Geoenvironmental factors related to high incidence of human urinary calculi (kidney stones) in Central Highlands of Sri Lanka

An area with extremely high incidence of urinary calculi was investigated in the view of identifying the relationship between the disease prevalence and the drinking water geochemistry. The prevalence of the kidney stone disease in the selected Padiyapelella–Hanguranketa area in Central Highlands of Sri Lanka is significantly higher compared with neighboring regions. Drinking water samples were collected from water sources that used by clinically identified kidney stone patients and healthy people. A total of 83 samples were collected and analyzed for major anions and cations. The anions in the area varied in the order HCO₃ ^? > Cl^? > SO₄ ^2? > NO₃ ^? and cations varied in the order Ca²⁺ > Mg²⁺ > Na⁺ > K⁺ > Fe²⁺. The dissolved silica that occurs as silicic acid (H₄SiO₄) in natural waters varied from 8.8 to 84 mg/L in prevalence samples, while it was between 9.7 and 65 mg/L for samples from non-prevalence locations. Hydrogeochemical data obtained from the two groups were compared using the Wilcoxon rank-sum test. It showed that pH, total hardness, Na⁺, Ca²⁺ and Fe²⁺ had significant difference (p < 0.005) between water sources used by patients and non-patients. Elemental ratio plots, Gibbs’ plot and factor analysis indicated that the chemical composition of water sources in this area is strongly influenced by rock–water interactions, particularly the weathering of carbonate and silicate minerals. This study reveals a kind of association between stone formation and drinking water geochemistry as evident by the high hardness/calcium contents in spring water used by patients.     

High-valent iron-based oxidants to treat perfluorooctanesulfonate and perfluorooctanoic acid in water

Perfluoroalkyl and polyfluoroalkyl substances are occurring in consumer and industrial products. They have been found globally in the aquatic environment including drinking water sources and treated wastewater effluents, which has raised concern of potential human health effects because these substances may be bioaccumulative and extremely persistent. The saturated carbon–fluorine bonds of the substances make them resistant to degradation by physical, chemical, and biological processes. There is therefore a need for advanced remediation methods. Iron-based methods involving high-valent compounds are appealing to degrade these substances due to their high oxidation potentials and capability to generate environmentally friendly by-products. This article presents for the first time the oxidation ability of tetraoxy anions of iron(V) (Fe^VO₄ ^3?, Fe(V)), and iron(IV) (Fe^IVO₄ ^4?, Fe(IV)), commonly called ferrates, in neutral and alkaline solutions. Solid compounds of Fe(V) (K₃FeO₄) and Fe(IV) (Na₄FeO₄) were added directly into buffered solution containing perfluorooctansulfonate and perfluorooctanoic acid at pH 7.0 and 9.0, and mixed solutions were subjected to analysis for remaining fluoro compounds after 5 days. The analysis was performed by liquid chromatography–mass spectrometry/mass spectrometry technique. Fe(IV) showed the highest ability to oxidize the studied contaminants; the maximum removals were 34 % for perfluorooctansulfonate and 23 % for perfluorooctanoic acid. Both Fe(V) and Fe(IV) had slightly higher tendency to oxidize contaminants at alkaline pH than at neutral pH. Results were described by invoking reactions involved in oxidation of perfluorooctansulfonate and perfluorooctanoic acid by ferrates in aqueous solution. The results demonstrated potentials of Fe(V) and Fe(IV) to degrade perfluoroalkyl substances in contaminated water.     

Interlinked seasonal variation in biogenic nutrient fluxes and pore-water nutrient concentrations in intertidal sediments

The seasonal variation in biogenic fluxes of NH₄ ⁺, PO₄ ^3? and SiO₂ calculated from the nutrient excretion rates of dominant bivalves (Ruditapes philippinarum and Arcuatula [=Musculista] senhousia), and pore-water nutrient (NH₄ ⁺, PO₄ ^3?, SiO₂ and NO₃ ^? + NO₂ ^?), sedimentary acid-volatile sulfide (AVS) and benthic chlorophyll-a (Chl-a) concentrations was assessed on an intertidal sandflat in the Seto Inland Sea (Japan) from summer 1994 to autumn 1995. In spite of the large variability between sampling dates and stations, significant correlations between biogenic nutrient fluxes and pore-water nutrient concentrations were found, suggesting a seasonal linkage between bivalve-mediated biological processes and chemical features of sediments. This linkage was stronger in surface (0–0.5 cm) than subsurface (0.5–2 cm) sediments, consistent with the autoecological characteristics of R. philippinarum and A. senhousia inhabiting the uppermost sediment layer. Significant temporal variation in pore-water NO₃ ^? + NO₂ ^?, sedimentary AVS and benthic Chl-a concentrations was also found, which was related to both occasional extreme events (e.g., dystrophy) and alternating periods of production and decomposition. This study may serve twofold in (1) contributing to unravel the ecological structure and functioning of natural tidal flats, and the scale of seasonal variability in biotic and sedimentary parameters and (2) providing useful information for assessing the effectiveness of the physico-chemical and biological structure of artificial tidal flats which are growing in number and extension worldwide.     

