Formation and stability of biogenic tooeleite during Fe(II) oxidation by Acidithiobacillus ferrooxidans.

Tooeleite is the only known ferric arsenite sulfate mineral and has environmental significance for arsenic remediation. This study investigated the formation and stability of biogenic tooeleite in Fe(II)-As(III)-SO42- environment using Acidithiobacillus ferrooxidans under the ambient conditions. The results show that bacteria facilitated the formation and crystallization of tooeleite owing to the microbial oxidation of Fe(II) to Fe(III). Due to the better growth of bacteria, the higher removal of As(III) by tooeleite formation was achieved under 8.978-10.806 g/L initial Fe(II) concentration and 2.00-3.00 initial pH, and the highest efficiency was ~95%. Fe(III) and As(III) precipitated simultaneously into two types of tooeleite. The relatively stable tooeleite is featured by the developed (020) crystal face and the bulk-like structure with thick flakes. This study yields a better understanding of biogenic tooeleite, and the importance of tooeleite formation in As(III)-rich environment for arsenic remediation.

Effect of simulated acid rain on stability of arsenic calcium residue in residue field.

In recent years, acid rain had a serious negative impact on the leaching behavior of industrial waste residue. Researches were mainly focused on the environmental hazards of heavy metal in the leachate, but ignored the effects of heavy metal speciation on the stability of waste residue in the subsequent stabilization process. In this study, the unstable calcium-arsenic compounds in the arsenic calcium residue were firstly removed by leaching process; subsequently, the crystallization agent was added to treat the remaining calcium-arsenic mixture. The results of the leaching process demonstrated that the decrease in particle size and pH value directly affected the increase in the cumulative leaching amount of arsenic, and the cumulative leaching ratio reached 1.55%. In addition, the concentration of arsenic decreased from 3583 to 49.1 mg L-1. After the crystallization process, the arsenic concentration was lower than the limit value of Identification Standards for Hazardous Wastes (GB 5085.3-2007). The SEM analysis showed the bulk structures, and XRD pattern confirmed that they were the stable compounds. Moreover, the result of XRD and SEM illustrated that acid concentration, chloride ions and sulfate ions were contributed to the transformation and growth of stable calcium arsenate compounds. Therefore, effective control of the acidity of acid rain, the type of anions in acid rain, and the particle size of residues would contribute to adjusting the arsenic speciation to be more stable. The leaching-crystallization process was of great significance to improve the stability of the arsenic-containing residue.

Multivariate Analyses and Human Health Assessments of Heavy Metals for Surface Water Quality in the Xiangjiang River Basin, China.

Pollution by heavy metals in river water is becoming a major subject of global drinking water concern, and the Xiangjiang River is one of the most heavily polluted rivers in China. Water samples were collected from 17 sites spanning the entire Xiangjiang watershed from 2005 to 2016 to investigate spatial-temporal distributions and potential human health risks related to 8 metal pollutants (As, Cd, Hg, Cr, Cu, Pb, Zn, and Se). The results of spatial-temporal distribution analyses proved that most metals were below the guideline limits the majority of the time. However, the hazard index and carcinogenic risk analyses indicated that As and Cr were associated with a potential risk of cancer, although noncarcinogenic heavy metals in general and carcinogenic risk declined year by year. A nonparametric seasonal Mann-Kendall's test revealed that there were notable decreasing trends in As, Cd, Zn, Cu, Cr, and Pb for most sites, whereas Se and Hg significantly increased in some areas over the targeted 12 yr. The results of principal component analysis agreed with those of dual hierarchical cluster analysis in the identification of pollution sources, the results of which are as follows: 1) As, Cd, Pb, Hg, and Zn were mainly derived from anthropogenic activities and the smelting industry; 2) Cr and Cu mainly originated from agricultural or industrial activities; and 3) Se was predominantly from natural erosion. The present study will be conducive to optimizing the distribution of water monitoring stations and drafting remediation strategies pertaining to the protection of public health in metal-polluted areas. Environ Toxicol Chem 2019;38:1645-1657. © 2019 SETAC.

Pollution characteristics and ecological risk assessment of 11 unheeded metals in sediments of the Chinese Xiangjiang River.

