Characterization of sulfur retained by soils exposed to sulfur dioxide

Abstract

Soils have substantial capacity for sorption of sulfur dioxide (SO₂) but little is known about the nature of the sorbed S. Three surface soils varying in pH, organic matter, CaCO₃ equivalent and surface area were exposed to air containing 5% SO₂ and subsequently analyzed by ten different procedures to characterize the sorbed S. Most of the sulfur retained by soils after exposure to SO₂ could be recovered as CaCl₂‐extractable S, Ca(H₂PO₄)₂‐extractable S, or S released as H₂S by hydriodic acid (HI). Only small amounts of sulfur could be recovered as tetrachloromercurate (TCM)‐extractable S, S released as SO₂ by HCl, or S released as H₂S by HCl + Zn, HCl + Sn, or Raney Ni and NaOH. However, large amounts of S released as SO₂ by HCl were recovered from the air‐dry Webster and the moist Storden soils indicating that SO₂ sorption is influenced by organic matter in air‐dry soils and by CaCO₃ in moist soils.     

Inorganic and organic ligands induced changes in Pb sorption of arid ‎clay and calcareous loamy sand soils

The objective of this study was to investigate sorption, desorption, and immobilization of Pb in the clay and calcareous loamy sand soils treated with inorganic ligands (NO₃^?, Cl^? and H₂PO₄^?). Pb sorption was also determined in the presence of oxalate and citrate. The maximum Pb sorption capacities (q) ranged from 42.2 to 47.1 mmol kg^?1 for the clay soil, and from 45.2 to 47.0 mmol kg^?1 for loamy sand soil. It was observed that the binding energy constant (k) for Pb sorbed onto loamy sand soil (528–1061) is higher than that for clay soil (24.38–55.29). The loamy sand soil-sorbed greater quantities of Pb compared to the clay soil when initial pH was ≥ 3. However, it had lower sorption capacity at the lowest initial pH of 2. Additionally, the greatest Pb sorption and immobilization occurred in the soil treated with H₂PO₄. In the clay soil, the sorption of Pb was depressed at 0.1 mol kg^?1 of Cl^?, as compared with other ligands. Concerning organic acids, citrate ligand showed the highest decrease in Pb sorption. It could be concluded that the nature of Pb sorption can depend on the type and quantity of ligands present, as well as the soil type.     

Phosphate sorption characteristics of major soils in Okinawa,Japan

Abstract

Phosphate sorption isotherms were determined for 16 representative major soils developed from different parent materials on Okinawa. Phosphate sorption characteristics were satisfactorily described by the Langmuir equation, which was used to determine phosphorus (P) sorption maxima of the soils. Phosphate sorption maxima ranged from 630 to 2208 mg P kg^‐1 soil (mean 1,362 mg P kg^‐1). The standard P requirement (i.e., the amount of P required to attain 0.2 mg P L^‐1 equilibrium solution) followed the same trend as sorption maximum (r =0.94***), with values ranging from 132 to 1,020 mg P kg^‐1 soil (mean 615 mg P kg^‐1). This mean value corresponds to fertilizer addition of 923 kg P ha^‐1 indicating that the soils have high P fertilizer requirements. Results of simple linear regression analysis indicated that sorption maximum was significantly correlated with clay content, organic matter, oxalate iron (Fe), pyrophosphate Fe, DCB aluminum (Al), oxalate Al, and pyrophosphate Al, but not with DCB Fe, pH, or available P content. The best regression model for predicting sorption maximum was the combination of clay, organic matter, pyrophosphate Fe, and DCB Al which altogether explained 79% of the variance in sorption maximum. The equation obtained could offer a rapid estimation of P sorption in Okinawan soils.     

Addition of a clay subsoil to a sandy topsoil changes the response of microbial activity to drying and rewetting after residue addition – a model experiment

