Sorption and desorption of salinomycin sodium in clay, loamy sand, and sandy soils

Salinomycin sodium (BIO-COX) is polyether ionophore, commonly used in the poultry industries for the prevention of coccidial infections and promotion of growth. Salinomycin sodium (SAL-Na) is very toxic, and may be fatal, if swallowed, inhaled, or absorbed through the skin than many other antibiotics, thus evaluating their fate in the soil environment is of importance. Sorption of SAL-Na was measured in clay, loamy sand, and sandy soil at different pH 4, 7, and 9, and desorption with phosphate buffer (pH 7) using batch equilibration technique. SAL-Na was sorbed by all the soils studied, the sorption of SAL-Na by the sandy soil increased as the pH decreased, while the sorption of salinomycin in clay and loamy sand soil increased as the pH increased. Desorption of salinomycin from the soil with phosphate buffer (pH 7) over the 24 h period was 80-95% of the amount added. The similar trend was observed in desorption with pH 4, 7 and at different concentrations and slight less desorption was observed in pH 9. When compared to clay and loamy sand soil, sandy soil was recorded maximum (95%) desorption.     

Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS)

Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied.     

Measurement of total antimony and antimony species in mine contaminated soils by ICPMS and HPLC-ICPMS

This paper describes the measurement of total antimony and antimony species in "real world" mine contaminated sediments using ICPMS and HPLC-ICPMS. Low and high temperature microwave extraction procedures (90 degrees C and 150 degrees C, respectively) using a range of nitric-hydrochloric acid combinations were examined as to their efficacy to extract antimony from six mine contaminated soils and a certified reference material. The use of the higher temperature with nitric-hydrochloric acid (1:2 (v/v)) was suitable to release antimony from sediments and the certified reference material, NIST 2710 Montana soil. Antimony concentrations obtained using this acid mixture were similar to those obtained using a more aggressive extraction with nitric, hydrochloric, perchloric and hydrofluoric acid mixture. A 25 mM citric acid solution at 90 degrees C for 15 min extracted 47-78% of antimony from soils. A Hamilton PRP X-100 anion exchange column with 20 mM EDTA mobile phase, pH 4.5, flow rate 1.5 mL min(-1) and column temperature of 50 degrees C was used to separate antimony species. Column recoveries ranged from 78-104%. The predominant form of antimony was Sb(5+). Little conversion of Sb(5+) occurred (<5%) during extraction, however, significant conversion of Sb(3+) occurred (approximately 36%). The extraction of antimony species with citric acid should be useful in the determination of inorganic antimony available to plants, as plants commonly excrete carboxylic acids, including citric acid, into their rhizospheres to mobilise trace elements for nutritional purposes.     

Iron and sulfur geochemistry in semi-arid mangrove soils (Ceará, Brazil) in relation to seasonal changes and shrimp farming effluents

Iron and sulfur are key elements in the biogeochemistry of estuarine soils, in which Fe and sulfate reduction (SR) pathways are important for organic matter decomposition. In the semi-arid coast of NE Brazil, mangroves are characterized by large seasonal variations in weather and the presence of numerous shrimp farms. The objective was to determine the impacts of shrimp farm effluents on iron and sulfur geochemistry in mangrove soils under the semi-arid climate of NE Brazil. A seasonal study was made of two mangrove forest soils (SF, a mangrove forest that directly receives wastewater from shrimp ponds and CS, a control site). Pyrite Fe, oxyhydroxides Fe, acid volatile sulfide, degree of pyritization (DOP), pH, Eh, total organic carbon (TOC) and total S were determined. There was a clear decrease in pyritic Fe and DOP in the SF soils, which may be related to the anaerobic oxidation of pyrite coupled with nitrate reduction, or to the dominance of denitrification over SR. Lower TOC contents in the SF site suggest that below ground decomposition increased in response to eutrophication. The seasonal variations led to important changes in the semi-arid mangrove soils. During the dry period, both soils experienced oxidizing conditions with remarkable loss of reduced and oxidized forms of Fe, which may have important environmental implications as Fe is biolimiting for marine primary production. The data show that both factors (seasonal weather variations and shrimp effluents) play important roles in the geochemical processes that occur in these soils and, thus, may affect their functioning and maintenance.     