With the change in global climate and environment, water scarcity has been of great concern around the word and exacerbated by serious pollution in water resources. Pollutants accumulated in sediments are threatening water safety and ecological security. Different from others focusing on prevalent heavy metals (Cu, Pb, Zn, As, Cd, Cr, Hg, etc.), in this study, some unheeded metal pollutants Tl, Sb, Mo, Sr, Co, V, Ti, Ca, Mg, Be and Li were monitored in sediments of the Xiangjiang River, China. It was found that there was no remarkable vertical variation with depth, but the seasonal characteristics of Tl, Sb, Mo, Be and Li. The enrichment, pollution and potential ecological risk of Tl, Sb and Mo were revealed by the enrichment factor (EF), geoaccumulation index (Igeo), pollution load index (PLIsite and PLIzone) and potential ecological risk index (RI). It is noticed that the pollution of Tl mainly occurred in summer at midstream and downstream and Mo pollution was much higher than Sb in summer and the reverse in other seasons. Additionally, sediment quality on east side was worse than on west side in Songbai section of the Xiangjiang River. For the first time, the toxic-response factor was figured out as Mo = 18, Tl = 17, Sb = 13, Sr = 6, Co = Be = 1, V = Li = 0, and importantly, the high potential ecological risk of Tl, Sb and Mo needs to be taken seriously for the comprehensive assessment on watershed environmental quality.

Determination of Fluorescent Whitening Agents in Cosmetics and Liquid Detergent by High-Performance Liquid Chromatography with Diode Array Detector in Tandem with Fluorescence Detector.

Five distyryl-type fluorescent whitening agents (FWA85, 210, 220, 351, and 353) were determined in cosmetics and liquid detergent by high-performance liquid chromatography with diode array detector in tandem with fluorescence detector. The samples were extracted with ultrasound in 33% acetonitrile for 10 minutes and the components were determined by ion-pair chromatography on an MG C18 column. The limits of detection were from 0.01 to 0.1 mg·kg-1 and the limits of quantification were from 0.04 to 0.4 mg·kg-1. The recovery was from 80.7 to 103.3%. A linear relationship was present from 0.10 to 100 µg·ml-1 of FWAs. The protocol was simple, sensitive, selective, and was successfully applied to analyze distyryl-type FWAs in cosmetics and liquid detergent. FWA351 and FWA85 were detected in several samples with the concentrations of 19.4-1,130 mg·kg-1.

Structural substitution for SO4 group in tooeleite crystal by As(V) and As(III) oxoanions and the environmental implications.

Two different SO4-free tooeleite were prepared for the first time through structural substitution for SO4 group by As(V) and As(III). As(III)-tooeleite and As(V)-tooeleite have similar crystalline structure to SO4-tooeleite but incorporate different anions in the interlayer space. The removal of As can reach 94% by forming SO4-free tooeleite crystals, and As leaching in TCLP tests can be much lower than that of SO4-tooeleite. Therefore, SO4-free tooeleite crystals are of great potential in As removal and immobilization. Moreover, our study indicates the different affinities of Fe(III) towards As(III), As(V) and SO4, which can explain that a) the coordination structure of As(III)-tooeleite is much closer to the ideal crystal structure but easily affected by As(V) and SO4 group; b) tooeleite mineral found in natural environments is commonly a SO4-containing mineral and associated with scorodite due to the abundance of As(V) and SO4 group.

Structure and spectroscopic study of aqueous Fe(III)-As(V) complexes using UV-Vis, XAS and DFT-TDDFT.

Aqueous complexes between ferric (Fe(III)) and arsenate (As(V)) are indispensable for understanding the mobility of arsenic (As) in Fe(III)-As(V)-rich systems. In this study, aqueous Fe(III)-As(V) complexes, FeH2AsO42+ and FeHAsO4+, were postulated based on the qualitative analysis of UV-Vis spectra in both Fe(III)-As(V)-HClO4 and Fe(III)-As(V)-H2SO4 systems. Subsequently, monodentate structures were evidenced by Fe K-edge EXAFS and modeled as [FeH2AsO4(H2O)5]2+ and [FeHAsO4(H2O)5]+ by DFT. The feature band at ∼280 nm was verified as electron excitation chiefly from Fe-As-bridged O atoms to d-orbital of Fe in [FeH2AsO4(H2O)5]2+ and [FeHAsO4(H2O)5]+. The structural and spectral information of Fe(III)-As(V) complexes will enable future speciation analysis in Fe(III)-As(V)-rich system.

Formation of tooeleite and the role of direct removal of As(III) from high-arsenic acid wastewater.

In this study, an earth-mimetic method was proposed for the direct removal of As(III) by the formation of tooeleite, a ferric arsenite sulfate mineral. A series of batch experiments was used to study the relationship between the formation of tooeleite and the removal of As(III). The results indicate that As(III) removal efficiency reached up to 99% under the treatment condition of pH 1.8-4.5, initial As(III) concentration higher than 0.75g/L, and Fe/As ranged from 0.8 to 2 at room temperature. Various characterizations confirm that the precipitate obtained by this treatment was tooeleite with relatively high stability. In addition, it is assumed that ferrihydrite exists as a precursor, which is vital to the formation of tooeleite and the removal of As(III). This study suggests that tooeleite formation may be an alternative method in the direct removal of As(III) from high-arsenic acid wastewater.