Pyrite oxidation in sediment samples from the German open‐cut brown coal mine Zwenkau: mineral formation and dissolution of silicates

Changes in mineral composition occurring in pyrite‐containing sediments under aerobic conditions are complex and not fully understood. The objective was to study the mineral formation and dissolution of silicates using ion activity product (IAP) calculations and x‐ray diffraction (XRD) on samples of different degrees of pyrite oxidation. Three sediment samples were obtained from the open‐cut brown coal mine of Zwenkau (Saxony, Germany) with low (ZL: 28 g kg^—1), medium (ZM: 67 g kg^—1) and high (ZH: 95 g kg^—1) pyrite contents. These samples were oxidized in the laboratory for 3, 20, 67, and 130 days to obtain four different degrees of pyrite oxidation for each sediment. Sequential batch experiments were carried out for each sediment and oxidation status. Additionally, cation exchange capacities were determined. XRD showed the formation of gypsum (all sediments), jarosite (ZM, ZH), and rozenite (ZH) with increasing pyrite oxidation. IAP calculations suggested an occurrence of gypsum in all samples, of schwertmannite in slightly (ZH) and moderately oxidized (ZM, ZL) samples, and of alunite in a moderately oxidized sample (ZL). The contents of feldspar (ZL), mica/illite (ZL, ZH), and kaolinite (ZH) decreased with increasing pyrite oxidation. The cation exchange capacities of the sediments decreased by 20 (ZH) to 70 mmol_c kg^—1 (ZM). The change in mineral phases with increasing oxidation status of the sediments also changed the activities of Al, Fe, and SO₄ in solution phases. The results obtained in this study suggested the usefulness of predictive models to estimate sediment and water acidification due to pyrite oxidation.     

Sorption of Phosphorus from Swine,Dairy, and Poultry Manures

In most phosphorus (P) sorption studies, P is added as an inorganic salt to a predefined background solution such as calcium chloride (CaCl₂) or potassium chloride (KCl); however, in many regions, the application of P to agricultural fields is in the form of animal manure. The purpose of this study, therefore, was to compare the sorption behavior of dissolved reactive P (DRP) in monopotassium phosphate (KH₂PO₄)–amended CaCl₂ and KCl solutions with sorption behavior of DRP in three different animal manure extracts. Phosphorus single‐point isotherms (PSI) were conducted on eight soils with the following solutions: KH₂PO₄‐amended 0.01 M CaCl₂ solution, KH₂PO₄‐amended 0.03 M KCl solution, water‐extracted dairy manure, water‐extracted poultry litter, and swine lagoon effluent. The PSI values for the dairy manure extract were significantly lower than the CaCl₂ solution for all eight soils and lower than the KCl solution for six soils. The PSI values were significantly higher, on the other hand, for poultry litter extract and swine effluent than the inorganic solutions in four and five of the soils, respectively. Our observations that the sorption of DRP in manure solutions differs significantly from that of KH₂PO₄‐amended CaCl₂ and KCl solutions indicates that manure application rates based on sorption data collected from inorganic P salt experiments may be inaccurate.     

Modeling the Effect of pH and Salinity on Biogeochemical Reactions and Metal Behavior in Sediment

A mathematical model is developed to investigate the effect of pH and salinity fluctuation on biogeochemical reactions and metals' behavior in sediments. The model includes one-dimensional vertical advective and diffusive transport of species, serial reductions of electron acceptors, and precipitation/dissolution of species, acid–base chemistry, and metal sorption to sediments. The model was tested using data obtained from laboratory microcosm experiments which exposed metal (Cd, Zn) contaminated sediment to alternating fresh and salty overlying water. The model successfully reproduces the contrasting metal's release behavior and the vertical profiles of pH, Cl^?, SO₄ ^2?, Mn and Fe in porewater and the acid volatile sulfides (AVS) and simultaneously extracted metals (SEM) in sediments. The model showed that FeOOH_(s) was the dominant sorption phase controlling the solubility of the metals at the surficial sediments while AVS controlled the solubility of the metals in anoxic sediments. The model also showed that the release of the metals to overlying water was controlled by the oxidation of metal sulfides in a very thin layer of oxic sediments (2–3 mm). The proposed model can be useful in managing metal contaminated sediments where pH and salinity are fluctuating by assessing the underlying biogeochemical processes and metals' behavior.     

