Oxidative transformation of carbamazepine by manganese oxides

This study presents oxidative transformation of carbamazepine by synthetic manganese oxide (??-MnO₂) as well as impact of variables including initial MnO₂ loading, pH, coexisting metal ions, and humic acid (HA) on transformation. Manganese oxide (??-MnO₂) was synthesized and stored in the form of suspension. The oxidative reactions were conducted in 50?mL polyethylene (PE) centrifuge tubes with constant pH maintained by buffers. The kinetic experiment was carried out in the solution of pH 2.72 containing 5.0?mg/L of carbamazepine and 130.5?mg/L of MnO₂. Effects of initial MnO₂ loading (0?C130.5?mg/L), pH (2.72?C8.58) and 0.01?M of coexisting solutes (metal ions and HA) on carbamazepine oxidation were also determined. Reaction kinetics indicated that carbamazepine was rapidly degraded in the first 5?min, and approximately 95?% of carbamazepine was eliminated within 60?min. The reaction exhibited pronounced pH dependence and increased with decreasing pH values. The transformation of carbamazepine was also accelerated with increasing MnO₂ loadings. Coexisting metal ions competed with carbamazepine for reactive sites leading to reduced carbamazepine removal, and the inhibitive capacity followed the order of Mn²⁺?>?Fe³⁺?>?Ca²⁺????Mg²⁺. Presence of HA in aqueous solution caused a significant reduction on the magnitude of carbamazepine transformation. This study indicated that carbamazepine can be effectively degraded by ??-MnO₂, and transformation efficiency was strongly dependent on reaction conditions. It suggests that amendment of soil with MnO₂ be a potential alternative to solve carbamazepine pollution.     

Impacts of simulated acid rain on recalcitrance of two different soils

Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H₂SO₄ plus HNO₃ at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH?2.0, whereas only cation exchange occurred above SAR pH?3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K⁺ and Mg²⁺ ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca²⁺?>?K⁺?>?Mg²⁺?>?Na⁺ for the Plinthudult and Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺ for the Paleudalfs soil. The SARs above pH?3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH?2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.     

Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO₂ at mild conditions (pH 4-9 and 22 °C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg²⁺ or Ca²⁺. Experimental results of TTC indicate that MnO₂ promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO₂ generate little iso-OTC, but occur mainly at the A ring’s dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO₂, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines.     

Oxidation of bisphenol F (BPF) by manganese dioxide

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO₂. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO₂ and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn²⁺ > Ca²⁺ > Mg²⁺ > Na⁺ and HPO₄²⁻ > Cl⁻ > NO₃⁻ ≈ SO₄²⁻, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.     

Effect of inorganic and organic solutes on zero-valent aluminum-activated hydrogen peroxide and persulfate oxidation of bisphenol A

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO₃^? (no inhibition)?<?Cl^? (250 mg/L)?=?SO₄^2??<?PO₄^3? for HP/ZVA and Cl^? (250 mg/L; no inhibition)?<?NO₃^??<?SO₄^2??<?PO₄^3? for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.     

Removal mechanisms and kinetics of trace tetracycline by two types of activated sludge treating freshwater sewage and saline sewage

Understanding the removal mechanisms and kinetics of trace tetracycline by activated sludge is critical to both evaluation of tetracycline elimination in sewage treatment plants and risk assessment/management of tetracycline released to soil environment due to the application of biosolids as fertilizer. Adsorption is found to be the primary removal mechanism while biodegradation, volatilization, and hydrolysis can be ignored in this study. Adsorption kinetics was well described by pseudo-second-order model. Faster adsorption rate (k ₂?=?2.04?×?10^?2?g?min^?1?μg^?1) and greater adsorption capacity (q _e?=?38.8 μg?g^?1) were found in activated sludge treating freshwater sewage. Different adsorption rate and adsorption capacity resulted from chemical properties of sewage matrix rather than activated sludge surface characteristics. The decrease of tetracycline adsorption in saline sewage was mainly due to Mg²⁺ which significantly reduced adsorption distribution coefficient (K _d) from 12,990?±?260 to 4,690?±?180 L?kg^?1. Species-specific adsorption distribution coefficients followed the order of $ K_{\mathrm{d}}^{{ + 00}} \gg K_{\mathrm{d}}^{{ + - 0}} > K_{\mathrm{d}}^{{ + - - }} $ . Contribution of zwitterionic tetracycline to the overall adsorption was >90 % in the actual pH range in aeration tank. Adsorption of tetracycline in a wide range of temperature (10 to 35 °C) followed the Freundlich adsorption isotherm well.     