Addressing analytical uncertainties in the determination of trichloroacetic acid in soil

Soil is an important compartment in the environmental cycling of trichloroacetic acid (TCA), but soil TCA concentration is a methodologically defined quantity; analytical methods either quantify TCA in an aqueous extract of the soil, or thermally decarboxylate TCA to chloroform in the whole soil sample. The former may underestimate the total soil TCA, whereas the latter may overestimate TCA if other soil components (e.g. humic material) liberate chloroform under the decarboxylation conditions. The aim of this work was to show that extraction and decarboxylation methods yield different TCA concentrations because the decarboxylation method can also determine "bound" TCA. Experiments with commercial humic acid solutions showed there was no additional chloroform formation under decarboxylation conditions, and that all TCA in a TCA-humic acid mixture could be quantitatively determined (108 +/- 13%). Anion exchange resin was used as a provider of solid-phase TCA binding; only 5 +/- 1% of a TCA solution mixed with the resin was present in the aqueous extract subsequently separated from the resin, yet the decarboxylation method yielded mass balance (123 +/- 22%) with TCA remaining in the resin. In aqueous extraction of a range of soil samples (with or without added TCA spike), the decarboxylation method was able to satisfactorily account for TCA in the extractant + residue post-extraction, compared with whole-soil TCA (+ spike) pre-extraction: e.g. mass balances for unspiked soil from Sikta spruce and larch forest were 99 +/- 8% and 93 +/- 6%, respectively, and for TCA-spiked forest and agricultural soils were 114 +/- 13% and 102 +/- 2%. In each case recovery of TCA in the extractant was substantially less than 100%(<20% for unspiked soils, <55% for spiked soils). Extraction efficiencies were generally lower in more organic soils. The results suggest that analytical methods which utilise aqueous extraction may underestimate whole-soil TCA concentrations. Application of both methodologies together may enhance insight into TCA behaviour in soil.     

Fractionation and elemental association of Zn, Cd and Pb in soils contaminated by Zn minings using a continuous-flow sequential extraction

Fractionation and elemental association of Zn, Cd, and Pb in soils near Zn mining areas were studied using a continuous-flow sequential extraction approach. The recently developed sequential extraction procedure not only gave fractional distribution data for evaluation of the mobility or potential environmental impact of the metals, but also the extraction profiles (extractograms) which were used for study of elemental association. In addition, the elemental atomic ratio plot extractogram can be used to demonstrate the degree of anthropogenic contamination. Seventy-nine soil samples were collected in the vicinity of a Zn mine and were fractionated into 4 phases i.e. exchangeable (F1), acid soluble (F2), reducible (F3) and oxidizable (F4) phases. Most samples were contaminated with Zn, Cd and Pb. The reducible phase is the most abundant fraction for Zn and Pb (>50%) while Cd is concentrated in the first 3 extraction steps. The distribution patterns of Cd were obviously affected by soil pH. 55% of Cd appears predominantly in the F1 fraction for acidic soils while in neutral and alkaline soils, it was mostly (70%) found in the F2 + F3 fractions. The extractograms obtained from the continuous-flow extraction system revealed close association between Zn, Cd, Pb and Fe in the acid soluble phase, Cd-Pb and Zn-Fe in the reducible phase for contaminated soils. A correlation study of the 3 metals using a correlation coefficient was also performed to compare the results with the elemental association revealed by the extractograms. Atomic ratio plot extractograms of Zn/Fe, Cd/Fe and Pb/Fe in the reducible phase, where contaminated metals are predominant, can be used to evaluate the degree of anthropogenic contamination. From the elemental atomic ratio plot, it is obvious that the contaminants Cd and Pb are mostly adsorbed on the surface of Fe oxides. Zn, which is present in an approximately 1 ratio 1 ratio with Fe in contaminated soils, does not show a similar trend to that found for Cd and Pb.     

