Global Centre for Environmental Remediation

Phytotoxicity of inorganic contaminants is influenced by the presence of competing ions at the site of uptake. In this study, interaction of soil pore-water constituents with arsenate toxicity was investigated in cucumber (Cucumis sativa L) using 10 contrasting soils. Arsenate phytotoxicity was shown to be related to soluble carbonate and phosphate. The data indicated that dissolved phosphate and carbonate had an antagonistic impact on arsenate toxicity to cucumber. To predict arsenate phytotoxicity in soils with a diverse range of soil solution properties, both carbonate and phosphate were required. The relationship between arsenic and pore-water toxicity parameters was established initially using multiple regression. In addition, based on the relationship with carbonate and phosphate we successively applied a terrestrial biotic ligand-like model (BLM) including carbonate and phosphate. Estimated effective concentrations from the BLM-like parametrization were strongly correlated to...

Since arsenic in groundwater was recognized as a potential threat to human life, much effort has been directed towards ensuring safe drinking water either through mitigation techniques or through finding alternative water sources. Even when alternate sources of water are ...

We report on a glassy carbon electrode modified with bismuth nanoparticles (NanoBiE) for the simultaneous determination Pb 2+ and Cd 2+ by anodic stripping voltammetry. Operational parameters such as bismuth nanoparticles labelling amount, deposition potential, deposition time and stripping parameters were optimized with respect to the determination of Pb 2+ and Cd 2+ in 0.1 M acetate buffer solution (pH 4.5). The NanoBiE gives well-defined, reproducible and sharp stripping peaks. The peak current response increases linearly with the metal concentration in a range of 5.0-60.0 μg L −1 , with a detection limit of 0.8 and 0.4 μg L −1 for Pb 2+ and Cd 2+ , respectively. The morphology and composition of the modified electrode before and after voltammetric measurements were analysed by scanning electron microscopy and energy dispersive X-ray analysis. The NanoBiE was successfully applied to analysis of Pb 2+ and Cd 2+ in real water samples and the method was validated by ICP-MS technique, suggesting that the electrode can be considered as an interesting alternative to the bismuth film electrode for possible use in electrochemical studies and electroanalysis.

Capillary zone electrophoresis (CZE) with UV detection was used to determine vanadium species. Nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA) and 2,6-pyridinedicarboxylic acid (PDCA) were investigated to determine whether these ligands formed stable anionic complexes with vanadium. Of all the ligands studied HEDTA was the most suitable ligand because it gave the largest UV response with reasonable migration time. Electrospray mass spectrometry (ES-MS) was used to confirm the formation of [VO 2 (HEDTA)] 2− and [VO(HEDTA)] 1− in solution. An electrolyte containing 25 mM phosphate, 0.25 mM tetradecyltrimethylammonium bromide (TTAB) at pH 5.5 was optimum for the separation of these anionic vanadium complexes. Sample stacking techniques, including large-volume sample stacking (LVSS) and field-amplified sample injection (FASI), were tested to improve the sensitivity. Best sensitivity was obtained using FASI, with detection limits of 0.001 M, equivalent to 0.4 g L −1 , for [VO 2 (HEDTA)] 2− and 0.01 M, equivalent to 3.4 g L −1 for [VO(HEDTA)] 1−. The utility of the method for the speciation of V(IV) and V(V) was demonstrated using ground water samples.

