Sorptive removal of cadmium using the attapulgite modified by the combination of calcination and iron.

Sorptive removal of cadmium (Cd) from the aqueous solutions using the easily available natural materials is an attractive method. However, the adsorption efficiencies of these materials, such as clays, are typically low. Besides, they are generally in relatively low stability and renewability, which restrict their application. Thus, modification of these materials to enhance their performance on Cd removal has gained growing attentions. Herein, the integration of calcination and ferric chloride (FeCl3) was used to modify a typical clay, i.e., attapulgite, to increase the adsorption sites, and thus to develop a robust adsorbent for Cd. Under the optimum conditions for attapulgite modification (i.e., the mass ratio of FeCl3 to attapulgite was 1:2, calcination temperature was 350 °C, and calcination time was 1.5 h) and Cd adsorption (i.e., initial pH of 6.0, adsorption temperature of 25 °C, and adsorbent dosage of 1.0 g/L), the maximum adsorption capacity of the modified attapulgite toward Cd was 149.9 mg/g. Mechanisms of surface complexation and electrostatic attraction were involved in the efficient removal of Cd. The adsorption of Cd increased with pH due to the increased electrostatic attraction. Metal cations inhibited the Cd adsorption through competing with the adsorption sites. The changes of Gibbs-free energy during the adsorption of Cd were lower than zero and decreased with temperature, suggesting the process was spontaneous and endothermic. The removal efficiency of Cd after 5 times of recycle maintained at 82% of that of the raw modified attapulgite demonstrated the stability of the adsorbent. These results suggested that the modified attapulgite is robust for Cd removal and is promising for land application.

Insight into the reactions of antimonite with manganese oxides: Synergistic effects of Mn(III) and oxygen vacancies.

Manganese oxides (MnxOy) are critical for determining the environmental behaviors and fate of antimonite (Sb(III)). However, little is known about the qualitative/quantitative connection between MnxOy structures and Sb(III) fate. Herein, the reactions of Sb(III) and six MnxOy with different structures were systematically investigated. The initial oxidation rates of Sb(III) (rinit) on six MnxOy decreased in the order of γ-MnO2>δ-MnO2>α-MnO2>γ-MnOOH>Mn3O4>ß-MnO2 (pHinitial=7.0), from 0.32 ± 0.04 to 11.17 ± 1.61 mmol/min/mol-Mn. The amounts of antimony retained (i.e., the sum of Sb(III) and antimonate (Sb(V))) on these MnxOy followed the same trend as that of oxidation. Oxidation of Sb(III) released Mn(II) and created more sites for adsorption. Outwardly, MnxOy with higher reduction potential (E0) and specific surface area (SSA) favored faster Sb(III) oxidation. Inwardly, Mn(III) and oxygen vacancies (Ov) exhibited a synergistic effect on Sb(III) oxidation. Mn(III) can easier accept electron than Mn(IV) based on the change in Gibbs free energy calculation. Ov can adsorb free oxygen to form surface oxygen (Osur) which is much more reactive than lattice oxygen (Olatt). Moreover, Ov is in close proximity to Mn(III) in high-valent MnxOy which facilitated the reactions between Sb(III) and Mn(III) through the enhancement of Sb(III) adsorption and electron transfer. Ov in low-valent MnxOy is adjacent to Mn(II), thus it showed weaker enhancement than that in high-valent MnxOy. Part of δ-MnO2 and almost all Mn3O4 were converted to γ-MnOOH during their reaction with Sb(III), while the other four MnxOy were barely changed. The results obtained provide mechanistic insight into the reactions occurring within Sb(III) and MnxOy, which are helpful for better understanding and prediction of the fate of Sb(III) in Mn-rich environments.

Advances in Sorptive Removal of Hexavalent Chromium (Cr(VI)) in Aqueous Solutions Using Polymeric Materials.