Thermal treatment of plasma-synthesized goethite improves Fenton-like degradation of orange II dye

Various iron oxides are used for Fenton reactions to degrade organic pollutants. The degradation efficiency may be improved by transforming an iron oxide phase to another. Here, we report on the transformation of goethite into hematite by thermal treatment at 400 °C. The products were analyzed by X-ray diffractometry, Raman spectroscopy, scanning electron microscopy and N₂-physisorption. The catalytic activities were measured for orange II bleaching at initial concentration of 25 mg L^?1, pH 3, catalyst concentration of 0.2 g L^?1; 5 mM H₂O₂, 30 °C. Results show that the synthesized goethite was successfully transformed into hematite, and the specific surface area of the material increased from 134 to 163 m² g^?1. The bleaching efficiency of the orange II dye reached 100 % for the hematite product, versus 78 % for goethite. Therefore, a moderate thermal treatment of a plasma-synthesized goethite improves the catalytic oxidation of organic pollutants.     

The composition of natrophosphate (sodium fluoride phosphate hydrate)

Natrophosphate is a common trace mineral in alkaline rocks and a major salt in alkaline nuclear waste that complicates waste processing. Natrophosphate has historically been assigned the composition Na₇F(PO₄)₂·19H₂O, but this conflicts with a more recent solubility study that claimed natrophosphate is a solid solution of NaF and Na₃PO₄. It is not possible to model the solubility of natrophosphate in nuclear waste until this controversy is resolved. The present study mixed stock solutions of 0.9 M NaF and Na₃PO₄ at different ratios at 8 °C. The compositions of the liquid phase and wet natrophosphate sample were measured by ion chromatography. Plotting the tie-lines between the solid and liquid phase composition showed convergence on a single composition, indicating that natrophosphate is not a solid solution. The resulting composition is approximately the same as the composition first reported more than 140 years ago. Thus, this study resolves the long-standing controversy in the literature concerning the composition of natrophosphate.     

Geochemistry and quality of groundwater of the Yarmouk basin aquifer,north Jordan

Quality of groundwater in the Yarmouk basin, Jordan has been assessed through the study of hydrogeochemical characteristics and the water chemistry as it is considered the main source for drinking and agriculture activities in the region. The results of the relationship between Ca²⁺ + Mg²⁺ versus HCO₃^? + CO₃^2?, Ca²⁺ + Mg²⁺ versus total cations, Na⁺ + K⁺ versus total cations, Cl^? + SO₄^2? versus Na⁺ + K⁺, Na⁺ versus Cl^?, Na⁺ versus HCO₃^? + CO₃^2?, Na⁺ versus Ca²⁺, and Na⁺: Cl^? versus EC describe the mineral dissolution mechanism through the strong relationship between water with rocks in alkaline conditions with the release of Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃^?, CO₃^2?, SO₄^2?, and F^? ions in the groundwater for enrichment. Furthermore, evaporation processes, groundwater depletion, and ion exchange contribute to the increased concentration of Na⁺ and Cl^? ions in groundwater. Anthropogenic sources are one of the main reasons for contamination of groundwater in the study area and for increasing the concentration of Mg²⁺, Na⁺, Cl^?, SO₄^2?, and NO₃^? ions. Results show the quality of groundwater in the study area is categorized as follows: HCO₃^? + CO₃^2? > Cl^? > SO₄^2? > NO₃^? > F^? and Na⁺ > Ca²⁺ > Mg²⁺ > K⁺. In conclusion, the results of TDS, TH, and chemical composition showed that 26% of the groundwater samples were unsuitable for drinking. About 28% of groundwater samples in the study area have a high concentration of Mg²⁺, Na⁺, and NO₃^? above the acceptable limit. Also, based on high SAR, 10% of the groundwater samples were not suitable for irrigation purposes.     

