Adsorption of arsenate on soils. Part 1: laboratory batch experiments using 16 Chinese soils with different physiochemical properties

Laboratory batch experiments were carried out to study the adsorption of arsenate on 16 Chinese soils with different physicochemical properties. Wide differences in arsenate adsorption were observed, and the Jiangxi and Hubei soils were more effective sorbents for arsenate than other soils. The Langmuir one-surface and two-surface equations were used to model the arsenate adsorption data. Except for the Jiangxi and Hubei soils, the Langmuir one-surface equation gave reasonably good fits to the arsenate adsorption data. However, the Langmuir two-surface equation generally provided a better fit than the Langmuir one-surface equation. For soils with relative high organic matter (OM), dissolved organic carbon (DOC) or extractable phosphate, the Langmuir one-surface and two-surface equations described the adsorption isotherms similarly. In contrast, for soils with relatively low contents of OM, DOC or extractable phosphate, the Langmuir two-surface equation gave the better fit to the arsenate adsorption data.     

Effect of arsenate on adsorption of Cd(II) by two variable charge soils

The effect of arsenate on Cd(II) adsorption in two variable charge soils and the desorption of Cd(II) pre-adsorbed in the presence of arsenate were studied. The batch type experiments showed, the presence of arsenate led to increase in Cd(II) adsorption and the desorption of pre-adsorbed Cd(II). Further it was observed that the extent of adsorption and desorption of Cd(II) was greatly influenced by the initial concentrations of arsenate and Cd(II), the solution pH, and the nature of the soils. In general the increase in arsenate concentration and pH favored the uptake of Cd(II). Moreover, the arsenate concentration influenced more in Hyper-Rhodic Ferralsol than Rhodic Ferralsol at least for the Cd(II) adsorption/desorption. This may be due to the content of Fe/Al oxides in these soils. The larger the content of Fe/Al oxides, the more the adsorption of arsenate by the soil, hence greater the uptake of Cd(II). It can be assumed that the enhanced Cd(II) adsorption was mainly due to the increase in net negative surface charge of the soil induced by the adsorption of arsenate, because the presence of arsenate led to the decrease in zeta potential of these soil suspensions. The increase of electrostatically adsorbed Cd(II) was responsible for the increase in the desorption of Cd(II) pre-adsorbed in the presence of arsenate.     

Effect of biosolid incorporation on arsenic distribution in Mollisol soils in central Chile

The effect of biosolid incorporation on arsenic distribution in Mollisol soils in central Chile was studied. Two soils were sequentially extracted for arsenic with a five-step method that accounts for the following arsenic forms: non-specifically adsorbed (F1), specifically adsorbed (F2), amorphous and poorly crystallized Fe and Al oxides (F3), well-crystallized Fe and Al oxides (F4) and residual (F5). The arsenic residual fraction was predominant in Pintué soil, whereas in Graneros soil, arsenic was mostly associated to amorphous Fe and Al oxides. Graneros soil exhibited a higher As(V) adsorbing capacity than Pintué soil, which relates to the higher clay and iron and aluminum oxides contents, confirming that these components participation is essential for the adsorption of this metalloid. Biosolid application at a rate of 100Mg ha(-1) caused an increase in arsenic bound to amorphous Fe and Al oxides and in the residual fraction, in Pintué soil. When Pintué soil was spiked with arsenic, aged for two months, and treated with biosolid (100Mg ha(-1)), the content of arsenic in the most labile fractions decreased, thus showing a favorable effect in its application to soils with few specific sites for arsenic adsorption. Arsenic speciation was carried out in the first two fractions of the sequential extraction procedure. As(V) was the main form in both fractions. Biosolid incorporation at a rate of 100Mg ha(-1) caused a significant increase in organic arsenic forms.     

