Degradation of carbendazim by UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> investigated by kinetic modelling

The transformation of the fungicide carbendazim (methyl-2 benzimidazole carbamate) induced by hydroxyl radical generated by the UV photolysis of H₂O₂ has been studied in dilute aqueous solution. The efficient reaction of hydroxyl radicals with carbendazim led to the rapid degradation of carbendazim. The study of reaction kinetics yielded a second order rate constant of 2.2±0.3 10⁹ M⁻¹ s⁻¹ for HO^· radicals with carbendazim. This value is in agreement with a high reactivity of HO^· radicals with carbendazim. Most degradation products were identified by high performance liquid chromatography mass spectrometry (HPLC-MS). In the presence of hydrogenocarbonate and carbonate ions, hydroxyl radicals were quenched and in turn carbonate radicals CO₃ ^·− were formed. Carbonate radicals are indeed known to react efficiently with compounds containing electron-rich sites such as nitrogen or sulfur atoms. The use of a kinetic modelling software gave evidence for the occurrence of such reactions with carbendazim. The second order rate constant of carbonate radical with carbendazim was equal to 6±2 10⁶ M⁻¹ s⁻¹. Electronic Publication     

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.     

Reactivity of sulfate radicals with natural organic matters

Advanced oxidation processes based on sulfate radicals (SO ₄ ^·? ) are capable of efficiently degrade organic pollutants from ground, surface and wastewaters. However, this degradation may be limited by aqueous natural organic matter (NOM). Here we measured the absolute rate constants of reaction of SO ₄ ^·? with four types of organic matter: two fulvic acids and two lake organic matter. We used laser flash photolysis technique to monitor the SO ₄ ^·? decay and the formation of the transients from organic matters. Reaction rate constants comprised between 1530 and 3500 s^?1 mgC^?1 L were obtained by numerical analysis of differential equations and the weighted average of the extinction coefficient of the generated organic matters radicals between 400 and 800 M^?1 cm^?1.     

CuCo2S4/sulfite reaction for efficient removal of tetracycline in water

Water pollution by antibiotics is an increasing concern, which may be addressed by advanced oxidation processes using sulfites as precursors of sulfate radicals (SO₄^·–), yet the efficiency of sulfite activation is limited. Here, we tested copper cobalt sulfide (CuCo₂S₄) to activate sulfite, based on the synergy among transition metals and the facilitation of transition metal redox circulation by reductive sulfur species. We analyzed CuCo₂S₄ structure by X-Ray photoelectron spectroscopy, and we studied the effect of pH and radical scavengers. Results show 90–100% abatement of tetracycline concentration at pH 8.0–10.0, with SO₄^·– and HO^· as the main reactive radicals. This finding is explained by the accelerated redox recycling of copper and cobalt by sulfur, and by the synergetic effect between active cobalt and copper sites.

     

S–O–C isotopic picture of sulphate–methane–carbonate system in freshwater lakes from Poland. A review

