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Comparative kinetic desorption of 60Co, 85Sr and 134Cs from a contaminated natural silica sand column: influence of varying physicochemical conditions and dissolved organic matter.

In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces.

Adsorption↗

Persistent organic pollutants and sedimentary organic matter properties: a case study in the Kishon River, Israel.

The Kishon River, the second largest coastal river in Israel, has been severely polluted for several decades. Sediments from upstream and downstream sites of the river were analyzed, lipid-extracted and evaluated for phenanthrene uptake. Total polycyclic aromatic hydrocarbon (PAH) concentration in downstream sediments was 299 microg kg(-1), consisting mostly of petrogenic-derived PAHs. Downstream sedimentary lipids were found to be dominated by fresh and decomposed petroleum-derived n-alkanes. The total PAH concentration in upstream sediments was 173 microg kg(-1), consisting mostly of pyrogenic-derived PAHs, whereas lipids from these sediments were mostly vegetation-derived. Spectroscopic data suggested an exceptionally high aromatic content in downstream humic acid, which originated from PAHs attached to its structure. Sorption data suggested that upstream sedimentary cuticle-derived lipids function as a sorption domain, while downstream sedimentary lipids, consisting of shorter-chain-length petroleum-derived alkanes, compete with phenanthrene for sorption sites.

Adsorption↗

Removal of harmful cyanobacterial blooms in Taihu Lake using local soils. III. Factors affecting the removal efficiency and an in situ field experiment using chitosan-modified local soils.

Effects of ionic strength, pH, organic content, cell concentration, and growth phase on the removal of MA cells using chitosan-modified sepiolite were studied in the laboratory. The MA removal efficiency increased with the increase of salinity for normal clay flocculation. In contrast, for chitosan-modified clays/soils, MA removal efficiency increased with the decrease of salinity. The removal efficiency of chitosan-modified sepiolite was not significantly affected by pH (6-9), but dropped dramatically beyond pH 10. Humic acid had a small negative effect on the removal of MA cells. Cells were removed more effectively by clays around the early senescence growth phase than other growth stages. The removal efficiency increased as the cell concentration increased. In a field enclosure of Taihu Lake, a loading of 0.025 g/L chitosan-modified local soils removed 99% algal cells and no increase of chlorophyll-a was observed during the following one month's monitoring process.

Aluminum Silicates↗

Effects of added PAHs and precipitated humic acid coatings on phenanthrene sorption to environmental Black carbon.

Black carbon (BC; soot and charcoal) can be an extremely strong sorbent for organic compounds. In a previous study, sorption of d(10)-phenanthrene (d(10)-PHE) to BC in an unmodified contaminated sediment was found to be nine times less than that for BC isolated from this sediment. To find out the mechanism of this sorption attenuation (competition for BC sites between d(10)-PHE and native PAHs or blocking of BC sites by natural organic matter), we determined the effect on d(10)-PHE-BC sorption isotherms of additions of either PAHs or precipitated humic acid. Addition of humic acid did not significantly decrease BC sorption, whereas PAH additions (equal to the native PAH content in the original sediment) did, by about one order of magnitude. Therefore, competition between d(10)-PHE and the native PAHs could explain the whole attenuation of sorption to BC in unmodified sediments.

Adsorption↗

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm.

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.

Acetanilides↗

Linking organic pollutant (bio)availability with geosorbent properties and biomimetic methodology: a review of geosorbent characterisation and (bio)availability prediction.

The interdependent link between structure and physico-chemical properties of geosorbents and sorption activity of hydrophobic organic pollutants (HOC) upon interaction with solid matrices has been established. The conclusions derived from these investigations have not been actively incorporated into risk assessment and remediation protocols since legislators prefer to adopt a conservative approach when the potential of contaminants to be released from soil matrices are evaluated. With the advent of spectroscopic techniques, it is possible to determine the molecular properties of the geosorbent organic matter which play a pivotal role in HOC retention. Physical-chemical and biological methods are employed to predict the potential for HOC release from sorbent matrices. This article serves as a review discussing the literature and reports the progress that has been made in these particular areas. The implication of employing molecular descriptor factors correlated with a biomimetic method to assess availability and risk is also considered.

Adsorption↗

Degradation of polycyclic aromatic hydrocarbons (PAHs) in an aged coal tar contaminated soil under in-vessel composting conditions.