Chemical and biological relationships relevant to the effect of acid rainfall on the soil-plant system

This paper deals with problems concerning measurements of rainfall acidity and interpretation in terms of possible effects on the soil-plant system. The theory of acidity relationships of the carbon dioxide-bicarbonate equilibria and its effect on rainfall acidity measurements is given. The relationship of a cation-anion balance model of acidity in rainfall to plant nutrient uptake processes is discussed, along with the relationship of this model to a rainfall acidity model previously proposed in the literature. These considerations lead to the conclusion that average H+ concentration calculated from pH measurements is not a satisfactory method of determining H⁺ loading from rainfall if the rain is not consistently acid. Calculating loading from H⁺ minus HCO₃ ^? , strong acid anions minus basic cations, or net titratable acidity is suggested. The flux of H⁺ ions in soil systems due to plant uptake processes and sulfur and nitrogen cycling is considered. H⁺ is produced by oxidation of reduced sulfur and nitrogen compounds mineralized during decomposition of organic matter. Plant uptake processes may result in production of either H⁺ or OH^? ions. Fluxes of H⁺ from these processes are much greater than rainfall H⁺ inputs, complicating measurement and interpretation of rainfall effects. The soil acidifying potential due to the oxidation of the NH₄ ⁺ rainfall is examined, with the conclusion that acidity from this source is of a similar magnitude to direct H⁺ inputs common in rainfall.     

Effects of temperature on phosphate sorption isotherms and phosphate desorption

Abstract

Phosphorus sorption isotherms were constructed for two Idaho soils with widely different chemical properties. The soils were equilibrated with various amounts of Ca(H₂PO₄)₂ in 0.01 M CaCl₂ for 1, 3, 7, and 11 days at temperatures of 5°C and 20°C. The two soils which had been equilibrated previously for 11 days at 20°C with various amounts of Ca(H₂PO₄)₂ in 0.01 M CaCl₂ were desorbed at 5°C and 20°C.

The rates of sorption and desorption were decreased as the equilibration temperatures were lowered. The effect of temperature on these processes was detected during the first day of equilibration. Less P was found in the equilibrating solution at the lower temperature. The two soils varied widely in sorption and desorption properties.     

Lysimeter study with a cambic arenosol exposed to artificial acid rain: II. Input-output budgets and soil chemical properties

The effects of artificial precipitation with different pH levels on soil chemical properties and element flux were studied in a lysimeter experiment. Cambic Arenosol (Typic Udipsamment) in monolith lysimeters was treated for 6 1/2 yr with 125 mm yr^?1 artificial rain in addition to natural precipitation. Artificial acid rain was produced from groundwater with H₂SO₄ added. pH levels of 6.1, 4 and 3 were used. ‘Rain’ acidity was buffered, mainly due to cation exchange with Ca²⁺ and Mg²⁺, which were increasingly leached due to the acid input. The H⁺ retention was not accompanied by a similar increase in the output of Al ions, but a slight increase in the leaching of Al ions was observed in the most acidic treatment. The net flux of SO₄ ^2? from the lysimeters increased with increasing input of H₂SO₄, but in the most acidified lysimeters significant sorption of SO₄ ^2? was observed. The sorption was, however, most likely a concentration effect. The ‘long-term’ acidification effects on soil were mainly seen in the upper O and Ah-horizons, where an impoverishment of exchangeable Ca²⁺ and Mg²⁺ was observed. An increased proportion of Al ions on exchange sites in the organic layer was observed in the pH 3-treated soil. By means of budget calculations the annual release of base cations due to weathering was estimated to be between 33 and 77 mmol_c m^?2.     

