged from <0.10 to 4.04 mg/L. The nitrate levels are much higher in the groundwater, ranging from <0.10 to 18.4 mg/L, and are of concern because they are found above the maximum contaminant level (MCL) of 10 mg/L. Atrazine concentrations in surface waters ranged from <0.05 to 10.3 ppb. Groundwater atrazine concentrations ranged from <0.05 to 0.28 ppb. The high atrazine concentrations in surface waters are of concern as they are above the MCL of 3 ppb, and the highest levels occur during the spring bird migration. Most sampled groundwaters had detectable tritium indicating a mix of modern (<5 to 10 years old) and submodern (older than 1950s) recharge. The groundwater also had differences in chemical and isotope composition, and in some cases, increased nitrate concentrations, between the two sampling periods. Modern groundwater tritium ages and changes in groundwater chemical and isotopic compositions may indicate connections with surface waters in the Rainwater Basin.