Nano-MnO<Subscript>2</Subscript>-mediated transformation of triclosan with humic molecules present: kinetics,products, and pathways

It has been shown that manganese dioxide (MnO₂) can mediate transformation of phenolic contaminants to form phenoxyl radical intermediates, and subsequently, these intermediates intercouple to form oligomers via covalent binding. However, the reaction kinetics and transformation mechanisms of phenolic contaminants with humic molecules present in nano-MnO₂-mediated systems were still unclear. In this study, it was proven that nano-MnO₂ were effective in transforming triclosan under acidic conditions (pH 3.5–5.0) during manganese reduction, and the apparent pseudo first-order kinetics rate constants (k?=?0.0599–1.5314 h^?1) increased as the pH decreased. In particular, the transformation of triclosan by nano-MnO₂ was enhanced in the presence of low-concentration humic acid (1–10 mg L^?1). The variation in the absorption of humic molecules at 275 nm supported possible covalent binding between humic molecules and triclosan in the nano-MnO₂-mediated systems. A total of four main intermediate products were identified by high-resolution mass spectrometry (HRMS), regardless of humic molecules present in the systems or not. These products correspond to a suite of radical intercoupling reactions (dimers and trimers), ether cleavage (2,4-dichlorophenol), and oxidation to quinone-like products, triggered by electron transfer from triclosan molecules to nano-MnO₂. A possible reaction pathway in humic acid solutions, including homo-coupling, decomposition, oxidation, and cross-coupling, was proposed. Our findings provide valuable information regarding the environmental fate and transformation mechanism of triclosan by nano-MnO₂ in complex water matrices.     

Degradation of bisphenol A in aqueous solution by persulfate activated with ferrous ion

Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO₄ ^?·), which was generated by the activation of persulfate (S₂O₈ ^2?) with ferrous ion (Fe²⁺). S₂O₈ ^2? was activated by Fe²⁺ to produce SO₄ ^?·, and iron powder (Fe⁰) was used as a slow-releasing source of dissolved Fe²⁺. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S₂O₈ ^2? or Fe²⁺ concentrations and then decreased with excess Fe²⁺ concentration. The adding mode of Fe²⁺ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe²⁺, while complete degradation was observed with continuous diffusion of Fe²⁺, and the latter achieved higher TOC removal rate. When Fe⁰ was employed as a slow-releasing source of dissolved Fe²⁺, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe⁰–S₂O₈ ^2? system, Fe⁰ as the activator of S₂O₈ ^2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe⁰–S₂O₈ ^2? system has perspective for future works.     

Hydrochemical characteristics and identification of groundwater pollution sources in tropical savanna

Groundwater pollution of the watershed is mainly influenced by the multifaceted interactions of natural and anthropogenic processes. In this study, classic chemical and multivariate statistical methods were utilized to assess the groundwater quality and ascertain the potential contamination sources affecting the groundwater quality of Galma sub-watershed in a tropical savanna. For this purpose, the data set of 18 groundwater quality variables covering 57 different sampling boreholes (BH) was used. The groundwater samples essentially contained the cations in the following order of dominance: Ca²⁺ ?>?Na⁺ ?>?Mg²⁺ ?>?K⁺. However, the anions had HCO₃^–?>?Cl^–?>?SO₄^–2?>?NO₃^– respectively. The hydrochemical facies classified the groundwater types of the sub-watershed into mixed Ca–Mg–Cl type of water, which means no cations and anions exceeds 50%. The second dominant water type was Ca–Cl. The Mg–HCO₃ water type was found in BH 9, and Na–Cl water type in BH 29 of the studied area. The weathering of the basement rocks was responsible for the concentrations of these ions in the groundwater chemistry of the sub-watershed. Hierarchical cluster analysis (HCA) grouped the groundwater samples (boreholes) into five clusters that are statistically significant regarding the similarities of groundwater quality characteristics. The principal component analysis (PCA) extracted two major principal components explained around 65% of the variance and suggested the natural and anthropogenic processes especially the agricultural pollutants including synthetic fertilizers, and leaching of agricultural waste as the main factors affecting the groundwater quality. The integrated method proved to be efficient and robust for groundwater quality evaluation, as it guaranteed the precise assessment of groundwater chemistry in the sub-watershed of the tropical savanna. The findings of this investigation could be useful to the policy makers for developing effective groundwater management plans for the groundwater resources and protection of the sub-watershed.