Toxicity and transfer of metal oxide nanoparticles from microalgae to sea urchin larvae

Nanoparticles (NPs) contained in commercial products are released and enter into the aquatic ecosystem, posing serious possible risks to the environment and affecting the food chain. Therefore, investigating the potential toxicity of NPs on aquatic organisms has become an important issue. This study assessed the toxicity and trophic transfer of metal oxide NPs from marine microalgae (Cricosphaera elongata) to the larvae of the sea urchin Paracentrotus lividus. Larvae (24 h old) were fed on 2000 cell mL^?1 48 h of microalgae contaminated with 5 mg L^?1 of several metal oxide NPs (SiO₂, SnO₂, CeO₂, Fe₃O₄) for 15 days. Larval viability and development were monitored from the 4-arm stage to the 8-arm pluteus stage. A significant decrease in survival was observed in larvae fed with microalgae exposed to SiO₂ and CeO₂ NPs. Abnormal development, characterised by skeletal degeneration and altered rudiment growth, was observed in all larvae fed with contaminated NP algae. Our findings revealed that SiO₂ and CeO₂ NPs exerted a toxic effect in the trophic interaction analysed, by reducing sea urchin larval viability, and all metal oxide NPs induced toxicological effects. In conclusion, metal oxide NPs may enter the food chain and become bioavailable for marine organisms, affecting their development.     

Mineralogical variables that control the antibacterial effectiveness of a natural clay deposit

As antibiotic-resistant bacterial strains emerge and pose increased global health risks, new antibacterial agents are needed as alternatives to conventional antimicrobials. Naturally occurring antibacterial clays have been identified which are effective in killing antibiotic-resistant bacteria. This study examines a hydrothermally formed antibacterial clay deposit near Crater Lake, OR (USA). Our hypothesis is that antibacterial clays buffer pH and Eh conditions to dissolve unstable mineral phases containing transition metals (primarily Fe²⁺), while smectite interlayers serve as reservoirs for time release of bactericidal components. Model pathogens (Escherichia coli ATCC 25922 and Staphylococcus epidermidis ATCC 14990) were incubated with clays from different alteration zones of the hydrothermal deposit. In vitro antibacterial susceptibility testing showed that reduced mineral zones were bactericidal, while more oxidized zones had variable antibacterial effect. TEM images showed no indication of cell lysis. Cytoplasmic condensation and cell wall accumulations of <100 nm particles were seen within both bacterial populations. Electron energy loss analysis indicates precipitation of intracellular Fe³⁺-oxide nanoparticles (<10 nm) in E. coli after 24 h. Clay minerals and pyrite buffer aqueous solutions to pH 2.5–3.1, Eh > 630 mV and contain elevated level (mM) of soluble Fe (Fe²⁺ and Fe³⁺) and Al³⁺. Our interpretation is that rapid uptake of Fe²⁺ impairs bacterial metabolism by flooding the cell with excess Fe²⁺ and overwhelming iron storage proteins. As the intracellular Fe²⁺ oxidizes, it produces reactive oxygen species that damage biomolecules and precipitates Fe-oxides. The ability of antibacterial clays to buffer pH and Eh in chronic non-healing wounds to conditions of healthy skin appears key to their healing potential and viability as an alternative to conventional antibiotics.     

Nitrogen limitation in the coastal heath at Anholt,Denmark

The purpose of the study was to investigate, whether the coastal grey dune vegetation at Anholt, Denmark, is limited by nitrogen or phosphorus. The island Anholt (22,37 km²) is situated in the centre of Kattegat A two factor fertilization experiment with nitrogen as NH₄NO₃ (N-addition) and phosphorus as KH₂PO₄ (P-addition) was carried out in the coastal grey dune vegetation of Anholt. The N-addition corresponded to 40 kg N ha^?1 year^?1 and the P-addition to 7 kg P ha^?1 year^?1 The experiment included N-, P-, N + P-addition and control. Lichens (genera: mainly Cladonia, Stereocaulon, Cetraria, Hypogymnia) and bryophytes (genera: Polytrichum, Racomitrium) cover most of the surface. Only two plant species, Corynephorus canescens and Empetrum nigrum, constitute nearly all vascular plant cover and biomass of this calcium poor coastal heath community. Corynephorus and Empetrum increased their cover significantly following N and N + P addition. No effect was observed by P addition alone. N limitation of this coastal heath vegetation remote from agricultural and industrial activities was evident. The effect on the plant species of the single application was short-lived. After two-three years of enhanced cover, the Corynephorus and Empetrum cover had returned to their level before the experiment. The lichen vegetation, however, changed more permanently, and after 12 years the subplots with N + P addition was dominated by rich growth of Cladina and Cetraria species. The results are discussed in relation to anthropogenic nitrogen deposition and conservation of this high priority ecosystem.     

Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces

This study examines the adsorption isotherms, kinetics and mechanisms of Pb²⁺ sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb²⁺ in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb²⁺ with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca²⁺ and PO₄ ^3? concentrations during the metal sorption processes. The Pb²⁺ sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb⁺. The sorption isotherm results indicated that Pb²⁺ sorption onto the Langmuir and Freundlich constant q _max and K _F is 9.52 and 8.18 mg g^?1, respectively. Sorption kinetics results indicated that Pb²⁺ sorption onto WCBP was pseudo-second-order rate constants K ₂ was 1.12 g mg^?1 h^?1. The main mechanism is adsorption or surface complexation (≡POPb⁺: 61.6%), co-precipitation or ion exchange [Ca_3.93 Pb_1.07 (PO₄)₃ (OH): 21.4%] and other precipitation [Pb 50 mg L^?1 and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb²⁺ removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb²⁺ indicates its potential as another promising way to remediate Pb²⁺-contaminated media.     

Accumulation and transfer of Hg, As, Se, and other metals in the sediment-vegetation-crab-human food chain in the coastal zone of the northern Brazilian state of Pará (Amazonia)

The high consumption of crabs (Ucides cordatus) stimulated interest in the present study on the northern coast of Brazil, which encompasses a preserved area of mangrove forest. The objective was to describe and quantify the transfer of metals from the muddy sediments to the leaves of the Rhizophora mangle, and thence the crabs and humans. The samples were collected along two transects, while samples of hair were obtained from local habitants. The pH, interstitial salinity, Eh (mV) were measured, the granulometry and mineralogical and multi-element chemical analyses were run, and the organic material determined. The sediments are silty-clayey, composed of quartz, kaolinite, iron oxides, and illite, as well as smaller portions of smectite, pyrite, halite, and high levels of SiO₂ (56.5 %), Al₂O₃ (18.5 %), and Fe₂O₃ (7 %). The elements Zn, Sr, As, and Zr are concentrated in the leaves, while the bioaccumulation of Zn, Se, Sr, and As was recorded in the crabs, of which, Se is the most concentrated in the tissue of the muscles and the hepatopancreas. The concentrations of nutrient and toxic elements were similar in all age groups (hair samples), with only Hg presenting an increasing concentration between infants and adults. The highest rates of transfer were recorded for the elements Zn and Se in the crabs and Hg in leaves and hair. The accumulation of metals in the leaves and crabs reflects the chemical composition of the sediments and low rates of sediment-vegetation-crab transfer, with the exception of Hg, which accumulated in the hair.     

Efficient oxidation of bisphenol A with oxysulfur radicals generated by iron-catalyzed autoxidation of sulfite at circumneutral pH under UV irradiation

There is actually a need for efficient methods to clean waters and wastewaters from pollutants such as the bisphenol A endocrine disrupter. Advanced oxidation processes currently use persulfate or peroxymonosulfate to generate sulfate radicals. There are, however, few reports on the use of sulfite to generate sulfate radicals, instead of persulfate or peroxymonosulfate, except for dyes. Here we studied the degradation of the bisphenol A using iron(III) as catalyst and sulfite as precursor of oxysulfur radicals, at initial pH of 6, under UV irradiation at 395 nm. The occurrence of radicals was checked by quenching with tert-butyl alcohol and ethanol. Bisphenol A degradation products were analyzed by liquid chromatography coupled with mass spectrometry (LC–MS). Results reveal that iron(III) or iron(II) have a similar oxidation efficiency. Quenching experiments show that the oxidation rate of bisphenol A is 47.7 % for SO ₄ ^·? , 37.3 % for SO ₅ ^·? and 15 % for HO^·. Bisphenol A degradation products include catechol and quinone derivatives. Overall, our findings show that the photo-iron(III)–sulfite system is efficient for the oxidation of bisphenol A at circumneutral pH.     