Sorptive removal of hexavalent chromium (Cr(VI)) bears the advantages of simple operation and easy construction. Customized polymeric materials are the attracting adsorbents due to their selectivity, chemical and mechanical stabilities. The mostly investigated polymeric materials for removing Cr(VI) were reviewed in this work. Assembling of robust functional groups, reduction of self-aggregation, and enhancement of stability and mechanical strength, were the general strategies to improve the performance of polymeric adsorbents. The maximum adsorption capacities of these polymers toward Cr(VI) fitted by Langmuir isotherm model ranged from 3.2 to 1185 mg/g. Mechanisms of complexation, chelation, reduction, electrostatic attraction, anion exchange, and hydrogen bonding were involved in the Cr(VI) removal. Influence factors on Cr(VI) removal were itemized. Polymeric adsorbents performed much better in the strong acidic pH range (e.g., pH 2.0) and at higher initial Cr(VI) concentrations. The adsorption of Cr(VI) was an endothermic reaction, and higher reaction temperature favored more robust adsorption. Anions inhibited the removal of Cr(VI) through competitive adsorption, while that was barely affected by cations. Factors that affected the regeneration of these adsorbents were summarized. To realize the goal of industrial application and environmental protection, removal of the Cr(VI) accompanied by its detoxication through reduction is highly encouraged. Moreover, development of adsorbents with strong regeneration ability and low cost, which are robust for removing Cr(VI) at trace levels and a wider pH range, should also be an eternally immutable subject in the future. Work done will be helpful for developing more robust polymeric adsorbents and for promoting the treatment of Cr(VI)-containing wastewater.

Phenylarsonics in concentrated animal feeding operations: Fate, associated risk, and treatment approaches.

Phenylarsonics are present as additives in animal feed in some countries. As only a small fraction of these additives is metabolized in animals, they mostly end up in the environment. A comprehensive investigation of the fate of these additives is crucial for evaluating their risks. This review aims to provide a clear understanding of the transformation mechanism of phenylarsonics in vivo and in vitro and to evaluate their fate and associated risks. Degradation of phenylarsonics releases toxic As species (mainly as inorganic arsenic (iAs)). Trivalent phenylarsonics are the metabolites or biotic degradation intermediates of phenylarsonics. The cleavage of As groups from trivalent phenylarsonics catalyzed by C-As lyase or other unknown pathways generates arsenite (As(III)). As(III) can be further oxidized to arsenate (As(V)) and methylated to methyl-arsenic species. The half-lives associated with abiotic degradation of phenylarsonics ranged from a few minutes to tens of hours, while those associated with biotic degradation ranged from several days to hundreds of days. Abiotic degradation resulted in a higher yield of iAs than biotic degradation. The use of phenylarsonics led to elevated total As and iAs levels in animal products and environmental matrices, resulting in As exposure risk to humans. The oxidation of phenylarsonics to As(V) facilitated the sorptive removal of As, which provides a general approach for treating these compounds. This review provides solid evidence that the use of phenylarsonics has adverse effects on both human health and environmental safety, and therefore, supports their withdrawal from the global market.

Benzotriazole Ultraviolet Stabilizers Promote Breast Cancer Cell Proliferation via Activating Estrogen-Related Receptors α and γ at Human-Relevant Levels.

Benzotriazole ultraviolet stabilizers (BUVSs) are ubiquitous emerging pollutants that have been reported to show estrogenic disruption effects through interaction with the classic estrogen receptors (ERs) in the fashion of low activity. The present study aims at revealing the potential disruption mechanism via estrogen-related receptors α and γ (ERRα and ERRγ) pathways. By the competitive binding assay, we first found that BUVSs bond to ERRγ ligand binding domain (ERRγ-LBD) with Kd ranging from 0.66 to 19.27 µM. According to the results of reporter gene assays, the transcriptional activities of ERRα and ERRγ were promoted by most tested BUVSs with the lowest observed effective concentrations (LOEC) from 10 to 100 nM, which are in the range of human exposure levels. At 1 µM, most tested BUVSs showed higher agonistic activity toward ERRγ than ERRα. The most effective two BUVSs promoted the MCF-7 proliferation dependent on ERRα and ERRγ with a LOEC of 100 nM. The molecular dynamics simulation showed that most studied BUVSs had lower binding free energy with ERRγ than with ERRα. The structure-activity relationship analysis revealed that molecular polarizability, electron-donating ability, ionization potential, and softness were the main structural factors impacting the binding of BUVSs with ERRγ. Overall, our results provide novel insights into the estrogenic disruption effects of BUVSs.

