Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume

The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH4, Fe(II), SO4, Cl, CH4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.     

Surface charge and adsorption from water onto quartz sand of humic acid

The surface charge of humic acid under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)) was determined by a titration method using a cationic polyelectrolyte as titrant. Adsorption isotherms in batch experiments of the polymer from water onto quartz sand were determined at 20 degrees C, 40 degrees C, and 60 degrees C and under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)). The data indicate significant decrease of humic acid surface charge by decreasing the pH value from 10.0 to 4.1. Similar decrease of humic acid surface charge was observed by increasing either the ionic strength or the affinity of the divalent cation toward the humic acid. At ambient temperature the adsorption of humic acid on the quartz sand seems to be controlled mainly by electrical interaction between the organic particle and the solid substrate. A correlation is found between the surface charge and the adsorbed amount of the polymer, the adsorbed amount increases when the surface charge of humic acid decreases. The increase of the adsorbed amount with the temperature suggests that adsorption process is endothermic.     

Reactive transport modeling of processes controlling the distribution and natural attenuation of phenolic compounds in a deep sandstone aquifer

Reactive solute transport modeling was utilized to evaluate the potential for natural attenuation of a contaminant plume containing phenolic compounds at a chemical producer in the West Midlands, UK. The reactive transport simulations consider microbially mediated biodegradation of the phenolic compounds (phenols, cresols, and xylenols) by multiple electron acceptors. Inorganic reactions including hydrolysis, aqueous complexation, dissolution of primary minerals, formation of secondary mineral phases, and ion exchange are considered. One-dimensional (1D) and three-dimensional (3D) simulations were conducted. Mass balance calculations indicate that biodegradation in the saturated zone has degraded approximately 1-5% of the organic contaminant plume over a time period of 47 years. Simulations indicate that denitrification is the most significant degradation process, accounting for approximately 50% of the organic contaminant removal, followed by sulfate reduction and fermentation reactions, each contributing 15-20%. Aerobic respiration accounts for less than 10% of the observed contaminant removal in the saturated zone. Although concentrations of Fe(III) and Mn(IV) mineral phases are high in the aquifer sediment, reductive dissolution is limited, producing only 5% of the observed mass loss. Mass balance calculations suggest that no more than 20-25% of the observed total inorganic carbon (TIC) was generated from biodegradation reactions in the saturated zone. Simulations indicate that aerobic biodegradation in the unsaturated zone, before the contaminant entered the aquifer, may have produced the majority of the TIC observed in the plume. Because long-term degradation is limited to processes within the saturated zone, use of observed TIC concentrations to predict the future natural attenuation may overestimate contaminant degradation by a factor of 4-5.     

UraniumVI sorption behavior on silicate mineral mixtures

UraniumVI sorption experiments involving quartz and clinoptilolite, important mineral phases at the proposed US nuclear waste repository at Yucca Mountain, NV, were conducted to evaluate the ability of surface complexation models to predict UVI sorption onto mineral mixtures based on parameters derived from single-mineral experiments. The experiments were conducted at an initial UVI aqueous concentration of approximately 2.0 x 10(-7) mol.l-1 (0.1 mol.l-1 NaNO3 matrix) and over the pH range approximately 2.5 to approximately 9.5. The UVI solutions were reacted with either quartz or clinoptilolite only, or with mixtures of the two minerals. The experiments were carried out under atmospheric pCO2(g) conditions (in loosely capped containers) or under limited pCO2(g) (in capped containers or in a glove box). Data from sorption experiments on quartz at atmospheric pCO2 conditions were used to derive UVI binding constants for a diffuse-layer surface complexation model (DLM). The DLM was then used with surface area as a scaling factor to predict sorption of UVI onto clinoptilolite and clinoptilolite/quartz mixtures under both atmospheric and low pCO2 conditions. The calculations reproduced many aspects of the pH-dependent sorption behavior. If this approach can be demonstrated for natural mineral assemblages, it may be useful as a relatively simple method for improving radionuclide transport models in performance-assessment calculations.     