Novel coprecipitation–oxidation method for recovering iron from steel waste pickling liquor

Waste pickling liquors (WPLs) containing high concentrations of iron and acid are hazardous waste products from the steel pickling processes. A novel combined coprecipitation–oxidation method for iron recovery by Fe₃O₄ nanoparticle production from the WPLs was developed in this study. An oxidation–reduction potential monitoring method was developed for real-time control of the Fe²⁺/Fe³⁺ molar ratio. The key coprecipitation–oxidation parameters were determined using the orthogonal experimental design method. The use of promoters greatly improved the Fe₃O₄ nanoparticle crystallinity, size, magnetization, and dispersion. X-ray diffraction patterns showed that the produced Fe₃O₄ nanoparticles were single phase. The Fe₃O₄ nanoparticles were approximately spherical and slightly agglomerated. Vibrating sample magnetometry showed that the Fe₃O₄ nanoparticles produced from the WPLs had good magnetic properties, with a saturation magnetization of 80.206 emu·g^–1 and a remanence of 10.500 emu·g^–1. The results show that this novel coprecipitation–oxidation method has great potential for recycling iron in WPLs.

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Fast and complete removal of the 5-fluorouracil drug from water by electro-Fenton oxidation

Cytostatic drugs are a troublesome class of emerging pollutants in water owing to their potential effects on DNA. Here we studied the removal of 5-fluorouracil from water using the electro-Fenton process. Galvanostatic electrolyses were performed with an undivided laboratory-scale cell equipped with a boron-doped diamond anode and a carbon felt cathode. Results show that the fastest degradation and almost complete mineralization was obtained at a Fe²⁺ catalyst concentration of 0.2 mM. The absolute rate constant for oxidation of 5-fluorouracil by hydroxyl radicals was 1.52 × 10⁹ M^?1 s^?1. Oxalic and acetic acids were initially formed as main short-chain aliphatic by-products, then were completely degraded. After 6 h the final solution mainly contained inorganic ions (NH₄ ⁺, NO₃ ^? and F^?) and less than 10% of residual organic carbon. Hence, electro-Fenton constitutes an interesting alternative to degrade biorefractory drugs.     

Enhanced degradation of the antibiotic tetracycline by heterogeneous electro-Fenton with pyrite catalysis

There is actually increasing concern about the accumulation of antibiotics, such as tetracycline, in soil and water bodies. There is therefore a need for efficient methods to degrade antibiotics and thus clean waters. Here we tested the degradation of tetracycline using the heterogeneous electro-Fenton-pyrite method and compared the results with the conventional electro-Fenton method. The reaction was performed with a boron-doped diamond or Pt anode and carbon-felt cathode allowing electrogeneration of H₂O₂ from O₂ reduction. Results show an increasing tetracycline mineralization using the following methods: anodic oxidation with electrogenerated H₂O₂, electro-Fenton and then electro-Fenton-pyrite using boron-doped diamond. Ion-exclusion HPLC revealed the complete removal of malic malonic, succinic, acetic, oxalic and oxamic acids. Nitrogen present in tetracycline was mainly mineralized in NH₄ ⁺. The higher efficiency of electro-Fenton-pyrite is explained by self-regulation of soluble Fe²⁺ and pH to 3.0 from pyrite catalyst favoring larger ^·OH generation from Fenton’s reaction.     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min^?1 when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min^?1 were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.     

The effect of limestone treatments on the rate of acid generation from pyritic mine gangue

Surface water enters the Haile Gold Mine, Lancaster County, South Carolina by means of a small stream and is ponded behind a dam and in an abandoned pit. This water is affected by acidic drainage. In spite of the large exposures of potentially acid producing pyritic rock, the flux of acid to the water is relatively low. Nevertheless, the resulting pH values of the mine water are low (around 3.5) due to negligible buffering capacity. In view of the observed low release of acidity, the potential for acid drainage abatement by limestone ameliorants appears feasible. This study investigated the effects of limestone treatment on acid generation rates of the Haile mine pyritic rocks through a series of leaching experiments. Below a critical alkalinity threshold value, solutions of dissolved limestone were found consistently to accelerate the rate of pyrite oxidation by varying degrees. The oxidation rates were further accelerated by admixing solid limestone with the pyritic rock. However, after a period of about a month, the pyrite oxidation rate of the admixed samples declined to a level lower than that of untreated pyrite. Leachates produced by the pyrite and limestone mixtures contained little if any iron. Further, in the mixtures, an alteration of the pyrite surface was apparent. The observed behaviour of the treated pyrite appears to be related to the immersion of the pyrite grains within a high alkalinity/high pH environment. The high pH increases the rate of oxidation of ferrous iron which results in a higher concentration of ferric iron at the pyrite surface. This, in turn, increases the rate of pyrite oxidation. Above a threshold alkalinity value, the precipitation of hydrous iron oxides at the pyrite surface eventually outpaces acid generation and coats the pyrite surface, retarding the rate of pyrite oxidation.     