New methods for quantification of Fenton's reagent addition based on aged sludge indicators to improve filterability.

Fenton oxidation can effectively improve the dewaterability of aged sludge. Quantification of the addition of optimal reagents is central to the conditioning and dewatering of aged sludge. Improving the accuracy of quantification is significant to promote cost effectiveness. The effects of reagent addition and the mechanism governing the improved filterability of the aged sludge need to be understood uniformly. In this study, the optimal reagent additions have been determined using the response surface method (RSM) for five out of the eight aged sludges that were investigated. The physicochemical characteristics of eight aged sludges, including the extracellular polymer substance, undissolved organic matter, and suspension structure network, were investigated. Meanwhile, a comprehensive correlation analysis of critical indicators was conducted to investigate the interactions among the properties of the aged sludge. The effects of these interactions on the conditioning and filtration processes were examined, and a unified understanding of the combination of factors affecting the optimal reagent addition was obtained. The key factors were aggregate size, dewatering extent, yield stress, and organic substance content. Based on these results, a new reagent addition quantification method was developed along with an empirical model of the relationship between physicochemical properties and the economically optimal reagent addition.

The potential endocrine disruption mechanism of anthelmintic drug niclosamide by activating estrogen receptors and estrogen-related receptors.

Niclosamide (NIC), a helminthic drug used widely for controlling schistosomiasis, can reportedly disrupt the endocrine system. However, its underlying mechanisms are still unclear. In this study, we revealed the potential endocrine disruption mechanism of NIC by activating estrogen receptors (ERs) and estrogen-related receptors (ERRs). The binding potency of NIC with ERα, ERß and ERRγ were determined by fluorescence competitive binding assays, which shows an IC50 (the concentration of NIC needed to displace 50 % of the probe from the receptor) of 90 ± 4.1, 10 ± 1.7 nM and 0.59 ± 0.07 nM respectively. The IC50 for ERRγ is the lowest one among the three detected receptors, which is three orders of magnitude lower than the known agonist GSK4716.The transcriptional activities of NIC on ERs and ERRs were detected by MVLN cells (stably transfected with ERs reporter gene) and HeLa cells (transiently transfected with ERRs reporter gene)-based luciferase reporter gene assay. The lowest observable effective concentration (LOEC) ranked as follows: ERRγ (0.5 nM) < ERRα (10 nM) < ERs (100 nM). The maximum observed induction rate for ERRγ (294 %) was higher than that for ERRα (191 %). The maximum observed induction rate of NIC for ERs was 30 % relative to 17ß-estradiol. In addition, we simulated the interactions of NIC with ERs and ERRs by molecular docking. NIC could dock into the ligand binding pockets of ERs and ERRs and form hydrogen bonds with different amino acids. The binding energy ranked as follows: ERRγ (-8.90 kcal/mol) < ERß (-7.57 kcal/mol) < ERRα (-7.15 kcal/mol) < ERα (-6.53 kcal/mol), which implied that NIC bound to ERRγ with higher binding affinity than the other receptors. Overall, we clarify that ERRγ might be the dominant target for NIC in cells rather than ERRα and ERs. We reveal potential novel mechanisms for the endocrine disruption effects of NIC by activating both ERRs and ERs at environmentally-related nanomolar levels.

Adsorption and desorption of phenylarsonic acid compounds on metal oxide and hydroxide, and clay minerals.