Inhibition of phosphorus sorption to goethite, gibbsite, and kaolin by fresh and decomposed organic matter

The direct effects of dissolved organic matter (DOM) on the sorption of orthophosphate onto gibbsite, goethite, and kaolin were examined using a one-point phosphorus sorption index and the linear Tempkin isotherm model. DOM extracted from fresh and decomposed agricultural residues, as well as model organic and humic acids, were used. Changes in the chemical and sorptive characteristics of the DOM in the absence and presence of added orthophosphate (50 mg l⁻¹) were also determined. For residue-derived materials, DOM sorption to all minerals correlated well with percent hydrophobicity, apparent molecular weight, and phenolic acidity in the absence of added orthophosphate. Sorption of DOM to goethite and gibbsite was significantly decreased in the presence of added P. The correlation coefficient values of percent hydrophobicity, apparent molecular weight, and phenolic acidity to sorption also declined in the presence of added P. Thus, the addition of P substantially lowered fractionation of DOM after sorption to goethite and gibbsite. In contrast, few significant P sorption-induced differences were observed in the kaolin system. According to one-point P sorption results, DOM in the form of Aldrich humic acid, oxalate, and decomposed clover and corn residue, significantly inhibited P sorption to goethite at concentrations of 50 and 200 mg total soluble carbon (C_TS l⁻¹). Phosphorus sorption to gibbsite was significantly inhibited by 50 mg C_TS l⁻¹ derived from decomposed corn residue, fresh dairy manure residue, and oxalate solution. At 200 mg C_TS l⁻¹, all DOM solutions were found to inhibit P sorption to gibbsite. This study suggests that DOM inhibition of P sorption depends on the chemical properties of both the sorbent and the DOM itself. In general, DOM from decomposed organic materials inhibited P sorption to a greater extent than did DOM derived from fresh materials. This stronger inhibition highlights the importance of microbial processes in the release of soluble soil P, a key determinant of P availability to plants.     

The Effects of Plastic Pollution on Aquatic Wildlife: Current Situations and Future Solutions

A series of miscible-displacement experiments was conducted to examine the impact of experiment conditions (detection limit, input pulse size, input concentration, pore-water velocity, contact time) on the performance of a mathematical solute transport model incorporating nonlinear, rate-limited sorption/desorption described by a continuous distribution reaction function. Effluent solute concentrations were monitored over a range of approximately seven orders of magnitude, allowing characterization of asymptotic tailing phenomenon. The model successfully simulated the extensive elution tailing observed for the measured data. Values for the mean desorption rate coefficient (ln k ₂) and the variance of ln k ₂ were obtained through calibration of the model to measured data. Similar parameter values were obtained for experiments with different input pulse size, input concentration, pore-water velocity, and contact time. This suggests that the model provided a robust representation of sorption–desorption for this system tested. The impact of analytical detection limit was examined by calibrating the model to subsets of the breakthrough curves wherein the extent of the elution tail was artificially reduced to mimic a poorer detection limit. The parameters varied as a function of the extent of elution tail used for the calibrations, indicating the importance of measuring as full an extent of the tail as possible.     

Effect of liming on phosphate sorption by acid soils

The sorption of phosphate (P) by four strongly acid Fijian soils from 0.01 M CaCl₂ decreased with increasing pH up to pH 5.5–6.0 and then increased again. The initial decrease in P sorption with increasing pH appears to result from an interaction between added P, negative charge, and the electrostatic potential in the plane of sorption. The results of a sorption study, involving KCl or CaCl₂ of varying concentrations as the background electrolyte and using Nadroloulou soil incubated with KOH or Ca(OH)₂, suggested that the increase in P sorption at pH values > 6.0 was caused by the formation of insoluble Ca-P compounds. For some soils this is consistent with the results of an isotopic-exchange study in which incubation with lime caused marked reductions in the amounts of exchangeable P at high pH.     

Coupled diffusion and oxidation of ferrous iron in soils. II. A model of the diffusion and reaction of O2, Fe2+, H+ and HCO3− in soils and a sensitivity analysis of the model

Kinetic equations are developed for a system in which a column of reduced soil is exposed to oxygen at one end. The equations are combined in a simulation model in which they are solved by finite-difference methods. The model predicts the consequent diffusion of oxygen into the column; the diffusion of ferrous iron towards the oxidation zone; the rate of formation and concentration profile of the ferric hydroxide formed; and the diffusion by acid-base transfer of the acidity produced in the oxidation reaction. A sensitivity analysis of the model, in which runs were made for a wide range of input parameters, showed that for most combinations of parameters, in water-saturated soil, substantial amounts of iron are transferred towards the air-exposed surface, leading to a well-defined zone of ferric hydroxide accumulation. The profile of total iron in this zone is often banded. The pH in the zone falls by at least two units. A small amount of air-filled pore space increases the depth of the oxidation front dramatically. The model indicates that coupled iron oxidation and diffusion reactions, which are very widespread in natural soils, may be understood quantitatively.     