Size and XAD fractionations of trihalomethane precursors from soils

Soil organic matter is an important source of allochthonous dissolved organic matter inputs to the Sacramento-San Joaquin Delta waterways, which is a drinking water source for 22 million people in California, USA. Knowledge of trihalomethane (THM) formation potential of soil-derived organic carbon is important for developing effective strategies for organic carbon removal in drinking water treatment. In this study, soil organic carbon was extracted with electrolytes (deionized H2O and Na- or Ca-based electrolytes) of electrical conductivity bracketing those found in Delta leaching and runoff conditions. The extracts were physically and chemically separated into different fractions: colloidal organic carbon (0.45-0.1 microm), fine colloidal organic carbon (0.1-0.025 microm), and dissolved organic carbon (DOC) (<0.025 microm); hydrophobic acid (HPOA), transphilic acid, and hydrophilic acid. Two representative Delta soils, Rindge Muck (a peat soil) and Scribner Clay Loam (a mineral soil) were examined. Results showed that less than 2% of soil organic carbon was electrolyte-extractable and heterogeneous organic fractions with distinct THM reactivity existed. Regardless of soil and electrolytes, DOC and HPOA fractions were dominant in terms of total concentration and THMFP. The amounts of extractable organic carbon and THMFP were dependent on the cation and to a lesser extent on electrical conductivity of electrolytes. Along with our previous study on temperature and moisture effects on DOC production, we propose a conceptual model to describe the impacts of agricultural practices on DOC production in the Delta. DOC is mainly produced in the surface peat soils during the summer and is immobilized by accumulated salt in the soils. DOC is leached from soils to drainage ditches and finally to the Delta channels during winter salt leaching practices.     

The ratio of clay content to total organic carbon content is a useful parameter to predict adsorption of the herbicide butachlor in soils

Thirteen soils collected from 11 provinces in eastern China were used to investigate the butachlor adsorption. The results indicated that the total organic carbon (TOC) content, clay content, amorphous Fe2O3 content, silt content, CEC, and pH had a combined effect on the butachlor sorption on soil. Combination of the data obtained from the 13 soils in the present study with other 23 soil samples reported by other researchers in the literature showed that Koc would be a poor predictive parameter for butachlor adsorption on soils with TOC content higher than 4.0% and lower than 0.2%. The soils with the ratio of clay content to TOC content (RCO) values less than 60 adsorbed butachlor mainly by the partition into soil organic matter matrix. The soils with RCO values higher than 60 apparently adsorbed butachlor by the combination of the partition into soil organic matter matrix and adsorption on clay surface.     

Adsorption and transport of arsenate in carbonate-rich soils: coupled effects of nonlinear and rate-limited sorption

The transport and fate of arsenate in carbonate-rich soil under alkaline conditions was investigated with multiple approaches combining batch, sequential extraction and column experiments as well as transport modeling studies. Batch experiments indicated that sorption isotherm was nonlinear over a wide range of concentration (0.1-200 mg L(-1)) examined. As(V) adsorption to the calcareous soil was initially fast but then continued at a slower rate, indicating the potential effect of rate-limited sorption on transport. Column experiments illustrated that transport of As(V) was significantly retarded compared to a non-reactive tracer. The degree of retardation decreased with increasing As(V) concentration. As(V) breakthrough curves exhibited nonideal transport behavior due to the coupled effects of nonlinear and rate-limited sorption on arsenate transport, which is consistent with the results of modeling studies. The contribution of nonlinear sorption to the arsenate retardation was negligible at low concentration but increased with increasing As(V) concentration. Sequential extraction results showed that nonspecifically sorbed (easily exchangeable, outer sphere complexes) fraction of arsenate is dominant with respect to the inner-sphere surface bound complexes of arsenate in the carbonate soil fraction, indicating high bioavailability and transport for arsenate in the carbonate-rich soils of which Fe and Al oxyhydroxide fractions are limited.     