The effect of drying and rewetting (DRW) on C mineralization has been studied extensively but mostly in absence of freshly added residues. But in agricultural soils large amounts of residues can be present after harvest; therefore, the impact of DRW in soil after residue addition is of interest. Further, sandy soils may be ameliorated by adding clay‐rich subsoil which could change the response of microbes to DRW. The aim of this study was to investigate the effect of DRW on microbial activity and growth in soils that were modified by mixing clay subsoil into sandy top soil and wheat residues were added. We conducted an incubation experiment by mixing finely ground wheat residue (20 g kg^–1) into top loamy sand soil with clay‐rich subsoil at 0, 5, 10, 20, 30, and 40% (w/w). At each clay addition rate, two moisture treatments were imposed: constantly moist control (CM) at 75% WHC or dry and rewet. Soil respiration was measured continuously, and microbial biomass C (MBC) was determined on day 5 (before drying), when the soil was dried, after 5 d dry, and 5 d after rewetting. In the constantly moist treatment, increasing addition rate of clay subsoil decreased cumulative respiration per g soil, but had no effect on cumulative respiration per g total organic C (TOC), indicating that the lower respiration with clay subsoil was due to the low TOC content of the sand‐clay mixes. Clay subsoil addition did not affect the MBC concentration per g TOC but reduced the concentration of K₂SO₄ extractable C per g TOC. In the DRW treatment, cumulative respiration per g TOC during the dry phase increased with increasing clay subsoil addition rate. Rewetting of dry soil caused a flush of respiration in all soils but cumulative respiration at the end of the experiment remained lower than in the constantly moist soils. Respiration rates after rewetting were higher than at the corresponding days in constantly moist soils only at clay subsoil addition rates of 20 to 40%. We conclude that in presence of residues, addition of clay subsoil to a sandy top soil improves microbial activity during the dry phase and upon rewetting but has little effect on microbial biomass.     

Retention of cobalt by an oxisol in relation to the content of iron and manganese oxides

Abstract

The study aims at determining the cobalt retention properties of various soil components. Therefore, cobalt (Co) sorptions and extractions were carried out using an Oxisol sample before (untreated) and after successive removal of organic matter and active manganese (Mn) oxides (H₂O₂‐treated) and iron (Fe) oxides (H₂O₂+CBD‐treated). A synthetic goethite was included for comparison. Sorption of the four sorbents was determined over a range of Co concentrations (initially 10^‐8 M to 10^‐4 M), pH values (3 to 8) and reaction times (2 hours to 504 hours). The Co species sorbed was Co(ll), since oxygen exclusion during sorption had no effect on the amount sorbed. The pH‐dependent sorption curve (sorption edge) was shifted to lower pH at decreasing initial Co concentration and increasing reaction time. The displacements, in particular of the sorption edges corresponding to the lowest initial Co concentrations, to successively higher pH following removal of Mn oxides, organic matter and Fe oxides could be attributed to sorption onto sites of decreasing Co affinity [Mn oxides (and organic matter) > Fe oxides > kaolinite]. Extractions of sorbed Co at pH 5.5–7.5 with 2 M HCI showed that the extractability decreased with increasing sorption time and decreasing initial Co concentration. The untreated and H₂O₂‐treated soil samples retained sorbed Co at least as firmly as the synthetic goethite, whereas the H₂O₂+CBD‐treated sample (kaolinite) was clearly less effective. The results emphasized the importance of the soil Mn and Fe oxides for Co retention in soils but also the necessity of taken interior sorption sites into consideration.     

Air Drying Affects Extractable Sulfate in Soils of Variable Charge: Test of Two Extraction and Two Quantification Methods

Abstract

Fertilizer recommendations need to be based on reliable soil sulfate determinations. Airdrying samples changes irreversibly many properties of soils with variable charge and might affect the extractable sulfate. In this study, sulfate extracted from air‐dry and field‐moist samples was compared. Two extracting solutions [water and 00.1 M Ca(H₂PO₄) ₂] and two quantification methods (turbidimetry and ion chromatography) were assayed on A and B horizon samples of five Humic Acrisols from southeast Mexico. Air drying increased water‐extractable sulfate in Ah horizons, whereas in Bt horizons, it increased the 00.1 M Ca(H₂PO₄)₂‐extractable sulfate. Airdrying increased dissolved organic carbon contents in all samples and increased soil acidity and oxalate extractable iron in 70 and 60% of the samples, respectively. Results showed larger coefficients of variation in air‐dried samples. Turbidimetry resulted less sensible than ion chromatography. To enhance sensitivity and reproducibility, particularly organic soil samples should be analyzed field‐moist and by ion chromatography.     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

Sorption of dimethylselenide by soils

Air-dry and moist soils were shown to possess the capacity to sorb substantial amounts of (⁷⁵Se)dimethylselenide produced by the yeast Candida humicola in culture, or by soil supplied with (⁷⁵Se)selenite, depending largely upon the organic matter content and selenium concentration of the soils. The sorption capacities of individual soil constituents followed the order; organic matter > clay minerals > manganese oxides > iron oxides > acid-washed sand.A chemical fractionation procedure applied to soils fumigated with (⁷⁵Se)dimethylselenide revealed that the majority of the selenium sorbed was converted after 1 month to other forms, extractable mainly with strong acid solutions. Experiments with sterilized (autoclaved and γ-irradiated) soils indicated that soil microorganisms played little, if any, part in the sorption process.The work reported here indicates that soil is an important natural “sink” for atmospheric dimethylselenide.     