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)

The kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) in aqueous solutions at various pH, temperature, oxidant concentration and ionic strength levels was studied. The MTBE degradation was found to follow a pseudo-first-order decay model. The pseudo-first-order rate constants of MTBE degradation by persulfate (31.5 mM) at pH 7.0 and ionic strength 0.11 M are approximately 0.13 x 10(-4), 0.48 x 10(-4), 2.4 x 10(-4) and 5.8 x 10(-4) S(-1) at 20, 30, 40 and 50 degrees C, respectively. Under the above reaction conditions, the reaction has an activation energy of 24.5 +/- 1.6 kcal/ mol and is influenced by temperature, oxidant concentration, pH and ionic strength. Raising the reaction temperature and persulfate concentration may significantly accelerate the MTBE degradation. However, increasing both pH (over the range of 2.5-11) and ionic strength (over the range of 0.11-0.53 M) will decrease the reaction rate. Reaction intermediates including tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were observed. These intermediate compounds were also degraded by persulfate under the experimental conditions. Additionally, MTBE degradation by persulfate in a groundwater was much slower than in phosphate-buffer solutions, most likely due to the presence of bicarbonate ions (radical scavengers) in the groundwater.     

A cation exchange model to describe Cs+ sorption at high ionic strength in subsurface sediments at Hanford site, USA

A theoretical and experimental study of cation exchange in high ionic strength electrolytes was performed using pristine subsurface sediments from the U.S. Department of Energy Hanford site. These sediments are representative of the site contaminated sediments impacted by release of high level waste (HLW) solutions containing 137Cs+ in NaNO3 brine. The binary exchange behavior of Cs+-Na+, Cs+-K+, and Na+-K+ was measured over a range in electrolyte concentration. Vanselow selectivity coefficients (Kv) that were calculated from the experimental data using Pitzer model ion activity corrections for aqueous species showed monotonic increases with increasing electrolyte concentrations. The influence of electrolyte concentration was greater on the exchange of Na+-Cs+ than K+-Cs+, an observation consistent with the differences in ion hydration energy of the exchanging cations. A previously developed two-site ion exchange model [Geochimica et Cosmochimica Acta 66 (2002) 193] was modified to include solvent (water) activity changes in the exchanger phase through application of the Gibbs-Duhem equation. This water activity-corrected model well described the ionic strength effect on binary Cs+ exchange, and was extended to the ternary exchange system of Cs+-Na+-K+ on the pristine sediment. The model was also used to predict 137Cs+ distribution between sediment and aqueous phase (Kd) beneath a leaked HLW tank in Hanfordd's S-SX tank using the analytical aqueous data from the field and the binary ion exchange coefficients for the pristine sediment. The Kd predictions closely followed the trend in the field data and were improved by consideration of water activity effects that were considerable in certain regions of the vadose zone plume.     

Large-scale modeling of reactive solute transport in fracture zones of granitic bedrocks

Final disposal of high-level radioactive waste in deep repositories located in fractured granite formations is being considered by several countries. The assessment of the safety of such repositories requires using numerical models of groundwater flow, solute transport and chemical processes. These models are being developed from data and knowledge gained from in situ experiments such as the Redox Zone Experiment carried out at the underground laboratory of Äspö in Sweden. This experiment aimed at evaluating the effects of the construction of the access tunnel on the hydrogeological and hydrochemical conditions of a fracture zone intersected by the tunnel. Most chemical species showed dilution trends except for bicarbonate and sulphate which unexpectedly increased with time. Molinero and Samper [Molinero, J. and Samper, J. Groundwater flow and solute transport in fracture zones: an improved model for a large-scale field experiment at Äspö (Sweden). J. Hydraul. Res., 42, Extra Issue, 157–172] presented a two-dimensional water flow and solute transport finite element model which reproduced measured drawdowns and dilution curves of conservative species. Here we extend their model by using a reactive transport which accounts for aqueous complexation, acid–base, redox processes, dissolution–precipitation of calcite, quartz, hematite and pyrite, and cation exchange between Na⁺ and Ca²⁺. The model provides field-scale estimates of cation exchange capacity of the fracture zone and redox potential of groundwater recharge. It serves also to identify the mineral phases controlling the solubility of iron. In addition, the model is useful to test the relevance of several geochemical processes. Model results rule out calcite dissolution as the process causing the increase in bicarbonate concentration and reject the following possible sources of sulphate: (1) pyrite dissolution, (2) leaching of alkaline sulphate-rich waters from a nearby rock landfill and (3) dissolution of iron monosulphides contained in Baltic seafloor sediments. Based on these results, microbially mediated processes are postulated as the most likely hypothesis to explain the measured increase of dissolved bicarbonates and sulphates after tunnel construction.     