Sorption of 2,4-d on natural and organic amended soils of different characteristics

The effect of one organic amendment consisting of an urban waste compost (UWC) was assessed on the sorption properties of the herbicide 2,4-D on four soils of different physicochemical characteristics. The soils chosen were a Typic Haphorthod (ST), a Typic Endoaquept (SR), an Entic Pelloxerert (TO), and a Typic Eutrochrept (AL). Adsorption experiments were performed on the original soils, and on mixtures of these soils with UWC at a rate of 6.25% (w/w). These mixtures were used just after preparation, and after aging for 8 and 25 weeks. 2,4-D adsorption was the highest on ST soil, whereas the lowest adsorption was for SR soil. This behavior is related to the high amount of organic matter (OM) and amorphous iron and aluminum oxides content on soil ST, whereas soil SR had the lowest OM content and specific surface area of the soils of this study. Addition of exogenous OM to soils caused an increase in the 2,4-D adsorption by three of the soils treated with UWC, with the only exception being ST soil, due to an observed decrease in its specific surface area. The adsorbed amounts of the herbicide on aged organic fertilized soils diminished in three of the amended soils, but was still greater than on unammended soils. In contrast, the ST soil showed the largest adsorption for unammended soil.     

The variations of aluminium species in mountainous forest soils and its implications to soil acidification

Aluminium (Al) speciation is a characteristic that can be used as a tool for describing the soil acidification process. The question that was answered is how tree species (beech vs spruce) and type of soil horizon affect Al speciation. Our hypotesis is that spruce and beech forest vegetation are able to modify the chemical characteristics of organic horizon, hence the content of Al species. Moreover, these characteristics are seasonally dependent. To answer these questions, a detailed chromatographic speciation of Al in forest soils under contrasting tree species was performed. The Jizera Mountains area (Czech Republic) was chosen as a representative mountainous soil ecosystem. A basic forestry survey was performed on the investigated area. Soil and precipitation samples (throughfall, stemflow) were collected under both beech and spruce stands at monthly intervals from April to November during the years 2008–2011. Total aluminium content and Al speciation, pH, and dissolved organic carbon were determined in aqueous soil extracts and in precipitation samples. We found that the most important factors affecting the chemistry of soils, hence content of the Al species, are soil horizons and vegetation cover. pH strongly affects the amount of Al species under both forests. Fermentation (F) and humified (H) organic horizons contain a higher content of water extractable Al and Al³⁺ compared to organo-mineral (A) and mineral horizons (B). With increasing soil profile depth, the amount of water extractable Al, Al³⁺ and moisture decreases. The prevailing water-extractable species of Al in all studied soils and profiles under both spruce and beech forests were organically bound monovalent Al species. Distinct seasonal variations in organic and mineral soil horizons were found under both spruce and beech forests. Maximum concentrations of water-extractable Al and Al³⁺ were determined in the summer, and the lowest in spring.     

Arsenic immobilization in soils amended with drinking-water treatment residuals

Use of Fe/Al hydroxide-containing materials to remediate As-contaminated sites is based on the general notion that As adsorption in soils is primarily controlled by Fe/Al (hydr)oxides. A low-cost and potentially effective substitute for natural Fe/Al hydroxides could be the drinking-water treatment residuals (WTRs). Earlier work in our laboratory has shown that WTRs are effective sorbents for As in water. We hypothesized that land-applied WTRs would work equally well for As-contaminated soils. Results showed that WTRs significantly (p<0.001) increased the soil As sorption capacity. All WTR loads (2.5, 5, and 10%) significantly (p<0.001) increased the overall amount of As sorbed by both soils when compared with that of the unamended controls. The amount of As desorbed with phosphate (7500 mg kg(-1) load) was approximately 50%. The WTR effectiveness in increasing soil As sorption capacities was unaffected by differences in both soils' chemical properties.     

Effects of thermal desorption on the composition of two coking plant soils: impact on solvent extractable organic compounds and metal bioavailability

To evaluate the efficiency and the influence of thermal desorption on the soil organic compartment, contaminated soils from coking plant sites (NM and H) were compared to their counterparts treated with thermodesorption. The extractable organic matter, and the metal content and distribution with soil compartments were studied.In both thermodesorbed soils, PAH (polycyclic aromatic hydrocarbon) degradation exceeded 90%. However, the thermal desorption led not only to a volatilization of the organic compounds but also to the condensation of extractable organic matter.The treatments only affected the Fe and Zn distribution within the more stable fractions, whereas the organic compound degradation did not affect their mobility and availability.     

