Modelling 2,4-dichlorophenol bioavailability and bioaccumulation by the freshwater fingernail clam Sphaerium corneum using artificial particles and humic acids

The complex and variable composition of natural sediments makes it very difficult to predict the bioavailability and bioaccumulation of sediment-bound contaminants. Several approaches have been proposed to overcome this problem, including an experimental model using artificial particles with or without humic acids as a source of organic matter. For this work, we have applied this experimental model, and also a sample of a natural sediment, to investigate the uptake and bioaccumulation of 2,4-dichlorophenol (2,4-DCP) by Sphaerium corneum. Additionally, the particle-water partition coefficients (K(d)) were calculated. The results showed that the bioaccumulation of 2,4-DCP by clams did not depend solely on the levels of chemical dissolved, but also on the amount sorbed onto the particles and the characteristics and the strength of that binding. This study confirms the value of using artificial particles as a suitable experimental model for assessing the fate of sediment-bound contaminants.     

Bioaccumulation of 14C-17alpha-ethinylestradiol by the aquatic oligochaete Lumbriculus variegatus in spiked artificial sediment

A bioaccumulation study was performed with the endobenthic freshwater oligochaete Lumbriculus variegatus MULLER exposed to the radiolabelled synthetic steroid 17alpha-ethinylestradiol (14C-EE2) in a spiked artificial sediment. Concentration of total radioactivity increased constantly and almost linearly during 35 days of exposure. The accumulation factor normalised to worm lipid content and sediment TOC (AFlipid/OC) was 75 at the end of the uptake period, but a steady state was not reached. Uptake kinetics were calculated fitting the measured AFs to a kinetic rate equation for constant uptake from sediment using iterative non-linear regression analysis. After 10 days of elimination in contaminant-free sediment 50% of the accumulated total radioactivity was excreted by the worms. Extracts from L. variegatus sampled at the end of the uptake phase were analysed by thin layer chromatography (TLC). The results showed that 6% of the total radioactivity incorporated by the worms was 14C-EE2. After treatment of extracts with beta-glucuronidase the amount of 14C-EE2 increased to 84%. These results suggest that L. variegatus has the potency to accumulate high amounts of conjugated EE2. Hence, a transfer of EE2 to benthivores and subsequent secondary poisoning of predators might be possible.     

Use of whole-body and subcellular Cu residues of Lumbriculus variegatus to predict waterborne Cu toxicity to both L. variegatus and Chironomus riparius in fresh water

We tested the use of whole-body and subcellular Cu residues (biologically-active (BAM) and inactive compartments (BIM)), of the oligochaete Lumbriculus variegatus to predict Cu toxicity in fresh water. The critical whole-body residue associated with 50% mortality (CBR₅₀) was constant (38.2-55.6 μg g⁻¹ fresh wt.) across water hardness (38-117 mg L⁻¹ as CaCO₃) and exposure times during the chronic exposure. The critical subcellular residue (CSR₅₀) in metal-rich granules (part of BIM) associated with 50% mortality was approximately 5 μg g⁻¹ fresh wt., indicating that Cu bioavailability is correlated with toxicity:subcellular residue is a better predictor of Cu toxicity than whole-body residue. There was a strong correlation between the whole-body residue of L. variegatus (biomonitor) and survival of Chironomus riparius (relatively sensitive species) in a hard water Cu co-exposure. The CBR₅₀ in L. variegatus for predicting mortality of C. riparius was 29.1-45.7 μg g⁻¹ fresh wt., which was consistent within the experimental period; therefore use of Cu residue in an accumulator species to predict bioavailability of Cu to a sensitive species is a promising approach.     

Influence of soil ageing on bioavailability and ecotoxicity of lead carried by process waste metallic ultrafine particles

Ultrafine particulate matters enriched with metals are emitted into the atmosphere by industrial activities and can impact terrestrial and aquatic ecosystems. Thus, this study investigated the environmental effects of process particles from a lead-recycling facility after atmospheric deposition on soils and potential run-off to surface waters. The toxicity of lead-enriched PM for ecosystems was investigated on lettuce and bacteria by (i) germination tests, growth assays, lead transfer to plant tissues determination and (ii) Microtox analysis.The influence of ageing and soil properties on metal transfer and ecotoxicity was studied using three different soils and comparing various aged, spiked or historically long-term polluted soils. Finally, lead availability was assessed by 0.01 M CaCl₂ soil extraction.The results showed that process PM have a toxic effect on lettuce seedling growth and on Vibrio fischeri metabolism. Soil-PM interactions significantly influence PM ecotoxicity and bioavailability; the effect is complex and depends on the duration of ageing. Solubilisation or stabilisation processes with metal speciation changes could be involved. Finally, Microtox and phytotoxicity tests are sensitive and complementary tools for studying process PM ecotoxicity.     