Evolution of surface properties and organic matter stabilisation in podzolic B horizons as assessed by nitrogen and phosphate sorption

In podzolic B horizons illuviated Al, Fe and organic matter (OM) increase with the ongoing of the pedogenic process. Depending on OM load on mineral surfaces, modifications of the soil surface properties are expected and may influence OM stabilisation. The proportion of labile organic pools should thus vary depending on the type of podzolic horizon. In this work, we selected B horizons at increasing intensity of podzolisation, evaluated the labile OM pools through oxidation with 2 % NaClO and characterised surface properties with N₂ and phosphate sorption. Before and after oxidation, we assessed the NaOH-extractable OM fractions. Oxidation was more effective on the least polar organic compounds and led to an increase in the fulvic to humic acid ratio. Specific surface area (SSA) increased after oxidation only in the least podzolised horizons, while selectively preserved OM induced a decrease in SSA in the more developed Bs, Bsm and Bhs. Phosphate sorption induced a release of OM and always decreased after oxidation, although variations in P affinity for the surfaces were observed. The effect of oxidation on surface parameters pointed to a specific association between organics and minerals that changed during soil development. At the very beginning of podzolisation, the dominant forms seemed related to organo-metallic complexes with little interaction with surfaces. With Bs development, weak interactions between mineral surfaces and OM appeared, while at a later stage OM differentiated into bulky structures and tightly bound, rigid ones, with extremely low N₂ accessibility. The latter were not sensitive to low concentration NaClO while the former were easily oxidised.     

Interactions of allophane with humic acid and cations

Allophanic soils are known to accumulate organic matter, but the underlying mechanism is not well understood. Here we have investigated the sorption of humic acid (HA) by an allophanic clay in the presence of varied concentrations of either CaCl₂ or NaCl as background electrolytes. Both the HA and the clay were separated from New Zealand soils. Much more HA was sorbed in CaCl₂ than in NaCl of the same ionic strength. Apparently Ca²⁺ ions were more effective than Na⁺ ions in screening the negative charge on HA. In CaCl₂ the HA molecule might also assume a more compact configuration than in NaCl. In the presence of CaCl₂ sorption increased, reached a maximum, and then declined as the concentration of HA in solution was increased. This behaviour was not observed in NaCl where sorption showed a gradual and steady increase with HA concentration. We propose that ligand exchange occurs between the surface hydroxyl groups of allophane and the carboxylate groups of HA. As a result, the allophane–HA complex acquires negative charges, requiring the co‐sorption of extraneous cations (Ca²⁺ or Na⁺) for charge balance. The Ca²⁺ co‐sorbed can attract more HA to the complex possibly by a cation‐bridging mechanism, giving rise to a maximum in sorption. The decline in sorption beyond the maximum may be ascribed to a decrease in the concentration of free Ca²⁺ ions through binding to HA molecules in solution. The increase in supernatant pH may be attributed to a ligand exchange reaction between the surface hydroxyls of allophane and the carboxylate groups of HA, and proton binding to the allophane–HA complex.     

Behaviour of Reduction–Sorption of Chromium (Vi) from an Aqueous Solution on a Modified Sorbent from Rice Husk

A carbonaceous sorbent produced from rice husk via sulphuric acid treatment was used to remove Cr(VI) from aqueous solutions varying contact time, pH, Cr(VI) concentration and sorbent status (wet and dry). Cr(VI) was removed from the aqueous solution via reduction to Cr(III) and sorption. Reduction and sorption processes were investigated in terms of kinetics and equilibrium. The rate of reduction removal of Cr(VI) at pH 2 followed a pseudo first-order model while the rate of sorption of total chromium followed pseudo second-order model. Chromium sorption was highly dependent on the initial pH value with reduction taking place in solution with pH up to 7 showing sorption maxima in the pH range 1.8–2.8 for concentration range 100–500 mg/l with an increase in the equilibrium pH. Carbon dioxide evolved from the sorption media was determined. Reduction–sorption mechanism was investigated via physicochemical tests including cation exchange capacity, base neutralization and sorbent acidity in addition to FTIR studies for sorbent samples before and after sorption reaction.     

