Preferential binding between intracellular organic matters and Al13 polymer to enhance coagulation performance

Coagulation is the best available method for removing intracellular organic matter (IOM), which is released from algae cells and is an important precursor to disinfection by-products in drinking water treatment. To gain insight into the best strategy to optimize IOM removal, the coagulation performance of two Al salts, i.e., aluminum chloride (AlCl₃) and polyaluminum chloride (PACl, containing 81.2% Al₁₃), was investigated to illuminate the effect of Al species distribution on IOM removal. PACl showed better removal efficiency than AlCl₃ with regard to the removal of turbidity and dissolved organic carbon (DOC), owing to the higher charge neutralization effect and greater stability of pre-formed Al₁₃ species. High pressure size exclusion chromatography analysis indicated that the superiority of PACl in DOC removal could be ascribed to the higher binding affinity between Al₁₃ polymer and the low and medium molecular weight (MW) fractions of IOM. The results of differential log-transformed absorbance at 254 and 350?nm indicated more significant formation of complexes between AlCl₃ and IOM, which benefits the removal of tryptophan-like proteins thereafter. Additionally, PACl showed more significant superiority compared to AlCl₃ in the removal of < 5?kDa and hydrophilic fractions, which are widely viewed as the most difficult to remove by coagulation. This study provides insight into the interactions between Al species and IOM, and advances the optimization of coagulation for the removal of IOM in eutrophic water.     

Mechanisms of photochemical release of dissolved organic matter and iron from resuspended sediments

Photochemical reactions can alter the transformation of sedimentary organic matter into dissolved organic matter (DOM) and affect its ultimate fate in water ecosystems. In the present study, the photorelease of DOM and Fe from resuspended lake sediments was investigated under different O₂ and NO₃^? concentration conditions to study the mechanisms of DOM and Fe photorelease. The amount of photoreleased Fe, which ranged from 0.22 to 0.70 μmol/L, was significantly linearly correlated with the amount of photoreleased DOM. O₂ and NO₃^? could promote the photochemical release of DOM and Fe, especially during the initial 4 h irradiation. In general, the order of the photorelease rates of DOM and Fe under different conditions was as follows: NO₃^?/aerobic > aerobic ≈ NO₃^?/anaerobic > anaerobic. The photorelease rates of DOM and Fe were higher for the initial 4 hr irradiation than these for the subsequent 8 hr irradiation. The photorelease of DOM and Fe is thought to proceed via direct photodissolution and indirect processes. The relative contributions of indirect processes (>60%) was much greater than that of direct photodissolution (<40%). The photoproduced H₂O₂ under aerobic and anaerobic conditions indicated that hydroxyl radicals (?OH) are involved in the photorelease of DOM. Using ?OH scavengers, it was found that 38.7%, 53.7%, and 77.6% of photoreleased DOM was attributed to ?OH under anaerobic, aerobic, and NO₃^?/aerobic conditions, respectively. Our findings provide insights for understanding the mechanisms and the important role of ?OH in the DOM and Fe photorelease from resuspended sediments.     

Comparison between UV and VUV photolysis for the pre- and post-treatment of coking wastewater

In this study, ultraviolet (UV) and vacuum ultraviolet (VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%-35.4% total organic carbon (TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand (COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD₅/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%-47% TOC within 8 hr irradiation. Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen (NH₄⁺-N), 17% more nitrite nitrogen (NO₂^--N), and 18% more total nitrogen (TN) than UV, producing 35% less nitrite nitrogen (NO₃^--N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Variation characteristics of fine particulate matter and its components in diesel vehicle emission plumes

A rapid reaction occurs near the exhaust nozzle when vehicle emissions contact the air. Twenty diesel vehicles were studied using a new multipoint sampling system that is suitable for studying the exhaust plume near the exhaust nozzle. The variation characteristics of fine particle matter (PM_2.5) and its components in diesel vehicle exhaust plumes were analyzed. The PM_2.5 emissions gradually increased with increasing distance from the nozzle in the plume. Elemental carbon emissions remained basically unchanged, organic carbon and total carbon (TC) increased with increasing distance. The concentrations of SO₄^2?, NO₃^? and NH₄⁺ (SNA) directly emitted by the vehicles were very low but increased rapidly in the exhaust plume. The selective catalytic reduction (SCR) reduced 42.7% TC, 40% NO₃^? emissions, but increased 104% SO₄^2? and 36% NH₄⁺ emissions, respectively. In summary, the SCR reduced 29% primary PM_2.5 emissions for the tested diesel vehicles. The NH₄NO₃ particle formation maybe more important in the plume, and there maybe other forms of formation of NH₄⁺ (eg. NH₄Cl). The generation of secondary organic carbon (SOC) plays a leading role in the generation of secondary PM_2.5. The SCR enhanced the formation of SOC and SNA in the plume, but comprehensive analysis shows that the SCR more enhanced the SNA formation in the plume, which is mainly new particles formation process. The inconsistency between secondary organic aerosol (SOA) and primary organic aerosol definitions is one of the important reasons for the difference between SOA simulation and observation.     

