The sorption of iodide by soil components

The sorption of iodide by several soil component materials was examined over a range of pH values and compared with sorption by a surface soil. A compost, prepared from grass roots which had been allowed to decompose for 24 weeks, sorbed substantial amounts of iodide from solution and showed changes in sorption, due to pH and drying, similar to those shown by the soil. Freshly precipitated hydrated ferric oxide also sorbed substantial amounts of iodide from solutions of pH < 5.5 but the amount decreased to zero as the pH approached 7. Sorption by freshly precipitated hydrated aluminium oxide was impossible to assess at pH < 5 owing to its solubility but at pH 5.5 to 7.5 its sorption was similar to that of ferric oxide. No sorption of iodide was detected by kaolinite, montmorillonite, chalk or limestone. Drying markedly reduced the capacity for iodide sorption of the compost and soil and had a smaller effect on the ferric and aluminium oxides.     

Phosphorus sorption by some coconut-growing acid soils of Sri Lanka and its relationship to selected soil properties

Phosphorus (P) sorption in the presence of 10^?2M calcium chloride by ten coconut-growing acid soil samples of Sri Lanka belonging to the Ultisol, Alfisol and Entisol orders was evaluated using the Langmuir sorption isotherm. The data for all samples fitted the single-site Langmuir sorption isotherm when equilibrium P was less than 1 μg ml^?1, but showed some deviations at larger concentrations of P. A two-site Langmuir sorption isotherm was successfully used to describe the sorption data of three samples at these high concentrations. The single-site Langmuir sorption maxima were greater for Ultisols (349–825 μg g^?1) than for the other soils (136–345 μg g^?1). These sorption maxima were significantly correlated with %-clay, %-silt, dithionite-extractable iron, and 1M ammonium acetate (pH 4.8)-extractable aluminium. Regression analysis of P sorption on different forms of iron (Fe) and aluminium (Al) indicated that crystalline ‘free Fe oxides’ (dithionite-extractable Fe minus 0.3M oxalate-extractable Fe) and ‘active Al’ which consists of hydroxy Al monomers and polymers [1M ammonium acetates, (pH 4.8)-extractable Al minus 1M potassium chloride extractable Al] were the important factors contributing towards P sorption.     

Sorption of oxytetracycline to iron oxides and iron oxide-rich soils

The sorption interactions of oxytetracycline with goethite, hematite, and two iron oxide-rich soils were investigated using batch sorption experiments. Oxytetracycline sorption coefficients for goethite and hematite increased with pH to maximum values at pH approximately 8. The sorption edge shape and desorption treatments were consistent with a surface complexation mechanism and could be described by the interaction of divalent anion species with the oxide surface. Oxytetracycline sorption to Georgeville and Orangeburg Ultisol soils decreased with pH. Chemical digestion treatments were used to deduce that soil sorption occurred by complexation to oxide coatings on clay and quartz grains. These results indicate that sorption models must consider the interaction of oxytetracycline, and other similar ionogenic compounds, with soil oxide components in addition to clays and organic matter when predicting sorption in whole soils.     

长沙烟区烟叶重金属含量与土壤重金属含量及其性质的相关性分析

为了解长沙烟区烟叶重金属含量与土壤重金属含量及土壤性质的关联规律,采用盆栽试验研究了该区域不同性质土壤烟叶中镉（Cd）、铅（Pb）、汞（Hg）、砷（As）及铬（Cr）的含量,并对烟叶中的重金属含量与对应的土壤中重金属含量及土壤理化性质进行了相关性分析。结果表明:烟叶中重金属富集系数Cd & gt; Hg & gt; Pb & gt; Cr & gt; As,表明烟叶是易富集Cd的作物;烟叶中Cd含量与土壤pH值和有机质含量呈显著负相关性,与速效磷呈显著正相关性;烟叶中Pb含量与土壤有机质含量呈极显著负相关性,与土壤CEC呈显著负相关性;烟叶中Cr含量与土壤有机质含量呈极显著负相关性;烟叶中As含量与土壤中速效磷呈极显著负相关性;烟叶中Cr、Cd和Pb含量分别与土壤中Cr、Cd和Pb存在显著正相关性。      

Sulphate contents and sorption in scottish soils

Phosphate-extractable inorganic sulphate contents of freely drained acid surface soils representing four contrasting soil series in north-east Scotland ranged from 13 to 60 mg S/kg soil. Of this an average of 59% was adsorbed under the conditions of extraction used. The soils were therefore well supplied with available sulphate and there are no known cases of deficiency in the area. Average group contents of adsorbed sulphate were closely related to the abilities of the soils to adsorb added sulpphate, and unlike phosphate retention, sulphate sorption seemed to depend more on active iron than aluminium.     