Natural concentrations and reference values of heavy metals in sedimentary soils in the Brazilian Amazon

The soils of the Brazilian Amazon exhibit large geochemical diversity reflecting the different soil formation processes in an area covering 49% of the Brazilian territory. Soil contamination by heavy metals is one of the threats to the sustainability of this Biome but establishing quality reference values (QRVs) for the region is a challenging owing to the immense territorial area of the Amazon. This study aimed to determine the natural background of heavy metals in soils from the southwestern Brazilian Amazon in order to propose QRVs for Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, and Zn for alluvial sedimentary soils. One hundred and twenty-eight soil samples were collected at a depth of 0.0–0.2 m in sites with minimal anthropogenic interference. Soil sample digestion was based on the EPA 3051A method and metal concentrations were determined by ICP-OES. QRVs calculated for the southwestern Brazilian Amazon are among the lowest recorded in Brazil (mg kg^?1): Ba (16.5), Cd (0.1), Cr (6.9), Cu (2.8), Fe (15.4), Mn (13.4), Ni (1.7), Pb (4.4), Sb (0.9), and Zn (5.7). The low metal concentration is likely a result of the sedimentary origin of the soils. The results of this study can serve as a basis for defining public policies to investigate the environmental impacts resulting from changes in land use in areas of the Brazilian Amazon.     

Phosphorus sorption–desorption behaviour of river bed sediments in the Abshineh river, Hamedan, Iran, related to their composition

Phosphorus (P) sorption by sediments may play a vital role in buffering P concentration in the overlying water column. To characterize P sorption–desorption in the river bed sediments, 17 bed sediment samples collected from Abshineh river, in a semi arid region, Hamedan, western Iran were studied through a batch experiment and related to sediment composition. The sorbed fraction ranged from 4.4% to 5.4% and from 38.5% to 86.0% of sorption maxima when 20 and 1,500 mg P kg^?1, respectively, was added to the sediment samples. Phosphorus sorption curves were well fitted to the Langmuir model. Zero equilibrium P concentration ranged from 0.10 to 0.51 mg P l^?1 and varied with sediment characteristics. Phosphorus desorption differed strongly among the studied bed sediments and ranged from 10.8% to 80.2% when 1,500 mg P kg^?1 was added. The results of the geochemical modelling indicated that even under low P addition (2 mg l^?1), the solutions are mainly saturated with respect to hydroxyapatite and ß-tricalcium phosphate minerals and undersaturated with respect to other Ca and Mg minerals, whereas under higher P addition (150 mg l^?1), most Ca–P solid phases, except the most soluble mineral (brushite), will likely precipitate. A Langmuir sorption maximum was positively correlated with carbonate calcium. Estimated P retention capacity of the bed sediments are generally lower and zero equilibrium P concentration values higher in upstream sites than at the downstream sites, suggesting that sediments in upstream and downstream may act as source and sink of P, respectively.     

Multiple kinetic Langmuir modeling to predict the environmental behaviour of As(v) in soils

A soil with a relatively high Fe content (2.82% [w/w]) was loaded for up to one year with As(v) by equilibrating it with a solution containing 1000 mg l(-1) As(v) at a soil mass-to-solution ratio of 0.1 kg l(-1). The incorporation of As(v) into the soil and its distribution over the soil phases were monitored by sampling at strategic time intervals using an operationally defined five-step sequential extraction procedure (Wenzel et al., Anal. Chim. Acta, 2001, 436, 309) and subsequent As measurement. A multiple kinetic Langmuir model was developed to retrieve the dynamic parameters (adsorption and desorption rate constants, capacities and Langmuir equilibrium constants) for each of the soil phases by numerical fitting of the experimental adsorption data to the model. Under the equilibration conditions used the adsorption rate constants for all five operationally defined soil phases were very similar but the desorption rate constants decreased by a factor of ca. 150 from soil phase 1 (non-specifically sorbed As) to 5 (residual phases). This implies that As(v) incorporation "deeper" into the soil leads to stronger binding which is associated with the Langmuir equilibrium constants (adsorption rate constants/desorption rate constants). Equilibration of the soil with As(v) was complete in ca. 10 days with As(v) predominantly bound to soil phase 2 (specifically sorbed As) and soil phase 3 (amorphous and poorly crystalline hydrous oxides). X-Ray absorption spectroscopy techniques revealed that these binding characteristics may be related to adsorption of As(v) on Si- and/or Al-containing structures and natural hydrous iron oxide (HFO) surface sites, respectively. Since the model is independent of the initial As(v) concentration in the solution and the soil mass-to-solution ratio, the behaviour of the thus characterized soil-As(v) system can be predicted for a range of conditions. Simulations showed that in an accidental As(v) spill the soil studied would actively scavenge As(v) by instantaneous adsorption onto all soil phases followed by redistribution of As(v) from weaker binding sites to stronger ones over time.     

