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.     

Photochemical reaction of peroxynitrite and carbon dioxide could account for up to 15 % of carbonate radicals generation in surface waters

The carbonate radical (CO ₃ ^?· ) is a photoinduced transient species occurring in surface waters. The carbonate radical can transform both natural compounds and xenobiotics. For instance, it can react with electron-rich substrates such as anilines, phenols and organic sulfur compounds. Here we used the APEX software to assess photochemical reactions, including the formation rates of transient species, based on water chemistry and depth, under summertime irradiation conditions. We found that the reaction between peroxynitrite and carbon dioxide is a potentially significant source of CO ₃ ^?· in sunlit surface waters, and could account for up to 10–15 % of the total CO ₃ ^?· formation. The peroxynitrite pathway to CO ₃ ^?· would be most significant at pH 7–8 and would be enhanced in waters with elevated nitrate and low alkalinity. Therefore, the proposed process could add to the known photochemical sources of CO ₃ ^?· in surface-water environments.     

Suppression of inhibition of substrate photodegradation by scavengers of hydroxyl radicals: the solvent-cage effect of bromide on nitrate photolysis

In this paper we show that bromide scavenges the ^·OH radicals formed upon photolysis of nitrate, before they leave the solvent cage. Bromide can thus inhibit the in-cage recombination between ^·OH and ^·NO₂. The consequence is an increased generation of ^·NO₂ and nitrite and of Br₂ ^?· + ^·OH, compared to ^·OH alone in the absence of bromide. We show that this effect compensates for the lower reactivity of Br ₂ ^?· compared to ^·OH toward certain organic substrates, e.g. phenol and tryptophan. Our findings could lead to a deep revision of the present views of the role of bromide in saltwater photochemistry.     

Kinetics of the oxidation of endocrine disruptor nonylphenol by ferrate(VI)

The kinetics of the oxidation of endocrine disruptor nonylphenol (NP) by potassium ferrate(VI) (K₂FeO₄) in water as a function of pH 8.0–10.9 at 25°C is presented. The observed second-order rate constants, k _obs, decrease with an increase in pH 269–32 M^?1 s^?1. The speciation of Fe(VI) (HFeO ₄ ^? and FeO ₄ ^2? ) and NP (NP–OH and NP–O^?) species was used to explain the pH dependence of the k _obs values. At a dose of 10 mg L^?1 (50 μM) K₂FeO₄, the half-life for the removal of NP by Fe(VI), under water treatment conditions, is less than 1 min.     

Ecotoxicological risks of the abandoned F–Ba–Pb–Zn mining area of Osor (Spain)

Due to its potential toxic properties, metal mobilization is of major concern in areas surrounding Pb–Zn mines. In the present study, metal contents and toxicity of soils, aqueous extracts from soils and mine drainage waters from an abandoned F–Ba–Pb–Zn mining area in Osor (Girona, NE Spain) were evaluated through chemical extractions and ecotoxicity bioassays. Toxicity assessment in the terrestrial compartment included lethal and sublethal endpoints on earthworms Eisenia fetida, arthropods Folsomia candida and several plant species, whereas aquatic tests involved bacteria Vibrio fischeri, microalgae Raphidocelis subcapitata and crustaceans Daphnia magna. Total concentrations of Ba (250–5110 mg kg^?1), Pb (940 to >5000 mg kg^?1) and Zn (2370–11,300 mg kg^?1) in soils exceeded intervention values to protect human health. Risks for the aquatic compartment were identified in the release of drainage waters and in the potential leaching and runoff of metals from contaminated soils, with Cd (1.98–9.15 µg L^?1), Pb (2.11–326 µg L^?1) and Zn (280–2900 µg L^?1) concentrations in filtered water samples surpassing US EPA Water Quality Criteria (2016a, b). Terrestrial ecotoxicity tests were in accordance with metal quantifications and identified the most polluted soil as the most toxic. Avoidance and reproduction tests with earthworms showed the highest sensitivity to metal contamination. Aquatic bioassays performed in aqueous extracts from soils confirmed the results from terrestrial tests and also detected toxic effects caused by the mine drainage waters. Algal growth inhibition was the most sensitive aquatic endpoint. In view of the results, the application of a containment or remediative procedure in the area is encouraged.     