Solid-solution partitioning of Cd, Cu, Ni, Pb, and Zn in the organic horizons of a forest soil

We report the solid-liquid partitioning of Cd, Cu, Ni, Pb, and Zn in 60 organic horizon samples of forest soils from the Hermine Watershed (St-Hippolyte, PQ, Canada). The mean Kd values are respectively 1132, 966, 802, 3337 and 561. Comparison of those Kd coefficients to published compilation values show that the Kd values are lower in acidic organic soil horizons relative to the overall mean Kd values compiled for mineral soils. But, once normalized to a mean pH of 4.4, the Kd values in organic soil horizons demonstrate the high sorption affinity of organic matter, which is either as good as or up to 30 times higher than mineral soil materials for sorbing trace metals. Regression analysis shows that, within our data set, pH and total metal contents are not consistent predictors of metal partitioning. Indeed, metal sorption by the solid phase must be studied in relation to complexation by dissolved organic ligands, and both processes may sometime counteract one another.     

Electron microprobe and synchrotron x-ray fluorescence mapping of the heterogeneous distribution of copper in high-copper vineyard soils

The response of microorganisms to metal contamination of soils varies significantly from one investigation to another. One explanation is that metals are heterogeneously distributed at spatial scales relevant to microbes and that microoorganisms are able to avoid zones of intense contamination. This article aims to assess the microscale distribution of Cu in a vineyard soil. The spatial distribution of Cu was measured at two resolutions (0.3 mm and 20 microm) in thin sections of the surface 4 cm of undisturbed soil by electron microprobe and synchrotron X-ray microfluo-rescence spectroscopy. Bulk physicochemical analyses of Cu, pH, organic matter, texture, and mineralogy were performed. The results indicate that the Cu distribution is strongly heterogeneous at both scales of observation. Entire regions of the thin sections are virtually devoid of Cu, whereas highly localized "hotspots" have Cu signal intensities thousands of times higher than background. The distribution of Rb, or Al and Si, indicators of clay minerals, or Fe (iron (hydr)oxides), show that Cu is not preferentially associated with these mineral phases. Instead, Cu hotspots are associated with particulate organic matter. These observations suggest modification of current sampling protocols, and design of ecotoxicological experiments involving microorganisms, for contaminated soils.     

Characterization of iron(III) in organic soils using extended X-ray absorption fine structure spectroscopy

The distribution of different iron (Fe) species in soils, sediments, and surface waters has a large influence on the mobility and availability of Fe, other nutrients, and potentially toxic trace elements. However, the knowledge about the specific forms of Fe that occurs in these systems is limited, especially regarding associations of Fe with natural organic matter (NOM). In this study, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to characterize Fe(III) in organic soils (pH 4.6-6.0) with varying natural Fe content. The EXAFS data were subjected to wavelet transform analysis, to facilitate the identification of the nature of backscattering atoms, and to conventional EXAFS data fitting. The collective results showed the existence of two pools of iron: mononuclear Fe(III)-NOM complexes and precipitated Fe(III) (hydr)oxides. In the soil with lowest pH (4.6) and Fe content mononuclear organic complexes were the completely dominating fraction whereas in soils with higher pH and Fe content increasing amounts of Fe (hydr)oxides were detected. These results are of environmental importance, as the different iron pools most likely have markedly different reactivities.     

