Catalytic destruction of pentachlorobenzene in simulated flue gas by a V2O5-WO3/TiO2 catalyst

Pentachlorobenzene (PeCB) in simulated flue gas was destructed by a commercial V₂O₅-WO₃/TiO₂ catalyst in this study. The effects of reaction temperature, oxygen concentration, space velocity and some co-existing pollutants on PeCB conversion were investigated. Furthermore, a possible mechanism for the oxidation of PeCB over the vanadium oxide on the catalysts was proposed. Results show that the increase of gas hourly space velocity (GHSV) and the decrease of operating temperature both resulted in the decrease of PeCB removal over the catalyst, while the effect of the oxygen content in the range of 5-20% (v/v) on PeCB conversion was negligible. PeCB decomposition could be obviously affected by the denitration reactions under the conditions because of the positive effect of NO but negative effect of NH₃. The introduction of SO₂ caused the catalyst poisoning, probably due to the sulfur-containing species formed and deposited on the catalyst surface. The PeCB molecules were first adsorbed on the catalyst surface, and then oxidized into the non-aromatic acyclic intermediates, low chlorinated aromatics and maleic anhydride.     

Structural and optical characterization of dissolved organic matter from the lower Athabasca River, Canada

Dissolved organic matter (DOM) is a ubiquitous constituent of natural waters and is comprised of a variety of chemically heterogeneous molecular structures and functional groups. DOM is often considered to be a major ligand for metals in most natural waters and its reactivity is thought to be strongly dependent on its chemical composition and structure. In this study, a combination of UV/visible, emission excitation matrix fluorescence (EEM) and ¹H NMR spectroscopies were used to characterize DOM from the Athabasca River (Alberta, Canada). The chemical characterization of river DOM showed that the most upstream samples located in agricultural areas were blue-shifted and less aromatic and contained more hydrogens connected with oxygen functional groups than those in the wetland dominated area in the Athabasca oil sand deposit region. The presence of paramagnetic ions (Fe and Al) was not found to significantly affect the structural composition of DOM as revealed by ¹H NMR. Such change in the quality of DOM may have a profound impact on metal binding in the Athabasca River watershed.     

Formation of PCDD/Fs from oxidation of 2-monochlorophenol over an Fe2O3/silica surface

The role of iron in surface-mediated formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from 2-chlorophenol (2-MCP) was investigated over the temperature range of 200-550 °C under oxidative conditions. In order to compare and contrast with previous work on copper and ferric oxide-mediated pyrolysis of 2-MCP, identical reaction conditions were maintained (50 ppm 2-MCP, model fly-ash particles containing 5% Fe₂O₃ on silica). Observed products included dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), dibenzofuran (DF), 4,6-dichlorodibenzofuran (4,6-DCDF), 2,4- and 2,6-dichlorophenol, 2,4,6-trichlorophenol, quinone, catechol, chloro-o-quinone, chlorocatechol and polychlorinated benzenes. Yields of DD and 1-MCDD were 2 and 5 times higher than under pyolysis conditions, respectively. Although 4,6-DCDF was the major PCDD/F product formed with a yield that was 2.5× greater than under pyrolysis, the yield of non-chlorinated DF, which was the dominant PCDD/F product under pyrolysis, decreased by a factor of 3. Furthermore, the ∼2× higher yield of PCDDs under oxidative conditions resulted in a PCDD to PCDF ratio of 0.75 compared to a relatively low ratio of 0.39 previously observed under pyrolytic conditions.     

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.     

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.     

超声辐射浸渍法制备Fe-Ni-Mn/Al_2O_3催化剂及性能研究

以Al2O3为载体,分别采用超声辐射浸渍法和普通浸渍方法制备Fe-Ni-Mn/Al2O3催化剂。采用BET、XRD和SEM对催化剂的理化性质和孔结构进行了分析,以模拟酸性绿B废水为研究对象考察催化剂的催化性能。实验结果表明,浸渍溶液pH值和焙烧温度显著影响催化剂的性能。与普通浸渍法相比,超声浸渍法制备的Fe-Ni-Mn/Al2O3催化剂对酸性绿B脱色反应表现出较高的催化活性。     

改性多壁碳纳米管对水中Cd~（2＋）的去除

为了增加多壁碳纳米管（multiwall carbon nanotubers,MWNTs）对水中Cd2＋的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2＋的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2＋去除量增加,共存的阳离子会降低对Cd2＋的吸附效果,对Cd2＋的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2＋能容易从碳纳米管上解吸。初步探讨了Cd2＋吸附机制。     

Fe3O4/SDS磁性纳米颗粒吸附水体中的Cd2+和Zn2+

一种新型纳米固相萃取吸附剂,由阴离子表面活性剂十二烷基磺酸钠(SDS)包裹在Fe3O4磁性纳米颗粒表面形成,用于吸附水溶液中的重金属离子。研究了吸附过程的主要影响因素(如SDS浓度、溶液pH等)以及解吸过程的最佳条件,并对其机理进行了初步的探讨。研究结果表明,共沉淀法制备的Fe3O4颗粒粒径分布均匀,平均粒径约为54 nm;SDS浓度为300 mg/L时,Fe3O4/SDS磁性纳米颗粒吸附Cd2+和Zn2+的能力最强;在一定浓度范围内,Fe3O4/SDS体系对Cd2+和Zn2+的吸附平衡数据符合Langmuir吸附等温方程,饱和吸附量分别为22.42 mg/g和13.95 mg/g。最终结果表明,Fe3O4/SDS磁性纳米颗粒具有较强磁分离能力和较好的吸附效果。