Usefulness of Mehlich-3 test in the monitoring of phosphorus dispersion from Polish arable soils

A considerable area of soils with low abundance of plant-available phosphorus and relatively low consumption of phosphorus fertilisers recorded in Poland over the last 20–25 years suggests that the dispersion of phosphates from arable soils in Poland can be low. The literature, however, provides reports on a considerable share of Polish agriculture in phosphorus pollution of Baltic Sea waters. The literature provides no data concerning phosphorus sorption parameters of arable soils in Poland. Due to this, the study involved the analysis of sorption properties: 1-point phosphorus sorption index (PSI) and degree of phosphorus saturation, based on molar ratio P, Al, and Fe determined by the Mehlich-3 method (DPS-1_M3?=?P / (Al?+?Fe) and DPS-2_M3?=?P / Al), 59 soils representing the main types of texture of soils in Poland, characterised by variable content of plant-available phosphorus by Egner-Riehm DL, organic carbon, and soil pH. The obtained results suggest that the soil texture has a lower effect on sorption properties (PSI) than the degree of acidification. Sorption parameters of soils increased with soil acidification as a result of an increase in the content of Al and Fe extracted by the Mehlich-3 extract in strongly acidified soils. An important finding of our study was evidencing that within the same class of abundance in plant-available phosphorus, the soils varied in the degree of phosphorus saturation and content of active phosphorus. This suggests the possibility of losses of phosphorus even from soils with low abundance of the component provided they are characterised by a high value of parameters DPS-1_M3 and DPS-2_M3.     

Antimony speciation in soil samples along two Austrian motorways by HPLC-ID-ICP-MS

Distribution of antimony and its inorganic species in soil samples along two traffic routes (A14, Rankweil and S36, Knittelfeld) in Austria was determined, since vehicle emissions are an important anthropogenic source of Sb in soil. The samples were taken along three parallel lines at about 0.2, 2 and 10 m distances from the edge of the road and in two depths range (0-5 and 5-10 cm from the soil surface). The optimized extraction was carried out using 100 mmol L(-1) citric acid at pH 2.08 applying an ultrasonic bath for 45 min at room temperature. Speciation analyses were done using on-line isotope dilution after a chromatographic separation of Sb species. Results of the two traffic routes confirmed significant accumulations of Sb at surface (0-5 cm depth) exceeding the natural background values by more than ten times at the S36 or four times at the A14. Concentrations of the extractable inorganic species decreased to natural background levels within a few meters from the edge of the traffic lane. The predominant Sb species was Sb(V). The Sb(III) concentrations at 5-10 cm depths range are nearly constant with distance from the edges of the two roads. Magnetic susceptibility data of all soil samples show the same distribution pattern as Sb and Sb(V) concentrations along the two traffic roads with an excellent correlation. This is an evidence for an anthropogenic source of Sb such as abrasions of motor vehicles surfaces or braking linings. The input of Sb and its inorganic species at one of the sampling sites (Knittelfeld) in samples taken in 2002 and in those taken recently (2005) was monitored. An increase in Sb (>or=30%), Sb(v)(>or=51%) and Sb(iii)(>or=10%) concentrations was only observed near the edge (相似文献   

Adsorption–desorption of metolachlor and atrazine in Indian soils: effect of fly ash amendment