土壤中Pb、Cd的稳定化修复技术研究进展

在众多重金属修复技术当中,稳定化技术具有花费少、环境损失小等诸多优势。综述了国内外土壤中Pb、Cd稳定化修复的研究进展;分析了稳定剂的作用机制、土壤中Pb、Cd的赋存形态;探讨了土壤中Pb、Cd稳定化修复的主要影响因素。最后,还提出了稳定化修复技术在土壤中Pb、Cd污染治理应用中尚存在的问题。     

The effects of chemical remediation treatments on the extractability and speciation of cadmium and lead in contaminated soils

Two rural soils contaminated by cadmium (Cd) and lead (Pb) were used to evaluate the effect of different chemical treatments on changes in speciation and extractability of Cd and Pb, and in phytoavailability to wheat. Triplicates of seven chemical treatments were tested to compare and evaluate the remediation techniques for contaminated soils using pot experiments. Treatments applied were calcium carbonate, a high quantity of phosphate salt, hog composts, iron oxide, manganese oxide, zeolite, and unamended control. Wheat (Triticum aestivum) was planted in the different amended soils for a further one month to evaluate the effectiveness of treatments on uptake of Cd and Pb by the wheat shoots. Results indicated that addition of calcium carbonate, manganese oxide, or zeolite reduces the extractability of Cd or Pb in both soils, and significantly reduce the uptake of Cd and Pb by wheat shoots. Changes in the extractability and metal sequential fractionations indicate that the exchangeable (or available) form of Cd and Pb in two soils can be transformed into unavailable forms after these amendments.     

DNAPL remediation with in situ chemical oxidation using potassium permanganate. II. Increasing removal efficiency by dissolving Mn oxide precipitates

In situ chemical oxidation (ISCO) schemes using MnO4- have been effective in destroying chlorinated organic solvents dissolved in ground water. Laboratory experiments and field pilot tests reveal that the precipitation of Mn oxide, one of the reaction products, causes a reduction of permeability, which can lead to flow bypassing and inefficiency of the scheme. Without a solution to this problem of plugging, it is difficult to remove DNAPL from the subsurface completely. In a companion paper, we showed with batch experiments that Mn oxide can be dissolved rapidly with certain organic acids. This study utilizes 2-D flow-tank experiments to examine the possibility of nearly complete DNAPL removal by ISCO with MnO4-, when organic acids are used to remove Mn oxide. The experiments were conducted in a small 2-D glass flow tank containing a lenticular silica-sand medium. Blue-dyed trichloroethylene (TCE) provided residual, the perched and pooled DNAPL. KMnO4 at 200 mg/l was flushed through the DNAPL horizontally. Once plugging reduced permeability and prevented further delivery of the oxidant, citric or oxalic acids were pumped into the flow tank to dissolve the Mn oxide precipitates. Organic ligands removed the Mn oxide precipitates relatively quickly, and permitted another cycle of MnO4- flooding. Cycles of MnO4-/acid flooding continued until all of the visible DNAPL was removed. The experiments were monitored with chemical analysis and visualization. A mass-balance calculation indicated that by the end of the experiments, all the DNAPL was removed. The results show also how heterogeneity adds complexity to initial redistribution of DNAPL, and to the efficiency of the chemical flooding.     