Copper recovery from waste printed circuit boards concentrated metal scraps by electrolysis

Copper recovery is the core of waste printed circuit boards (WPCBs) treatment. In this study, we proposed a feasible and efficient way to recover copper from WPCBs concentrated metal scraps by direct electrolysis and factors that affect copper recovery rate and purity, mainly CuSO₄·5H₂O concentration, NaCl concentration, H₂SO₄ concentration and current density, were discussed in detail. The results indicated that copper recovery rate increased first with the increase of CuSO₄·5H₂O, NaCl, H₂SO₄ and current density and then decreased with further increasing these conditions. NaCl, H₂SO₄ and current density also showed a similar impact on copper purity, which also increased first and then decreased. Copper purity increased with the increase of CuSO₄·5H₂O. When the concentration of CuSO₄·5H₂O, NaCl and H₂SO₄ was respectively 90, 40 and 118 g/L and current density was 80 mA/cm², copper recovery rate and purity was up to 97.32% and 99.86%, respectively. Thus, electrolysis proposes a feasible and prospective approach for waste printed circuit boards recycle, even for e-waste, though more researches are needed for industrial application.

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Comparison of chemical compositions in air particulate matter during summer and winter in Beijing,China

The development of industry in Beijing, the capital of China, particularly in last decades, has caused severe environmental pollution including particulate matter (PM), dust–haze, and photochemical smog, which has already caused considerable harm to local ecological environment. Thus, in this study, air particle samples were continuously collected in August and December, 2014. And elements (Si, Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Mo, Cd, Ba, Pb and Ti) and ions (\({\text{NO}}_{3}^{-}\), \({\text{SO}}_{4}^{2-}\), F^?, Cl^?, Na⁺, K⁺, Mg²⁺, Ca²⁺ and \({\text{NH}}_{4}^{+}\)) were analyzed by inductively coupled plasma mass spectrometer and ion chromatography. According to seasonal changes, discuss the various pollution situations in order to find possible particulate matter sources and then propose appropriate control strategies to local government. The results indicated serious PM and metallic pollution in some sampling days, especially in December. Chemical Mass Balance model revealed central heating activities, road dust and vehicles contribute as main sources, account for 5.84–32.05 % differently to the summer and winter air pollution in 2014.     

Evaluation of acidity in late Permian outcrop coals and its association with endemic fluorosis in the border area of Yunnan,Guizhou, and Sichuan in China

The junction area of Yunnan, Guizhou, and Sichuan provinces is the heaviest coal-burning endemic fluorosis zones in China. To better understand the pathogenicity of endemic fluorosis in this area, 87 coal samples from the late Permian outcrop or semi-outcrop coal seams were collected in eight counties of the junction area of Yunnan, Guizhou, and Sichuan provinces. The total fluorine and sulfate content, etc. in the coal was determined using combustion-hydrolysis/fluoride-ion-selective electrode method and ion chromatography, respectively. The results show that the total fluorine concentrations in the samples ranged from 44 to 382 µg g^?1, with an average of 127 µg g^?1. The average pH of the coals is 5.03 (1.86–8.62), and the sulfate content varied from 249 to 64,706 µg g^?1 (average 7127 µg g^?1). In addition, the coals were medium- and high-sulfur coals, with sulfur mass fraction ranging from 0.08 to 13.41%. By heating the outcrop coals, HF release from the coal was verified quantitatively without exception, while simulated combustion directly confirmed the release of sulfuric acid (H₂SO₄). The acid in coal may be in the form of acidic sulfate (\({\text{HSO}}_{4}^{ - }\)/H₂SO₄) because of a positive relationship between pH and \(p\left( {{\text{SO}}_{4}^{2 - } } \right)\) in the acidic coal. The possible reaction mechanism would be that a chemical reaction between the acid (H₂SO₄ or \({\text{HSO}}_{4}^{ - }\)) and fluorine in the coal occurred, thereby producing hydrogen fluoride (HF), which would be the chemical form of fluorine released from coal under relatively mild conditions. The unique chemical and physical property of HF may bring new insight into the pathogenic mechanism of coal-burning endemic fluorosis. The phenomenon of coal-burning fluorosis is not limited to the study area, but is common in southwest China and elsewhere. Further investigation is needed to determine whether other endemic fluorosis areas are affected by this phenomenon.     