Experimental and modeling studies on sorption and diffusion of radium in bentonite

The sorption and desorption behavior of radium on bentonite and purified smectite was investigated as a function of pH, ionic strength and liquid to solid ratio by batch experiments. The distribution coefficients (Kd) were in the range of 10(2) to > 10(4) ml g-1 and depended on ionic strength and pH. Most of sorbed Ra was desorbed by 1 M KCl. The results for purified smectite indicated that Ra sorption is dominated by ion exchange at layer sites of smectite, and surface complexation at edge sites may increase Ra sorption at higher pH region. Reaction parameters between Ra and smectite were determined based on an interaction model between smectite and groundwater. The reaction parameters were then used to explain the results of bentonite by considering dissolution and precipitation of minerals and soluble impurities. The dependencies of experimental Kd values on pH, ionic strength and liquid to solid ratio were qualitatively explained by the model. The modeling result for bentonite indicated that sorption of Ra on bentonite is dominated by ion exchange with smectite. The observed pH dependency was caused by changes of Ca concentration arising from dissolution and precipitation of calcite. Diffusion behavior of Ra in bentonite was also investigated as a function of dry density and ionic strength. The apparent diffusion coefficients (Da) obtained in compacted bentonite were in the range of 1.1 x 10(-11) to 2.2 x 10(-12) m2 s-1 and decreased with increasing in dry density and ionic strength. The Kd values obtained by measured effective diffusion coefficient (De) and modeled De were consistent with those by the sorption model in a deviation within one order of magnitude.     

Coupled modeling of cement/claystone interactions and radionuclide migration

The interactions between cement and a clayey host-rock of an underground repository for intermediate-level radioactive waste are studied with the reactive transport code HYTEC for supporting performance assessment. Care is taken in using relevant time scales (100,000 years) and dimensions. Based on a literature review, three hypotheses are considered with respect to the mineralogical composition of the claystone and the neo-formed phases. In the long term, the pH is buffered for all hypotheses and important mineral transformations occur both in cement and the host-rock. The destruction of the primary minerals is localized close to the cement/claystone interface and is characterized by the precipitation of secondary phases with retention properties (illite, zeolite). However, beyond the zone of intense mineral transformations, the pore water chemistry is also disturbed over a dozen meters due to an attenuated but continuous flux of hydroxyl, potassium and calcium ions. Four interdependent mechanisms control the profile in the whole system: diffusion of the alkaline plume, mineralogical buffering, ion exchange and clogging of the pore space at the cement/claystone interface. The migration of a selected group of radionuclides (Cs, Ra, Tc and U) is explicitly integrated in the simulations of the strongly coupled system. Theoretical profiles of distribution coefficient (Kd) and solubility limit values are derived from the simulations, and their sensitivity with respect to the system evolution is estimated.     

Solvent and surfactant enhanced solubilization, stabilization, and degradation of amitraz

In an effort to help with the development of effective dip vat management and waste disposal strategies this study determined how solution properties such as pH, buffer composition, ionic strength, temperature, solubility in organic solvents and the addition of commonly used solubilizing agents influenced the hydrolysis of amitraz. Amitraz degrade by means of hydrolysis described by a pseudo-first order rate process and a type ABCD pH rate profile. Hydrolysis increased with temperature and was fastest at low pH, slowest at neutral to slightly alkaline pH, and slightly increased above pH 10. However, buffer concentration and ionic strength influenced the hydrolysis rate and had to be accounted for before constructing a pH rate profile. Hydrolysis seems to depend on the dielectric constant of solvent mixtures and was fastest in water, slower in propylene glycol and ethanol solutions, and slowest in DMSO mixtures. In surfactant solutions, anionic micelles enhanced and cationic micelles retarded the hydrolysis rate. The magnitude of micellar effects decreased with increasing concentrations of the surfactants. The increased solubility and faster hydrolysis of amitraz in the sodium lauryl sulfate solutions showed that anionic surfactants potentially could be used for cleaning up amitraz spills, because it both solubilized the drug and catalyzed hydrolysis.     

