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The geochemical model PHREEQC, abbreviated from PH (pH), RE (redox), EQ (equilibrium), and C (program written in C), was employed on the datasets generated by the USEPA Everglades Regional Environmental Monitoring and Assessment Program (R-EMAP) to determine the speciation distribution of inorganic mercury (iHg) in Everglades water and to explore the implications of iHg speciation on mercury cycling. The results suggest that sulfide and DOM were the key factors that regulate inorganic Hg speciation in the Everglades. When sulfide was present at measurable concentrations (>0.02 mg/L), Hg-S complexes dominated iHg species, occurring in the forms of HgS 2 2− , HgHS 2 − , and Hg(HS) 2 that were affected by a variety of environmental factors. When sulfide was assumed nonexistent, Hg-DOM complexes occurred as the predominant Hg species, accounting for almost 100% of iHg species. However, when sulfide was presumably present at a very low, environmentally relevant concentration (3.2 × 10 −7  mg/L), both Hg-DOM and Hg-S complexes were present as the major iHg species. These Hg-S species and Hg-DOM complex could be related to methylmercury (MeHg) in environmental matrices such floc, periphyton, and soil, and the correlations are dependent upon different circumstances (e.g., sulfide concentrations). The implications of the distribution of iHg species on MeHg production and fate in the Everglades were discussed. [ABSTRACT FROM AUTHOR]

Managed Aquifer Recharge (MAR) is becoming an attractive water management option, with more than 223 sites operating in European countries. The quality of the produced water, available for drinking or irrigation processes is strongly depended on the aquifer's hydrogeochemical characteristics and on the MAR system design and operation. The objective of this project is the assessment of the operation efficiency of a MAR system in Cyprus. The coupling of alternative methodologies is used such as water quality monitoring, micro-scale sediment sorption experiments, simulation of groundwater flow and phosphate and copper transport in the subsurface using the FEFLOW model and evaluation of the observed change in the chemical composition of water due to mixing using the geochemical model PHREEQC. The above methodology is tested in the Ezousa MAR project in Cyprus, where treated effluent from the Paphos Waste Water Treatment Plant, is recharged into the aquifer through five sets of artificial ponds along the riverbed. Additionally, groundwater is pumped for irrigation purposes from wells located nearby. A slight attenuation of nutrients is observed, whereas copper in groundwater is overcoming the EPA standards. The FEFLOW simulations reveal no effective mixing in some intermediate infiltration ponds, which is validated by the inverse modeling simulation of the PHREEQC model. Based on the results, better control of the infiltration capacity of some of the ponds and increased travel times are some suggestions that could improve the efficiency of the system. [ABSTRACT FROM AUTHOR]

Arsenic contamination of groundwaters in South and Southeast Asia is a major threat to public health. In order to better understand the geochemical controls on the mobility of arsenic in a heavily arsenic-affected aquifer in northern Kandal Province, Cambodia, key changes in inorganic aqueous geochemistry have been monitored at high vertical and lateral resolution along dominant groundwater flow paths along two distinct transects. The two transects are characterized by differing geochemical, hydrological and lithological conditions. Arsenic concentrations in groundwater are highly heterogenous, and are broadly positively associated with iron and negatively associated with sulfate and dissolved oxygen. The observed correlations are generally consistent with arsenic mobilization by reductive-dissolution of iron (hydr)oxides. Key redox zones, as identified using groupings of the PHREEQC model equilibrium electron activity of major redox couples (notably ammonium/nitrite; ammonium/nitrate; nitrite/nitrate; dissolved oxygen/water) have been identified and vary with depth, site and season. Mineral saturation is also characterized. Seasonal changes in groundwater chemistry were observed in areas which were (i) sandy and of high permeability; (ii) in close proximity to rivers; and/or (iii) in close proximity to ponds. Such changes are attributed to monsoonal-driven surface-groundwater interactions and are consistent with the separate provenance of recharge sources as identified using stable isotope mixing models. [ABSTRACT FROM AUTHOR]