Modeling interactions of Hg(II) and bauxitic soils

The adsorptive interactions of Hg(II) with gibbsite-rich soils (hereafter SOIL-g) were modeled by 1-pK surface complexation theory using charge distribution multi-site ion competition model (CD MUSIC) incorporating basic Stern layer model (BSM) to account for electrostatic effects. The model calibrations were performed for the experimental data of synthetic gibbsite-Hg(II) adsorption. When [NaNO(3)] > or = 0.01M, the Hg(II) adsorption density values, of gibbsite, Gamma(Hg(II)), showed a negligible variation with ionic strength. However, Gamma(Hg(II)) values show a marked variation with the [Cl(-)]. When [Cl(-)] > or = 0.01M, the Gamma(Hg(II)) values showed a significant reduction with the pH. The Hg(II) adsorption behavior in NaNO(3) was modeled assuming homogeneous solid surface. The introduction of high affinity sites, i.e., >Al(s)OH at a low concentration (typically about 0.045 sites nm(-2)) is required to model Hg(II) adsorption in NaCl. According to IR spectroscopic data, the bauxitic soil (SOIL-g) is characterized by gibbsite and bayerite. These mineral phases were not treated discretely in modeling of Hg(II) and soil interactions. The CD MUSIC/BSM model combination can be used to model Hg(II) adsorption on bauxitic soil. The role of organic matter seems to play a role on Hg(II) binding when pH>8. The Hg(II) adsorption in the presence of excess Cl(-) ions required the selection of high affinity sites in modeling.     

Generalized models for prediction of pentachlorophenol dissipation dynamics in soils

Dissipation of pentachlorophenol (PCP) in soil was investigated and the chemical relationships with soil properties were addressed. The results indicate that the dissipation of extractable PCP residues can be described using first-order kinetics equations, with a half-dissipation time (T(1/2)) ranging from 6.5 to 173.3d. The sharply different patterns of PCP dissipation in different soils were closely related to soil properties. Correlations of stepwise regression equations obtained were significant at 0.01 probability level between soil parameters and extractable PCP residues (R(2)=0.974**) as well as T(1/2) values (R(2)=0.882**). Using pH together with organic carbon content (OC) and soil particle size distribution, the dissipation dynamics of PCP in soil could be accurately predicted.     

An investigation of inorganic antimony species and antimony associated with soil humic acid molar mass fractions in contaminated soils

The presence of antimony compounds is often suspected in the soil of apple orchards contaminated with lead arsenate pesticide and in the soil of shooting ranges. Nitric acid (1M) extractable Sb from the shooting range (8300 microg kg(-1)) and the apple orchard (69 microg kg(-1)) had considerably higher surface Sb levels than the control site (<1.5 microg kg(-1)), and Sb was confined to the top approximately 30 cm soil layer. Sb(V) was the principal species in the shooting range and the apple orchard surface soils. Size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS) analysis of humic acids isolated from the two contaminated soils demonstrated that Sb has complexed to humic acid molar mass fractions. The results also indicate that humic acids have the ability to arrest the mobility of Sb through soils and would be beneficial in converting Sb(III) to a less toxic species, Sb(V), in contaminated areas.     

Distribution and availability of arsenic in soils from the industrialized urban area of Beijing, China

Concentrations of arsenic (As) were determined in soils of 5 industrial sites in an urban area of Beijing, China. Fifty seven typical surface soils were sampled to determine total concentrations of metals, pH and dissolved organic carbon (DOC). One hundred and eight deep soils were submitted to a four-step, sequential extraction to assess the relative mobility and bioavailability of As in the soil profiles. Total concentrations of As in surface soils ranged from 5.7 to 2.3 x 10(1) mg kg(-1), dw with greater concentrations inside the perimeter of the chemical plant which had greater concentrations than did other plants. 75.4% of surface soil samples in the industrial area contained concentrations of As that were greater than was considered to be the background concentration of 7.8 mg kg(-1), dw for the region. The mean concentration (9.9 mg kg(-1), dw) in the industrial soils was greater than that soils from other type of land use. Concentrations of As were significantly and negatively correlated with soil pH and DOC in industrial soils. Although mean concentration of total As in the soils from all sites were less at greater depths, the entire range from 0 to 180 cm (especially 0-80 cm) contained concentrations of As that were greater than background. Sequential extractions of soil indicated that only some surface soils had relatively great amount of extractable fraction of As. Most soils had relatively great amount of residual As. This result suggests that most arsenic in Beijing industrial soils should be immobile and of limited bioavailability.     

