Dissolution Of Mineral Phases Research Articles

Elimination of malachite green from aqueous and saline water by laterite-derived Na-polyferrosialate and polyferrophosphosialate geopolymers: A comparative study

In this study, two laterites (LA)-based geopolymers were synthesized using alkalination (GPAL) and phosphoric acid-activation (GPAC) approaches and applied to scavenge malachite green (MG) dye from aqueous (non-saline) and saline water. The precursor (LA) and geopolymers were characterized by XRF, XRD, TG/DTA SEM, and FTIR techniques. Alkalination and acid-activation resulted in morphologically distinguishable geopolymers with different porosity structures. The dissolution of mineral phases and chemical composition was dependent on the activation medium, resulting in Na-polyferrosialate and polyferrophosphosialate geopolymers for GPAL and GPAC, respectively. The adsorption kinetics data were best described by the pseudo-first-order (PFO) model wherein the adsorption rate, denoted by rate constant (k1), increased with an increase in ionic strength (salinity). The equilibrium data were best modelled by the Sips isotherm. GPAL had a higher maximum adsorption capacity (Qms) than GPAC in both aqueous (non-saline) and saline water. The adsorption capacities were increased in saline solution relative to aqueous solutions without NaCl, from 12.4 to 54.1 mg/g and from 57.1 to 92.0 mg/g for GPAC and GPAL, respectively. The adsorption mechanism entailed electrostatic interactions, hydrogen bonding and hydrophobic interactions. Salinity decreased the solubility of MG and increased the hydrophobic interactions and affinity of MG, implied by apparent equilibrium constant (Ka), resulting in increased adsorption density (Qms). These results indicate that alkaline-based geopolymers are better candidates for scavenging MG dye from water, especially in saline environments.

Trace metals in CO 2 -rich Green River springs, Utah, USA: an analogue for engineered storage

Abstract Sedimentary rocks with high natural CO 2 concentrations provide invaluable analogues for the long-term engineered storage of CO 2 . Some previous studies have reported high trace metal concentrations in sandstone aquifers exposed to CO 2 , a cause for concern should stored CO 2 leak into underground sources of drinking water. However, the intensively studied Jurassic sandstone aquifer in the San Rafael–Green River (Utah, USA) area has trace metal concentrations that are within US Environmental Protection Agency's limits for drinking water. Exceptions are As which is plausibly introduced into the aquifer by saline brines external to the aquifer, and salinity which largely is. This shows that CO 2 in aquifers does not inevitably cause trace metal contamination. CO 2 –water–rock batch experiments elucidated the controls on the trace metal concentrations. After the addition of CO 2 , the experiments reproduce Cu, Cd, Hg, Ni and Zn well, with less good agreement for Cr and Pb although these are still low compared to drinking water standards. Major cations used as fingerprints for mobilization mechanisms suggest that the trace metals are largely derived by desorption, possibly from grain-coating Fe-oxides, rather than by the dissolution of mineral phases. Possible exceptions are Pb and Ni, plus As which is derived from saline brines.

Integrating geochemical investigations and geospatial assessment to understand the evolutionary process of hydrochemistry and groundwater quality in arid areas.

Groundwater is the key for life in arid areas. Aquifer overexploitation and climatic conditions can significantly deteriorate groundwater quality. The Al-Qassim area in central Saudi Arabia is characterized by dense agricultural use and is irrigated mainly by fossil groundwater from the Saq Aquifer. Understanding the area's hydrochemistry, major factors governing groundwater quality, and alternative uses of the groundwater are the main goals of this study. Groundwater samples were collected and examined for major, minor, and trace elements. Ionic relationships, hydrochemical facies, geospatial distributions, and multivariate analyses were conducted to assess the hydrochemical processes at play. The salinity and nitrate concentrations of the Saq Aquifer's groundwater were found to increase in the outcrop areas more than the confined areas. The spatial distributions were fragmented by three main factors: (i) modern recharge by relatively brackish water, (ii) irrigation return flow in intensive farming areas, and (iii) overexploitation and draining of deep and relatively saline zones of the aquifer. Seven water types were found representing the alkaline water with a predominance of sulfate-chloride ions and earth alkaline water with a predominance of sulfate and chloride. Mixing between fresh and brackish water, dissolution of mineral phases, silicate weathering, and reverse ion exchange were recognized as the evolutionary processes, while evaporation played a minor role. Cluster analyses characterized the fresh groundwater zone, modern groundwater recharge zone, and anthropogenic influence zone. In the confined areas, nearly all the groundwater was appropriate for domestic use and irrigation. In the outcrop areas, some limitations were found due to unsuitable conditions.