Bioaccumulation of paraquat by Lumbriculus variegatus in the presence of dissolved natural organic matter and impact on energy costs, biotransformation and antioxidative enzymes

Dissolved organic matter from natural sources (DNOM) is omnipresent in aquatic ecosystems. Besides affecting bioavailability of substances including xenobiotics, it directly influences physico-chemistry of the habitat and there is increasing evidence for it is interaction with organisms. We investigated direct and interacting effects of DNOM from three sources, Lake Valkea-Kotinen, Svartberget Brook, and Lake Fuchskuhle with the herbicide paraquat on the oligochaete worm Lumbriculus variegatus. Bioavailability of paraquat to L. variegates as well as activities of antioxidative enzymes catalase (CAT) and peroxidase (POD) and biotransformation enzyme soluble glutathione S-transferase (sGST) were assessed without and in the presence of DNOM. Furthermore, metabolic heat dissipation due to the exposure was quantified. Uptake of paraquat into the worms was concentration dependently reduced by DNOM, and with differences concerning the DNOM sources. sGST and CAT responded with increased activities to DNOM (5 and 25 mg C l-1) and paraquat (5.0, 50, and 500 microg l-1) separately. Paraquat at 5.0 microg l-1 and DNOM in combination caused increased activities of sGST, especially at 5 mgC l-1, but inhibition of CAT activities. The latter probably occurred due to saturation of the enzyme. Changes in enzyme activities were independent from the source of DNOM. Increasing DNOM concentrations raised metabolic heat dissipation in L. variegatus with maximum at 3h of exposure. In the combined treatments, metabolic heat dissipation changed more due to the source of DNOM than due to the bioavailability of paraquat.     

DNAPL remediation with in situ chemical oxidation using potassium permanganate. Part I. Mineralogy of Mn oxide and its dissolution in organic acids

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 A. The chemical formula is K(0.854)Mn(1.786)O(4).1.55H(2)O. It has a relatively small specific surface area at 23.6+/-0.82 m(2)/g. Its point of zero charge (pzc) was measured as 3.7+/-0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m(2)/h for citric acid, 1.35 mM/m(2)/h for oxalic acid, and 5.176 mM/m(2)/h for EDTA. These rates compare with 0.0025 mM/m(2)/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant potential in using these organic acids to remove precipitates formed during the oxidation reaction.     

Bench-scale visualization of DNAPL remediation processes in analog heterogeneous aquifers: surfactant floods and in situ oxidation using permanganate

We have conducted well-controlled DNAPL remediation experiments within a 2-D, glass-walled, sand-filled chamber using surfactants (Aerosol MA and Tween 80) to increase solubility and an oxidant (permanganate) to chemically degrade the DNAPL. Initial conditions for each remediation experiment were created by injecting DNAPL as a point source at the top of the chamber and allowing the DNAPL to migrate downward through a water-filled, heterogeneous, sand-pack designed to be evocative of a fluvial depositional environment. This migration process resulted in the DNAPL residing as a series of descending pools. Lateral advection across the chamber was used to introduce the remedial fluids. Photographs and digital image analysis illustrate interactions between the introduced fluids and the DNAPL. In the surfactant experiments, we found that DNAPL configured in a series of pools was easily mobilized. Extreme reductions in DNAPL/water interfacial tension occurred when using the Aerosol MA surfactant, resulting in mobilization into low permeability regions and thus confounding the remediation process. More modest reductions in interfacial tension occurred when using the Tween 80 surfactant resulting in modest mobilization. In this experiment, capillary forces remained sufficient to exclude DNAPL migration into low permeability regions allowing the excellent solubilizing properties of the surfactant to recover almost 90% of the DNAPL within 8.6 pore volumes. Injection of a potassium permanganate solution resulted in precipitation of MnO2, a reaction product, creating a low-permeability rind surrounding the DNAPL pools. Formation of this rind hindered contact between the permanganate and the DNAPL, limiting the effectiveness of the remediation. From these experiments, we see the value of performing visualization experiments to evaluate the performance of proposed techniques for DNAPL remediation.     

Physicochemical and biological quality of soil in hexavalent chromium-contaminated soils as affected by chemical and microbial remediation