The effect of two fly ashes as soil amendment on the adsorption–desorption of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylphenyl)] and atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was studied in alluvial and laterite soils. The adsorption data for both the herbicides fitted well the Freundlich equation, and Freundlich adsorption coefficient (K _f) increased with an increase of fly ash amount. Both the fly ashes differed in their extent to increase herbicide sorption, and the effect was different in different soils. Atrazine was sorbed more in the soils/soils?+?fly ash mixtures than the metolachlor. The K _f values showed significant correlation with the amount of fly ash amendment (correlation coefficient, R?>?0.982). The desorption isotherms also fitted the Freundlich equation, and desorption showed hysteresis which increased with an increase in the content of fly ash amendment. The free energy change (ΔG) indicated that the sorption process is exothermic, spontaneous, and physical in nature. The study has shown that fly ash as soil amendment significantly increased the sorption of metolachlor and atrazine, but the effect is soil- and fly ash-specific.     

Sorption of carbon tetrachloride,ethylene dibromide,and trichloroethylene on soil and clay

The sorption of carbon tetrachloride, ethylene dibromide, and trichloroethylene in two silty clay loam soils and aluminium (Al³⁺) or calcium (Ca²⁺) saturated montmorillonite clay was studied. When the adsorbents were exposed to environmental levels of these chemicals (10 to 1000 ppb in water) the amounts of each of the chemicals sorbed were 6% or less of that available except for a 17% sorption of trichloroethylene by Al-saturated clay. In the case of the Ca-saturated clay, there was no apparent sorption of carbon tetrachloride or trichloroethylene. When soil sorption was normalized based on the soil organic carbon content (K _oc) a correlation was found between the K _oc, water solubility, and octanol/water partitioning coefficients of the chemicals. However, carbon tetrachloride did not behave according to with the predicted relationships.     

Effects of pH and low molecular weight organic acids on competitive adsorption and desorption of cadmium and lead in paddy soils

The bioavailability and ultimate fate of heavy metals in the environment are controlled by adsorption-desorption process. Batch equilibrium experiments were performed to assess the effects of pH and low molecular weight organic acids (LMWOAs) on competitive adsorption and desorption of cadmium and lead in paddy soils from China. The results indicated that both soils exhibited greater sorption capacity for lead (Pb) (1.37-1.61-fold) than cadmium (Cd) as estimated by the maximum sorption parameter (Q) from the Langmuir equation. The Langmuir bonding energy coefficient (b) and distribution coefficient (K (d)) were greater for Pb than for Cd, furthermore, b (binary) and K (d) (single) were greater than b (single) and K (d binary), indicating that competition for sorption sites promote the retention of both metals on more specific sorption sites. Both Cd and Pb desorption as a function of solution pH was characteristic of "S" pattern. The presence of LMWOAs inhibited Cd or Pb desorption at the low concentrations (≤0.1 mmol L(-1)) but promoted Cd and Pb desorption at higher concentrations (≥0.5 mmol L(-1) for citric acid and ≥1 mmol L(-1) for malic and oxalic acid). The two paddy soils had a greater d (Cd) than d (Pb) in the presence of LMWOAs, indicating that Cd desorption was more affected by the presence of LMWOAs in binary metal system.     

Baseline concentrations of trace elements in residential soils from Southeastern Missouri

Anthropogenic sources of pollution can significantly contribute to elevated concentrations of toxic elements in soils. A preliminary survey of trace elements content and their availability in residential soils from New Madrid County, Missouri was undertaken. Mean elemental concentrations (mg kg⁻¹, dry wt) of sixty two soil samples were: As 6.6, Be 0.8, Cd 1.6, Co 9.7, Cr 24.5, Cu 18.1, Fe 9951, Mn 298, Ni 15.6, Pb 48.8, V 42.1, Zn 95.5 and Hg 0.05. The US EPA preliminary remediation goals (PRGs) was only exceeded by As (7 % of samples) and V (8% of samples). The Missouri average background values were exceeded by Pb (69%), Zn (31%), Cu (27%), As (23%), Be (19%), Co (18%), Ni (16%), V (8%) and Mn (2%). Crustal enrichments (EF_c) for As (97), Cr (6), Cu (10), Pb (121), V (7), and Hg (17) were highest for North Lilbourn soils. Fractionation experiment revealed that Fe (54–79%) was in the residual phase while Zn (70–90%), Mn (88–92%), As (59–81%) and Pb (63–79%) were potentially available in soils. Factor loadings of the element concentrations on principal components 1, 2 and 3 accounted for over 81% variance of the data set. The factor loadings suggested that apart from natural contributions of trace elements to the soils, human activities possibly accounted for other inputs in soils.     