River–aquifer interfaces are essential for ecosystem functioning in terms of nutrient exchange and biological habitat, but are greatly threatened world-wide. This study examined geochemical aspects of river–aquifer interaction in one regulated and one unregulated boreal river in Northern Sweden to determine whether the geochemical functioning of the hyporheic zone is affected by hydrological alterations, e.g. regulated river discharge and river–aquifer connectivity. In the unregulated Kalix River, the hyporheic pore water was well-oxygenated with orthogonal fluxes (≈ 0.6–0.7 m d − 1 ) and acted as a sink for Fe, Mn, Al, NH 4 , and Ca, with fractional losses of 95%, 92%, 45%, 31%, and 15%, respectively. A corresponding elevation in the concentrations of these elements in the hyporheic sediment was observed, with higher saturation indices of Fe-, Mn-, and Al-bearing secondary minerals in hyporheic waters. In the regulated Lule River, hydraulic connectivity at the river–aquifer interface was altered by the presence of a clogging layer (0.04 m d − 1 ). In addition, the river discharge oscillated daily, severely reducing exchange flows across the riverbed (< 0.01 m d − 1 ). As a result, the hyporheic pore water was suboxic, with elevated concentrations of filtered Fe and Mn (fractional increases of ≈ 3700% and ≈ 2500%, respectively) and other solutes (NH 4 , Si, S, Ca). A conceptual model revealed functional differences between geochemical features of the hyporheic zone of regulated and unregulated rivers. Overall, the results showed that hyporheic processes are altered along regulated rivers, with resulting impacts on the geochemistry of riverine, riparian and related marine ecosystems. [ABSTRACT FROM AUTHOR]

Abstract: Enhanced reductive dehalogenation is an attractive treatment technology for in situ remediation of chlorinated solvent DNAPL source areas. Reductive dehalogenation is an acid-forming process with hydrochloric acid and also organic acids from fermentation of the electron donors typically building up in the source zone during remediation. This can lead to groundwater acidification thereby inhibiting the activity of dehalogenating microorganisms. Where the soils'' natural buffering capacity is likely to be exceeded, the addition of an external source of alkalinity is needed to ensure sustained dehalogenation. To assist in the design of bioremediation systems, an abiotic geochemical model was developed to provide insight into the processes influencing the groundwater acidity as dehalogenation proceeds, and to predict the amount of bicarbonate required to maintain the pH at a suitable level for dehalogenating bacteria (i.e., >6.5). The model accounts for the amount of chlorinated solvent degraded, site water chemistry, electron donor, alternative terminal electron-accepting processes, gas release and soil mineralogy. While calcite and iron oxides were shown to be the key minerals influencing the soil''s buffering capacity, for the extensive dehalogenation likely to occur in a DNAPL source zone, significant bicarbonate addition may be necessary even in soils that are naturally well buffered. Results indicated that the bicarbonate requirement strongly depends on the electron donor used and availability of competing electron acceptors (e.g., sulfate, iron (III)). Based on understanding gained from this model, a simplified model was developed for calculating a preliminary design estimate of the bicarbonate addition required to control the pH for user-specified operating conditions. [Copyright &y& Elsevier]