Effects of preharvest calcium sprays on apple and pear quality

Fruit from apple (Malus domestica Borkh.) and pear (Pyrus communis L.) trees sprayed with calcium chloride (CaCl₂) had higher fruit calcium (Ca) concentrations by 10% or more than the unsprayed control trees. In ‘Delicious’ and ‘Golden Delicious’ apples, the incidences of bitter pit, scald, and internal breakdown were substantially reduced with CaCl₂ sprays. In most instances, firmness, total acidity, and juiciness ratings of apples were improved with CaCl₂ sprays. In ‘Anjou’ pears, the incidence of cork spot was reduced with CaCl₂ sprays. Only sprays of NutriCal and CaCl₂ + Regulaid showed substantial increases in fruit firmness of ‘Anjou’ pear. In 1991, yield of ‘Anjou’ pear trees was increased by 36% with CaCl₂ sprays compared with the control trees.     

Affinity constants and behavior of Cd sorption in some acid soils

Cadmium sorption was studied in several acidic soils in a pH range from 4.5 to 6.5. The soils had two classes of surfaces with acidity constants (pKa₁ = 4.09 and pKa₂ = 6.39) similar to those for weakly and very weakly cidic carboxyls, and N-containing groups in fulvic acid. Titratable H and acidity constants were used to estimate the number of exchange sites at each pH level. Sorption of Cd was closely related to Cd concentration, pH, and soil type. Although the inclusion of pH and organic C contents in a regression accounted for some variations in the Cd distribution coefficient defined as the ratio of the quantity of Cd sorbed to the solution Cd concentration, the number of sorption sites was a more appropriate factor to explain the variability. Because of a negligible contribution to the number of exchange sites from Fe oxides, the sorption of Cd at pH = 4.5 was considered to be of a one-surface Langmuir type. A two-surface Langmuir equation was considered to model sorption at higher pH values. The average affinity constants (log K) were 3.61 and 4.89 for Cd sorption by the two classes of surfaces.     

The impact of reduced atmospheric depositions on soil microbial parameters in a strongly acidified Norway spruce forest at Solling,Germany

To simulate a future ion input reduction scenario in forests, a large scale field experiment was set up in a (1999) 66‒year‒old Norway spruce plantation at Solling, central Germany. Throughfall input of H⁺, SO₄^2—, and N‒compounds is artificially reduced by means of a permanent roof construction below the canopy and a de‒ionizing equipment since 1991. Here we present long term soil solution records for SO₄^2—, NO₃^—, Al³⁺ and the pH of the 10 cm mineral soil sampling depth. A significant decrease in ion concentrations since the start of the treatment is observed, but no change of the soil solution pH. Even in the fourth year pH values remained well within the aluminium buffer range (pH < 4.2). Three years after the start of the experiment (July 1994) it was examined whether microbial biomass (C_mic), specific activity (heat production per unit biomass), and the percentage of C_mic in organic C material indicated any changes. Furthermore chemical standard parameters (CEC, base saturation, pH) were analyzed for all soil samples. Results indicate that despite of drastic decreases of soil solution ion concentrations in the upper soil horizons microbial parameters were not affected and that the soil solid phase is not deacidified by the treatment until now.     