     

Activation of cadmium under simulated solar illumination and its impact on the mobility of Cd in flooded soils

In waterlogged paddy soils, cadmium (Cd) can be precipitated as cadmium sulfide (CdS) under reductive environment, thereby limiting the absorption of Cd by plants. Multiple environmental factors (such as water, pH, and Eh) played a role in the control of Cd mobility and bioavailability. In this study, we investigated the influence of the solar irradiation on the photodissolution of synthetic CdS-montmorillonite composites (CdS-M) in solution and the stability of Cd in natural soil. The release kinetic of Cd²⁺ showed that after the irradiation of simulated sunlight, CdS-M composites became less stable compared to the dark control. The solar irradiation seemed to enhance the release of Cd²⁺ from CdS significantly and continuously. Electron paramagnetic resonance (EPR) and quenching experiments confirmed that the photogenerated holes, ?O₂^? and ?OH, were possibly involved in the photo-induced release of Cd²⁺, while the holes was primarily responsible for the reaction. Irradiation under alkaline solution or the presence of DOM, PO₄^3?, CO₃^2?, and urea markedly inhibited the photodissolution process of CdS. The photo-mediated activation of Cd was further confirmed in paddy soil under natural sunlight, with a nearly threefold increase in concentration of extractable Cd during the 15 days of irradiation. This study highlights the importance of photochemical transformation of Cd in the environmental water and soil.

     

Degradation of bisphenol A by the UV/H2O2 process: a kinetic study

A theoretical and experimental study of bisphenol A (BPA) degradation by the UV/H₂O₂ process in water is presented. The effects of the H₂O₂ concentration and the specific rate of photon emission (E_P,0) on BPA degradation were investigated. A kinetic model derived from a reaction sequence was employed to predict BPA and hydrogen peroxide concentrations over time using an annular photochemical reactor in batch recirculation mode. The local volumetric rate of photon absorption (LVRPA) inside the photoreactor was computed using a Line Source with Parallel Plane emission model (LSPP). From the proposed kinetic model and the experimental data, the second order rate constants of the reactions between hydroxyl radicals and the main reacting species (H₂O₂ and BPA) were estimated applying a nonlinear regression method. A good agreement between the kinetic model and experimental data, for a wide range of operating conditions, was obtained. For BPA, H₂O₂, and TOC concentrations, the calculated root means square errors (RMSE) were 2.3?×?10^??2, 9.8?×?10^??1, and 9.0?×?10^??2 mmol L^??1, respectively. The simplified kinetic model presented in this work can be directly applied to scaling-up and reactor design, since the estimated kinetic constants are independent of the reactor size, shape, and configuration. Further experiments were made by employing low BPA initial concentration (100 μg L^??1) in water and real wastewater. A lower degradation rate of BPA was observed in the real wastewater, although the UV/H₂O₂ process has also been able to completely degrade the target pollutant in less than 1 h.

     

Role of some organic inhibitors on the oxidation of dissolved sulfur dioxide by oxygen in rainwater medium

In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R _o = k _o[S(IV)]], where k _o is the first-order rate constant and R _o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k _obs = k _o/(1 + B [Inh]), where k _obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10^?5 to 1.5?×?10^?4 s^?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?10⁴) (ethanol) and (3.95?±?2.36)?×?10⁴ (2-butanol) at 25 °C.     