Recently, a demand regarding the assessment of release of dangerous substances from construction products was raised by European Commission which has issued the Mandate M/366 addressed to CEN. This action is in relation with the Essential Requirement No. 3 “Hygiene, Health and Environment” of the Construction Products Directive (89/106/EC). The potential hazard for environment and health may arise in different life cycle stages of a construction product. During the service life stage, the release of substances due to contact with the rain water is the main potential hazard source, as a consequence of the leaching phenomenon. The objective of this paper is to present the development of a coupled chemical-transport model for the case of a concrete based construction product, i.e. concrete paving slabs, exposed to rain water under outdoor exposure conditions. The development of the model is based on an iterative process of comparing the experimental results with the simulated results up to an acceptable fit. The experiments were conducted at laboratory scale (equilibrium and dynamic leaching tests) and field scale. The product was exposed for one year in two types of leaching scenarios under outdoor conditions, “runoff” and “stagnation”, and the element release was monitored. The model was calibrated using the experimental data obtained at laboratory scale and validated against measured field data, by taking into account the specific rain water balance and the atmospheric CO2 uptake as input parameters. The numerical tool used in order to model and simulate the leaching behaviour was PHREEQC, coupled with the Lawrence Livermore National Laboratory (LLNL) thermodynamic data base. The simulation results are satisfying and the paper demonstrates the feasibility of the modelling approach for the leaching behaviour assessment of concrete type construction materials. [Copyright &y& Elsevier]

Abstract: Spatial and temporal variations in groundwater chemistry indicate that the use of low TDS lake water for irrigation, on land located just south of the City of Dixon, Solano County, California, is primarily responsible for improving groundwater quality with regards to salts. The stable isotopes of water further support this finding and suggest that TDS concentrations decrease as groundwater evolves to a more highly evaporated state. This seemingly contradictory finding was primarily attributed to infiltration of low TDS Lake Berryessa surface water, which has an isotopic signature indicative of an evaporated source and is used extensively for irrigation in the area, mixing with poorer quality locally recharged shallow groundwater. Geochemical modeling using the program PHREEQC further supports the anthropogenic aquifer freshening hypotheses through computed reductions in the saturation state of carbonate minerals in the vicinity of land irrigated by lake derived water, which is undersaturated with regards to modeled carbonates. Additionally, δ18O and δ2H were found to be useful in estimating climatic variables such as temperature and humidity, illustrating the potential for applying these models in hydrologic investigations within the area. It was however found that USDA NRCS soils data and measured water chemistry were not well correlated and thus the use of soils classifications to assess potential groundwater quality impacts was of limited utility. [Copyright &y& Elsevier]

For agriculturally used areas, which are contaminated by the debris from a nuclear accident, the use of chemical amendmends (e.g. potassium chloride and lime) is among the most common soil-based countermeasures. These countermeasures are intended to reduce the plant uptake of radionuclides (mainly137Cs and 90Sr) by competitive inhibition by chemically similar ions. So far, the impacts of countermeasures on soil solution composition — and thus, their effectiveness — have almost exclusively been established experimentally, since they depend on mineral composition and chemical characteristics of the soil affected. In this study, which focuses on caesium contamination, the well-established code PHREEQC was used as a geochemical model to calculate the changes in the ionic compositions of soil solutions, which result from the application of potassium or ammonium in batch equilibrium experiments. The simple ion exchange model used by PHREEQC was improved by taking into account selective sorption of Cs+, NH4+ and K+ by clay minerals. Calculations were performed with three different initial soil solution compositions, corresponding to particular soil types (loam, sand, peat). For loamy and sandy soils, our calculational results agree well with experimental data reported by Nisbet (Effectiveness of soil-based countermeasures six months and one year after contamination of five diverse soil types with caesium-134 and strontium-90. Contract Report NRPB-M546, National Radiation Protection Board, Chilton, 1995.). For peat, discrepancies were found indicating that for organic soils a reliable set of exchange constants of the relevant cations still has to be determined experimentally. For cesium, however, these discrepancies almost disappeared if selective sites were assumed to be inaccessible. Additionally, results of sensitivity analyses are presented by which the influence of the main soil parameters on Cs+ concentrations in solution after soil treatment has been systematically studied. It is shown that calculating the impacts of soil-based chemical countermeasures on soil solution chemistry using geochemical codes such as PHREEQC offers an attractive alternative to establishing these impacts by often time-consuming and site-specific experiments. [Copyright &y& Elsevier]