Chemical and microbial methods are the main remediation technologies for chromium-contaminated soil. These technologies have progressed rapidly in recent years; however, there is still a lack of methods for evaluating the chemical and biological quality of soil after different remediation technologies have been applied. In this paper, microbial remediation with indigenous bacteria and chemical remediation with ferrous sulphate were used for the remediation of soils contaminated with Cr(VI) at two levels (80 and 1,276 mg kg^?1) through a column leaching experiment. After microbial remediation with indigenous bacteria, the average concentration of water-soluble Cr(VI) in the soils was reduced to less than 5.0 mg kg^?1. Soil quality was evaluated based on 11 soil properties and the fuzzy comprehensive assessment method, including fuzzy mathematics and correlative analysis. The chemical fertility quality index was improved by one grade using microbial remediation with indigenous bacteria, and the biological fertility quality index increased by at least a factor of 6. Chemical remediation with ferrous sulphate, however, resulted in lower levels of available phosphorus, dehydrogenase, catalase and polyphenol oxidase. The result showed that microbial remediation with indigenous bacteria was more effective for remedying Cr(VI)-contaminated soils with high pH value than chemical remediation with ferrous sulphate. In addition, the fuzzy comprehensive evaluation method was proven to be a useful tool for monitoring the quality change in chromium-contaminated soils.     

Assessment of the bioavailability of rare earth elements in soils by chemical fractionation and multiple regression analysis

The bioavailability of rare earth elements (REEs) in soils was evaluated, based on the combination of chemical fractionation and multiple regression analysis. REEs in soils were partitioned by a sequential extraction procedure into water soluble (F(ws)), exchangeable (F(ec)), bound to carbonates (F(cb)), bound to organic matter (F(om)), bound to Fe-Mn oxides (F(fm)) and residual (F(rd)) fractions. Alfalfa (Medicago Staiva Linn.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 35 days. The concentrations of REEs in fractions and plant were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Chemical fractionation showed that (F(ws)) fraction of REEs was less than 0.1% and residual (F(rd)) was the dominant form, more than 60% in soils. Bioaccumulation of REEs was observed in Alfalfa. REE availability to the plant was evaluated by multiple regression analysis. F(ws), F(ec), F(cb) and F(om) fractions were significantly correlated with REE uptake by alfalfa. But the exchangeable Pr(F(ec)) was significantly correlated with Pr concentration in alfalfa. F(ec), F(cb) and F(om) greatly contributed to La and Nd bioavailability; F(ec) and F(om) to Ce, Gd and Dy; F(ec) and F(cb) to Yb; and F(ws), F(ec) and F(om) to total REEs. This meant that the bioavailability of different species of REEs varied with individual REE. The results of this study indicated that the sequential extraction procedure, in conjunction with multiple regression analysis, may be useful for the prediction of plant uptake of REEs from soils.     

Recombinant luminescent bacterial sensors for the measurement of bioavailability of cadmium and lead in soils polluted by metal smelters

Environmental hazard of heavy metals in soils depends to a large extent on their bioavailability. The approach used in this study enables the determination of bioavailable metals in solid-phase samples. Two recombinant bacterial sensors, one responding specifically to cadmium and the other to lead and cadmium by increase of luminescence (firefly luciferase was used as a reporter) were used to determine the bioavailability of these metals in soil-water suspensions (a contact assay) and respective particle-free extracts. Fifty agricultural soils sampled near zinc and lead smelters in the Northern France containing up to (mg/kg) 20.1 of Cd, 1050 of Pb and 1390 of Zn were analysed. As the soil matrix interferes with the assay, recombinant luminescent control bacteria lacking the metal recognizing protein and corresponding promoter (thus, being not metal-inducible) but otherwise comparable to the sensor bacteria (the same host bacterium and plasmid encoding luciferase) were used in parallel to take into account the possible quenching and/or stimulating effects of the sample on the luminescence of the sensor bacteria. Both, chemical and sensor analysis showed that only microg/l levels of metals were extracted from the soil into the water phase (0.1% of the total Cd, 0.07% of Pb and 0.5% of Zn). However, 115-fold more Cd and 40-fold more Pb proved bioavailable if the sensor bacteria were incubated in soil suspensions (i.e., in the contact assay). The bioavailability of metals in different soils varied (depending probably on soil type) ranging from 0.5% to 56% for cadmium and from 0.2% to 8.6% for lead.     