Mg2+ improves biomass production from soybean wastewater using purple non-sulfur bacteria

Soybean wastewater was used to generate biomass resource by use of purple non-sulfur bacteria (PNSB). This study investigated the enhancement of PNSB cell accumulation in wastewater by Mg²⁺ under the light-anaerobic condition. Results showed that with the optimal Mg²⁺ dosage of 10 mg/L, biomass production was improved by 70% to 3630 mg/L, and biomass yield also was improved by 60%. Chemical Oxygen Demand (COD) removal reached above 86% and hydraulic retention time was shortened from 96 to 72 hr. The mechanism analysis indicated that Mg²⁺ could promote the content of bacteriochlorophyll in photosynthesis because Mg²⁺ is the bacteriochlorophyll active center, and thus improved adenosine triphosphate (ATP) production. An increase of ATP production enhanced the conversion of organic matter in wastewater into PNSB cell materials (biomass yield) and COD removal, leading to more biomass production. With 10 mg/L Mg²⁺, bacteriochlorophyll content and ATP production were improved by 60% and 33% respectively.     

Fabrication of Bi-Bi3O4Cl plasmon photocatalysts for removal of aqueous emerging contaminants under visible light

Photocatalytic oxidation of emerging contaminants (ECs) in water has recently gained extensive attentions. In this study, bismuth oxychloride-based plasmon photocatalysts (Bi-Bi₃O₄Cl) exhibiting high performance were successfully developed by reducing Bi³⁺ on the surface of Bi₃O₄Cl. Consequently, the photocatalysts were used to remove ECs from water. The effects of developmental process and Bi metal plasmon resonance on the photoelectric performances of Bi-Bi₃O₄Cl were investigated through a series of characterizations. The UV-vis diffuse reflection and photoluminescence spectra revealed that the light absorption range of the photocatalyst gradually increased and the electron recombination rate gradually decreased with the introduction of Bi metals. The optimal removal rates of ciprofloxacin and tetrabromobisphenol A by Bi-Bi₃O₄Cl were 93.8% and 96.4%; the respective reaction rate constants were 5.48 and 4.93 times higher than that of Bi₃O₄Cl. The mechanism study indicated that main reactants in the photocatalytic system were •O₂⁻ radicals and photogenerated holes, and the existence of oxygen vacancies and Bi metals promoted electron transfer in photocatalyst. In conclusion, this research produces a novel, green, highly efficient, and stable visible light photocatalyst for the removal of ECs from water.     

Regioselective oxidation of tetracycline by permanganate through alternating susceptible moiety and increasing electron donating ability

Permanganate has attracted much attention in wide range of chemistry and particularly in degradation of environmental pollutants. However, few studies have discussed the feature of regioselective reactivity of permanganate with specific moiety of the target compound. Herein, we studied the reaction between permanganate and tetracycline that is an emerging micropollutant with different species containing several electron-rich groups. The second-order rate constants increased from 6.0 to 9.0 and could be quantitatively modeled by considering the speciation of both reactants, yielding k_TC⁰?=?11.7 (mol/L)^?1?sec^?1, k_TC^??=?35.7 (mol/L)^?1?sec^?1, k_TC^2??=?43.1 (mol/L)^?1?sec^?1 for individual reaction channels. Degradation products were then identified as the hydroxylated and demethylated compounds. The result suggested a rate-limiting step of simple hydroxylation at the phenolic and/or alkene moieties, while the demethylation should be caused by the unavoidably formed manganese oxide via single electron oxidation. This is supported by the DFT calculation, indicating the primary oxidation of phenolic group of TC⁰ with activation barrier of 44.5?kcal/mol and of alkene group of TC^? and TC^2? with activation barriers of 44.0 and 43.4?kcal/mol, respectively. This is in agreement with the experimental results, implying the alternation of regioselectivity associated with the deprotonation process. The result was further supported by performing the Fukui function and electrostatic potential analysis, reflecting the more probable site and better electron donating tendency beneficial to the permanganate oxidation.     