Methylated arsenic, antimony and tin species in soils

Methylated species of antimony, arsenic and tin were examined in urban soils of the Ruhr basin, near the cities of Duisburg and Essen, Germany. The main aim of this study was to investigate the occurrence of mono-, di- and trimethylated species of these elements in urban soils. The influence of historical and present land use upon the species content was examined. The distribution of inorganic As, Sb and Sn and their methylated species along the profile depth was investigated. As, Sb and Sn speciation was performed by pH-gradient hydride generation purge and trap gas chromatography, followed by inductively-coupled plasma mass spectrometry (HG-PT-GC/ICP-MS). Species' structures were confirmed by GC-EI/MS-ICP-MS. Monomethylated Sb and As were the dominant species detected: the concentration of these metal(loid) species varied between <0.07-56 microg kg(-1) per dry mass. All dimethylated species and monomethyltin concentrations were between <0.01-7.6 microg kg(-1) per dry mass, and for the trimethylated species of all examined elements, concentrations between <0.001-0.63 microg kg(-1) per dry mass were detected. The highest organometal(loid) concentrations were observed in agricultural soils and garden soils; lower concentrations were found in the soils of abandoned industrial sites (wasteland, primary forest and grassland) and a flood plain soil of the Rhine. This result can be ascribed to both the cultivation and the increased biological activity of the agricultural soils, and the generally higher contamination, the disturbed structure and the artificial substrates (deposits from industrial sources) of the abandoned industrial soils. Due to periodical sedimentation, the flood plain profile was the only one where no depth dependence of organometal(loid) species concentration was detected. The other soil profiles showed a decrease of species content with increasing depth; this was particularly noticeable in soils with a clear change from a horizon with an organic character towards a mineral horizon, i.e. decreasing vitality from profile top to bottom. It is not as yet clear whether the organometal(loid) species are formed in the mineral horizons of the profiles or whether they are displaced from the organic, biologically-active horizons towards the mineral horizons. Field studies revealed that soil parameters like pH, water content or temperature did not correlate significantly with the degree of biomethylation observed. In contrast to the lower in vitro biomethylation efficiency of Sb vs. As in microbial incubations, we consistently detected higher proportions of transformed Sb compounds in situ in soil samples. These data may indicate a need to re-examine the currently accepted model of Sb biogeochemical cycling in the real environment.     

广东某含铊硫酸冶炼堆渣场土壤中重金属的污染特征

选取广东某硫酸厂工业堆渣周围土壤样品,重点研究了土壤剖面T1、cd、Pb、Zn四种重金属元素总量及形态分布特征.研究结果表明,该废渣在自然淋滤条件下已经对周围土壤产生了T1、Cd、Pb、Zn污染,并且T1、Pb、Cd较Zn污染严重.形态分析表明,堆渣场周围土壤中这些重金属主要是以残渣态和铁锰氧化物(氢氧化物)结合态存在.外围土壤受到的这些重金属污染及对环境的潜在危害大于废渣下伏土壤,其中在堆渣下伏土壤中主要以富集为主,而外围土壤中主要以迁移为主,且已经向土壤深处约30cm处进行了迁移.这些重金属污染物在表层土壤中未达到饱和状态,将继续在下伏土壤表层发生累积作用并且使横向土壤受污染的范围进一步扩大.     