Dissolved organic carbon from sewage sludge and manure can affect estrogen sorption and mineralization in soils

In this study, effects of sewage sludge and manure borne dissolved organic carbon (DOC) on 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) sorption and mineralization processes were investigated in three agricultural soils. Batch equilibrium techniques and equilibrium dialysis methods were used to determine sorption mechanisms between DOC, estrogens and the soil solid phase. It was found that that the presence of organic waste borne DOC decreased estrogen sorption in soils which seems to be controlled by DOC/estrogen complexes in solution and by exchange processes between organic waste derived and soil borne DOC. Incubation studies performed with ¹⁴C-estrogens showed that DOC addition decreased estrogen mineralization, probably due to reduced bioavailability of estrogens associated with DOC. This increased persistence combined with higher mobility could increase the risk of estrogen transport to ground and surface waters.     

Phosphorus fractions in grassland soils

The partitioning of P among major chemical forms was studied in 110 non-fertilized, semi-natural grassland soils of southeastern Sweden, comprising a wide range of soil acidity and other chemical properties. The P fractions bound to Ca and Fe were closely related to soil acidity, expressed as pH-KCl, especially when calculated as % of the total pool of mineral P. The relationship was inversely linear for log10P-Fe, whereas it was strongly positively curvilinear for log10P-Ca, with a sudden decrease of this fraction below pH-KCl 4.5. Phosphate bound to Al was inversely related to pH-KCl, but the variability accounted for was rather low. Easily exchangeable phosphate, interpreted as the most labile form of P-Al, was more closely related to soil acidity, with very low values at pHg-KCl > 5.5. Soil concentration of organic P was mainly a function of its contents of organic matter. Data were treated by PCA and stepwise regression analysis.     

Effect of pH and the role of organic matter in the adsorption of isoproturon on soils

Equilibrium measurements were carried out with the herbicide isoproturon on natural adsorbents (brown forest-, chernozem-, sandy soils and quartz) in different buffered media (pH 5, 7, 8 phosphate buffer). Adsorption isotherms were fitted by a multi-step adsorption equation providing numerical information used in the environmental propagation models and risk assessment works. In the adsorption of the slightly polar isoproturon the dissolved organic matter of the soil and the pH play an important role. At molecular level, results are interpreted by taking into consideration the hydrophobic interaction and the formation of hydrogen bonds between the surface and the solute. The observed adsorption behavior indicates that the organic matter content of the soils and its soluble fulvic acid, alkaline soluble humic acid and insoluble humin fractions were considerable different. The chernozem soil containing the highest amount of insoluble organic fraction proved to be a very efficient adsorbent. The brown forest and the sandy soils exhibit rather similar adsorbent properties but at pH 7 the latter containing more fulvic acid adsorbs less isoproturon due to the enhanced solubility of the soil organic matter. In alkaline conditions the negatively charged solute and the surface repel each other and the hydrophobic interactions are also weaker than in neutral media.     

