Recycling of EDTA solution after soil washing of Pb, Zn, Cd and As contaminated soil

Soil washing with EDTA is known to be an effective means of removing toxic metals from contaminated soil. A practical way of recycling of used soil washing solution remains, however, an unsolved technical problem. We demonstrate here, in a laboratory scale experiment, the feasibility of using acid precipitation to recover up to 50% of EDTA from used soil washing solution obtained after extraction of Pb (5330 mg kg⁻¹), Zn (3400 mg kg⁻¹), Cd (35 mg kg⁻¹) and As (279 mg kg⁻¹) contaminated soil. Up to 100% of EDTA residual in the washing solution and 100%, 97%, 98% and 100% of initial Pb, Zn, Cd and As concentration in the solution, respectively, were removed in an electrolytic cell using a graphite anode. We employed the recovered EDTA and treated washing solution to prepare recycled soil washing solution with the same potential for extracting toxic metals from soil as the original. The efficiency of soil washing depends on the EDTA concentration. Using twice recycled 30 mmol EDTA kg⁻¹ soil, we removed 44%, 20%, 53% and 61% of Pb, Zn, Cd and As, respectively, from contaminated soil.     

Photocatalytic oxidation of monuron in the suspension of WO3 under the irradiation of UV-visible light

A comprehensive study of the degradation of monuron, one of the phenylurea herbicides, was conducted by UV-Vis/WO₃ process. It was found that hydroxyl radicals played a major role in the decay of monuron while other radicals (e.g. superoxide) and hole might also contribute to the decomposition of monuron. The oxidation path likely plays a major role in the generation of hydroxyl radicals. The effects of initial pH level, initial concentration of monuron, and inorganic oxidants on the performance of UV-Vis/WO₃ process were also investigated and optimized. Comparison between monuron decay pathways by UV-Vis/WO₃ and UV/TiO₂ was conducted. The decay mechanisms, including N-terminus demethylation, dechlorination and direct hydroxylation on benzene ring, were observed to be involved in the oxidation of monuron in these two processes. Sixteen intermediates were identified during the photodegradation of monuron and degradation pathways were proposed accordingly.     

Catalytic destruction of pentachlorobenzene in simulated flue gas by a V2O5-WO3/TiO2 catalyst

Pentachlorobenzene (PeCB) in simulated flue gas was destructed by a commercial V₂O₅-WO₃/TiO₂ catalyst in this study. The effects of reaction temperature, oxygen concentration, space velocity and some co-existing pollutants on PeCB conversion were investigated. Furthermore, a possible mechanism for the oxidation of PeCB over the vanadium oxide on the catalysts was proposed. Results show that the increase of gas hourly space velocity (GHSV) and the decrease of operating temperature both resulted in the decrease of PeCB removal over the catalyst, while the effect of the oxygen content in the range of 5-20% (v/v) on PeCB conversion was negligible. PeCB decomposition could be obviously affected by the denitration reactions under the conditions because of the positive effect of NO but negative effect of NH₃. The introduction of SO₂ caused the catalyst poisoning, probably due to the sulfur-containing species formed and deposited on the catalyst surface. The PeCB molecules were first adsorbed on the catalyst surface, and then oxidized into the non-aromatic acyclic intermediates, low chlorinated aromatics and maleic anhydride.     

Identification of relevant micropollutants in Austrian municipal wastewater and their behaviour during wastewater treatment

The European Union has defined environmental quality standards (EQSs) for surface waters for priority substances and several other pollutants. Furthermore national EQSs for several chemicals are valid in Austria. The study investigated the occurrence of these compounds in municipal wastewater treatment plant (WWTP) effluents. In a first screening of 15 WWTPs relevant substances were identified, which subsequently were monitored in 9 WWTPs over 1 year (every 2 months). Out of 77 substances or groups of substances (including more than 90 substances) 13 were identified as potentially relevant in respect to water pollution and subjected to the monitoring, whereas most other compounds were detected in concentrations far below the respective EQS for surface waters and therefore not further considered. The preselected 13 compounds for monitoring were cadmium (Cd), nickel (Ni), copper (Cu), selenium (Se), zinc (Zn), diuron, polybrominated diphenyl ethers (PBDEs), di(ethyl-hydroxyl)phthalate (DEHP), tributyltin compounds (TBT), nonylphenoles (NP), adsorbable organic halogens (AOX) and the complexing agents ethylenediaminetetraacetic acid (EDTA) as well as nitrilotriacetic acid (NTA). In the effluents of WWTPs the concentrations of the priority substances Cd, NP, TBT and diuron frequently exceeded the respective EQS, whereas the concentrations for DEHP and Ni were below the respective EQS. The effluent concentrations for AOX, EDTA, NTA, Cu, Se and Zn frequently are in the range or above the Austrian EQS for surface waters. Besides diuron and EDTA all compounds are removed at least partially during wastewater treatment and for most substances the removal via the excess sludge is the major removal pathway. For the 13 compounds which were monitored in WWTP effluents population equivalent specific discharges were calculated. Since for many compounds no or only few information is available, these population equivalent specific discharges can be used to assess emissions from municipal WWTPs to surface waters as well as to make a first assessment of the impact of a discharge on surface waters chemical status. Comparing discharges and river pollution on a load basis, the influence of diffuse sources becomes obvious and therefore should also be taken into consideration in river management.     