Influence of seasonal temperature change on autotrophic nitrogen removal for mature landfill leachate treatment with high-ammonia by partial nitrification-Anammox process

In this study, a denitrification (DN)–partial nitritation (PN)–anaerobic ammonia oxidation (Anammox) system for the efficient nitrogen removal of mature landfill leachate was built with a zone-partitioning self-reflux biological reactor as the core device, and the effects of changes in seasonal temperature on the nitrogen removal in non-temperature-control environment were explored. The results showed that as the seasonal temperature decreased from 34°C to 11.3°C, the total nitrogen removal rate of the DN-PN-Anammox system gradually decreased from the peak value of 1.42 kg/(m³?day) to 0.49 kg/(m³?day). At low temperatures (<20°C), when the nitrogen load (NLR) of the system is not appropriate, the fluctuation of high NH₄⁺-N concentration in the landfill leachate greatly influenced the stability of the nitrogen removal. At temperatures of 11°C–15°C, the NLR of the system is controlled below 0.5 kg/(m³?day), which can achieve stable nitrogen removal and the nitrogen removal efficiency can reach above 96%. The abundance of Candidatus Brocadia gradually increased with the decrease of temperature. Nitrosomonas, Candidatus Brocadia and Candidatus Kuenenia as the main functional microorganisms in the low temperature.     

Exploration of reaction rates of chlorine dioxide with tryptophan residue in oligopeptides and proteins

Chlorine dioxide (ClO₂), an alternative disinfectant to chlorine, has a superior ability to inactivate microorganisms, in which protein damage has been considered as the main inactivation mechanism. However, the reactivity of ClO₂ with amino acid residues in oligopeptides and proteins remains poorly investigated. In this research, we studied the reaction rate constants of ClO₂ with tryptophan residues in five heptapeptides and four proteins using stopped-flow or competition kinetic method. Each heptapeptide and protein contain only one tryptophan residue and the reactivity of tryptophan residue with ClO₂ was lower than that of free tryptophan (3.88 × 10⁴ (mol/L)^?1sec^?1 at pH 7.0). The neighboring amino acid residues affected the reaction rates through promoting inter-peptide aggregation, changing electron density, shifting pK_a values or inducing electron transfer via redox reactions. A single amino acid residue difference in oligopeptides can make the reaction rate constants differ by over 60% (e.g. 3.01 × 10⁴ (mol/L)^?1sec^?1 for DDDWNDD and 1.85 × 10⁴ (mol/L)^?1sec^?1 for DDDWDDD at pH 7.0 (D: aspartic acid, W: tryptophan, N: asparagine)). The reaction rates of tryptophan-containing oligopeptides were also highly pH-dependent with higher reactivity for deprotonated tryptophan than the neutral specie. Tryptophan residues in proteins spanned a 4-fold range reactivity toward ClO₂ (i.e. 0.84 × 10⁴ (mol/L)^?1sec^?1 for ribonuclease T1 and 3.21 × 10⁴ (mol/L)^?1sec^?1 for melittin at pH 7.0) with accessibility to the oxidant as the determinating factor. The local environment surrounding the tryptophan residue in proteins can also accelerate the reaction rates by increasing the electron density of the indole ring of tryptophan or inhibit the reaction rates by inducing electron transfer reactions. The results are of significance in advancing understanding of ClO₂ oxidative reactions with proteins and microbial inactivation mechanisms.     

Hg0 removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron (III) chloride were studied on alab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analy-ses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg⁰, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg⁰) into oxidized mercury (Hg²⁺). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg⁰. Therefore, the Hg⁰ removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl₃-HZSM-5 was mainly in the form of mercuric chloride(HgCl₂), while on FeCl₃-NaX and FeCl₃-NaA it was mainly mercuri coxide(HgO).     