Improvement of sludge dewaterability with modified cinder via affecting EPS

The relationship between the improvement of sludge dewaterability and variation of organic matters has been studied in the process of sludge pre-conditioning with modified cinder, especially for extracellular polymeric substances (EPS) in the sludge. During the conditioning process, the decreases of total organic carbon (TOC) and soluble chemical oxygen demand (SCOD) were obviously in the supernatant especially for the acid modified cinder (ACMC), which could be attributed to the processes of adsorption and sweeping. The reduction of polysaccharide and protein in supernatant indicated that ACMC might adsorb EPS so that the tightly bound EPS (TB-EPS) decreased in sludge. In the case of ACMC addition with 24 g·L^–1, SRF of the sludge decreased from 7.85 × 10¹² m·kg^–1 to 2.06 × 10¹² m·kg^–1, and the filter cake moisture decreased from 85% to 60%. The reconstruction of “floc mass” was confirmed as the main sludge conditioning mechanism. ACMC promoted the dewatering performance through the charge neutralization and adsorption bridging with the negative EPS, and provided firm and dense structure for sludge floc as skeleton builder. The passages for water quick transmitting were built to avoid collapsing during the high-pressure process.

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Impact of dissolved oxygen on the production of nitrous oxide in biological aerated filters

Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and microelectrode technology were employed to evaluate the Nitrous oxide (N₂O) production in biological aerated filters (BAFs) under varied dissolved oxygen (DO) concentrations during treating wastewater under laboratory scale. The average yield of gasous N₂O showed more than 4-fold increase when the DO levels were reduced from 6.0 to 2.0 mg?L^–1, indicating that low DO may drive N₂O generation. PCR-DGGE results revealed that Nitratifractor salsuginis were dominant and may be responsible for N₂O emission from the BAFs system. While at a low DO concentration (2.0 mg?L^–1), Flavobacterium urocaniciphilum might play a role. When DO concentration was the limiting factor (reduced from 6.0 to 2.0 mg?L^–1) for nitrification, it reduced NO ₂ ^- -N oxidation as well as the total nitrification. The data from this study contribute to explain how N₂O production changes in response to DO concentration, and may be helpful for reduction of N₂O through regulation of DO levels.

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Decomposition of perfluorooctanoic acid by microwaveactivated persulfate: Effects of temperature, pH, and chloride ions

Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S₂O ₈ ^2? ) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects of pH (pH = 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01?C0.15 mol·L^?1), and temperature (60°C, 90°C, and 130°C) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol·L^?1 at 90°C and 0.06 mol·L^?1 at 60°C, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.     

Nanostructured semiconducting materials for efficient hydrogen generation

Massive production of hydrogen by water decomposition triggered by a solar light active photocatalyst is a major objective in chemistry and a promising avenue to overcome the global energy crisis. The development of efficient, stable, economically viable and eco-friendly photocatalysts for hydrogen production is a challenging task. This article reviews the use of nanocomposite in three combinations: metal oxide–metal oxide semiconductor, metal–metal oxide semiconductor and metal chalcogenide–metal oxide core–shell nanostructures. These core–shell structures occur in two forms: a simple form where the photocatalyst is either in the core or the shell or in a more complex system where the core–shell structure comprises a co-catalyst deposited on a semiconducting material. We discuss the design, synthesis and development of semiconductor-based nanocomposite photocatalysts for hydrogen production. The major points are the role of catalytic active sites, the chemical nature of sacrificial agents, the effect of light sources, the variable light intensity and the energy efficiency calculation. For TiO₂-based nanocomposites, the metal oxide or metal co-catalyst loading of 1.0–3.0 wt% was optimal. TiO₂ nanotube–CuO hybrid nanocomposites produce 1,14,000 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\), whereas TiO₂/Au nanocomposites display 1,60,000 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\). For core–shell catalysts, a shell thickness of 2–20 nm was found for the best activity, and its performance is as follows: (a) CdS–NiO system produces around 19,949 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\) and (b) CuO–Cr₂O₃ as co-catalyst immobilized on TiO₂ system produces around 82,390 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\).     