An on-column complexation method has been developed for the simultaneous determination of V(IV) and V(V). Vanadium species were chelated with aminopolycarboxylic acids to form anionic complexes which were separated by capillary zone electrophoresis (CZE) with direct UV detection. Ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentacetric acid (DTPA), nitrilotriacetic acid (NTA), and N-2-hydroxyethylethlendiaminetriacetric acid (HEDTA) were investigated as both ligand and running electrolyte. Of the ligands studied the complexes of EDTA with V(IV) and V(V) resulted in the highest selectivity and UV response. The conditions used for on-column complexation and separation, including pH, and electrolyte ligand concentration, were examined to achieve reasonable separation selectivity and detection sensitivity. The optimum separation of the anionic forms of V(IV) and V(V) was obtained by use of CZE with UV detection at 185 nm and an electrolyte containing 5 mmol L-1 EDTA at pH 4.0. Linear calibration plots were obtained in the concentration range 10-300 µmol L-1 ; detection limits were 3 µmol L-1 for V(IV) and 1 µmol L-1 for V(V). The proposed method was demonstrated for the determination of vanadium in groundwater spiked with V(IV) and V(V).

The effects of lime, fertilizer and manure applications on soil organic matter status and soil physical properties are of importance to agricultural sustainability. Their effects are complex and many interactions can occur. In the short-term, liming can result in dispersion of clay colloids and formation of surface crusts. As pH is increased the surface negative charge on clay colloids increases and repulsive forces between particles dominate. However, at higher lime rates, Ca 2+ concentrations and ionic strength in soil solution increase causing compression of the electrical double layer and renewed flocculation. When present in sufficient quantities, both lime and hydroxy-Al polymers formed by precipitation of exchangeable Al, can act as cementing agents bonding soil particles together and improving soil structure. Liming often causes a temporary flush of soil microbial activity but the effect of this on soil aggregation is unclear. It is suggested that, in the long-term, liming will increase crop yields, organic matter returns, soil organic matter content and thus soil aggregation. There is a need to study these relationships on existing long-term liming trials. Fertilizers are applied to soils in order to maintain or improve crop yields. In the long-term, increased crop yields and organic matter returns with regular fertilizer applications result in a higher soil organic matter content and biological activity being attained than where no fertilizers are applied. As a result, long-term fertilizer applications have been reported, in a number of cases, to cause increases in water stable aggregation, porosity, infiltration capacity and hydraulic conductivity and decreases in bulk density. Fertilizer additions can also have physico-chemical effects which influence soil aggregation. Phosphatic fertilizers and phosphoric acid can favour aggregation by the formation of Al or Ca phosphate binding agents whilst where fertilizer NH 4 + accumulates in the soil at high concentrations, dispersion of clay colloids can be favoured. Additions of organic manures result in increased soil organic matter content. Many reports have shown that this results in increased water holding capacity, porosity, infiltration capacity, hydraulic conductivity and water stable aggregation and decreased bulk density and surface crusting. Problems associated with large applications of manure include dispersion caused by accumulated K + , Na + and NH 4 + in the soil and production of water-repellant substances by decomposer fungi.

The MgAl-LDH adsorbent (2:1) was developed by the urea method and used as an adsorbent for the removal of methyl orange from aqueous solution. The synthesized adsorbent was characterized by a different analytical technique: scanning electron microscope SEM, X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The effect of adsorption parameters such as solution pH, initial concentration of dye, and the temperature was studied using a static system. X-ray diffraction analysis of the samples confirms the crystal structure of the MgAl-LDH material. The MgAl-LDH adsorbent was efficient in removing MO from aqueous solution, and maximum removal of 98.5 % was observed in the pH range from 2 to 10. The maximum adsorption capacity of MgAl-LDH (2:1) was calculated from the Langmuir isotherm; the maximum quantity is 1250 mg. g-1. The determination of the thermodynamic parameters indicates that the reaction between methyl orange and MgAl-LDH (2:1) is spontaneous and exothermic (ΔH°<0 and ΔG°<0).It can be concluded that LDH adsorbent can be used effectively for the removal of anionic dyes from industrial wastewater.