Manganese extracted from different chemical fractions of bulk and rhizosphere soil as affected by method of sample preparation

Abstract

Rhizosphere soils had higher amounts of ‘readily soluble’, ‘weakly adsorbed’, ‘carbonate bound’ and ‘specifically adsorbed’ Mn, but had lower amounts of ‘oxide‐Mn’, than did bulk soils. This observation was true regardless of whether the comparison was based on values within moist or air‐dried treatments. Observed trends in Mn distribution between different soil fractions were qualitatively similar regardless of method of sample preparation. However, there were substantial quantitative differences depending on the method of sample preparation. Air‐dried samples increased significantly in the ‘oxide‐Mn’ fraction and decreased in its soluble and adsorbed fractions relative to moist soil samples. There was a significant effect of method of air‐drying on the distribution of Mn in rhizosphere samples. Samples that were extracted moist at first and then air‐dried accumulated more adsorbed Mn and were depleted in ‘oxide‐Mn’ relative to samples that were air‐dried initially. There was a significant rhizosphere x air‐drying interaction. Air‐drying of some rhizosphere samples resulted in a significant underestimation of the ‘readily soluble’, ‘specifically adsorbed’, and ‘oxide‐Mn’ fractions beyond the overall effect of air‐drying. The results of this study suggested that soil samples used for Mn analyses be extracted immediately in a moist condition rather than air‐dried, particularly for analyses of rhizosphere soil samples.     

Addition of phosphorus to soils with low to medium phosphorus retention capacities. I. effect on soil phosphorus sorption properties

Abstract

Twelve soils with low‐medium phosphorus (P) retention capacities were equilibrated for 3 months with soluble phosphate at a rate of 100 mg P kg^‐1 soil. The P sorption properties of these soils both with and without added P were studied, including equilibrium P concentration (EPCo), standard P requirement (SPR), soil P sorption capacity (b), maximum buffer capacity (MBC), and P sorption index (P‐SI). In general, the soils with no added P showed low values of all the above parameters. Oxalate extractable aluminum appeared to be the major responsible element for the control of P sorption in these soils. The addition of P to these soils had a considerable effect on their P sorption properties. The changes in EPCo were well correlated with P sorption index (r=0.80; p≤0.01 ). The EPCo values of the soils with and without added P were closely correlated to bicarbonate extractable P (P_0lsen) and calcium chloride extractable P (P_CaC12), with r=0.80, and r=0.99 (p≤0.001), respectively. Ninety percent of the variability in EPCo was explained by the corresponding variability in P_Olsen when a curvilinear relationship was adopted. The P sorption properties examined appear to be useful parameters to assess the environmental impact of soil P on the quality of surface waters.     

Evaluation of an aluminum digestion block for routine total soil phosphorus determination by alkaline hypobromite oxidation

Abstract

Total soil P was determined in six soils differing in pH, and in organic matter, total Fe, clay and sand contents. This study was undertaken to determine whether replacement of a sand bath.digestion procedure by an Al‐block digestion procedure affected the efficacy of an alkaline NaOBr method for determining total soil P. An Al digestion block was used for soil oxidation with NaOBr‐NaOH and the results were compared with a sand bath NaOBr method and a HC1O4 method. Temperature variability was very low in the digestion block (S.D.= ±1.4°C) when compared with the sand bath (S.D.= +20.1°C). The digestion block resulted in a greater precision in total P determination when compared to the sand bath (S.D.= ±3.7 vs. ±5.6, respectively). Linear relationships were obtained with the sand bath digestion technique (R² = 0.981) and with the HC1O₄ method (R² = 0.982). Using an Al digestion block for NaOBr‐NaOH oxidation of soils for total P determination allows for a simple, precise alternative to sand bath digestion and to potentially hazardous HClO₄ procedures.     

Determination of total organic‐C in soils by an improved chromic acid digestion and spectrophotometric procedure

Abstract

An improvement to the Walkley‐Black wet digestion method for the rapid determination of organic carbon over the range 0.2–5.5% in air‐dry soil is described. It permits total recovery of the organic‐C in finely ground soil samples digested with the heat of dilution from mixing N K₂ Cr₂ O₇ with concentrated H₂SO₄. in test tubes followed by external heating from a hot‐plate digestor. The organic‐C concentrations are determined directly, as the Cr product in diluted soil digests, by absorptiometry at 600 nm with calibration against similarly treated sucrose standards in solution. For the soils tested, there were negligible interferences from carbonates, wood charcoal, coke, Fe⁺² and readily reducible Mn; Cl does not interfere with the organic‐C assay in non‐saline soils but for saline soils a correction based on 1/12 Cl^‐ assay of the soil is necessary. The present method is compared with Tabatabai and Bremner's dry combustion procedure and Allison's manometric adaptation for calcareous soils. The procedure described here does not require carbonate to be determined and is therefore simpler. In addition it is cheaper, faster and more effective in controlling interferences than dry combustion procedures.     