Proton buffering and metal leaching in sandy soils

Recent developments in acidification research focused on the leaching of metals from contaminated soil. In this paper the buffering of sandy soils upon acidification is studied in relation to the release of major (Al, Ca, Mg) and trace metals (Cu, Cd, Ni, Zn) from the soil reactive surface. The buffering process and the (de)sorption of metals are described with a mechanistic multisurface model, expressing the sorption onto different soil surfaces (organic matter, clay, Fe (hydr)oxides). The pH of sandy soil samples is predicted upon proton addition in combination with the behavior of major and trace metals. Acidification of contaminated sandy soil samples, with different pH levels and metal contents, is performed in a flow-through reactor by flushing the samples with acid solution. Acidification has taken place in successive steps of proton addition and followed by sampling. Prediction of pH upon acidification with a multisurface model gives satisfying results for all samples studied. The pH is modeled reasonably well between pH 6 and 4. Below pH 4 the predicted pH values are slightly too low, probably due to the buffering by Al-containing minerals (e.g., Al hydroxide), which are not included in the model. Desorption of major and trace metals upon pH decrease is, in general, predicted well, within a factor of 1-5 on a linear scale. Overall prediction of proton buffering in combination with desorption of metals in sandy soil samples, over a wide pH range and metal content, is done quite well for the studied metals with the multisurface model.     

Hydrophilic and hydrophobic sorption of organic acids by variable charge soils: effect of chemical acidity and acidic functional group

Sorption of organic acids by variable-charge soil occurs through both hydrophilic and hydrophobic sorption. In this study, the effect of chemical acidity and the type of acidic functional group on the relative contribution of hydrophilic and hydrophobic processes to sorption by a gibbsite-dominated and a kaolinite-dominated variable-charge soils was quantified by measuring sorption isotherms from different electrolytes (CaCl2, Ca(H2PO4)2, and KCl). The A1 soil is dominated by gibbsite whereas the DRC soil is primarily kaolinite. The organic acids investigated include five chlorinated phenols (pentachlorophenol, 2,3,4,6-tetrachlorophenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, and 2,4-dichlorophenol) with pKa values ranging from 4.69 to 7.85 and two acidic herbicides (2,4-D (pKa = 2.8) and prosulfuron (pKa = 3.76)) that contain carboxyl and urea functional groups, respectively. Anion exchange of chlorinated phenols and prosulfuron on both variable-charge soils as well as 2,4-D sorption on the A1 soil was linearly correlated to chemical acidity. The effective positive surface charge [AEC/(AEC + CEC)] and the anionic fraction of the organic acid in solution, which are both pH-dependent, were sufficient to estimate the contribution of anion exchange to organic acid sorption except for 2,4-D sorption by DRC soil. The latter was much greater than would be predicted from the pKa of 2,4-D. Calcium bridging between silanol edge group and 2,4-D was hypothesized and corroborated by differences in sorption measured from KCl and CaCl2 solutions. For predicting contributions from hydrophobic processes, a log-log linear relationship between pH-dependent octanol-water (Kow(pH)) and organic carbon-normalized sorption coefficients (Koc(pH)) appeared adequate.     

Modeling kinetics of Cu and Zn release from soils

Kinetics of Cu and Zn release from soil particles was studied using two surface soils with a stirred-flow method. Different solution pH, dissolved organic matter (DOM) concentrations, and flow rates were tested in this study. A model for kinetics controlled sorption/desorption reactions between soils and solutions was globally fit to all experimental data simultaneously. Results were compared to a model that assumes local instantaneous equilibrium. We obtained one unique set of model parameters applicable to different pH, dissolved organic carbon (DOC), and flow conditions. We included DOM complexation of copper ions, which decreased their sorption. The effect of pH was included by assuming proton competition with metal ions for binding sites on soil particles. These results provide the basis for developing predictive models for metal release from soil particles to surface waters and soil solution.     