Formation of organic chloride in the treatment of textile dyeing sludge by Fenton system

In the oxidation treatment of textile dyeing sludge, the quantitative and transformation laws of organic chlorine are not clear enough. Thus, this study mainly evaluated the treatment of textile dyeing sludge by Fenton and Fenton-like system from the aspects of the influence of Cl⁻, the removal of polycyclic aromatic hydrocarbons (PAHs) and organic carbon, and the removal and formation mechanism of organic chlorine. The results showed that the organic halogen in sludge was mainly hydrophobic organic chlorine, and the content of adsorbable organic chlorine (AOCl) was 0.30 mg/g (dry sludge). In the Fenton system with pH=3, 500 mg/L Cl⁻, 30 mmol/L Fe²⁺ and 30 mmol/L H₂O₂, the removal of phenanthrene was promoted by chlorine radicals (•Cl), and the AOCl in sludge solid phase increased to 0.55 mg/g (dry sludge) at 30 min. According to spectral analysis, it was found that •Cl could chlorinate aromatic and aliphatic compounds (excluding PAHs) in solid phase at the same time, and eventually led to the accumulation of aromatic chlorides in solid phase. Strengthening the oxidation ability of Fenton system increased the formation of organic chlorines in liquid and solid phases. In weak acidity, the oxidation and desorption of superoxide anion promoted the removal and migration of PAHs and organic carbon in solid phase, and reduced the formation of total organic chlorine. The Fenton-like system dominated by non-hydroxyl radical could realize the mineralization of PAHs, organic carbon and organic chlorines instead of migration. This paper builds a basis for the selection of sludge conditioning methods.     

Contaminant removal from low-concentration polluted river water by the bio-rack wetlands

The bio-rack is a new approach for treating low-concentration polluted river water in wetland systems. A comparative study of the efficiency of contaminant removal between four plant species in bio-rack wetlands and between a bio-rack system and control system was conducted on a small-scale (500 mm length × 400 mm width × 400 mm height) to evaluate the decontamination effects of four different wetland plants. There was generally a significant difference in the removal of total nitrogen (TN), ammonia nitrogen (NH₃-N) and total phosphorus (TP), but no significant difference in the removal of permanganate index (COD_Mn) between the bio-rack wetland and control system. Bio-rack wetland planted with Thalia dealbata had higher nutrient removal rates than wetlands planted with other species. Plant fine-root (root diameter ≤ 3 mm) biomass rather than total plant biomass was related to nutrient removal efficiency. The study suggested that the nutrient removal rates are influenced by plant species, and high fine-root biomass is an important factor in selecting highly effective wetland plants for a bio-rack system. According to the mass balance, the TN and TP removal were in the range of 61.03--73.27 g/m² and 4.14--5.20 g/m² in four bio-rack wetlands during the whole operational period. The N and P removal by plant uptake constituted 34.9%--43.81% of the mass N removal and 62.05%--74.81% of the mass P removal. The study showed that the nitrification/denitrification process and plant uptake process are major removal pathways for TN, while plant uptake is an effective removal pathway for TP.     

Demulsification performance and mechanism of oil droplets by electrocoagulation: Role of surfactant

Surfactants are widely used to improve the solubility of oil in water in petrochemical, making it more difficult to remove oil–water emulsions during the water treatment process. Electrocoagulation (EC) is an appropriate method for treating oily wastewater and destabilizing emulsions. However, the demulsification mechanism of oil–water droplets emulsified by surfactants with different charges have not been investigated systematically. The demulsification performance of electrocoagulation on emulsions wastewater containing cationic, non-ionic, and anionic surfactants was studied. The results showed that the removal rate of total organic carbon (TOC) in oily wastewater with anionic surfactant by EC reached 92.98% ± 0.40% at a current density of 1 mA/cm², while that of the non-ionic surfactant was 84.88% ± 0.63%. The characterization of flocs showed that EC has the highest coagulation and demulsification of oil droplets with a negative charge on the surface (−70.50 ± 10.25 mV), which indicated that the charge neutralization of oil droplets was beneficial for the destabilization of the formed oily flocs. However, when the zeta potential of the oil droplets reached 75.50 ± 1.25 mV, the TOC removal efficiency was only 11.80% ± 1.43%. The TOC removal could achieve 33.23% ± 3.21% when the current density improved from 1 mA/cm² to 10 mA/cm². The enhanced removal was due to the sweep coagulation rather than charge neutralization. This study provides a fundamental basis for the electrochemical treatment of oily wastewater.     