Fractionation and distribution of selenium in soils

Abstract

A modified selenium (Se) fractionation procedure was used to study Se distribution in three soils (two silt loams and one silty clay). This sequential procedure consisted of: i) 0.2 M potassium sulfate (K₂SO₄)‐soluble fraction, ii) 0.1 M potassium dihydrogen phosphate (KH₂PO₄)‐exchangeable fraction, iii) 0.5 M ammonium hydroxide (NH₃H₂O)‐soluble fraction, iv) 6 M hydrochloric acid (HCl)‐extractable fraction, and v) residual fraction digested with perchloric (HClO₄) and sulfuric (H₂SO₄) acids. The fractionation procedure had high recovery rates (92.5 to 106%). The Se distribution in soil was controlled by soil properties, such as pH, oxide, clay, and calcium carbonate (CaCO₃) contents. In the untreated soil samples, residual Se fraction was dominant. In the Se‐enriched soils, the silty clay had significantly more Se in the NH₃H₂O and residual fractions while in the two silt loams the largest were KH₂PO₄ and residual fractions. The Se availability in the two silt loams was higher than in the silty clay. The Se availability pattern in the untreated soils was: unavailable (HCl + residual fractions) >> potentially available (KH₂PO₄ + NH₃H₂O fractions) > available (K₂SO₄ fraction), while in the Se‐enriched soils it was potentially available > unavailable > available.     

Response of soil exchangeable and crop potassium concentrations to variable fertilizer and cropping regimes in long-term field experiments on different soil types

Annual potassium (K) balances have been calculated over a 40‐year period for five field experiments located on varying parent materials (from loamy sand to clay) in south and central Sweden. Each experiment consisted of a number of K fertilizer regimes and was divided into two crop rotations, mixed arable/livestock (I) and arable only (II). Annual calculations were based on data for K inputs through manure and fertilizer, and outputs in crop removal. Plots receiving no K fertilizer showed negative K balances which ranged from 30 to 65 kg ha^?1 year^?1 in rotation I, compared with 10–26 kg ha^?1 year^?1 for rotation II. On sandy loam and clay soils, the K yield of nil K plots (rotation I) increased significantly with time during the experimental period indicating increasing release of K from soil minerals, uptake from deeper soil horizons and/or depletion of exchangeable soil K (K_ex). Significant depletion of K_ex in the topsoil was only found in the loamy sand indicating a K supply from internal sources in the sandy loam and clay soils. On silty clay and clay soils, a grass/clover ley K concentration of ～2% (dry weight) was maintained during the 40‐year study period on the nil K plots, but on the sandy loam, loam and loamy sand, herbage concentrations were generally less than 2% K.     

Effect of wetting and drying on DTPA‐extractable Fe,Zn, Mn,and Cu in soils

Abstract

The study reported herein was intended to determine the effect of (i) wet‐incubation and subsequent air‐drying, and (ii) oven‐drying on DTPA‐Fe, Zn, Mn, and Cu.

Analysis of wet‐incubated soils showed significant decreases in DTPA‐Fe, Mn, and Cu at the 1% and Zn at the 10% level of probability. Air‐drying of these moist‐incubated soils increased the levels of Fe, Zn, and Cu to values close to their original levels. Levels of Mn sharply deviated from their original values after air‐drying of incubated soils. Correlation coefficients (r) between the amounts of extractable nutrients in original air‐dry soils and wet‐incubated soils were 0.54, 0.87, 0.91, and 0.13 for Fe, Zn, Cu, and Mn, respectively. Oven‐drying increased the levels of DTPA‐extractable micronutrients from 2 to 6 fold.     