Cadmium adsorption and desorption behaviour on goethite at low equilibrium concentrations: effects of pH and index cations

The transport and bioavailability of cadmium is governed mainly by its adsorption-desorption reactions with minerals such as goethite--a common iron oxide mineral in variable charged and highly weathered tropical soils. Soil factors such as pH, temperature, solution Cd concentration, ionic strength and ageing affect Cd adsorption on goethite. The desorption behaviour of Cd from goethite at low concentrations is not fully understood. This study investigates the adsorption-desorption of Cd at low Cd concentrations (Cd adsorbed on goethite from 20 to 300 microM Cd solutions) in Na and Ca nitrate solutions of 0.03 M nominal ionic strengths. Synthetic goethite prepared by ageing a ferric hydroxide gel at high pH and room temperature was used for Cd adsorption and desorption studies. For desorption experiment 10 successive desorptions were made for the whole range of initial Cd concentrations (20-300 microM) in the presence of 0.01 M Ca(NO3)2 or 0.03 M NaNO3 solutions. Cadmium adsorption was found to be higher in Na+ than Ca2+ probably due to the competition of Ca2+ ions with Cd2+ ions for adsorption sites on the surfaces of goethite. The effect of index cation on Cd adsorption diminished with increase in pH from 5.0 to 6.0. Cadmium desorption decreased with increase in pH from 5.0 to 6.0 in both Na and Ca systems. After 10 successive desorptions with 0.03 M NaNO3 at the lowest initially adsorbed Cd approximately 45%, 20% and 7% of the adsorbed Cd was desorbed at pH 5.0, 5.5 and 6.0, respectively. The corresponding desorptions in the presence of 0.01 M Ca(NO3)2 were 49%, 22% and 8%, respectively. The Freundlich parameter, k, based on each progressive step of desorption at different adsorbed concentration increased with increasing desorption step, which may indicates that a fraction of Cd was resistant to desorption. Low Cd desorbability from goethite may be due to its specific adsorption and/or possibly as a result of Cd entrapment in the cracks or defects in goethite structure.     

Accelerated transport of (90)Sr following a release of high ionic strength solution in vadose zone sediments

Numerical simulation of cation exchange and mineral precipitation/dissolution reactions using the multiphase reactive geochemical transport code TOUGHREACT has provided important insight into the distribution of (90)Sr among layers of geologic strata in a complex vadose zone at the U. S. Department of Energy's Idaho National Laboratory. During a transfer operation in November 1972, 70.4 m(3) of acidic, high ionic strength liquid containing 15,900 Ci of (90)Sr was released over five days into alluvial gravels 137 m above the Snake River Plain Aquifer. Sampling data from perched water zones 33 m below the release contain very high levels of (90)Sr as do soil samples obtained nearer the point of release. Use of traditional simulation approaches using laboratory-measured constant partitioning coefficients (K(d)) cannot simultaneously explain perched water and soil concentrations. To address the discrepancy, a reactive transport approach was adopted to include competitive cation exchange, dissolution/precipitation of calcite, carbon dioxide gas production and transport, and gibbsite precipitation. Simulation results using this model suggest that some of the (90)Sr could have been transported very rapidly immediately after the release with the acceleration facilitated by competition for cation exchange sites with high sodium concentrations in the released liquid and calcium dissolved from calcite, and to a lesser extent by formation of aqueous complexes with nitrate. Once the leading edge of the liquid assemblage was flushed from the alluvium, the mobility of the remaining (90)Sr decreased significantly in the absence of the competing cations. Calculations indicate that there should be a net increase in calcite, suggesting that (90)Sr could be entrained in the mineral lattice, but insufficient field data exist for confirmation. Sensitivity studies show that the cation exchange selectivity coefficients were the most sensitive individual parameters determining the (90)Sr distribution. However, the most sensitive overall quantity was the total ion exchange capacity which is a function of the moles of exchange sites per volume of pore water, the cation exchange capacity, and the total volume wetted by the infiltrating solution. In contrast, the future mobility of (90)Sr was found to be relatively insensitive to the normal range in the composition of influxing precipitation and anthropogenic waters.     

Impacts of simulated acid rain on recalcitrance of two different soils

Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H₂SO₄ plus HNO₃ at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH?2.0, whereas only cation exchange occurred above SAR pH?3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K⁺ and Mg²⁺ ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca²⁺?>?K⁺?>?Mg²⁺?>?Na⁺ for the Plinthudult and Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺ for the Paleudalfs soil. The SARs above pH?3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH?2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.     