Adsorption and desorption of p-arsanilic acid (p-ASA) and roxarsone (ROX) on six soil minerals, including hematite (α-Fe2O3), goethite (α-FeOOH), ferrihydrite (Fe(OH)3), aluminum oxide (α-Al2O3), manganese oxide (γ-MnO2), and kaolinite, were studied, and the impact of solution matrices on their adsorption was systematically evaluated. Adsorption of p-ASA/ROX on the metal (hydro)oxide and clay minerals occurred quickly (mostly within 2 h), and could be well described by the pseudo second-order kinetic model. The apparent maximum adsorption capacities of α-Fe2O3, α-FeOOH, Fe(OH)3, α-Al2O3, γ-MnO2, and kaolinite (at an initial pH of 7.0) for p-ASA were 1.7, 0.9, 2.5, 0.08, 1.1, and 0.02 µmol/m2, while those for ROX were 1.6, 0.7, 2.4, 0.1, 0.5, and 0.05 µmol/m2, respectively. Besides adsorbing p-ASA/ROX, γ-MnO2 also caused their oxidation. Experimental results suggest that formation of inner-sphere complexes through the arsonic acid group is the primary mechanism for adsorption of p-ASA/ROX on iron (hydro)oxides and γ-MnO2, while outer-sphere complexation plays a critical role in their adsorption on α-Al2O3 and kaolinite. Adsorption of p-ASA/ROX on the metal (hydro)oxide and clay minerals was affected by solution pH, co-existing metal ions (Ca2+, Mg2+, Al3+, Cu2+, Fe3+, and Zn2+), oxyanions (H2PO4-, HCO3-, and SO42-), and humic acid. The solid-to-liquid partition coefficients of p-ASA during the desorption from α-Fe2O3, α-FeOOH, Fe(OH)3, α-Al2O3, γ-MnO2, and kaolinite were 0.47, 2.69, 4.38, 0.03, 30.4, and 0.1 L/g, while those of ROX were 0.28, 1.68, 3.48, 0.02, 4.0, and 0.02 L/g, respectively. Agricultural soils with lower contents of organic carbon exhibited higher adsorption capacities towards p-ASA/ROX, which indicates that soil minerals play a key role in the adsorption of phenylarsonic acid compounds while organic matter could have strong inhibitory effect. These findings could help better understand and predict the transport and fate of p-ASA/ROX in surface soils with low contents of organic matter.

Bioaccumulation and human health risk assessment of DDT and its metabolites (DDTs) in yellowfin tuna (Thunnus albacares) and their prey from the South China Sea.

DDTs were detected in yellowfin tuna (Thunnus albacares, 92.1-221.8 ng‧g-1 lipid weight) and their prey (54.9-93.5 ng‧g-1 lipid weight) from the South China Sea (SCS). DDT levels reported in this study were lower than those of the previous studies indicated the recent mitigation of DDT contamination in the SCS. Higher DDT levels were observed in fat abdominal muscle than lean dorsal muscle in adult yellowfin tuna. Meanwhile, DDT levels in adult yellowfin tuna were higher than the young ones. The composition profiles of DDT and its metabolites suggested DDTs in fish in the SCS were mainly derived from the historical use of technical DDTs. DDTs were biomagnified through food chains with the trophic magnification factor of 2.5. Risk assessment results indicated that dietary exposure to DDTs through lifetime fish consumption from the SCS would pose little cancer and noncarcinogenic risk to coastal residents.

Evidence for the charge disproportionation of iron in extraterrestrial bridgmanite.

Bridgmanite, MgSiO3 with perovskite structure, is considered the most abundant mineral on Earth. On the lower mantle, it contains Fe and Al that strongly influence its behavior. Experimentalists have debated whether iron may exist in a mixed valence state, coexistence of Fe2+ and Fe3+ in bridgmanite, through charge disproportionation. Here, we report the discovery of Fe-rich aluminous bridgmanite coexisting with metallic iron in a shock vein of the Suizhou meteorite. This is the first direct evidence in nature of the Fe disproportionation reaction, which so far has only been observed in some high-pressure experiments. Furthermore, our discovery supports the idea that the disproportionation reaction would have played a key role in redox processes and the evolution of Earth.