Glyphosate adsorption in soils compared to herbicides replaced with the introduction of glyphosate resistant crops

Use of glyphosate resistant crops was helpful in addressing observed increases in environmental contamination by herbicides. Glyphosate is a broad-spectrum herbicide, and its behaviour-as well as that of other herbicides-in soils is an important consideration for the overall environmental evaluation of genetically resistant crop introduction. However, few data have been published comparing glyphosate behaviour in soil to that of the herbicides that would be replaced by introduction of glyphosate resistant crops. This work compares glyphosate adsorption in soil with that of other herbicides frequently used in rape (trifluralin and metazachlor), sugarbeet (metamitron) and corn (sulcotrione). Herbicide adsorption was characterised in surface soils and in the complete soils profiles through kinetics and isotherms using batch equilibration methods. Pedological and molecular structure factors controlling the adsorption of all five herbicides were investigated. Glyphosate was the most strongly adsorbed herbicide, thus having the weakest potential for mobility in soils. Glyphosate adsorption was dependent on its ionisable structure in relation to soil pH, and on soil copper, amorphous iron and phosphate content. Trifluralin adsorption was almost equivalent to glyphosate adsorption, whereas metazachlor, metamitron and sulcotrione adsorption were lower. Trifluralin, metazachlor and metamitron adsorption increased with soil organic carbon content. Sulcotrione was the least adsorbed herbicide in alkaline soils, but its adsorption increased when pH decreased. Ranking the adsorption properties among the five herbicides, glyphosate and trifluralin have the lowest availability and mobility in soils, but the former has the broadest spectrum for weed control.     

Copper extraction effectiveness and soil dissolution issues of EDTA-flushing of artificially contaminated soils

Ethylenediaminetetraacetic acid (EDTA) was used as a reference chelating agent in column experiments to investigate the effectiveness of chelant-enhanced flushing of soils artificially contaminated under various conditions (low/high Cu loading, and aging). The associated soil dissolution issues were of particular concern. Dissolution of indigenous Fe/Al oxides, Ca carbonates and organic matter was monitored over the course of flushing. Regardless of contamination condition, above 85% extraction efficiency could be accomplished by 10(-2) and 10(-3)M EDTA-flushing, but not 10(-4)M. The Cu extraction kinetics positively correlated to EDTA concentration but inversely to Cu loading in soils. In addition to extraction from weakly sorbed fractions, a large portion of Cu was extracted from oxide, organic matter and residual fractions, which appears to derive from soil dissolution. Cumulative dissolved amounts of Fe, Al, and Ca were found to reach as high as hundreds of mgkg(-1), which were comparable to Cu contamination. Soil organic matter, which is known to strongly interact with Fe and Al oxides, was also mobilized. The rate and extent of these soil dissolutions were also positively correlated to EDTA concentration. Therefore, the co-extraction of soil minerals and organic matter during chelant-enhanced flushing, which would alter both physical structure and chemical properties of the soils, is detrimental to future land use and deserves greater attention. The concentration of chelating agent is the most crucial factor for an effective soil flushing with minimal damage.     

Insights into the mercury(II) adsorption and binding mechanism onto several typical soils in China

To better understand the Hg(II) adsorption by some typical soils and explore the insights about the binding between Hg(II) and soils, a batch of adsorption and characteristic experiments was conducted. Results showed that Hg(II) adsorption was well fitted by the Langmuir and Freundlich. The maximum adsorption amount of cinnamon soil (2094.73 mg kg^?1) was nearly tenfold as much as that of saline soil (229.49 mg kg^?1). The specific adsorption of Hg(II) on four soil surface was confirmed by X-ray photoelectron spectroscopy (XPS) owing to the change of elemental bonding energy after adsorption. However, the specific adsorption is mainly derived from some substances in the soil. Fourier transform infrared spectroscopy (FTIR) demonstrated that multiple oxygen-containing functional groups (O–H, C=O, and C–O) were involved in the Hg(II) adsorption, and the content of oxygen functional groups determined the adsorption capacity of the soil. Meanwhile, scanning electron microscopy combined with X-ray energy dispersive spectrometer (SEM–EDS) more intuitive revealed the binding of mercury to organic matter, metal oxides, and clay minerals in the soil and fundamentally confirmed the results of XPS and FTIR to further elucidate adsorptive phenomena. The complexation with oxygen-containing functional groups and the precipitation with minerals were likely the primary mechanisms for Hg(II) adsorption on several typical soils. This study is critical in understanding the transportation of Hg(II) in different soils and discovering potential preventative measures.