Efficient oxidation of sulfides into sulfoxides catalyzed by a chitosan–Schiff base complex of Cu(II) supported on supramagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

Sulfoxides are versatile synthetic intermediates for the preparation of biological products. Therefore, there is a need for efficient methods to oxidize sulfides into sulfoxides. Such oxidation may be catalyzed by magnetic nanocatalysts due to their good stability, easy synthesis, high surface area, low toxicity and easy separation by magnetic forces. Here we prepared a nanocatalyst by immobilization of the chitosan–Schiff base complex on supramagnetic Fe₃O₄ nanoparticles. The chitosan–Schiff base complex has been previously prepared by functionalization of chitosan with 5-bromosalicylaldehyde and metalation with copper(II) acetate. The catalyst was characterized by Fourier transform infrared, powder X-ray diffraction, transmission electron microscope, scanning electron microscopy, energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Results show that the Fe₃O₄ nanoparticles and nanocatalyst were spherical in shape with an average size of 20 nm. Upon the covalently anchoring of chitosan–Schiff base Cu complex on the magnetic Fe₃O₄ nanoparticles, the average size increased to 60 nm. The prepared Fe₃O₄–chitosan–Schiff base Cu complex catalyzed very efficiently the oxidation of sulfides to sulfoxides with 100 % selectivity in all cases under green reaction conditions and excellent yields. Additionally, ease of recovery and reusability up to four cycles without noticeable loss of catalytic activity make the present protocol beneficial from industrial and environmental viewpoint.     

Solar-induced generation of singlet oxygen and hydroxyl radical in sewage wastewaters

Singlet oxygen (¹O₂) and hydroxyl radical (·OH) play an important role in the degradation of pollutants in surface waters. However, the mechanism underlying the photochemical generation of ¹O₂ and ·OH in wastewaters is poorly known. Here we studied the photo-induced generation of ¹O₂ and ·OH in different sewage treatment plant units. The correlation between the generation of ¹O₂ and ·OH and the water constituents was discussed. Our results show that in sewage units the ¹O₂ formation rate ranges from 2.19 × 10^?8 to 6.74 × 10^?8 mol L^?1 s^?1, and the ·OH formation rate ranges from 1.7 × 10^?11 to 3.06 × 10^?10 mol L^?1 s^?1. The average ¹O₂ formation rates in the various sewage units are similar to those in wetland and estuarine waters containing rich dissolved organic matter and 2–4 times higher than those in lake and seawater samples. The average ·OH formation rates of the sewage units are 5–50 times higher than for other water samples reported. The ·OH generation rate increased with the iron content with a correlation coefficient of 0.85, which indicates that the photo-Fenton reaction plays a dominant role in ·OH generation in sewage wastewater.     

Assessment of Young Dong tributary and Imgok Creek impacted by Young Dong coal mine,South Korea

An initial reclamation of the Young Dong coal mine site, located in northeastern South Korea, was completed in 1995. Despite the filling of the adit with limestone, acid rock drainage (ARD) enters Young Dong tributary and is then discharged to Imgok Creek. This ARD carries an average of 500 mg CaCO₃/l of mineral acidity, primarily as Fe(II) and Al. Before spring runoff, the flow of Imgok Creek is 3.3–4 times greater than that of the tributary and has an alkalinity of 100 mg CaCO₃/l, which is sufficient to eliminate the mineral acidity and raise the pH to about 6.5. From April through September 2008, there were at least two periods of high surface flow that affects the flow of ARD from the adit. Flow of ARD reaches 2.8 m³/min during spring runoff. This raised the concentrations of Fe and Al in the confluence with Imgok Creek. However, by 2 km downstream the pH of the Imgok Creek is 6.5 and only dissolved Fe is above the Korean drinking water criteria (0.30 mg/l). This suggests only a minor impact of Young Dong Creek water on Imgok Creek. Acid digestion of the sediments in Imgok Creek and Young Dong Tributary reveals considerable abundances of heavy metals, which could have a long-term impact on water quality. However, several water-based leaching tests, which better simulate the bioavailable metals pool, released only Al, Fe, Mn, and Zn at concentrations exceeding the criteria for drinking water or aquatic life.