Experimental and theoretical insights into kinetics and mechanisms of hydroxyl and sulfate radicals-mediated degradation of sulfamethoxazole: Similarities and differences.

Hydroxyl radical (•OH)- and sulfate radical ()-based advanced oxidation technologies (AOTs) have been proven an effective method to remove antibiotics in wastewater treatment plants (WWTPs). This study aims to gain insights into kinetics and mechanisms of neutral sulfamethoxazole (SMX) degradation, a representative antibiotic, by •OH and using an experimental and theoretical approach. First, the second-order rate constants (k) of SMX with •OH and were determined to be (7.27 ± 0.43) × 109 and (2.98 ± 0.32) × 109 M-1 s-1 in UV/H2O2 and UV/persulfate (UV/PS) systems, respectively. The following theoretical calculations at the M06-2X level of theory revealed that addition of radicals to the benzene ring is the most favorable first-step reaction for both •OH and , but that exhibits higher energy barriers and selectivity than •OH due to steric hindrance. We further analyzed subsequent reactions and, interestingly, our findings closely corroborated HOMO/LUMO distributions of SMX to the oxidation pathways. Finally, the estimation of energy consumption for UV alone, •OH-, and -mediated oxidation processes was compared. These comparative results, for the first time, provide insights into the similarities and differences of degradation of SMX by •OH/ at the molecular level and can help improve antibiotics removal using radical based AOTs in WWTPs.

A simple treatment method for phenylarsenic compounds: Oxidation by ferrate (VI) and simultaneous removal of the arsenate released with in situ formed Fe(III) oxide-hydroxide.

p-Arsanilic acid (p-ASA) and roxarsone (ROX) are two major phenylarsenic feed additives that are still widely used in many countries, and the land application of animal waste containing these compounds could introduce large quantities of arsenic into the environment. In this study, we proposed a treatment scheme for animal waste that involves leaching of p-ASA/ROX out of the manure first by water, then oxidation by ferrate (Fe(VI)) and removal of the arsenate released by in situ formed Fe(III) oxide-hydroxide. The effects of solution pH, dosage of Fe(VI), solution ionic strength, and matrix species on the treatment performance were systematically evaluated. Initial solution pH values of 4.1 and 2.0 were chosen for the oxidation of p-ASA and ROX, respectively, while efficient arsenate removal could be achieved with relatively small adjustment of the final solution pH (to 4.0). The pH-dependent second-order rate constants for the reactions between ferrate and p-ASA and ROX over the pH range of 2.0-12.0 were estimated to be 7.13 × 105-2.01 × 10-1 and 8.91 × 103-1.65 × 10-1 M-1 s-1, respectively. The degradation pathways of p-ASA/ROX during ferrate oxidation were proposed based on the inorganic and organic intermediates identified. Depending on the levels of p-ASA/ROX, effective treatment could be achieved through flexible adjustment of the Fe(VI) dosage. p-ASA/ROX (10 mg-As/L) in swine manure leachate could be efficiently treated by ferrate oxidation within 5 min, with the overall arsenic removal efficiency higher than 99.2%. The treatment performance was barely affected by the presence of common ions (K+, Ca2+, Na+, Mg2+, SO42-, NO3-, and Cl-), while humic acid, Mn2+, Ni2+, Fe3+, and Co2+ inhibited p-ASA/ROX oxidation. The presence of PO43- and NH4+ could accelerate the oxidation of p-ASA/ROX, but PO43- and humic acid compromised sorptive removal of the released arsenate due to their competitive sorption on the Fe(III) oxide-hydroxide precipitate. Ferrate oxidation is green and fast, and the operation is simple, thus it could serve as a promising and environment-friendly option for mitigating the risk of phenylarsenic feed additives in animal waste.