The role of humic non-exchangeable binding in the promotion of metal ion transport in groundwaters in the environment

Metal ions form strong complexes with humic substances. When the metal ion is first complexed by humic material, it is bound in an 'exchangeable' mode. The metal ion in this fraction is strongly bound, however, if the metal-humic complex encounters a stronger binding site on a surface, then the metal ion may dissociate from the humic substance and be immobilised. However, over time, exchangeably-bound metal may transfer to a 'non-exchangeable' mode. Transfer into this mode and dissociation from it are slow, regardless of the strength of the competing sink, and so immobilisation may be hindered. A series of coupled chemical transport calculations has been performed to investigate the likely effects of non-exchangeable binding upon the transport of metal ions in the environment. The calculations show that metal in the non-exchangeable mode will have a significantly higher mobility than that in the exchangeable mode. The critical factor is the ratio of the non-exchangeable first-order dissociation rate constant and the residence time in the groundwater column, metal ion mobility increasing with decreasing rate constant. A second series of calculations has investigated the effect of the sorption to surfaces of humic/metal complexes on the transport of the non-exchangeably bound metal. It was found that such sorption may reduce mobility, depending upon the humic fraction to which the metal ion is bound. For the more weakly sorbing humic fractions, under ambient conditions (humic concentration etc.) the non-exchangeable fraction may still transport significantly. However, for the more strongly sorbed fractions, the non-exchangeable fraction has little effect upon mobility. In addition to direct retardation, sorption also increases the residence time of the non-exchangeable fraction, giving more time for dissociation and immobilisation. The non-exchangeable dissociation reaction, and the sorption reaction have been classified in terms of two Damkohler numbers, which can be used to determine the importance of chemical kinetics during transport calculations. These numbers have been used to develop a set of rules that determine when full chemical kinetic calculations are required for a reliable prediction, and when equilibrium may be assumed, or when the reactions are sufficiently slow that they may be ignored completely.     

Monitoring of total and bioavailable heavy metals concentration in agricultural soils

The aim of this paper is to evaluate total and bioavailable concentration of heavy metals in agricultural soils in order to estimate their distribution, to identify the possible correlations among toxic elements and the pollution sources, to distinguish the samples in relation to sampling site or to sampling depth, and to evaluate the available fraction providing information about the risky for plants. In particular, we reinvestigated total concentrations of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V, and Zn and available concentrations of As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, and Zn in soil from Apulia (Southern Italy). Analytical results showed that total concentrations, for all soils, are in the range permitted by regulations in force in Italy, but some soils evidence slight enrichment of Cd, Cr, Cu, Pb, and Zn. All the heavy metals in the available fraction were below the detection limits of the analytical techniques used except Cu, Ni, Pb, and Zn.     

Effects of decaying wood on eluviation,podzolization, acidification,and nutrition in soils with different moisture regimes

One possible impact of large accumulations of decaying wood on forest sites is an increase in (1) eluviation, podzolization and acidification of, and (2) leaching and loss of nutrients from, the soil directly under decaying wood. As an exploratory investigation, we sampled soils beneath forest floors with and without large accumulations of decaying wood (lignic and algnic forest floors respectively) on three soil moisture regimes. Nine sites were located, three in each of central British Columbia, east Vancouver Island, and east of Vancouver. Among the moist sites, there were no differences in Ae horizon thickness between the alignic and lignic forest floors. However, the Ae horizon was thicker beneath the lignic forest floors (mean 4.2 cm) compared to the alignic forest floors (mean 0.7 cm) in slightly dry and fresh sites. Lignic and alignic forest floors differed (p<0.01) in pH, total C, total N, mineralizable N, available S, available P, extractable Mg, K and Ca, lipids, C in fraction B (soluble polysaccharide fraction), C in humic acid, C in fulvic acid, and polyphenol C in fulvic acid for all soil moisture regimes. There were no significant differences in the measures of nutrients or indicators of podzolization as measured by organically complexed Fe and Al, the total non-crystalline Fe and Al, and the poorly crystalline Fe and Al, in the underlying 10 cm of the Bf horizon between the two substrates regardless of the soil moisture regime. Further investigations are needed to establish the relationships between soil productivity and the observed soil chemical measures.