Montmorillonite-Cu(II)/Fe(III) oxides magnetic material as adsorbent for removal of humic acid and its thermal regeneration

In this work, the adsorption features of montmorillonite and the magnetic properties of Cu(II)/Fe(III) oxides were combined in a material to produce magnetic adsorbent, which can be separated from the medium by a simple magnetic process after adsorption. The magnetic material is effective for the removal of humic acid. At pH 6.1, 96% removal was observed from 4.4 mg l(-1) humic acid solution containing 0.02 M NaCl. The adsorption is pH and ionic strength dependent. Adsorption is favored at lower pH values and dissolved NaCl can enhance the adsorption. The adsorption mechanism of humic acid to the magnetic material was suggested to be the ligand exchange reaction between carboxylic groups of humic acid molecules and the magnetic material surface. The magnetic material can be thermally regenerated. The temperature and time required to achieve good regeneration efficiency were determined to be 300 degrees C and 3 h, respectively. The regenerated adsorbent is still magnetic and approximately has as high specific saturation magnetization and good adsorption capacities as the as-prepared adsorbent.     

Desorption of cadmium from goethite: effects of pH, temperature and aging

Cadmium is perhaps environmentally the most significant heavy metal in soils. Bioavailability, remobilization and fate of Cd entering in soils are usually controlled by adsorption-desorption reactions on Fe oxides. Adsorption of Cd on soil colloids including Fe oxides has been extensively studied but Cd desorption from such soil minerals has received relatively little attention. Some factors that affect Cd adsorption on goethite include pH, temperature, aging, type of index cations, Cd concentrations, solution ionic strength and presence of organic and inorganic ions. This research was conducted to study the influence of pH, temperature and aging on Cd desorption from goethite. Batch experiments were conducted to evaluate Cd desorption from goethite with 0.01 M Ca(NO3)2. In these experiments Cd desorption was observed at 20, 40 and 70 degrees C in combination with aging for 16 h, 30, 90 and 180 d from goethite that adsorbed Cd from solutions containing initial Cd concentrations of 20, 80 and 180 microM. Following the adsorption step Cd desorption was measured by 15 successive desorptions after aging at various temperatures. At the lowest amount of initially adsorbed Cd and equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 17% with aging from 16 h to 180 d and the corresponding decrease at equilibrium pH 6.0 was from 32% to 3%. There was a substantial decrease in Cd desorption with increasing equilibration temperature. For example, in goethite with the lowest amount of initial adsorption at equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 31% with increase in temperature from 20 to 70 degrees C, even after 16 h. Dissolution of Cd adsorbed goethite in 1M HCl, after 15 successive desorptions with 0.01 M Ca(NO3)2, indicated that approximately 60% of the Cd was surface adsorbed. Overall, dissolution kinetics data revealed that 23% to 88% Cd could not be desorbed, which could possibly be diffused into the cracks and got entrapped in goethite crystals. At elevated temperature increased equilibrium solution pH favoured the formation of CaCO3 and CdCO3 which reasonably decreased Cd desorption. Cadmium speciation showed the formation of calcite and otavite minerals at 40 and 70 degrees C due to increase in pH (>9.5) during aging. X-ray diffraction analysis (XRD) of these samples also revealed the formation of CaCO3 at elevated temperatures with aging. While mechanisms such as Cd diffusion and/or entrapment into fissures and cracks in goethite structure with increase in temperature and aging are possible.     

Humic acid complexation of basic and neutral polycyclic aromatic compounds

Complexation by humic acid (HA) of basic (quinoline) and neutral (naphthalene) polycyclic aromatic compounds (PACs) was compared using fluorescence spectroscopy and equilibrium dialysis (ED). These compounds sorb to HA via cation exchange and hydrophobic interactions, respectively. Ionization of quinoline strongly affects its sorption to HA; maximum sorption is observed at pH close to logKb (4.92), and competition with H+ and electrolyte cation (Li+) is evident. Spectroscopic experiments indicate that quinolinium (QH+) cation fluorescence is quenched via a static mechanism (i.e., a dark complex is formed) when the protonated form is adsorbed via ion exchange to HA. The extent of sorption, calculated from fluorescence data using the Stern-Volmer equation, was compared to independent ED measurements. Although both methods indicated the same trends with solution chemistry, fluorescence quenching data suggested more extensive complexation than that measured using ED. In contrast to ionizable PACs, studied here and previously, interaction of naphthalene with HA is unaffected by changes in solution conditions (pH, ionic strength).     