Extensive sorption of organic compounds to black carbon, coal, and kerogen in sediments and soils: mechanisms and consequences for distribution, bioaccumulation, and biodegradation

Evidence is accumulating that sorption of organic chemicals to soils and sediments can be described by "dual-mode sorption": absorption in amorphous organic matter (AOM) and adsorption to carbonaceous materials such as black carbon (BC), coal, and kerogen, collectively termed "carbonaceous geosorbents" (CG). Median BC contents as a fraction of total organic carbon are 9% for sediments (number of sediments, n approximately 300) and 4% for soils (n = 90). Adsorption of organic compounds to CG is nonlinear and generally exceeds absorption in AOM by a factor of 10-100. Sorption to CG is particularly extensive for organic compounds that can attain a more planar molecular configuration. The CG adsorption domain probably consists of surface sites and nanopores. In this review it is shown that nonlinear sorption to CG can completely dominate total sorption at low aqueous concentrations (<10(-6) of maximum solid solubility). Therefore, the presence of CG can explain (i) sorption to soils and sediments being up to 2 orders of magnitude higher than expected on the basis of sorption to AOM only (i.e., "AOM equilibrium partitioning"), (ii) low and variable biota to sediment accumulation factors, and (iii) limited potential for microbial degradation. On the basis of these consequences of sorption to CG, it is advocated that the use of generic organic carbon-water distribution coefficients in the risk assessment of organic compounds is not warranted and that bioremediation endpoints could be evaluated on the basis of freely dissolved concentrations instead of total concentrations in sediment/soil.     

Sorption of sulphate and distribution of total,sulphate and mineralisable sulphur in some tropical soil profiles in tanzania

The forest soils from Arusha generally contained more total S (129–439, average 277 μg S g^?1) throughout the profile than the cultivated ones from Mbeya (32–408, average 143 μg S g^?1). Total S in the surface horizons was in the range of 120–439, average 292 μg S g^?1. The contents of total and organic S in the profiles were significantly (P <0.001) correlated with the contents of organic C and total N. Although both extractants—0.5M-NH₄OAC and 0.01M-CaCl₂—yielded nearly similar results, the latter tended to extract a little more sulphate than the former from organic matter rich soils. Sulphate distribution in a profile was related to sorption capacities of the soils from various horizons. Its content in the profiles was in the range of 1–34, average 15 μg S g^?1, and was significantly (P <0.05) but negatively correlated with the ratios of C:N and C:S. Maximum S mineralisation occurred in the surface soil of most of the profiles. Less mineralisation or marked immobilisation took place in the subsurface soil. Mineralisation-immobilisation relationship was mainly affected by C: S ratio of the soil. A soil C: S ratio of 200:1 was found to be critical below which net mineralisation and above which immobilisation took place.     

Understanding the effects of soil characteristics on phytotoxicity and bioavailability of nickel using speciation models

Acidity (pH) has been realized to be the most important soil characteristic that modulates bioavailability of heavy metals by affecting both the chemical speciation of metals in soil and the metal binding to the active sites on biota. In this work, we show that besides soil pH, metal bioavailability also depends to a certain extent on the type of soil. A better understanding of the role of soil type in regulating metal availability can be achieved with the analysis of soil composition and with calculations using chemical speciation models. Results of pot experiments, in which three different soils were spiked with nickel, show that the EC50 of total nickel in decreasing the biomass production of oats varies widely (0.7-22.5 mmol kg(-1) soil, more than 30 times). pH (4.7-7.0) is the most important factor, explaining up to a factor of 14 difference of nickel bioavailability in the soils. The remaining variation is caused by other differences in soil composition (soil type). The bioavailability and toxicity of nickel in the organic matter-rich soil studied is less than half of that in the sandy and clay soil studied at a similar pH. The chemical calculations using a multi-surface speciation model show that soil organic matter binds Ni much stronger than clay silicates and iron (hydr)oxides within the acidic pH range, which supports the experimental findings. In all three soils, the EC50 of Ni expressed in terms of Ni in 0.01 M CaCl2 soil extraction is rather stable (24-58 microM), suggesting the possibility to use this extraction as an estimation of metal availability in soil.     