Influence of chemical speciation on photochemical transformation of three fluoroquinolones (FQs) in water: Kinetics, mechanism, and toxicity of photolysis products.

This study investigated the contribution of direct, indirect, and self-sensitized photolysis to the photochemical fate of three model fluoroquinolones (FQs), i.e., lomefloxacin (LOM), norfloxacin (NOR), and ofloxacin (OFL), and demonstrated the influence of chemical speciation on their photodegradation behavior, a topic that has received relatively little attention. Results suggest that these FQs in water transformed mainly via direct photolysis, while hydroxyl radical played a key role in their indirect and self-sensitized photolysis. Chemical speciation of such zwitterionic compounds significantly affected the kinetics of their phototransformation, with the quantum yields of photodegradation decreased in the order of zwitterionic (FQsH) > anionic (FQs-) > cationic (FQsH2+). The photodegradation pathways of FQs depended on both their structures and chemical speciation. Defluorination for LOM in C-8 and NOR in C-6 was more significant when they were present in zwitterionic form than in the other forms. Cationic FQs underwent direct piperazinyl ring cleavage, and zwitterionic ones underwent piperazinyl ring oxidation, while the degradation pathway of piperazinyl ring for FQs in anionic form was structure dependent. Decarboxylation for zwitterionic FQs occurred more slowly compared to both cationic and anionic ones, and the FQs bearing electron-donating groups in C-8 position degraded more easily in cationic form than the anionic ones, while the opposite was true for the FQs without such a group in C-8 position. Results of Vibrio fischeri bioluminescence inhibition tests showed the toxicity of zwitterionic NOR and OFL significantly decreased after photodegradation, while the degradation products of LOM exhibited greater toxicity. These findings indicate that chemical speciation of zwitterionic compounds could affect the kinetics and pathways of their photochemical transformation, and thus have important implications on their fate and risk in aquatic environment.

Heavy metal pollution caused by small-scale metal ore mining activities: A case study from a polymetallic mine in South China.

Although metal ore mining activities are well known as an important source of heavy metals, soil pollution caused by small-scale mining activities has long been overlooked. This study investigated the pollution of surface soils in an area surrounding a recently abandoned small-scale polymetallic mining district in Guangdong province of south China. A total of 13 tailing samples, 145 surface soil samples, and 29 water samples were collected, and the concentrations of major heavy metals, including Cr, Mn, Co, Ni, Cu, Zn, As, Cd, Pb, and Se, were determined. The results show that the tailings contained high levels of heavy metals, with Cu, Zn, As, Cd, and Pb occurring in the ranges of 739-4.15 × 103, 1.81 × 103-5.00 × 103, 118-1.26 × 103, 8.14-57.7, and 1.23 × 103-6.99 × 103 mg/kg, respectively. Heavy metals also occurred at high concentrations in the mine drainages (15.4-17.9 mg/L for Cu, 21.1-29.3 mg/L for Zn, 0.553-0.770 mg/L for Cd, and 1.17-2.57 mg/L for Pb), particularly those with pH below 3. The mean contents of Cu, Zn, As, Cd, and Pb in the surface soils of local farmlands were up to 7 times higher than the corresponding background values, and results of multivariate statistical analysis clearly indicate that Cu, Zn, Cd, and Pb were largely contributed by the mining activities. The surface soils from farmlands surrounding the mining district were moderately to seriously polluted, while the potential ecological risk of heavy metal pollution was extremely high. It was estimated that the input fluxes from the mining district to the surrounding farmlands were approximately 17.1, 59.2, 0.311, and 93.8 kg/ha/yr for Cu, Zn, Cd, and Pb, respectively, which probably occurred through transport of fine tailings by wind and runoff, and mine drainage as well. These findings indicate the significant need for proper containment of the mine tailings at small-scale metal ore mines.