Microbial oxidation of organic compounds (including methane), in freshwater sediments, may result in precipitation of carbonates, which may become an important geochemical archive of paleoenvironmental variations. Most probably low δ¹³C value in calcite in eutrophic systems results from an advanced oxidation of organic compounds in turbulent or/and sulphate-rich conditions. Likewise, high δ¹³C value in calcite from organic-rich sediments may evidence low redox potential of the freshwater system. Oxidation of methane and organic matter results in significant isotope effects in sulphates dissolved in water. Therefore, to better understand the origin of carbon isotope signal in carbonates, concentration and stable isotope measurements in dissolved sulphate (water column), bubble methane and calcite (freshwater sediments) have been carried out in 24 lakes, 2 ponds and 4 rivers in Poland. The highest concentration of sulphate has been detected in rivers (85.47 SO₄ ²⁻ mg/l) and an artificial lake (70.30 SO₄ ²⁻ mg/l) located in the extremely SO₄ ²⁻-polluted region called the “Black Triangle”. The lowest concentration of sulphate is found in dystrophic and mountain lakes (from 0.5 SO₄ ²⁻ to about 3 mg/l). The lowest δ³⁴S(SO₄ ²⁻) and δ¹⁸O(SO₄ ²⁻) values occur in unpolluted lakes in eastern Poland (−0.94 and 1.38‰, respectively). The highest S and O isotopic ratios are found in a polluted lake in western Poland (δ¹⁴S(SO₄ ²)=12.95‰) and in a dystrophic lake in eastern Poland (δ¹⁸O(SO₄ ²) = 16.15‰) respectively. It is proposed that δ³⁴SO₄ ²⁻ and (¹⁸O(SO₄ ²⁻) values in lakes represent a good tool to assess and quantify anthropogenic impact by acid precipitation and to monitor variations in the trophic state and redox processes controlled by biodegradation of organic compounds in sediments and water column. In general, increasing depth (up to 12 m) of the water column is associated with decreasing trend the δ¹³C(CH₄) value from about –35 to about –78‰. However, δ¹³C value in sedimentary calcite (δ¹³C vary from –10 to 0.5‰) shows opposite trends as compared to the corresponding methane. This is probably due to redox processes and distribution of heavy isotopes between methane and calcite. Likewise, turbulent water (river) show high δ¹³C value in methane and low δ¹³C value in calcite—this is probably due to an enhanced oxidation of methane producing ¹³C-depleted CO₂. In contrast to clean lakes, it is observed that an increase of the δ¹³C(CH₄) value occurs with increasing depth of the water column in a strongly SO₄ ²⁻-contaminated lake. This is probably due to a loss of biological buffering potential of the lake accompanied by an active oxidation of methane precursors.     

Geochemistry of leachates from the El Fraile sulfide tailings piles in Taxco, Guerrero, southern Mexico

Leachates from the El Fraile tailings impoundment (Taxco, Mexico) were monitored every 2 months from October 2001 to August 2002 to assess the geochemical characteristics. These leachates are of interest because they are sometimes used as alternative sources of domestic water. Alternatively, they drain into the Cacalotenango creek and may represent a major source of metal contamination of surface water and sediments. Most El Fraile leachates show characteristics of Ca–SO₄, (Ca+Mg)–SO₄, Mg–SO₄ and Ca–(SO₄+HCO₃) water types and are near-neutral (pH=6.3–7.7). Some acid leachates are generated by the interaction of meteoric water with tailings during rainfall events (pH=2.4–2.5). These contain variable levels of SO₄ ²⁻ (280–29,500 mg l⁻¹) and As (<0.01–12.0 mg l⁻¹) as well as Fe (0.025–2352 mg l⁻¹), Mn (0.1–732 mg l⁻¹), Zn (<0.025–1465 mg l⁻¹) and Pb (<0.01–0.351 mg l⁻¹). Most samples show the highest metal enrichment during the dry seasons. Leachates used as domestic water typically exceed the Mexican Drinking Water Guidelines for sulfate, hardness, Fe, Mn, Pb and As, while acidic leachates exceed the Mexican Guidelines for Industrial Discharge Waters for pH, Cu, Cd and As. Speciation shows that in near-neutral solutions, metals exist mainly as free ions, sulfates and bicarbonates, while in acidic leachates they are present as sulfates and free ions. Arsenic appears as As^(V) in all samples. Thermodynamic and mineralogical evidence indicates that precipitation of Fe oxides and oxyhydroxides, clay minerals and jarosite as well as sorption by these minerals are the main processes controlling leachate chemistry. These processes occur mainly after neutralization by interaction with bedrock and equilibration with atmospheric oxygen.     

Degradation of diuron by the electro-Fenton process

The degradation of the herbicide diuron has been undertaken by electrochemical advanced oxidation in aqueous solution. This process generates catalytically hydroxyl radicals that are strong oxidizing reagents for the oxidation of organic substances. Hydroxyl radicals degrade diuron in less than 10 min. Kinetic results evidence a pseudo-first-order degradation, with a rate constant of reaction between diuron and hydroxyl radicals of 4.8x10⁹ M^–1 s^–1. Several degradation products were identified by chromatography-mass spectrometry (LC-MS). The mineralization degree of a 1.7x10^–4 M diuron solution reached 93% at 1,000 coulombs.     