Groundwater residence time in a dissected and weathered sandstone plateau: Kulnura–Mangrove Mountain aquifer, NSW, Australia

Groundwater residence time in the Kulnura–Mangrove Mountain aquifer was assessed during a multi-year sampling programme using general hydrogeochemistry and isotopic tracers (H2O stable isotopes, δ13CDIC, 3H, 14C and 87Sr/86Sr). The study included whole-rock analysis from samples recovered during well construction at four sites to better characterise water–rock interactions. Based on hydrogeochemistry, isotopic tracers and mineral phase distribution from whole-rock XRD analysis, two main groundwater zones were differentiated (shallow and deep). The shallow zone contains oxidising Na–Cl-type waters, low pH, low SC and containing 3H and 14C activities consistent with modern groundwater and bomb pulse signatures (up to 116.9 pMC). In this shallow zone, the original Hawkesbury Sandstone has been deeply weathered, enhancing its storage capacity down to ∼50 m below ground surface in most areas and ∼90 m in the Peats Ridge area. The deeper groundwater zone was also relatively oxidised with a tendency towards Ca–HCO3-type waters, although with higher pH and SC, and no 3H and low 14C activities consistent with corrected residence times ranging from 11.8 to 0.9 ka BP. The original sandstone was found to be less weathered with depth, favouring the dissolution of dispersed carbonates and the transition from a semi-porous groundwater media flow in the shallow zone to fracture flow at depth, with both chemical and physical processes impacting on groundwater mean residence times.Detailed temporal and spatial sampling of groundwater revealed important inter-annual variations driven by groundwater extraction showing a progressive influx of modern groundwater found at >100 m in the Peats Ridge area. The progressive modernisation has exposed deeper parts of the aquifer to increased NO3− concentrations and evaporated irrigation waters. The change in chemistry of the groundwater, particularly the lowering of groundwater pH, has accelerated the dissolution of mineral phases that would generally be inactive within this sandstone aquifer triggering the mobilisation of elements such as aluminium in the aqueous phase.

Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release

Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite.

Hydrogeochemical modelling of fluid–rock interactions triggered by seawater injection into oil reservoirs: Case study Miller field (UK North Sea)

Abstract A hydrogeochemical model is presented and applied to quantitatively elucidate interdependent reactions among minerals and formation water–seawater mixtures at elevated levels of CO 2 partial pressure. These hydrogeochemical reactions (including scale formation) occur within reservoir aquifers and wells and are driven by seawater injection. The model relies on chemical equilibrium thermodynamics and reproduces the compositional development of the produced water (formation water–seawater mixtures) of the Miller field, UK North Sea. This composition of the produced water deviates from its calculated composition, which could result solely from mixing of both the end members (formation water and seawater). This indicates the effect of hydrogeochemical reactions leading to the formation and/or the dissolution of mineral phases. A fairly good match between the modelled and measured chemical composition of produced water indicates that hydrogeochemical interactions achieve near-equilibrium conditions within the residence time of formation water–seawater mixtures at reservoir conditions. Hence the model enables identification of minerals (including scale minerals), to quantitatively reproduce and to predict their dissolution and/or formation. The modelling results indicate that admixing of seawater into formation water triggers the precipitation of Sr–Barite solid solution, CaSO 4 phases and dolomite. In contrast, calcite and microcrystalline quartz are dissolved along the seawater flow path from the injection well towards the production well. Depending on the fraction of seawater admixed, interdependent reactions induce profound modifications to the aquifer mineral phase assemblage. At low levels of seawater admixture, Ba–Sr sulfate solid solution is precipitated and coupled to concurrent dissolution of calcite and microcrystalline quartz. Massive dissolution of calcite and the formation of CaSO 4 phases and dolomite are triggered by intense seawater admixture. Hydrogeochemical modelling to reproduce observed compositional trends, resulting from an increase of the seawater fraction, can help (1) to explain changing production properties and (2) to predict the type and the degree of scaling depending on the content of injected seawater.

Sources and controls for the mobility of arsenic in oxidizing groundwaters from loess-type sediments in arid/semi-arid dry climates – Evidence from the Chaco–Pampean plain (Argentina)

In oxidizing aquifers, arsenic (As) mobilization from sediments into groundwater is controlled by pH-dependent As desorption from and dissolution of mineral phases. If climate is dry, then the process of evaporative concentration contributes further to the total concentration of dissolved As. In this paper the principal As mobility controls under these conditions have been demonstrated for Salí River alluvial basin in NW Argentina (Tucumán Province; 7000 km 2), which is representative for other basins or areas of the predominantly semi-arid Chaco–Pampean plain (1,000,000 km 2) which is one of the world’s largest regions affected by high As concentrations in groundwater. Detailed hydrogeochemical studies have been performed in the Salí River basin where 85 groundwater samples from shallow aquifers (42 samples), deep samples (26 samples) and artesian aquifers (17 samples) have been collected. Arsenic concentrations range from 11.4 to 1660 μg L −1 leaving 100% of the investigated waters above the provisional WHO guideline value of 10 μg L −1. A strong positive correlation among As, F, and V in shallow groundwaters was found. The correlations among those trace elements and U, B and Mo have less significance. High pH (up to 9.2) and high bicarbonate (HCO 3) concentrations favour leaching from pyroclastic materials, including volcanic glass which is present to 20–25% in the loess-type aquifer sediments and yield higher trace element concentrations in groundwater from shallow aquifers compared to deep and artesian aquifers. The significant increase in minor and trace element concentrations and salinity in shallow aquifers is related to strong evaporation under semi-arid climatic conditions. Sorption of As and associated minor and trace elements (F, U, B, Mo and V) onto the surface of Fe-, Al- and Mn-oxides and oxi-hydroxides, restricts the mobilization of these elements into groundwater. Nevertheless, this does not hold in the case of the shallow unconfined groundwaters with high pH and high concentrations of potential competitors for adsorption sites (HCO 3, V, P, etc.). Under these geochemical conditions, desorption of the above mentioned anions and oxyanions occurs as a key process for As mobilization, resulting in an increase of minor and trace element concentrations. These geochemical processes that control the concentrations of dissolved As and other trace elements and which determine the groundwater quality especially in the shallow aquifers, are comparable to other areas with high As concentrations in groundwater of oxidizing aquifers and semi-arid or arid climate, which are found in many parts of the world, such as the western sectors of the USA, Mexico, northern Chile, Turkey, Mongolia, central and northern China, and central and northwestern Argentina.