Natural diamond formation by self-redox of ferromagnesian carbonate.

Formation of natural diamonds requires the reduction of carbon to its bare elemental form, and pressures (P) greater than 5 GPa to cross the graphite-diamond transition boundary. In a study of shocked ferromagnesian carbonate at the Xiuyan impact crater, we found that the impact pressure-temperature (P-T) of 25-45 GPa and 800-900 °C were sufficient to decompose ankerite Ca(Fe2+,Mg)(CO3)2 to form diamond in the absence of another reductant. The carbonate self-reduced to diamond by concurrent oxidation of Fe2+ to Fe3+ to form a high-P polymorph of magnesioferrite, MgFe3+2O4 Discovery of the subsolidus carbonate self-reduction mechanism indicates that diamonds could be ubiquitously present as a dominant host for carbon in the Earth's lower mantle.

Discovery of the Fe-analogue of akimotoite in the shocked Suizhou L6 chondrite.

We report the first natural occurrence of the Fe-analogue of akimotoite, ilmenite-structured MgSiO3, a missing phase among the predicted high-pressure polymorphs of Fe-pyroxene, with the composition (Fe2+0.48Mg0.37Ca0.04Na0.04Mn2+0.03Al0.03Cr3+0.01)Σ=1.00Si1.00O3. The new mineral was approved by the International Mineralogical Association (IMA 2016-085) and named hemleyite in honour of Russell J. Hemley. It was discovered in an unmelted portion of the heavily shocked L6 Suizhou chondrite closely associated to olivine, clinoenstatite and Fe-bearing pyroxene with a composition nearly identical to that of hemleyite. We also report the first single-crystal X-ray diffraction study of a Si-bearing, ilmenite-structured phase. The fact that hemleyite formed in a meteorite exposed to high pressures (<20 GPa) and temperatures (<2000 °C) during impact-induced shocks indicates that it could play a crucial role at the bottom of the Earth's mantle transition zone and within the uppermost lower mantle.

Mechanism, kinetics, and pathways of self-sensitized sunlight photodegradation of phenylarsonic compounds.

Being highly water-soluble, phenylarsonic feed additives discharged in animal wastes can easily accumulate in surface water bodies. The photodegradation mechanism, kinetics, and pathways of p-arsanilic acid (p-ASA), 4-hydrophenylarsonic acid (4-HPAA), and phenylarsonic acid (PAA) in water under simulated and natural sunlight irradiation were investigated. The -AsO(OH)2 group was cleaved from the aromatic ring during photodegradation, and p-benzoquinone and p-hydroquinone were formed as the major organic degradation intermediates. Experimental results did not indicate any significant direct photolysis of the phenylarsonic compounds under simulated and natural sunlight irradiation, but consistently showed that they sensitized the formation of singlet oxygen, which was responsible for their photodegradation and oxidation of the As(III) released. A simple (1)O2-based "heterogeneous" model was developed, which could well describe the kinetics of (1)O2 formation and phenylarsonic compound photodegradation under various conditions. Indirect photolysis caused by inorganic ions commonly present in natural waters was negligible, while natural organic matter could significantly inhibit their photodegradation. The half-lives of p-ASA, 4-HPAA, and PAA photodegradation under simulated sunlight irradiation (765 W m(-2), 25 °C) were 11.82 ± 0.19, 20.06 ± 0.10, and 135 ± 6.0 min, respectively, while their degradation rates under natural sunlight in the Pearl River Delta of southern China were 5 times slower due to lower irradiation intensity and water temperatures (19-23 °C).

Rapid degradation of p-arsanilic acid with simultaneous arsenic removal from aqueous solution using Fenton process.