Sorption of cadmium on suspended matter under estuarine conditions; competition and complexation with major sea-water ions

Sorption of Cd at low concentrations onto river Rhine suspended matter was examined in terms of sorption rate, reversibility and factors such as competition and complexation with major inorganic sea-water ions. More than 90% of the final amount of Cd is sorbed within the first few hours. Desorption experiments show that the process is virtually reversible. In experiments with diluted sea water the sorption of Cd strongly decreases even at low salinity. Sorption isotherms show that the sorption of Cd in NaNO₃ solutions is regulated by the free Cd²⁺ activity. In a Ca(NO₃)₂ environment the Cd sorption decreases with increasing Ca²⁺ concentrations, which implies competition between Ca²⁺ and Cd²⁺ for the different sorption sites. In different electrolyte solutions of similar ionic strength the sorption of Cd decreases in the solution order NaNO₃ > NaCl > NaCl+MgCl₂+CaCl₂ > diluted sea water. Although inorganic speciation calculations show that even at low salinities dissolved Cd is dominated by Cd-chloro complexes, chloride accounts for only about one third of the increased mobility of Cd. As a result of addition of Ca²⁺ and Mg²⁺ the sorption capacity of suspended matter for Cd is further reduced by a factor three.     

Biogeochemistry of a Hyperacidic and Ultraconcentrated Pyrite Leachate in San Telmo mine (Iberian Pyrite Belt, Spain)

This work describes recent research carried out in an extremely acidic (pH 0.61–0.82) and hypersaline (e.g., 134 g/L SO₄ ^2-, 74 g/L Fe, 7.5 g/L Al, 3 g/L Mg, 2 g/L Cu, 1 g/L Zn) leachate which seeps from a pyrite pile in San Telmo mine (Huelva, SW Spain) and forms evaporative pools of ultra-concentrated water in which attractive crystals of Zn-rich melanterite (Fe^IISO₄ 7H₂O) are formed. Geochemical modeling with the Pitzer method indicates that the acidic brine was near saturation with respect to melanterite (SI_Mel?=?0?±?0.2). The microbiological investigation has revealed a surprisingly high biomass (1.4?×?10⁶ cells mL^?1) and an exotic ecosystem composed of acidophilic, Fe-oxidizing archaea (mainly Ferroplasma spp., representing 52% of the microbial population), and minor numbers of acidophilic bacteria (including Leptospirillum spp. (3.2%), Acidithiobacillus spp. (1.6%), and Alphaproteobacteria (2.8%)). The microbial production of Fe^III allows the oxidative dissolution of pyrite and other sulphides, which results in additional inputs of Fe^II, SO₄ ^2- and acidity to the system. The surfaces of the pyrite crystals show a typical etch-pitted texture, as well as blobs of elemental sulphur, which are both compatible with this indirect, microbially mediated oxidation mechanism. The composition of the acidic leachate seems to result from the combination of several processes which include: (1) formation of melanterite within the pile during relatively dry seasons, (2) subsequent dissolution of melanterite during rainy episodes, (3) microbial oxidation of Fe^II, (4) sulphide oxidation mediated by Fe^III, (5) dissolution of chlorite and other aluminosilicates present in the pile, and (6) cooling and/or evaporation of seepage from the pile and consequent melanterite precipitation.     

Effects of soil-cation composition on reactions of four herbicides in a candler fine sand

Sorption, persistence and transport of herbicides in soils depend on the relative saturation of soils with cations from various soil amendments. Current research was conducted to study the effect of preequilibration of a Candler fine sand (Hyperthermic uncoated typic Quartzipsamments; 0–30 cm depth) with AlCl₃, CaCl₂, CuCl₂, FeCl₃, or KCl salt solutions on sorption in bromacil, simazine, norflurazon, and diuron herbicides commonly used in Florida citrus groves. Preequilibration of the soil with either FeCl₃, or AlCl₃ significantly decreased the sorption and therefore increased internal leaching potential, of all four herbicides as compared to their sorption in untreated soil. This decrease in sorption was much greater for bromacil and simazine (24 to 35%) than for norflurazon and diuron (7 to 8%). The desorption of bromacil and diuron in 1M NH₄OAc was also significantly lower in soils preequilibrated with FeCl₃ or AlCl₃ than the untreated soil. However, the reverse was true in the case of simazine and norflurazon. Preequilibration of the soil with CuCl₂, KCl, and CaCl₂ resulted in a significant decrease in sorption of norflurazon, diuron, and simazine but did not affect bromacil sorption. Accordingly, the species of adsorbed cation had varying effects on the sorption/desorption of each of the herbicides and varied their leaching potential.