The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Mutagenicity of particulate matter fractions in areas under the impact of urban and industrial activities

Organisms in the environment are exposed to a mixture of pollutants. Therefore the purpose of this study was to analyze the mutagenicity of organic and inorganic responses in two fractions of particulates (TSP and PM2.5) and extracts (organic and aqueous). The mutagenicity of organic and aqueous particulate matter extracts from urban-industrial and urban-residential areas was evaluated by Salmonella/microsome assay, through the microsuspension method, using strain TA98 with and without liver metabolization. Additionally, strains YG1021 and YG1024 (nitro-sensitive) were used for organic extracts. Aqueous extracts presented negative responses for mutagenesis and cytotoxicity was detected in 50% of the samples. In these extracts the presence of potential bioavailable metals was identified. All organic extracts presented mutagens with a higher potential associated with PM2.5. This study presents a first characterization of PM2.5 in Brazil, through the Salmonella/microsome assay. The evaluation strategy detected the anthropic influence of groups of compounds characteristically found in urban and industrial areas, even in samples with PM values in accordance with quality standards. Thus, the use of a genotoxic approach in areas under different anthropic influences will favor the adoption of preventive measures in the health/environment relation.     

Thioarsenate formation upon dissolution of orpiment and arsenopyrite

Thioarsenates were previously determined as dominant species in geothermal and mineral waters with excess sulfide. Here, we used batch leaching experiments to determine their formation upon weathering or industrial leaching of the arsenic-sulfide minerals orpiment (As₂S₃) and arsenopyrite (FeAsS) under different pH and oxygen conditions. Under acidic conditions, as expected based on their known kinetic instability at low pH, no thioarsenates formed in either of the two mineral systems. Under neutral to alkaline conditions, orpiment dissolution yielded mono-, di- and trithioarsenate which accounted for up to 43-55% of total arsenic. Thioarsenate formation upon arsenopyrite dissolution was low at neutral (4%) but significant at alkaline pH, especially under suboxic to sulfidic conditions (20-43%, mainly as monothioarsenate). In contrast to orpiment, we postulate that recombination of arsenite and sulfide in solution is of minor importance for monothioarsenate formation during alkaline arsenopyrite dissolution. We propose instead that hydroxyl physisorption lead to formation of As-OH-S surface complexes by transposition of hydroxyl anions to arsenic or iron sites. Concurrently formed ironhydroxides could provide re-sorption sites for the freshly released monothioarsenate. However, sorption experiments with goethite showed slower sorption kinetics of monothioarsenate compared to arsenite, but comparable with arsenate. The discovery that thioarsenates are released by natural weathering and industrial leaching processes and that, once they are released, have a higher mobility than the commonly-investigated species arsenite and arsenate requires future studies to consider them when assessing arsenic release in sulfidic natural or mining-impacted environments.     

实时荧光定量PCR对A2/O短程硝化系统内氨氧化菌的定量分析

通过控制好氧区低DO浓度以及缩短好氧实际水力停留时间(actual hydraulic retention time,AHRT),在处理低C/N比实际生活污水的A2/O工艺中,成功启动并维持了短程硝化反硝化;系统亚硝酸盐积累率稳定维持在90%左右,氨氮去除率在95%以上。通过提取富集氨氧化菌(ammonia oxidizing bacteria,AOB)的基因组DNA,经两次常规PCR扩增和琼脂糖凝胶电泳,以纯化回收的DNA扩增片段作为实时荧光定量PCR检测AOB数量的DNA标准品,建立了检测AOB数量的实时荧光定量PCR标准曲线。利用实时荧光定量PCR技术比较了A2/O系统在不同运行条件及亚硝酸盐积累率情况下AOB菌群数量。结果表明,随着系统亚硝酸盐积累率的上升,系统内AOB菌群数量也大幅上升。全程硝化和短程硝化时,系统内的AOB菌群数量分别为5.28×109cells/g MLVSS和3.95×1010cells/g MLVSS。此外,亚硝酸盐积累率的下降相对于AOB菌群数量的下降有一定的滞后性。     