Photolytical property of L(+)-α-phenylglycine in aqueous solution

A wide range of pharmaceutical compounds have been identified in the environment, and their existence is a topic of growing concern, both for human and ecological health. The work described here has investigated the photolytic properties of L(+)-α-phenylglycine (L-α-PG-H) in aqueous solution as it can be degraded by photo-catalysis. In 266 nm laser flash photolysis of aqueous solution of L-α-PG-H saturated with nitrogen, two transient absorption bands are observed at 280–330 nm and 450–800 nm, respectively, due to L-α-PG-H radical cation and hydrated electrons (e_aq⁻). Then e_aq⁻ reacts with L-α-PG-H to form the L-α-PG-H radical anion. Decaying rate constants of e_aq⁻ observed at 720 nm is to be 8.9 × 10⁸ dm³ mol⁻¹ s⁻¹. The rate constant for oxidation of L-α-PG-H by SO₄ ⁻ is calculated as 4.5 × 10⁸ and 4.3 × 10⁸ s⁻¹ mol⁻¹ dm³, respectively. The dissociation constants (pKa) of L-α-PG-H is 3. Excited triplet of L-α-PG-H in solution is formed by laser flash photolysis. The quench rate constant of L-α-PG-H excited triplet (k _s) is determined to be 1.3 × 10⁷ dm³ mol⁻¹ s⁻¹ and k ₀ is equal to 1.7 × 10⁵ s⁻¹.     

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.     

Assessment of the chemical components of Famenin groundwater,western Iran

The Faminin area in the semi-arid Hamadan state, western Iran is facing a serious deficiency in groundwater resources due to an increasing demand associated with rapid population growth and agricultural development. The chemical composition of 78 well samples throughout the Faminin area was determined with the aim of evaluating the concentration of the background ions and identifying the major hydrogeochemical processes that control the groundwater chemistry. The similarity between rock and groundwater chemistries in the recharge area indicates a significant rock-water interaction. The hydrochemical types Na–HCO₃ and Na–SO₄ are the predominate forms in the groundwater, followed by water types Ca–HCO₃ and Na–Cl. The high values of electrical conductivity and high concentrations of Na⁺, Cl⁻, SO₄²⁻ and NO₃⁻ in the groundwater appeared to be caused by the dissolution of mineral phases and would appeared to be caused by anthropogenic activities, such as intense agricultural practices (application of fertilizers, irrigation practice), urban and industrial waste discharge, among others.     

Sulphur isotope mass balance of dissolved sulphate ion in a freshwater dam reservoir

We show that sulphur isotopic composition can be a useful tool to discriminate between various sources of sulphate and a tool for better understanding of the sulphur cycling and mass balance. Our investigations, carried out in a dam reservoir, demonstrate differences in sulphur biogeochemistry between different seasons, caused by recharge water supply in spring and intensive sulphate reduction in summer. In the riverine-affected part of the reservoir δ³⁴S(SO₄ ²⁻) varied from 4.7 to 5.9‰ in spring, and from 4.1 to 4.6‰ in summer. In the lacustrine-affected part δ³⁴S(SO₄²⁻) varied from 4.0 to 5.0‰ in spring, and from 4.5 to 5.4‰ in summer. Diurnal variations of δ³⁴S(SO₄ ²⁻) were negligible as compared to seasonal variations.     