Organic surfactants modified clay minerals are usually used as adsorbents for hydrophobic organic contaminants remediation; this work however has shown organoclays can also work as adsorbents for hydrophilic anionic contaminant immobilization. Organoclays were prepared based on halloysite, kaolinite and bentonite and used for nitrate adsorption, which are significant for providing mechanism for the adsorption of anionic contaminants from waste water. XRD was used to characterize unmodified and surfactants modified clay minerals. Thermogravimetric analysis (TG) was used to determine the thermal stability and actual loading of surfactant molecules. Ion chromatography (IC) was used to determine changes of nitrate concentration before and after adsorption by these organoclays. These organoclays showed different removal capacities for anionic ions from water and adsorption mechanism was investigated.

Among the clay minerals, montmorillonite is the most extensively studied material using as adsorbents, but palygorskite and its organically modified products have been least explored for their potential use in contaminated water remediation. In this study, an Australian palygorskite was modified with cationic surfactants octadecyl trimethylammonium bromide and dioctadecyl dimethylammonium bromide at different doses. A full structural characterization of prepared organo-palygorskite by X-ray diffraction, infrared spectroscopy, surface analysis and thermogravimetric analysis was performed. The morphological changes of palygorskite before and after modification were recorded using scanning electron microscopy, which showed the surfactant molecules can attach on the surface of rod-like crystals and thus can weaken the interactions between palygorskite single crystals. Real surfactants loadings on organopalygorskites were also calculated based on thermogravimetric analysis. 1 CEC, 2 CEC octadecyl trimethylammonium bromide modified palygorskites, 1 CEC and 2 CEC dioctadecyl dimethylammonium bromide modified palygorskites absorbed as much as 12 mg/g, 42 mg/g, 9 mg/g and 25 mg/g of 2,4-dichlorophenoxyacetic acid respectively. This study has shown a potential on organo-palygorskites for organic herbicide adsorption especially anionic ones from waste water. In addition, equilibration time effects and the Langmuir and Freundlich models fitting were also investigated in details.

A bacterium, identified as Brevibacterium sp. MM1, readily hydrolysed fenamiphos, a widely used organophosphorus insecticide and its toxic oxides (fenamiphos sulfoxide, fenamiphos sulfone), which all contain a common P-O-C bond, in a mineral salts medium. The bacterium also hydrolysed fenamiphos and its oxides in soil and groundwater. Interestingly, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, formed during bacterial hydrolysis of fenamiphos and its oxides, persisted in the mineral salts medium, but were transitory in soil and groundwater due to their further metabolism by indigenous microorganisms. The cell-free preparation (crude enzyme) of this bacterium was very effective in hydrolysing fenamiphos. This is the first report on exceptionally rapid hydrolysis of fenamiphos by a bacterium in pure cultures, soil and groundwater.

This study was conducted to assess whether the addition of exogenous nutrients and bioaugmentation by arsenic (As) methylating fungi could accelerate the rate of As volatilisation in cattle dip soils containing mixed As and DDT contamination. Increasing levels of manure application resulted in a greater loss of As from contaminated soils [30% (w/w) > 15% (w/w) > 5% (w/w) manure]. Loss of As was more pronounced at 75% of field capacity than at 35% of field capacity. The supplement of 30% (w/w) manure at 75% field capacity exerted the greatest reduction of As (8.3% loss of total As) in a contaminated dip soil containing 1390 mg As kg −1 and 194 mg DDT kg −1 over a 5-month incubation. The rates of As loss and microbial respiration (CO 2 production) were correlated with the levels of manure amendment (P ≤ 0.05). Augmentation by As methylating fungi (Penicillium sp. and Ulocladium sp.) was able to enhance arsine evolution rates in field contaminated soils and in freshly spiked soils. The amounts of arsine dissipated in augmented long-term contaminated soils and soils spiked with As alone were 3.7 and 8.3 orders of magnitude greater than uninoculated soils, respectively. DDT appears to inhibit the rates of microbial formation of arsine in the contaminated dip soils.