地下水PRB原位生物修复中一种释氧材料的改进技术及效果分析

释氧材料经济有效的释氧是地下水原位生物修复的关键因素。实验通过在释氧材料中加入膨润土、磷酸二氢钾和硫酸铵等,改进释氧材料的性能。柱实验结果显示,该释氧材料释氧速率缓慢,释氧时间长,可以使溶液中DO长期保持在5 mg/L以上;另外,释氧材料中添加的缓冲剂及天然含水层介质对pH值有较好的缓冲作用,可以使pH值达到后续生物修复的要求。     

含锰废渣的氧化-活化再生回用工艺

为实现紫苏醛生产过程中二氧化锰（氧化剂）的循环利用,采用一种新型的氧化-活化工艺再生得到活性二氧化锰,即以紫苏醇合成紫苏醛过程中产生的含锰废渣为原料,首先采用氯酸钠氧化含锰废渣得到初级二氧化锰,然后使用高锰酸钾对初级二氧化锰进一步活化得到活性二氧化锰。实验表明,制取初级二氧化锰的最佳工艺条件为：反应时间为4h,反应温度为90～95℃,硫酸摩尔浓度为1.5 mol/L,氯酸钠加量为理论量的130%。制取活性二氧化锰的合适条件为：反应温度在60℃时,反应时间为1.5 h;反应温度在50℃时,反应时间为2.5 h。采用氧化-活化法再生的活性二氧化锰氧化紫苏醇,紫苏醛的产率可达52.8%,与使用电解二氧化锰氧化得到的紫苏醛的产率53.1%相当,而使用初级二氧化锰,紫苏醛的产率仅为14.9%。     

氨水土壤混合物脱除CO2温室气体的实验研究

为了脱除CO2温室气体,提出了利用氨水土壤混合物去除CO2的新方法.分别考察了土壤颗粒粒径、CO2初始流量、氨水浓度(质量比)和温度对CO2脱除量和脱除率的影响.实验结果表明,该方法去除CO2的量较土壤物理吸附量和氨水化学吸收量的总和提高了大约15%;随着氨水浓度的增大,CO2的脱除率和脱除量都增大;随着土壤颗粒粒径和CO2初始流量的增大,CO2的脱除率和脱除量都减小;当温度由22℃升高到31℃,CO2的脱除率随着温度的升高而增大,但是继续升高温度到40 ℃,CO2的脱除率反而下降.     

Gas/particle partitioning of atmospheric PCDD/Fs in a satellite town in Eastern China

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air was investigated in a satellite town in Eastern China from April 2007 to January 2008 comprehending large temperature variations (from 3 to 34 °C, daily average). Molecular weight, molecular structure and ambient temperatures are the three major factors that govern the gas/particle partitioning of atmospheric PCDD/Fs throughout the year. Generally, good agreements were obtained (except for winter) between measured particulate fractions and theoretical estimates of both the Junge–Pankow adsorption model and Harner Bidleman absorption model using different sets of subcooled liquid vapor pressure and octanol–air partition coefficient (K_oa), respectively. Models utilizing estimates, derived from gas chromatographic retention indices (GC-RIs), are more accurate than that of entropy-based. Moreover, during winter, the K_oa-based model using the GC-RIs approach performs better on lower chlorinated PCDD/Fs than that of -based. Furthermore, possible sources of mismatch between measured and predicted values in winter (3–7 °C) were discussed. Gas adsorption artifact was demonstrated to be of minor importance for the phenomena observed. On the other hand, large deviations of slopes (m_r) and intercepts (b_r) in logK_p vs. plots from theoretical values are observed in the literature data and these are found to be linearly correlated with ambient temperatures (P<0.001) in this study. This indicates that the non-equilibrium partitioning of PCDD/Fs in winter may be significantly influenced by the colder temperatures that may have slowed down the exchange between gaseous and particulate fractions.