Nutrient leaching from conifer needles in relation to foliar apoplast cation exchange capacity

Limited evidence to date suggests that acidic precipitation promotes leaching of nutrient cations from conifer foliage. In order to evaluate the relative contribution of the apoplast cation exchange complex and symplast nutrient pools to the leached ions, the magnitude of foliar leaching in response to acidic solutions was compared to foliar apoplast cation exchange capacity (CEC) for two conifer tree species (Pseudotsuga menziesii and Picea engelmanii). Leaching potential was determined by immersing detached needles in acidic solutions (pH5.6, 3.1, 2.1) over a range of time intervals (1, 4, 8, 24 h) and foliar apoplast cation exchange capacity was determined by potentiometric titration. Leaching increased with decreasing pH and increasing time of immersion. At pH values 2.1 and 3.1, equivalents of H+ depleted from the acidic solutions approximated equivalents of base cations gained by the solutions. Maximum amounts leached were less than 40 microeq g(-1) dry weight of needles for the combination of calcium, magnesium and potassium. Measured foliar apoplast CEC for these species was approximately 120 microeq g(-1) dry weight of needles. These relative magnitudes indicate that the apoplast rather than the symplast provided the leached ions. Because the apoplast foliar cation exchange capacity appears to be large relative to the rates of H+ diffusion across the cuticle, it may help to insulate the symplast nutrient reservoir from exposure to the H+ of acidic solutions bathing the foliage.     

Arsenic release from iron rich mineral processing waste: Influence of pH and redox potential

This paper presents the effect of pH and redox potential on the potential mobility of arsenic (As) from a contaminated mineral processing waste. The selected waste contained about 0.47 g kg(-1) of As and 66.2 g kg(-1) of iron (Fe). The characteristic of the waste was identified by acid digestion, X-ray diffraction and sequential extraction procedures. Less than 2% of the total As was acid extractable with the remaining 98% associated with Fe-oxyhydroxides and oxides. Batch leaching tests at different pH conditions showed a strong pH dependence on arsenic and iron leaching. Arsenic leaching followed a "V" shaped profiles with significant leaching in the acidic and alkaline pH region. Acid extractable phases dissolved at acidic pH, while desorption of arsenic due to increase in pH resulted in high arsenic concentration at alkaline pH. Under aerobic conditions and pH 7, As solubility was low, probably due to its precipitation on Fe-oxyhydroxides. Maximum As solubilization occurred at pH 11 (3.59 mg l(-1)). Similarity in the As and Fe leaching profiles suggested that the release of As was related to the dissolution of Fe in the low pH region. In general, redox potential did not play a significant role in arsenic or iron solubilization. It was thus concluded that for this solid waste, desorption was the predominant mechanism in arsenic leaching. A simple thermodynamic model based on arsenic and iron redox reactions was developed to identify the more sensitive redox couple.     

Investigation of solution chemistry effects on sorption behavior of Cu(II) on ZSM-5 zeolite

The sorption of Cu(II) from an aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. Sorption was investigated as a function of pH, ionic strength, foreign ions, humic substances, and temperature. The results indicate that the sorption of Cu(II) on ZSM-5 zeolite is strongly dependent on pH. Sorption is dependent on ionic strength at low pH, but independent of ionic strength at high pH values. The presence of humic/fluvic acid (HA/FA) enhances the sorption of Cu(II) on ZSM-5 zeolite at low pH values, and reduces Cu(II) sorption at high pH values. Sorption isotherms were well simulated by the Langmuir model. Thermodynamic parameters (i.e., deltaH0, deltaS0 and deltaG0) for the sorption of Cu(II) were determined from temperature-dependent sorption isotherms at 293.15, 313.15, and 333.15 K, respectively. Results indicate that the sorption process of Cu(II) on ZSM-5 zeolite is spontaneous and endothermic.     

The adsorption of short single-stranded DNA oligomers to mineral surfaces

We studied the adsorption of short single-stranded deoxyribonucleic acid (ssDNA) oligomers, of approximately 30 nucleotides (nt) in length, of varying sequence, adenine + guanine + cytosine (AGC) content, and propensity to form secondary structure, to equal surface area samples of olivine, pyrite, calcite, hematite, and rutile in 0.1 M NaCl, 0.05 M pH 8.1 KHCO₃ buffer. Although the mineral surfaces have widely varying points of zero charge, under these conditions they show remarkably similar adsorption of ssDNA regardless of oligomer characteristics. Mineral surfaces appear to accommodate ssDNA comparably, or ssDNA oligomers of this length are able to find binding sites of comparable strength and density due to their flexibility, despite the disparate surface properties of the different minerals. This may partially be due charge shielding by the ionic strength of the solutions tested, which are typical of many natural environments. These results may have some bearing on the adsorption and accumulation of biologically derived nucleic acids in sediments as well as the abiotic synthesis of nucleic acids before the origin of life.