Characterization of major pollution events (dust, haze, and two festival events) at Agra, India

Total suspended particulate (TSP) samples were collected during dust, haze, and two festival events (Holi and Diwali) from February 2009 to June 2010. Pollutant gases (NO₂, SO₂, and O₃) along with the meteorological parameters were also measured during the four pollution events at Agra. The concentration of pollutant gases decreases during dust events (DEs), but the levels of the gases increase during other pollution events indicating the impact of anthropogenic emissions. The mass concentrations were about two times higher during pollution events than normal days (NDs). High TSP concentrations during Holi and Diwali events may be attributed to anthropogenic activities while increased combustion sources in addition to stagnant meteorological conditions contributed to high TSP mass during haze events. On the other hand, long-range transport of atmospheric particles plays a major role during DEs. In the dust samples, Ca²⁺, Cl^?, NO₃ ^?, and SO₄ ^2? were the most abundant ions and Ca²⁺ alone accounted for 22 % of the total ionic mass, while during haze event, the concentrations of secondary aerosols species, viz., NO₃ ^?, SO₄ ^2?, and NH₄ ⁺, were 3.6, 3.3, and 5.1 times higher than the normal days. During Diwali, SO₄ ^2? concentration (17.8 μg?m^?3) was highest followed by NO₃ ^?, K⁺, and Cl^? while the Holi samples were strongly enriched with Cl^? and K⁺ which together made up 32.7 % of the total water-soluble ions. The ion balances indicate that the haze samples were acidic. On the other hand, Holi, Diwali, and DE samples were enriched with cations. The carbonaceous aerosol shows strong variation with the highest concentration during Holi followed by haze, Diwali, DEs, and NDs. However, the secondary organic carbon concentration follows the order haze > DEs > Diwali > Holi > NDs. The scanning electron microscope/EDX results indicate that KCl and carbon-rich particles were more dominant during Holi and haze events while DE samples were enriched with particles of crustal origin.     

Chemical and strontium isotope characterization of rainwater in karst virgin forest,Southwest China

Strontium isotope ratios and concentrations of Ca²⁺, NH₄⁺, Na⁺, K⁺, Mg²⁺, Cl^?, SO₄^2?, NO₃^? and Al³⁺, Sr²⁺ were measured for 52 rainwater samples collected in virgin forest in a rural region between May 2007 and Dec. 2008. The rainwater pH values vary from 4.1 to 7.2 with a volume weight mean (VWM) value of 5.40. 40 of 52 samples have pH value above 5.0, indicating that the regional rainwater was not acidic. Among anions and cations, sulphate concentration (40.4 μeq l^?1, VWM) is the highest in the rainwater, followed by ammonium and calcium (30.2 and 20.8 μeq l^?1, VWM). Rainwater quality is characterized by low salinity and neutralized pH.The chemical compositions and ⁸⁷Sr/⁸⁶Sr ratios of the rainwater samples vary considerably. Using Na⁺ concentration as an indicator of marine origin, the proportions of sea salt and crustal elements were estimated from elemental ratios. The ⁸⁷Sr/⁸⁶Sr ratios were used to characterize different sources base on the data sets of this study and those from literatures. Such sources include weathering of limestone (⁸⁷Sr/⁸⁶Sr = 0.7075), remote soil dust (⁸⁷Sr/⁸⁶Sr > 0.7135) and anthropogenic source (fertilizers: ⁸⁷Sr/⁸⁶Sr = 0.7079). The results of the present study suggest that one likely source for high ammonium and calcium concentration is local soil. Due to a large contribution of these cations to the sulphate neutralization action, the rainwater in this region displays non-acidity, and thus has not significant environmental impact. The wet precipitation in the karst virgin forest in Guizhou province is strongly influenced by natural sources rather than anthropogenic sources.     

Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

Cadmium (Cd2+) removal by nano zerovalent iron: surface analysis, effects of solution chemistry and surface complexation modeling

Nano zerovalent iron (nZVI) is an effective remediant for removing various organic and inorganic pollutants from contaminated water sources. Batch experiments were conducted to characterize the nZVI surface and to investigate the effects of various solution properties such as pH, initial cadmium concentration, sorbent dosage, ionic strength, and competitive ions on cadmium removal by nZVI. Energy-dispersive X-ray and X-ray photoelectron spectroscopy results confirmed removal of Cd²⁺ ions by nZVI through adsorption. Cd²⁺ adsorption decreased in the presence of competitive cations in the order: Zn²⁺?>?Co²⁺?>?Mg²⁺?>?Mn²⁺?=?Cu²⁺?>?Ca²⁺?>?Na²⁺?=?K⁺. Higher concentrations of Cl^? significantly decreased the adsorption. Cadmium removal increased with solution pH and reached a maximum at pH 8.0. The effects of various solution properties indicated Cd²⁺ adsorption on nZVI to be a chemisorption (inner-sphere complexation) process. The three surface complexation models (diffuse layer model, constant capacitance model, and triple layer model) fitted well to the adsorption edge experimental data indicating the formation of nZVI–Cd bidentate inner-sphere surface complexes. Our results suggest that nZVI can be effectively used for the removal of cadmium from contaminated water sources with varying chemical conditions.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Sorption and leaching of flucetosulfuron in soil

Abstract

The adsorption–desorption and leaching of flucetosulfuron, a sulfonylurea herbicide, was investigated in three Indian soils. Freundlich adsorption isotherm described the sorption mechanism of herbicide with adsorption coefficients (K_f) ranging from 17.13 to 27.99 and followed the order: Clayey loam?>?Loam?>?Sandy loam. The K_f showed positive correlation with organic carbon (OC) (r?=?0.910) and clay content (r?=?0.746); but, negative correlation with soil pH (r = ?0.635). The adsorption isotherms were S-type suggesting that herbicide adsorption was concentration dependent and increased with increase in concentration. Desorption followed the sequence: sandy loam?>?clayey loam?>?loam . Hysteresis (H) was observed in all the three soils with H?<?1. Leaching of flucetosulfuron correlated positively with the soil pH; but, negatively with the OC content. Sandy loam soil (OC- 0.40%, pH ?7.25) registered lowest adsorption and highest leaching of flucetosulfuron while lowest leaching was found in the loam soil (pH ? 7.89, OC ? 0.65%). The leaching losses of herbicide increased with increase in the rainfall intensity. This study suggested that the soil OC content, pH and clay content played important roles in deciding the adsorption–desorption and leaching behavior of flucetosulfuron in soils.     

Recycling of wastes from fish beneficiation by composting: chemical characteristics of the compost and efficiency of their humic acids in stimulating the growth of lettuce

Waste from the beneficiation of fish was composted with crushed grass aiming to characterize their chemical composition and investigate the possibility of the use of the final compost as source of humic acids (HA) able to stimulate the growth of lettuce. Compost presented pH value, C/N ratio, and electrical conductivity that allow its use as an organic fertilizer. The element content was present in the following order of abundance in the compost: P?>?Ca?>?N?>?Mg?>?K?>?Fe?>?Zn?>?Mn?>?Mo?>?Cu, and the humus composition was similar to that observed in others kind of organic residues composted. The high content of oxygen pointed out a high level of oxidation of HA, in line with the predominance of phenolic acidity in the functional groups. The ¹³C-NMR spectra showed marked resonances due to the presence of lipids and other materials resistant to degradation as methoxy substituent and N-alkyl groups. A concentration of 20 mg L^?1 HA increased significantly both dry and wet root matter in lettuce but the CO₂ assimilation, stomatal conductance, and number of lateral roots of the plants were not affected. However, increases of 64% in the water-use efficiency was observed due to the HA addition, probably related to the root morphology alteration which resulted in 1.6-fold increase of lateral root average length and due to the higher H⁺ extrusion activity. Reuse of residues from the fish beneficiation activity by composting may represent a safe tool to increase the value of recycled organic residues and generate HA with potential use as plant growth stimulants.