Although banned in some developed countries, p-arsanilic acid (p-ASA) is still used widely as a feed additive for swine production in many countries. With little uptake and transformation in animal bodies, nearly all the p-ASA administered to animals is excreted chemically unchanged in animal wastes, which can subsequently release the more toxic inorganic arsenic species upon degradation in the environment. For safe disposal of the animal wastes laden with p-ASA, we proposed a method of leaching the highly water-soluble p-ASA out of the manure first, followed by treatment of the leachate using the Fenton process to achieve fast oxidation of p-ASA and removal of the inorganic arsenic species released (predominantly arsenate) from solution simultaneously. The effects of solution pH, dosages of H2O2 and Fe(2+), and the presence of dissolved organic matter (DOM) on the treatment efficiency were systematically investigated. Under the optimum treatment conditions (0.53 mmol L(-1) Fe(2+), 2.12 mmol L(-1) H2O2, and initial pH of 3.0), p-ASA (10 mg-As L(-1)) could be completely oxidized to As(V) within 30 min in pure water and 4 natural water samples, and at the final pH of 4.0, the residual arsenic levels in solution phase were as low as 1.1 and 20.1-43.4 µg L(-1) in the two types of water matrixes, respectively. The presence of humic acid significantly retarded the oxidation of p-ASA by scavenging HO, and inhibited the As(V) removal through competitive adsorption on ferric hydroxide. Due to the high contents of DOM in the swine manure leachate samples (TOC at ∼500 mg L(-1)), much higher dosages of Fe(2+) (10.0 mmol L(-1)) and H2O2 (40.0 mmol L(-1)) and a longer treatment time (120 min) were required to achieve near complete oxidation of p-ASA (98.0%), while maintaining the levels of residual arsenic in the solution at <70.0 µg L(-1). The degradation pathway of p-ASA in the Fenton process was proposed based on the major degradation products detected. Together, the results demonstrate that the Fenton process is promising as an efficient, robust, and low-cost treatment method for controlling the risk of p-ASA in the animal wastes generated at factory farms.

Arsenic pollution of agricultural soils by concentrated animal feeding operations (CAFOs).

Animal wastes from concentrated animal feeding operations (CAFOs) can cause soil arsenic pollution due to the widespread use of organoarsenic feed additives. This study investigated the arsenic pollution of surface soils in a typical CAFO zone, in comparison with that of agricultural soils in the Pearl River Delta, China. The mean soil arsenic contents in the CAFO zone were elevated compared to those in the local background and agricultural soils of the Pearl River Delta region. Chemical speciation analysis showed that the soils in the CAFO zone were clearly contaminated by the organoarsenic feed additive, p-arsanilic acid (ASA). Transformation of ASA to inorganic arsenic (arsenite and arsenate) in the surface soils was also observed. Although the potential ecological risk posed by the arsenic in the surface soils was relatively low in the CAFO zone, continuous discharge of organoarsenic feed additives could cause accumulation of arsenic and thus deserves significant attention.

Quantitative evaluation of environmental risks of flotation tailings from hydrothermal sulfidation-flotation process.

Floatation tailings (FT) are the main by-products of the hydrothermal sulfidation-flotation process. FT (FT1 and FT2) were obtained by treating two different neutralization sludges (NS) (NS1 and NS2). This paper quantitatively evaluated the environmental risks of heavy metals (Zn, Cd, Cu, Pb, and As) in FT versus NS. The total concentration and leaching rates (R 2) of heavy metals in FT were much lower than those in NS, demonstrating that the hydrothermal sulfidation-flotation process was able to effectively suppress the mobility and leachability of heavy metals. The BCR-three sequence leaching procedure of FT confirmed that all metals were transformed into more stable forms (residue and oxidizable forms) than were found that in NS. The potential ecological risk index indicated that the overall risks caused by heavy metals decreased significantly from 6627.59 and 7229.67 (very serious risk) in NS1 and NS2, respectively, to 80.26 and 76.27 (low risk) in FT1 and FT2, respectively. According to the risk assessment code, none of the heavy metals in FT posed significant risk to the natural environment except Zn (with low risk). In general, the risk of heavy metals in FT had been well controlled.