Kinetic and product studies of the reactions of NO3 with a series of unsaturated organic compounds

Rate coefficients for the reaction of NO₃ radicals with 6 unsaturated volatile organic compounds (VOCs) in a 7300 L simulation chamber at ambient temperature and pressure have been determined by the relative rate method. The resulting rate coefficients were determined for isoprene, 2-carene, 3-carene, methyl vinyl ketone (MVK), methacrolein (MACR) and crotonaldehyde (CA), as (6.6 ± 0.8) × 10^?13, (1.8 ± 0.6) × 10^?11, (8.7 ± 0.5) × 10^?12, (1.24 ± 1.04) × 10^?16, (3.3 ± 0.9) × 10^?15 and (5.7 ± 1.2) × 10^?15 cm³/(molecule?sec), respectively. The experiments indicate that NO₃ radical reactions with all the studied unsaturated VOCs proceed through addition to the olefinic bond, however, it indicates that the introduction of a carbonyl group into unsaturated VOCs can deactivate the neighboring olefinic bond towards reaction with the NO₃ radical, which is to be expected since the presence of these electron-withdrawing substituents will reduce the electron density in the π orbitals of the alkenes, and will therefore reduce the rate coefficient of these electrophilic addition reactions. In addition, we investigated the product formation from the reactions of 2-carene and 3-carene with the NO₃ radical. Qualitative identification of an epoxide (C₁₀H₁₆OH⁺), caronaldehyde (C₁₀H₁₆O₂H⁺) and nitrooxy-ketone (C₁₀H₁₆O₄NH⁺) was achieved using a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and a reaction mechanism is proposed.     

Changes of DOM and its correlation with internal nutrient release during cyanobacterial growth and decline in Lake Chaohu, China

The seasonal changes in dissolved organic matter (DOM), and its correlation with the release of internal nutrients during the annual cycle of cyanobacteria in the eutrophic Lake Chaohu, China, were investigated from four sampling periods between November 2020 and July 2021. The DOM fluorescence components were identified as protein-like C1, microbial humic-like C2, and terrestrial humic-like C3. The highest total fluorescence intensity (F_T) of DOM in sediments during the incubation stage is due to the decomposition and degradation of cyanobacteria remains. The lowest humification of DOM and the highest proportion of C1 in waters during the initial cyanobacterial growth indicate that fresh algae are the main source. The highest molecular weight of DOM and F_T of the C2 in sediments during cyanobacterial outbreaks indicate the concurrent deposition of undegraded cyanobacterial remains and microbial degradation. The components of DOM are affected mainly by the dissolved total phosphorus in waters, while the temperature drives the annual cycle of cyanobacteria. The decreasing C1 in sediments and increasing nutrients in waters from the cyanobacterial incubation to outbreak indicate that mineralization of algal organic matter contributes importantly to the release of internal nutrients, with the strongest release of phosphorus observed during the early growth of cyanobacteria. The humic-like C2 and C3 components could also affect the dynamics of internal phosphorus through the formation of organic colloids and organic–inorganic ligands. The results show that the degradation of DOM leads to nutrients release and thus supports the continuous growth of cyanobacteria in eutrophic Lake Chaohu.     

Investigations on removal of SO2 from flue gas by aerosol formation in pulsed corona discharge process

The removal of SO₂ from flue gas by pulsed corona discharge in presence of ammonia was experimentally investigated. The results showed that the SO₂ removal mainly depends on thermal reaction of SO₂ with NH₃ and enhancements of 0%—25% by pulsed corona discharge in the range of the specific energy 0—5 Wh/Nm³. The aerosol mass concentration, mainly composed of ammonium sulfate, increased with specific energy dissipated into the reactor. With an initial concentration of 2000—2100 ppmv SO₂ and energy consumption of 3 Wh/Nm³, when a stoichiometric amount of ammonia is injected, the removal efficiency of SO₂ and percentage of ammonium sulfates in reaction products are all ≥80%. The collection efficiency of the reactor for aerosol is about 74% at a flue gas temperature of 60 to 65℃ and a water vapor content of 9% to 11% volume.     