In-vessel composting of polycyclic aromatic hydrocarbons (PAHs) present in contaminated soil from a manufactured gas plant site was investigated over 98 days using laboratory-scale in-vessel composting reactors. The composting reactors were operated at 18 different operational conditions using a 3-factor factorial design with three temperatures (T, 38 degrees C, 55 degrees C and 70 degrees C), four soil to green waste ratios (S:GW, 0.6:1, 0.7:1, 0.8:1 and 0.9:1 on a dry weight basis) and three moisture contents (MC, 40%, 60% and 80%). PAH losses followed first order kinetics reaching 0.015 day(-1) at optimal operational conditions. A factor analysis of the 18 different operational conditions under investigation indicated that the optimal operational conditions for degradation of PAHs occurred at MC 60%, S:GW 0.8:1 and T 38 degrees C. Thus, it is recommended to maintain operational conditions during in-vessel composting of PAH-solid waste close to these values.

Coal Tar↗

Sequential extraction combined with isotope analysis as a tool for the investigation of lead mobilisation in soils: application to organic-rich soils in an upland catchment in Scotland.

Sequential extraction (modified BCR procedure) combined with isotope analysis has been investigated as a tool for assessing mobilisation of lead into streams at an upland catchment in NE Scotland. The maximum lead concentrations (up to 110 mg kg(-1) in air-dried soil) occurred not at the surface but at about 10 cm depth. The lowest (206)Pb/(207)Pb ratios in any profile occurred, with one exception, at 2.5-5 cm depth. In the one exception, closest to the only road in the area, significantly lower (206)Pb/(207)Pb ratios in the surface soil together with much increased chloride concentrations (in comparison to other surface waters) indicated the possible mobilisation of roadside lead and transfer to the stream. The (206)Pb/(207)Pb ratios in extractable fractions tended at depth towards the ratio measured in the residual phase but the ratios in the oxidizable fraction increased to a value higher than that of the residual phase.

Environmental Monitoring↗

Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay.

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV).

Adsorption↗

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing.

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.

Chelating Agents↗

Cosorption study of organic pollutants and dissolved organic matter in a soil.

In this study we have evaluated the effects of dissolved organic matter (DOM) on sorption of imidacloprid, 3,4-dichloroaniline (3,4-DCA) and 4-bromoaniline (4-BA) on a typical calcareous soil (Luvic Xerosol) from south-eastern Spain. Two different types of DOM were used, that is to say, dissolved natural organic matter extracts from a commercial peat (DNOM) and a high-purity tannic acid (TA) solution. The experiments were carried out in a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results indicated that the presence of both DNOM and TA, over a concentration range of 15-100 mg L(-1), produced an increase in the amount of 3,4-DCA and 4-BA sorbed and a decrease in the amount of imidacloprid retained on the soil studied. A modified distribution coefficient, K(doc), has been proposed as a safer parameter for soil sorption predictions of organic pollutants and it could be of help to model the fate of these in the environment.

Adsorption↗

Eco-toxicological studies of diesel and biodiesel fuels in aerated soil.

The goal of this study was to compare diesel fuel to biodiesel fuel by determining the toxicity of analyzed materials and by quantitatively evaluating the microbial transformation of these materials in non-adapted aerated soil. The toxicity levels were determined by measuring the respiration of soil microorganisms as well as the activity of soil dehydrogenases. The quantitative evaluation of biotransformation of analyzed materials was based on the principle of balancing carbon in the following final products: (a) carbon dioxide; (b) humus compounds; (c) the remainder of non-biodegraded analyzed material; and (d) intermediate biodegradation products and the biomass of microorganisms. The results of these studies indicate that diesel fuel has toxic properties at concentrations above 3% (w/w), while biodiesel fuel has none up to a concentration of 12% (w/w). The diesel fuel is more resistant to biodegradation and produces more humus products. The biodiesel is easily biotransformed.

Biodegradation, Environmental↗

Study of the trace metal ion influence on the turnover of soil organic matter in cultivated contaminated soils.

The role of metals in the behaviour of soil organic matter (SOM) is not well documented. Therefore, we investigated the influence of metals (Pb, Zn, Cu and Cd) on the dynamic of SOM in contaminated soils where maize (C4 plant) replaced C3 cultures. Three pseudogley brown leached soil profiles under maize with a decreasing gradient in metals concentrations were sampled. On size fractions, stable carbon isotopic ratio (delta13C), metals, organic carbon and nitrogen concentrations were measured in function of depth. The determined sequence for the amount of C4 organic matter in the bulk fractions: M3 (0.9)>M2 (0.4)>M1 (0.3) is in agreement with a significant influence of metals on the SOM turnover. New C4 SOM, mainly present in the labile coarser fractions and less contaminated by metals than the stabilised C3 SOM of the clay fraction, is more easily degraded by microorganisms.