Evidence for the involvement of Fe(IV) in water treatment by Fe(III)-activated sulfite

Water contamination by emerging organic pollutants is calling for advanced methods of remediation such as iron-activated sulfite-based advanced oxidation. Sulfate radical, SO₄^??, and hydroxyl radical, ^?OH, are the primary reactive intermediates formed in the Fe(III)/sulfite system, yet the possible involvement of Fe(IV) produced from Fe(II) and persulfates is unclear. Here we explored the role of Fe(IV) in the Fe(III)/sulfite system by methyl phenyl sulfoxide (PMSO) probe assay, electron paramagnetic resonance spectra analysis, alcohol scavenging experiment, and kinetic simulation. Results show that PMSO is partially transformed into methyl phenyl sulfone (PMSO₂), thus evidencing Fe(IV) formation. The remaining degradation of PMSO is due to SO₄^?? and ^?OH. The contribution of Fe(IV) versus free radicals is progressively promoted when the Fe(III)-sulfite reaction proceeds, with an upper limit of 80–90%. The contribution of Fe(IV) versus free radicals increases with Fe(III) and sulfite dosages, and decreases with increasing pH. Overall, our findings demonstrate the involvement of Fe(IV) in the Fe-catalyzed sulfite auto-oxidation process.

     

High removal of phosphate from wastewater using silica sulfate

This report shows that silica sulfate is removing phosphate from wastewater very efficiently. Phosphorus removal and recovery from wastewater is a worldwide issue due to pollution of natural waters by phosphate and depletion of phosphate ores. Adsorption is a process that can remove phosphate at low concentrations. Adsorption also allows the recovery of phosphate for possible re-use. Here, we studied the adsorption of phosphate from wastewater using commercial Zr ferrite, Zr-MCM 41 and silica sulfate. We calculated equilibrium isotherms, kinetic models and thermodynamic effects under conditions similar to real wastewaters. We found that the equilibrium data for the adsorption of phosphate were best fitted to the Freundlich model. The results show that the maximum uptake of phosphate was 3.36 mg g⁻¹ for Zr-MCM, 27.73 mg g⁻¹ for Zr ferrite and 46.32 mg g⁻¹ for silica sulfate. The kinetic results of the three adsorbents were satisfactorily predicted using a pseudo-second-order model. We found that silica sulfate provided excellent characteristics in terms of the maximum adsorption and rate constant for the adsorption of phosphate. The thermodynamic data showed that increasing the temperature enhanced the adsorption of phosphate onto silica sulfate. Our findings will help to define efficient methods to remove phosphate from wastewater.     

Photocatalytic degradation of chlorophenols using Ru(bpy) 3 2+ /S2O 8 2−

Advanced oxidation processes, such as photocatalysed oxidation, provide an important route for degradation of wastes. In this study, the lowest excited state (³MLCT) of Ru(bpy)₃²⁺ is used to break down chlorophenol pollutant molecules to harmless products. This has the advantage of using visible light and a short-lived catalytically active species. Photolysis of deaerated aqueous solutions of a variety of mono- and poly-substituted chlorophenols has been followed in the presence of Ru(bpy)₃²⁺/S₂O₈²⁻ with near visible light (λ > 350 nm) by UV/visible absorption spectroscopy, luminescence, potentiometry, NMR and HPLC techniques. Upon irradiation, a decrease is observed in the chlorophenol concentration, accompanied by the formation of Cl⁻, H⁺ and SO₄²⁻ ions as the main inorganic products. Benzoquinone, phenol, dihydroxybenzenes and chlorinated compounds were the dominant organic products. As the ruthenium(II) complex is regenerated in the reaction, the scheme corresponds to an overall catalytic process. The kinetics of the rapid chlorophenol photodechlorination has been studied, and are described quite well by pseudo-first order behaviour. Further studies on this were made by following Cl⁻ release with respect to the initial Ru(bpy)₃²⁺ and S₂O₈²⁻ concentrations. A comparison is presented of the photodechlorination reactivity of the mono and polychlorophenols studied at acidic and alkaline pH.     