One DDT-contaminated soil and two uncontaminated soils were used to enumerate DDT-resistant microbes (bacteria, actinomycetes and fungi) by using soil dilution agar plates in media either with 150 g DDT ml −1 or without DDT at different temperatures (25, 37 and 55 • C). Microbial populations in this study were significantly (p<0.001) affected by DDT in the growth medium. However, the numbers of microbes in long-term contaminated and uncontaminated soils were similar, presumably indicating that DDT-resistant microbes had developed over a long time exposure. The tolerance of isolated soil microbes to DDT varied in the order fungi>actinomycetes>bacteria. Bacteria from contaminated soil were more resistant to DDT than bacteria from uncontaminated soils. Microbes isolated at different temperatures also demonstrated varying degrees of DDT resistance. For example, bacteria and actinomycetes isolated at all incubation temperatures were sensitive to DDT. Conversely fungi isolated at all temperatures were unaffected by DDT.

Current knowledge of sorption processes in tropical soils is reviewed. Landscapes throughout the tropics are dominated by oxisols which occupy extensive areas of potentially highly productive soils. These soils are dominated by low-activity sesquioxide minerals and clays that have variable charge surfaces. The limited information on tropical soils available suggests that the composition of the ambient soil solution can influence sorption through changes in particle surface-charge density. Thus the observed decrease in sorption in the presence of divalent index cations may be related to the effect of ionic charge on the double-layer thickness which is manifested through a change in surface-charge characteristics. However, much work needs to be done to differentiate the effect of cation charge on surface-charge density from the competitive effect between the index cation and heavy-metal ions for the sorption sites. The effects of inorganic and organic ligands on adsorption of Cd by variable charge surfaces are also reviewed.

Petroleum hydrocarbons are widespread environmental pollutants. Although biodegradation of petroleum hydrocarbons has been the subject of numerous investigations, information on their toxicity to microorganisms in soil is limited, with virtually no work conducted on soil algae. We carried out a screening experiment for total petroleum hydrocarbons (TPH) and their toxicity to soil algal populations, microbial biomass, and soil enzymes (dehydrogenase and urease) in a long-term TPH-polluted site with reference to an adjacent unpolluted site. Microbial biomass, soil enzyme activity, and microalgae declined in medium to high-level (5,200-21,430 mg kg Ϫ1 soil) TPH-polluted soils, whereas low-level (Ͻ2,120 mg kg Ϫ1 soil) pollution stimulated the algal populations and showed no effect on microbial biomass and enzymes. However, inhibition of all the tested parameters was more severe in soil considered to have medium-level pollution than in soils that were highly polluted. This result could not be explained by chemical analysis alone. Of particular interest was an observed shift in the species composition of algae in polluted soils with elimination of sensitive species in the medium to high polluted soils. Also, an algal growth inhibition test carried out using aqueous eluates prepared from polluted soils supported these results. Given the sensitivity of algae to synthetic pollutants, alteration in the algal species composition can serve as a useful bioindicator of pollution. The results of this experiment suggest that chemical analysis alone is not adequate for toxicological estimations and should be used in conjunction with bioassays. Furthermore, changes in species composition of algae proved to be more sensitive than microbial biomass and soil enzyme activity measurements. Enormous quantities of petroleum and its products are produced annually, refined, and transported on land and sea across the world. Consequently, risks and concern over petroleum hydro

h i g h l i g h t s Vapour intrusion is a major exposure pathway for volatile hydrocarbons. Certainty in transport processes enhances vapour intrusion model precision. Detailed understanding of vadose zone vapour transport processes save resources. Variation of subsurface environment equitably affects vapour intrusion processes.

Abstract. A two-phase soil washing biosorption process was developed for the remediation of p, p - DDT-contaminated soil. The process involved desorption of contaminants from soil using dilute primary alcohols (40% 1-propanol) followed by contaminant removal from ...

Abstract. A bench scale, two-phase soil washing-biosorption process was developed for the remedi-ation of p,p -DDT-contaminated soil (containing 990 and 7750 mg kg−1 of p,p -DDT). Removal of p,p -DDT from contaminated soil was achieved by washing the soil ...