Biogeochemical Redox Processes and their Impact on Contaminant Dynamics

Life and element cycling on Earth is directly related to electron transfer (or redox) reactions. An understanding of biogeochemical redox processes is crucial for predicting and protecting environmental health and can provide new opportunities for engineered remediation strategies. Energy can be released and stored by means of redox reactions via the oxidation of labile organic carbon or inorganic compounds (electron donors) by microorganisms coupled to the reduction of electron acceptors including humic substances, iron-bearing minerals, transition metals, metalloids, and actinides. Environmental redox processes play key roles in the formation and dissolution of mineral phases. Redox cycling of naturally occurring trace elements and their host minerals often controls the release or sequestration of inorganic contaminants. Redox processes control the chemical speciation, bioavailability, toxicity, and mobility of many major and trace elements including Fe, Mn, C, P, N, S, Cr, Cu, Co, As, Sb, Se, Hg, Tc, and U. Redox-active humic substances and mineral surfaces can catalyze the redox transformation and degradation of organic contaminants. In this review article, we highlight recent advances in our understanding of biogeochemical redox processes and their impact on contaminant fate and transport, including future research needs.

Assessment of the chemical components of Famenin groundwater, western Iran

The Faminin area in the semi-arid Hamadan state, western Iran is facing a serious deficiency in groundwater resources due to an increasing demand associated with rapid population growth and agricultural development. The chemical composition of 78 well samples throughout the Faminin area was determined with the aim of evaluating the concentration of the background ions and identifying the major hydrogeochemical processes that control the groundwater chemistry. The similarity between rock and groundwater chemistries in the recharge area indicates a significant rock-water interaction. The hydrochemical types Na-HCO(3) and Na-SO(4) are the predominate forms in the groundwater, followed by water types Ca-HCO(3) and Na-Cl. The high values of electrical conductivity and high concentrations of Na(+), Cl(-), SO (4) (2-) and NO (3) (-) in the groundwater appeared to be caused by the dissolution of mineral phases and would appeared to be caused by anthropogenic activities, such as intense agricultural practices (application of fertilizers, irrigation practice), urban and industrial waste discharge, among others.

Module-oriented modeling of reactive transport with HYTEC

The paper introduces HYTEC, a coupled reactive transport code currently used for groundwater pollution studies, safety assessment of nuclear waste disposals, geochemical studies and interpretation of laboratory column experiments. Based on a known permeability field, HYTEC evaluates the groundwater flow paths, and simulates the migration of mobile matter (ions, organics, colloids) subject to geochemical reactions. The code forms part of a module-oriented structure which facilitates maintenance and improves coding flexibility. In particular, using the geochemical module CHESS as a common denominator for several reactive transport models significantly facilitates the development of new geochemical features which become automatically available to all models. A first example shows how the model can be used to assess migration of uranium from a sub-surface source under the effect of an oxidation front. The model also accounts for alteration of hydrodynamic parameters (local porosity, permeability) due to precipitation and dissolution of mineral phases, which potentially modifies the migration properties in general. The second example illustrates this feature.

Coordinative interactions between soil solids and water — An aquatic chemist's point of view

Almost all the problems associated with understanding the rate processes that control the composition of our environment concern interfaces. Oxides, especially those of Si, Al, Fe and Mn are abundant components of the earth's crust. The oxygen donor atoms present on the hydrous oxide surfaces tend to undergo protolysis and to form complexes with metal ions, and to become exchanged for other ligands (anions or weak acids). Many of these surface complexes are of an inner-sphere nature. The rates of processes occurring at the hydrous oxide surface, such as precipitation (heterogeneous nucleation on oxide surfaces) of minerals and dissolution of mineral phases — of importance in the weathering of rocks, in the formation of soils and sediments, in the corrosion of metals and their inhibition — are critically dependent on the coordinative interactions taking place on these surfaces. Rate laws showing dependence on the concentration of surface ligand complexes and on surface protonation are derived.