Occurrence and behavior of pharmaceuticals in sewage treatment plants in eastern China

The occurrence and removal efficiency of seven pharmaceuticals (norfloxacin, trimethoprim, roxithromycin, sulfamethoxazole, ibuprofen, diclofenac and carbamazepine) were determined in three sewage treatment plants (STPs) with anaerobic/anoxic/oxic, anoxic/oxic and oxidation ditches processes in Xuzhou City, Eastern China. The results showed that seven pharmaceuticals were detected in the influent samples with concentrations ranging from 93 to 2540 ng·L⁻¹. The removal of these substances among the three different STPs varied from 36 to 84%, with the highest performance obtained by the wastewater treatment works with tertiary treatment (sand filtration). Most of the compounds were removed effectively during biologic treatment while sand filtration treatment also made a contribution to the total elimination of most pharmaceuticals. The efficiency comparison of the three sewage treatment processes showed that the STP which employed anaerobic/anoxic/oxic was more effective to remove pharmaceuticals than the oxidation ditches and anoxic/oxic.     

Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication     

Effect of temperature on seawater desalination-water quality analyses for desalinated seawater for its use as drinking and irrigation water

The effect of feed seawater temperature on the quality of product water in a reverse osmosis process was investigated using typical seawater at Urla Bay, Izmir region, Turkey. The tests were carried out at different feed seawater temperatures (11–23°C) using two RO modules with one membrane element each. A number of variables, including pH, conductivity, total dissolved solids, salinity, rejection percentage of a number of ions (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, HCO₃ ⁻, and SO₄ ²⁻), and the levels of boron and turbidities in collected permeates, were measured. The suitability of these permeates as irrigation and drinking water was checked by comparison with water quality standards.     

Effect of nutrient enrichment in the field on the biomass, growth and calcification of the giant clam Tridacna maxima

Nutrients were added separately and combined to an initial concentration of 10 μM (ammonium) and/or 2 μM (phosphate) in a series of experiments carried out with the giant clam Tridacna maxima at 12 microatolls in One Tree Island lagoon, Great Barrier Reef, Australia (ENCORE Project). These nutrient concentrations remained for 2 to 3 h before returning to natural levels. The additions were made every low tide (twice per day) over 13 and 12 mo periods for the first and second phase of the experiment, respectively. The nutrients did not change the wet tissue weight of the clams, host C:N ratio, protein content of the mantle, calcification rates or growth rates. However, ammonium (N) enrichment alone significantly increased the total population density of the algal symbiont (Symbiodinium sp.: C = 3.6 · 10⁸ cell clam⁻¹, N = 6.6 · 10⁸ cell clam⁻¹, P = 5.7 · 10⁸ cell clam⁻¹, N + P = 5.7 · 10⁸ cell clam⁻¹; and C = 4.1 · 10⁸ cell clam⁻¹, N = 5.1 · 10⁸ cell clam⁻¹, P = 4.7 · 10⁸ cell clam⁻¹, N + P = 4.5 · 10⁸ cell clam⁻¹, at the end of the first and second phases of the experiment, respectively), although no differences in the mitotic index of these populations were detected. The total chlorophyll a (chl a) content per clam but not chlorophyll a per cell also increased with ammonium addition (C = 7.0 mg chl a clam⁻¹, N = 13.1 mg chl a clam⁻¹, P = 12.9 mg chl a clam⁻¹, N + P = 11.8 mg chl a clam⁻¹; and C = 8.8 mg chl a clam⁻¹, N = 12.8 mg chl a clam⁻¹; P = 11.2 mg chl a clam⁻¹, N + P = 11.3 mg chl a clam⁻¹, at the end of the first and second phases of the experiment, respectively). The response of clams to nutrient enrichment was quantitatively small, but indicated that small changes in inorganic nutrient levels affect the clam–zooxanthellae association. Received: 2 June 1997 / Accepted: 9 June 1997     

Evaluation of the levels and sources of trace elements in urban particulate matter

An assessment of air quality of Belgrade, Serbia, was performed by determining the trace element content in airborne daily PM₁₀ and PM_2.5 samples collected from a central urban area. The ambient concentrations of Zn were the highest in PM_2.5 (1,998.0 ng m⁻³). Multivariate receptor modelling (principal component analysis and cluster analysis) has been applied to determine the contribution of different sources of specific metallic components in airborne particles. The obtained results showed that vehicle traffic and fossil fuel combustion in stationary objects were the main sources of trace metals in Belgrade urban aerosols.