Genotoxicity of sediment extracts of the Berre lagoon (France)

To evaluate the genotoxic risk that contaminated sediment could constitute for benthic organisms, three contaminated (VA, VC and VN) and one uncontaminated (RN) sediment samples were collected in the Berre lagoon (France). Potentially bioavailable contaminants in sediments were obtained using sediment extraction with synthetic seawater adjusted to pH 4 or pH 6, simulating the range of pH prevailing in the digestive tract of benthic organisms. The genotoxic activities of these extracts were evaluated by three short-term bioassays: the Salmonella mutagenicity test using the Salmonella typhimurium strain TA102, the alkaline comet assay and the micronucleus assay on the Chinese Hamster Ovary cells CHO-K1. Results of the Salmonella mutagenicity assay detected a mutagenic response for RN extract at pH 6, and for VA extract at pH 4. Results of the comet and micronucleus assays detected low genotoxic/clastogenic activities for VA and VC extracts at pH 6 and higher activities for RN, VA and VC extracts at pH 4. To identify if metals (Al, Fe, Mn, As, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn) were involved in these genotoxic activities, their concentrations were determined in the extracts, and their speciation was assessed by thermodynamic calculations. Results showed that extracts from sites VA, VC and VN generally presented the highest trace metal contents for both extractants, while the site RN presented lower trace metal contents but the highest Fe and Mn contents. Thermodynamic calculations indicated that Fe, Mn, As and in a lower extend Co, Ni and Zn were mainly present under free forms in extracts, and were consequently, more likely able to induce a genotoxic effect. Results globally showed no correspondence between free metal contents and genotoxic activities. They suggested that these positive results could be due to uncharacterized compounds, acting as direct genotoxic agents or enhancing the genotoxic properties of analyzed metals.     

The exposition of a calcareous Mediterranean soil to toxic concentrations of Cr, Cd and Pb produces changes in the microbiota mainly related to differential metal bioavailability

The involvement of the bacterial community of an agricultural Mediterranean calcareous soil in relation to several heavy metals has been studied in microcosms under controlled laboratory conditions. Soil samples were artificially polluted with Cr(VI), Cd(II) and Pb(II) at concentrations ranging from 0.1 to 5000 mg kg⁻¹ and incubated along 28 d. The lowest concentrations with significant effects in soil respirometry were 10 mg kg⁻¹ Cr and 1000 mg kg⁻¹ Cd and Pb. However, only treatments showing more than 40% inhibition of respirometric activity led to significant changes in bacterial composition, as indicated by PCR-DGGE analyses. Presumable Cr- and Cd-resistant bacteria were detected in polluted microcosms, but development of the microbiota was severely impaired at the highest amendments of both metals. Results also showed that bioavailability is an important factor determining the impact of the heavy metals assayed, and even an inverted potential toxicity ranking could be achieved if their soluble fraction is considered instead of the total concentration. Moreover, multiresistant bacteria were isolated from Cr-polluted soil microcosms, some of them showing the capacity to reduce Cr(VI) concentrations between 26% and 84% of the initial value. Potentially useful strains for bioremediation were related to Arthrobacter crystallopoietes, Stenotrophomonas maltophilia and several species of Bacillus.     

The chemical exploitation of nickel phytoextraction: An environmental, ecologic and economic opportunity for New Caledonia

Herein, we explore the outlines of an innovative method based on the chemical recovery of metal-rich biomass produced in phytoextraction technologies. Taking advantage of the adaptive capacity of some New Caledonian plants to hyperaccumulate Ni²⁺ cations in their aerial parts, this technique is based on the direct use of metals derived from plants as “Lewis acid” catalysts in organic chemistry. Metallic cations contained in New Caledonian nickel hyperaccumulators are recovered through a simple cost-effective process and serve the preparation of heterogeneous catalysts used in synthetic transformations allowing access to molecules with high added-value. The design of all processes is in line with the principles of green chemistry; it is adapted to the new economic constraints; it offers a new relevant outlet for metal-rich biomass; and it represents an alternative to non-renewable mineral materials.     

Effect of inoculation methods on the composting efficiency of municipal solid wastes

Four types of inoculation methods were studied during the composting of municipal solid wastes and dry grass (MSWG). The methods included a control group as well as initial-stage, two-stage, and multi-stage inoculations. Fulvic acids were extracted from the composting materials and characterized by spectroscopic techniques. The results showed that inoculation of microbes in MSWG enhanced the biodegradation of aliphatics, proteins, and polysaccharides. The inoculation also increased the molecular weight, humic- and fulvic-like compound content, as well as humification degree of the composting products. The inoculation of microbes in MSWG significantly improved composting process and efficiency. The improvement efficiency was in the order of initial-stage < two-stage < multi-stage inoculations. Inoculation of microbes based on composting organic matter composition and temperature enhanced composting efficiency.     

Distribution and bioavailability of ceria nanoparticles in an aquatic ecosystem model

Along with the increasing utilization of engineered nanoparticles, there is a growing concern for the potential environmental and health effects of exposure to these newly designed materials. Understanding the behavior of nanoparticles in the environment is a basic need. The present study aims to investigate the distribution and fate of ceria nanoparticles in an aquatic system model which consists of sediments, water, hornworts, fish and snails, using a radiotracer technique. Concentrations of ceria in the samples at regular time intervals were measured. Ceria nanoparticles were readily removed from the water column and partitioned between different organisms. Both snail and fish have fast absorption and clearance abilities. Hornwort has the highest bioaccumulation factors. At the end of the experiment, sediments accumulated most of the nanoparticles with a recovery of 75.7 ± 27.3% of total ceria nanoparticles, suggesting that sediments are major sinks of ceria nanoparticles.