Identification of particles containing chromium and lead in road dust and soakaway sediment by electron probe microanalyser

Individual particles containing Cr and/or Pb and other major components were identified in road dust from a heavily used road (hereinafter 'heavy traffic road dust'), road dust from a residential area and soakaway sediment by electron probe microanalyser to locate their sources and carrier particles. Individual particles containing high levels of Cr and/or Pb (>or=0.2%) were identified using wavelength dispersive spectrometry (WDS) map analysis. Chromium, Pb and other major elements were then determined by means of a combination of WDS and energy-dispersive spectrometry in all identified particles, 50 particles containing neither Cr nor Pb from each type of road dust and soakaway sediment, and yellow road line markings. WDS map analysis revealed that many particles containing both Cr and Pb were present among the identified particles in heavy traffic road dust, whereas they were minor components in road dust from the residential area and soakaway sediment. The plots of X-ray intensities of Cr vs. Pb were linear for the identified particles containing both Cr and Pb in heavy traffic road dust, and the line closely fitted the plots for the three yellow road line marking samples. Individual particles were then classified using cluster analysis of element components. The results revealed that the adsorption of source materials or released metals onto soil minerals occurred in road dust and soakaway sediment, that the yellow road line markings were sources of Cr and Pb in heavy traffic road dust, and that materials containing Fe as a major component, such as stainless steel, were additional sources of Cr in both road dust and soakaway sediment.     

Enhanced remediation of dioxins-spiked soil by a plant-microbe system using a dibenzofuran-degrading Comamonas sp. and Trifolium repens L

In this study, rhizoremediation technology was applied to dioxins-spiked soil. A dibenzofuran-degrading bacterium Comamonas sp. strain KD7, reported in the previous paper, was used in combination with white clover (Trifolium repens L.). First, the effect of strain KD7 on clover seed germination and root elongation was examined in the presence of dioxins compounds. As a result, the white clover seeds inoculated with strain KD7 exhibited a higher germination efficiency and increased root elongation compared with uninoculated white clover. Next, the recovery efficiency of two extraction methods were considered for analyzing the dioxin concentration in soil samples, then, the potential of the plant-microbe combination was evaluated for the remediation of dioxins-spiked soil. After 12 week of growth, significant reductions in the soil were confirmed for most compounds. Our results demonstrated that clover can function as a carrier in order to increase the dioxin-degrading activity of strain KD7. The association of clover and strain KD7 is considered to be a potential tool in the remediation of dioxin-contaminated soil.     

Development of a technique for the determination of lead and bromine in atmospheric particles by X-ray fluorescence

A methodology has been developed for determining the lead and bromine content of atmospheric particles collected on membrane filters. In a novel calibration procedure, standards were prepared by drying fine precipitates of lead molybdate and silver bromide on to filters. Such standards were evidently free from bromine loss during analysis and storage, and more accurately represent real samples than conventional solution-impregnated filters. Elemental loadings in the range 0.1–10μg could be measured. Inhomogeneous efficiency of detection across the surface of samples was noted, and was accounted for by applying correction factors obtained from an intercomparison of XRF and atomic absorption analyses. Good comparability between Br determinations by XRF and neutron activation analysis was found. Problems of noncomparability between standards and samples of low concentration were noted in some cases.     

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe⁰, Fe/Ni, Fe₃O₄, Fe_3???x Ni _x O₄). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H₂O₂ or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe₃O₄) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe⁰ and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe⁰ and Fe/Ni (18–19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250–500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.     

Removal of arsenic from drinking water by chemical precipitation--a modeling and simulation study of the physical-chemical processes.

A dynamic mathematical model was developed for removal of arsenic from drinking water by chemical coagulation-precipitation and was validated experimentally in a bench-scale set-up. While examining arsenic removal efficiency of the scheme under different operating conditions, coagulant dose, pH and degree of oxidation were found to have pronounced impact. Removal efficiency of 91-92% was achieved for synthetic feed water spiked with 1 mg/L arsenic and pre-oxidized by potassium permanganate at optimum pH and coagulant dose. Model predictions corroborated well with the experimental findings (the overall correlation coefficient being 0.9895) indicating the capability of the model in predicting performance of such a treatment plant under different operating conditions. Menu-driven, user-friendly Visual Basic software developed in the study will be very handy in quick performance analysis. The simulation is expected to be very useful in full-scale design and operation of the treatment plants for removal of arsenic from drinking water.     

Modeling of carbon dioxide fixation by microalgae using hybrid artificial intelligence (AI) and fuzzy logic (FL) methods and optimization by genetic algorithm (GA)

Environmental Science and Pollution Research - In this study, we are reporting a novel prediction model for forecasting the carbon dioxide (CO2) fixation of microalgae which is based on the hybrid...