Agriculture↗

Linking biosensor responses to Cd, Cu and Zn partitioning in soils.

Soils bind heavy metals according to fundamental physico-chemical parameters. Bioassays, using bacterial biosensors, were performed in pore waters extracted from 19 contrasting soils individually amended with Cd, Cu and Zn concentrations related to the EU Sewage Sludge Directive. The biosensors were responsive to pore waters extracted from Zn amended soils but less so to those of Cu and showed no toxicity to pore water Cd at these environmentally relevant amended concentrations. Across the range of soils, the solid-solution heavy metal partitioning coefficient (K(d)) decreased (p<0.01) with increasing amendments of Cu and Zn; Cu exhibited the highest K(d) values. Gompertz functions of Cu and Zn, K(d) values against luminescence explained the relationship between heavy metals and biosensors. Consequently, biosensors provide a link between biologically defined hazard assessments of metals and standard soil-metal physico-chemical parameters for determining critical metal loadings in soils.

Biosensing Techniques↗

Remediation efficiency of vapour extraction of sandy soils contaminated with cyclohexane: Influence of air flow rate, water and natural organic matter content.

This work reports the analysis of the efficiency and time of soil remediation using vapour extraction as well as provides comparison of results using both, prepared and real soils. The main objectives were: (i) to analyse the efficiency and time of remediation according to the water and natural organic matter content of the soil; and (ii) to assess if a previous study, performed using prepared soils, could help to preview the process viability in real conditions. For sandy soils with negligible clay content, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) the increase of soil water content and mainly of natural organic matter content influenced negatively the remediation process, making it less efficient, more time consuming, and consequently more expensive; and (ii) a previous study using prepared soils of similar characteristics has proven helpful for previewing the process viability in real conditions.

Air Movements↗

Physicochemical and biological characterisation of different dredged sediment deposit sites in France.

The aim of this work is to determine sediment properties, metal contents and transfers of Cd and Zn from dredged sediments to plants. To this end 10 deposit sites with different contexts were visited in France. The main agronomic characteristics and metal contents for surface soil layers were measured, the plant species present at the sites, such as Brassicaceae and Fabaceae, were listed, and the distribution of their root systems described. Soil characteristics such as available P (Olsen) varied between sites, with values ranging from 0.01 to 0.49 g kg(-1). Total contents and enrichment factors were studied, highlighting metal contamination in most of the sites. Despite carrying out principal component analyses, it was not possible to group deposits by age or geographical localisation. However, deposits could be distinguished as a function of proximity of industrial facilities, sediment grain size and carbonate content. Associations between metals were also highlighted: (1) Cd, Pb and Zn, and (2) Al, Cr, Cu and Fe. Consequently, we propose classifying them as technogenic anthrosols.

Aluminum↗

Distribution of sorbed phenanthrene and pyrene in different humic fractions of soils and importance of humin.

Contributions of fulvic-humic acids (FA/HA) and humin (HM) to sorption of phenanthrene (PHE) and pyrene (PYR) in a soil were differentiated using a humic separation procedure after multi-concentration sorption experiments. It was found that the amount of solutes in FA/HA did not change significantly after 48 h, while that in HM increased continuously and slowly up to the end of the experimental period (720 h), indicating that HM was the main region for slow sorption. Based on the fitting results using Freundlich equation, it was found that nonlinearity of both solutes was greater in HM than in FA/HA, consistent with the sorption characteristics of individually extracted HA and HM in a separate experiment. The observed nonlinearity of the solute distribution was confirmed by using three other soil samples with organic carbon contents ranging from 0.7 to 7.9%. Distribution dynamics of PHE and PYR among various fractions were also discussed.

Adsorption↗

Effects of pH, organic acids, and inorganic ions on lead desorption from soils.

The desorption characteristics of lead in two variable charge soils (one developed from Arenaceous rock (RAR) and the other derived from Quaternary red earths (REQ)) were studied, and the effects of pH value, organic acid, and competitive ions were examined. Desorption of Pb(2+) decreased from nearly 100.0 to 20.0% within pH 1.0-4.0 in both soils, and then the decrease diminished at pH > 4.0. Organic ligands at relatively low concentrations (< or =10(-3) mol L(-1)) slightly inhibited Pb(2+) desorption, but enhanced Pb(2+) desorption at higher concentrations. In this study, citric acid or acetic acid at higher concentrations (>10(-3) mol L(-1)) had the greatest improvement of Pb(2+) desorption, followed by malic acid; and the smallest was oxalic acid. Desorption of the adsorbed Pb(2+) increased greatly with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Pb(2+) desorption more than Zn(2+) at the same loading.

Acetic Acid↗