Particle size distributions, PM2.5 concentrations and water-soluble inorganic ions in different public indoor environments: a case study in Jinan, China

In this study, we collected particles with aerodynamic diameter ?2.5 μm (PM_2.5) from three different public indoor places (a supermarket, a commercial office, and a university dining hall) in Jinan, a medium-sized city located in northern China. Water-soluble inorganic ions of PM_2.5 and particle size distributions were also measured. Both indoor and outdoor PM_2.5 levels (102.3–143.8 μg·m^?3 and 160.2–301.3 μg·m^?3, respectively) were substantially higher than the value recommended by the World Health Organization (25 μg·m^?3), and outdoor sources were found to be the major contributors to indoor pollutants. Diurnal particle number size distributions were different, while the maximum volume concentrations all appeared to be approximately 300 nm in the three indoor locations. Concentrations of indoor and outdoor PM_2.5 were shown to exhibit the same variation trends for the supermarket and dining hall. For the office, PM_2.5 concentrations during nighttime were observed to decrease sharply. Among others, SO ₄ ^2? , NH ₄ ⁺ and NO ₃ ^? were found to be the dominant water-soluble ions of both indoor and outdoor particles. Concentrations of NO ₃ ^? in the supermarket and office during the daytime were observed to decrease sharply, which might be attributed to the fact that the indoor temperature was much higher than the outdoor temperature. In addition, domestic activities such as cleaning, water usage, cooking, and smoking also played roles in degraded indoor air quality. However, the results obtained here might be negatively impacted by the small number of samples and short sampling durations.     

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.     

Preparing graphene from anode graphite of spent lithium-ion batteries

With extensive use of lithium ion batteries (LIBs), amounts of LIBs were discarded, giving rise to growth of resources demand and environmental risk. In view of wide usage of natural graphite and the high content (12%–21%) of anode graphite in spent LIBs, recycling anode graphite from spent LIBs cannot only alleviate the shortage of natural graphite, but also promote the sustainable development of related industries. After calcined at 600°C for 1 h to remove organic substances, anode graphite was used to prepare graphene by oxidation-reduction method. Effect of pH and N₂H₄·H₂O amount on reduction of graphite oxide were probed. Structure of graphite, graphite oxide and graphene were characterized by XRD, Raman and FTIR. Graphite oxide could be completely reduced to graphene at pH 11 and 0.25 mL N₂H₄·H₂O. Due to the presence of some oxygen-containing groups and structure defects in anode graphite, concentrated H₂SO₄ and KMnO₄ consumptions were 40% and around 28.6% less than graphene preparation from natural graphite, respectively.

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Occurrence and profiles of polybrominated diphenyl ethers (PBDEs) in riverine sediments of Shanghai: a combinative study with human serum from the locals

Herein, we studied the occurrence and profiles of thirteen PBDE congeners in 30 river sediment samples from Shanghai, China. The concentrations of Σ₁₃PBDEs ranged from 110 to 13,071 pg g ^?1 dw, with an average value of 2,841 pg g ^?1 dw. BDE-209 was the predominant congener accounting for more than 65 % of total PBDEs, demonstrating that the major source of PBDEs in sediment samples was associated with the prevalent use of technical deca-BDE products. Moreover, low brominated BDEs in sediments also came from the degradation of higher brominated BDEs. In addition, taking into consideration of dietary exposure, PBDEs in serum samples collected from the locals were also detected with range of 419–26,744 pg g^?1 (average 5,561 pg g ^?1), which suggested a relatively low burden of PBDEs contamination to human body compared with the condition in other place. And in serum, low brominated compounds constituted the majority of total PBDE congeners.     

Degradation of carbon tetrachloride in thermally activated persulfate system in the presence of formic acid

The thermally activated persulfate (PS) degradation of carbon tetrachloride (CT) in the presence of formic acid (FA) was investigated. The results indicated that CT degradation followed a zero order kinetic model, and CO ₂ ^– · was responsible for the degradation of CT confirmed by radical scavenger tests. CT degradation rate increased with increasing PS or FA dosage, and the initial CT had no effect on CT degradation rate. However, the initial solution pH had effect on the degradation of CT, and the best CT degradation occurred at initial pH 6. Cl^– had a negative effect on CT degradation, and high concentration of Cl^– displayed much strong inhibition. Ten mmol·L^–1HCO ₃ ^– promoted CT degradation, while 100 mmol·L^–1NO ₃ ^– inhibited the degradation of CT, but SO ₄ ^2– promoted CT degradation in the presence of FA. The measured Cl–concentration released into solution along with CT degradation was 75.8% of the total theoretical dechlorination yield, but no chlorinated intermediates were detected. The split of C-Cl was proposed as the possible reaction pathways in CT degradation. In conclusion, this study strongly demonstrated that the thermally activated PS system in the presence of FA is a promising technique in in situ chemical oxidation (ISCO) remediation for CT contaminated site.