Study on the simultaneous reduction of methylmercury by SnCl2 when analyzing inorganic Hg in aqueous samples

Mercury (Hg) is among the most concerned contaminants in the world. It has three major chemical forms in the environment, including Hg⁰, Hg^2 +, and methylmercury (MeHg). Due to their differences in toxicity, mobility, and bioavailability, speciation analysis is critical for understanding Hg cycling and fate in the environment. SnCl₂ reduction-atomic fluorescence spectrometry detection is the most commonly used method for analyzing inorganic Hg. However, it should be noted that MeHg may also be reduced by SnCl₂, which would result in the overestimation of inorganic Hg. In this study, the reduction of MeHg by SnCl₂ in both de-ionized (DI) water and four natural waters was investigated. The results showed that MeHg could be reduced by SnCl₂ in DI water whereas this reaction was hard to occur in tested natural waters. By investigating the effects of water chemical characteristics (dissolved organic matter, pH and common anions and cations) on this reaction, SO₄^2 ? was identified to be the dominant factor prohibiting SnCl₂ induced MeHg reduction in natural waters. SO₄^2 ? in natural waters was evidenced to be reduced to S^2 ? by SnCl₂ and the generated S^2 ? can complex with MeHg to form MeHgS^? which is hard to be reduced by SnCl₂. Findings of this study indicate that the effect of MeHg reduction by SnCl₂ on inorganic Hg analysis is negligible in natural waters; however, at simulated experimental systems without SO₄^2 ?, SO₄^2 ? should be added as protecting agents to prevent MeHg reduction when analyzing inorganic Hg if it would not cause any other unwanted effects.     

Spatiotemporal variations of nitrate sources and dynamics in a typical agricultural riverine system under monsoon climate

Nitrogen pollution is a serious environmental issue in the Danjiangkou Reservoir region (DRR), the water source of the South-to-North Water Diversion Project of China. In this research, seasonal surveys and a bi-weekly time series survey were conducted in the Qihe River Basin, one of the most densely populated agricultural basins in the DRR. Hydrochemical compositions (NO₃^? and Cl^?), dual isotopes (δD-H₂O, δ¹⁸O-H₂O, δ¹⁵N-NO₃^?, and δ¹⁸O-NO₃^?), and a Markov Chain Monte Carlo isotope mixing model were jointly applied to unravel the sources, migrations, and transformations of the nitrate (NO₃^?) in the basin. It was revealed that the mixing between different sources was the main process controlling the isotopic compositions of the riverine NO₃^? in the upper-middle reaches. In contrast, denitrification occurred in the lower reaches. For the first time, the sources of NO₃^? were quantified at a basin scale in the DRR. Overall, the river transported 484.2 tons/year of NO₃-N to the reservoir, of which 32.6%, 36.4%, 28.0%, and 3.0% was from soil organic nitrogen, chemical fertilizer, residential sewage and atmospheric precipitation, respectively. The NO₃-N fluxes of the different sources were regulated by the monsoon climate and anthropogenic activities. For example, high precipitation and intense fertilization resulted in severe nonpoint source pollution. Denitrification thrived in soils and reservoirs in wet seasons. Temperature could regulate the migration, nitrification and denitrification processes. Based on the results, we suggest that the management strategies dealing with nitrogen pollution issue in the DRR should follow the specific spatiotemporal characteristics of NO₃^? sources, migration and transformation mechanisms.     

Variation on leaching behavior of caustic compounds in bauxite residue during dealkalization process

Bauxite residue, a byproduct of alumina manufacture, is a serious environmental pollutant due to its high leaching contents of metals and caustic compounds. Four typical anions of CO₃^2?, HCO₃^?, Al(OH)₄^? and OH^? (represented caustic compounds) and metal ions (As, B, Mo and V) were selected to assess their leaching behavior under dealkalization process with different conditions including liquid/solid ratio (L/S ratio), temperature and leaching time. The results revealed that washing process could remove the soluble composition in bauxite residue effectively. The leaching concentrations of typical anions in bauxite residue decreased as follows: c(CO₃^2?) > c(HCO₃^?) > c[Al(OH)₄^?] > c(OH^?). L/S ratio had a more significant effect on leaching behavior of OH^?, whilst the leaching concentration of Al(OH)₄^? varied larger underleaching temperature and time treatment. Under the optimal leaching, the total alkaline, soluble Na concentrations, exchangeable Ca concentrations were 79.52, 68.93, and 136.0 mmol/L, respectively, whilst the soluble and exchangeable content of As, B, Mo and V in bauxite residue changed slightly. However, it should be noted that water leaching has released metal ions such as As, B, Mo and V in bauxite residue to the surrounding environment. The semiquantitative analysis of XRD revealed that water leaching increased the content of gismondine from 2.4% to 6.4%. The SEM images demonstrated the dissolution of caustic compounds on bauxite residue surface. The correlation analysis indicated that CO₃^2? and HCO₃^? could effectively reflect the alkalinity of bauxite residue, and may be regarded as critical dealkalization indicators to evaluate alkalinity removal in bauxite residue.