Sorption of sulfur gases by soils

Gas Chromatographie studies showed that air-dry and moist soils have the capacity to sorb dimethyl sulfide (CH₃SCH₃), dimethyl disulfide (CH₃SSCH₃). carbonyl sulfide (COS) and carbon disulfide (CS₂), but do not sorb sulfur hexafluoride (SF₆). Moist soils sorb larger amounts of CH₃SCH₃. CH₃SSCH₃. COS or CS₂, than do air-dry soils, but the capacity of moist (or air-dry) soils for Sorption of these gases is much smaller than their capacity for sorption of H₂S. SO₂ or CH₃SH. The ability of moist soils to sorb COS is considerably greater than their ability to sorb CH₃SCH₃, CH₃SSCH₃ or CS₂. and sorption of COS by moist soils is accompanied by release of small amounts of CS₂.Experiments with sterilized (autoclaved) soils indicated that soil microorganisms are partly responsible for the sorption of CH₃SCH₃. CH₃SSCH₃. COS and CS₂ by moist soils. Support for this conclusion was obtained from experiments showing that the rate of sorption of these gases by moist soils increases with time.The work reported provides further evidence that soil is an important natural sink for gaseous atmospheric pollutants, but indicates that soils have little, if any, potential value for removal of CH₃SCH₃. CH₃SSCH₃. COS or CS₂, from industrial emissions polluted by these gases. The finding that soils have no capacity for sorption of SF₆ is significant in relation to use of this gas as a tracer for atmospheric research and as an internal standard for gas Chromatographie studies of evolution and sorption of gases by soils.     

Sorption of copper (II) and sulphate to different biochars before and after composting with farmyard manure

Biochar application has been suggested for reducing toxic levels of metals in contaminated soils and enhancing nutrient retention in agro‐ecosystems. We studied sorption of copper (Cu(II)) and sulphate‐sulphur (SO₄‐S) to charcoal, gasification coke and flash‐pyrolysis biochar in order to relate sorption to char properties. Furthermore, we investigated the effect of composting of charcoal and gasification coke on sorptive properties. Langmuir sorption affinity coefficients for Cu(II) for non‐composted biochars increased in the order flash‐pyrolysis char < charcoal < gasification coke. The sorption capacity for Cu(II) of the chars decreased in the order gasification coke (629 mg kg^?1) > flash‐pyrolysis char (196 mg kg^?1) > charcoal (56 mg kg^?1). Composting significantly increased the sorption affinity coefficient approximately by a factor of 5 for charcoal (up to 1.1 l mg^?1) and by a factor of 3–4 for gasification coke (up to 3.2 l mg^?1). Whereas Cu(II) sorption to gasification coke (composted or not) was largely irreversible, sorption to flash‐pyrolysis char and charcoal showed higher reversibility. Relationships between Cu(II) sorption and biochar properties such as cation exchange capacity, specific surface area or aromaticity suggest that sorption was largely determined by complexation with organic matter. Sorption of SO₄‐S was negligible by non‐composted and composted biochars. Composted gasification coke might be suited to reducing toxic Cu(II) concentrations in contaminated soils. Composted charcoal can potentially improve Cu(II) retention in a plant available form in acidic, sandy soils with small organic matter contents. Transient effects of biochars on soil pH can over‐ride the influence of sorption to biochars on concentrations of trace elements in soil solution and their availability to plants.     

The effect of sulphur dioxide on extractable manganese in soils

Abstract

The treatment of soil with SO₂ caused rapid increases in concentrations of water soluble plus exchangeable (extractable) Mn. The extractable Mn increased with increasing pressure of SO₂ and time of exposure, and increased with increasing water contents up to field capacity but decreased beyond this point. The addition of peat to a sandy loam increased the effect of SO₂ on extractable Mn while the addition of lime decreased the effect. Reactive Mn oxides in soils may contribute significantly to SO₂ sorption by soils.     

Validation of water sorption‐based clay prediction models for calcareous soils

Soil particle size distribution (PSD), particularly the active clay fraction, mediates soil engineering, agronomic and environmental functions. The tedious and costly nature of traditional methods of determining PSD prompted the development of water sorption‐based models for determining the clay fraction. The applicability of such models to semi‐arid soils with significant amounts of calcium carbonate and/or gypsum is unknown. The objective of this study was to validate three water sorption‐based clay prediction models for 30 calcareous soils from Iran and identify the effect of CaCO₃ on prediction accuracy. The soils had clay content ranging from 9 to 61% and CaCO₃ from 24 to 97%. The three water sorption models considered showed a reasonably fair prediction of the clay content from water sorption at 28% relative humidity (RMSE and ME values ranging from 10.6 to 12.1 and −8.1 to −4.2, respectively). The model that considers hysteresis had better prediction accuracy than the other two that do not. Moreover, the prediction errors of all three models arose from under‐prediction of the clay content. The amount of hygroscopic water scaled by clay content decreased with increasing CaCO₃ content. The low organic carbon content of the soils and the low fraction of low‐activity clay minerals like kaolinite suggested that the clay content under‐predictions were due to large CaCO₃ contents. Thus, for such water‐sorption based models to work accurately for calcareous soils, a correction factor that considers the reduction of water content due to large CaCO₃ content should be included.