不同土壤类型养分垂直分布特征

以昆明烟区几种典型土壤类型为研究对象,运用相关性分析法探讨了不同土壤类型剖面理化性状和真菌、细菌、放线菌数量与耕作深度的关系。结果表明,紫色土、水稻土和红壤的有机质、速效氮、速效钾和真菌、细菌及放线菌数量与剖面深度呈极显著负相关关系,水稻土的交换性钙和交换性镁含量均与剖面深度呈极显著负相关关系,而紫色土和红壤呈负相关关系;三种土壤类型剖面的各养分含量及真菌、细菌、放线菌数量具有较强的表聚性特征,自上而下存在明显的递减性;从养分含量及微生物数量的递减幅度来看,紫色土耕作深度以20 cm左右为宜,红壤和水稻土耕作深度以20～30 cm为宜。生产中,若耕作深度大于30 cm,3种土壤的养分均存在下降的风险。因此,针对深耕地块,建议合理提高施肥水平。     

Sorption-desorption of ionogenic compounds at the mineral-water interface: study of metal oxide-rich soils and pure-phase minerals

Sorption of the ionic compounds 2,4-D and quinmerac onto iron oxide-rich, variable charged soils was strongly influenced by mineralogy, particularly soil iron and aluminum oxides, whereas sorption of the neutral norflurazon was only related to total soil C. An appreciable fraction of the mass sorbed in stirred-flow studies was easily desorbed by deionized water, and desorption of ionic compounds was initially more rapid than sorption. This sorption-desorption behavior, although contrary to desorption hysteresis commonly observed in batch studies, suggests that the reversibly sorbed fraction is weakly bound to the soil surface. 2,4-D sorption to iron oxide-rich soils and pure-phase metal oxides appears to be driven by nonspecific electrostatic attraction, with specific electrostatic attraction and van der Waals interactions being secondary. Both the carboxylate and the heterocyclic N groups may participate in sorption of quinmerac, facilitated by specific and nonspecific electrostatic attraction and surface complexation. The heterocyclic N, amine, and carbonyl groups of norflurazon do not appear to interact with soil minerals.     

Organic sulphur fractions in scottish soils

Over 90% of the sulpher in some acid surface soils derived from different parent materials in north-east Scotland was in organic combination. N:S ratios in the majority of the soils fell within the narrow limits of 6.0–7.5, and showed less variation than C:S ratios. Organic sulphur was poorly correlated with organic phosphorus, and high correlations with categories of soluble aluminium and iron seemed to reflect similar relationships between these elements and the whole organic matter. A group of calcareous soils derived from shelly sand deposits contained a lower proportion of organic sulphur. An average 64% of organic sulphur in the acid soils occurred as organic sulphate, compared with only 23% in the calcareous soils. Organic sulphate was less well correlated with carbon and nitrogen than was total organic sulphur. Total carbon-bonded sulphur was best determined as the difference between total organic sulphur and organic sulphate, because direct measurement by Raney-nickel reduction underestimated the amount present in most of the soils, due to the presence of chemically unreactive compounds. Good correlations between the reactive carbon-bonded sulphur and carbon, nitrogen and organic sulphur, suggested that a well-defined group of compounds was being measured. There were no consistent effects of drainage conditions on organic sulphur contents, or on the amounts and proportions of organic sulphur present as sulphate or in carbon-bonded form. The freely drained soils derived from basic igneous drift, however, contained more organic sulphur than poorly drained samples, but this is attributed to differences in the organic matter content. Several features of the results indicated that organic sulphur, unlike organic phosphorus, was predominantly an integral part of the soil organic matter.     

Soil tests for available copper and zinc in soils of Western Nigeria

Four soil tests for copper and zinc were evaluated for their ability to predict Cu and Zn uptake by oats (Avena sativa, L., Lodi var.) grown on 28 soils from Western Nigeria. Statistical analyses showed that EDTA was a better extractant for predicting Cu uptake than was DTPA, 0.1 N -HCl or 1 N -HCl. Copper uptake was more strongly correlated with inorganic soil fractions than with organic matter and was not significantly affected by soil pH. The best prediction of Zn uptake was provided by a combination of 0.1 N -HCl extractable Zn, pH, organic matter and the silt plus clay fraction in a multiple regression analysis. All four extractants predicted plant Zn uptake better on soils of pH less than 6.0 than on soils of pH greater than 6.0. A significant amount of Cu and Zn in the soils appeared to be associated with sesquioxides, part of which was available for plant use.