Preferential sorption of some natural organic matter fractions to titanium dioxide nanoparticles: influence of pH and ionic strength

Natural organic matter (NOM) sorption to nanoparticles (NPs) can influence their transport and bioavailability in the aquatic environment. The sorption affinity of NOM to surfaces including NPs is size dependent, and depending on environmental conditions, NOM may enhance or mitigate NPs toxicity. The aim of this study was to investigate the preferential sorption of different-sized fractions of NOM to titanium dioxide (TiO₂) NPs. We specifically investigated the influence of pH, ionic strength, and NOM concentration on the extent of this preferential sorption using a constant sorbent concentration (400 mg/L TiO₂ NPs). Additionally, sorption of NOM to TiO₂ NPs at varying pH was investigated. The nonsorbed NOM was separated from the sorbed, by 50 nm polycarbonate membrane filters and ultracentrifugation. High-performance size exclusion chromatography (HPSEC) was used to determine the average molecular weights of NOM (MWw). Corroborative evidence of preferential sorption of different-sized molecular weight fractions of NOM was obtained from optical techniques such as absorbance and fluorescence spectrophotometry. The total organic carbon was measured by the Total Organic Carbon Analyzer—Shimadzu (TOC-VCPH). The results indicated that there is preferential sorption of larger sized fractions of NOM to TiO₂ NPs irrespective of NOM concentration. It was observed that the sorption of larger sized fractions of NOM was much enhanced at lower pH and at higher ionic strength. Both absorbance and fluorescence spectrophotometric techniques gave credible corroborative evidence on the extent of preferential sorption of lager sized fractions of NOM with respect to pH and ionic strength. The sorption results demonstrated higher sorption at lower pH than at higher pH. Overall, the results of this study suggest that the environmental conditions are key factors that can contribute to NOM’s fractional preferential sorption to NPs in the aquatic environment.     

三唑酮在设施栽培土壤及大白菜中的消解动态及残留

为评价三唑酮在大白菜施用后的环境安全性,建立了GC测定蔬菜及土壤中三唑酮残留的方法,进行露地与设施栽培条件三唑酮在大白莱和土壤中的消解动态和最终残留研究.在大白菜和土壤中的最低检测质量分数均为0.001 mg/kg,三唑酮的平均加标回收率为81.5％～110.6％,变异系数为1.32％～6.04％.消解动态试验为2倍推荐使用剂量施药1次,三唑酮在设施栽培大白菜的半衰期分别为2.72～3.30 d和3.21～3.35 d;露地栽培为2.35～2.87 d和2.30～3.12 d.设施栽培大白菜中三唑酮残留量与用药量正相关,随着施药量的增加,消解速度减慢,残留量相应增大.研究可为制定三唑酮设施栽培大白菜上最大残留限量和合理使用准则以及风险评估提供科学依据.     

Characterization of cation-pi interactions in aqueous solution using deuterium nuclear magnetic resonance spectroscopy

Chemical interactions of aromatic organic contaminants control their fate, transport, and toxicity in the environment. Recent molecular modeling studies have suggested that strong interactions can occur between the pi electrons of aromatic molecules and metal cations in aqueous solutions and/or on mineral surfaces, and that such interactions may be important in some environmental systems. However, spectroscopic evidence for these so-called cation-pi interactions has been extremely limited to date. In this paper, cation-pi interactions in aqueous salt solutions were characterized via 2H nuclear magnetic resonance (NMR) spin-lattice relaxation times (T1) and calculations of molecular correlation times (tau(c)) for a series of perdeuterated (d6-benzene) benzene-cation complexes. The T1 values for d6-benzene decreased with increasing concentrations of LiCl, NaCl, KCl, RbCl, CsCl, and AgNO3, with the largest effects observed in the AgNO3 and CsCl solutions. Upon normalizing tau(c) values by solution viscosity effects, an overall affinity trend of Ag+ > Cs+ > K+ > Rb+ > Na+ > Li+ was derived for the d6-benzene-cation complexes. The ability of Ag+ to complex d6-benzene was significantly reduced upon addition of NH3, which strongly coordinates Ag+ at high pH. Results with d6-benzene, d8-naphthalene, d2-dichloromethane, and d12-cyclohexane in 0.1 M methanolic salt solutions confirmed that spin-lattice relaxation rates are characterizing cation-pi interactions. The relatively strong cation-pi bonding observed between Ag+ and aromatic hydrocarbons probably results from covalent interactions between the aromatic pi electrons and the d orbitals of Ag+, in addition to the normal electrostatic interaction.     

Cation-pi bonding: a new perspective on the sorption of polycyclic aromatic hydrocarbons to mineral surfaces

Recent molecular modeling and spectroscopic studies have suggested that relatively strong interactions can occur between aromatic pi donors and metal cations in aqueous solutions. The objective of this study was to characterize potential cation-pi interactions between pi donors and exchangeable cations accumulated at mineral surfaces via both spectroscopic and batch sorption methods. Quadrupolar splitting in deuterium nuclear magnetic resonance ((2)H NMR) spectroscopy for d(2)-dichloromethane, d(6)-benzene, and d(8)-toluene (C(6)D(5)- moiety) in aqueous suspensions of a Na-saturated reference montmorillonite unambiguously indicated the ordering of solute molecules with respect to the clay surface. The half line broadening (Delta nu(1/2)) of (2)H NMR of d(6)-benzene in montmorillonite suspensions showed that soft exchangeable cations generally resulted in more benzene sorption compared with harder cations (e.g., Ag(+) > Cs(+) > Na(+) > Mg(2+), Ba(2+)). In batch sorption experiments, saturating minerals (e.g., porous silica gels, kaolinite, vermiculite, montmorillonite) with a soft transition metal or softer base cations generally increased the polycyclic aromatic hydrocarbon (PAH) sorption relative to harder cations (e.g., Ag(+) > Cs(+) > K(+) > Na(+); Ba(2+) > Mg(2+)). Sorption of phenanthrene to Ag(+)-saturated montmorillonite was much stronger compared with 1,2,4,5-tetrachlorobenzene, a coplanar non-pi donor having slightly higher hydrophobicity. In addition, a strong positive correlation was found between the cation-dependent sorption and surface charge density of the minerals (e.g., vermiculite, montmorillonite > silica gels, kaolinite). These results, coupled with the observations in (2)H NMR experiments with montmorillonite, strongly suggest that cation-pi bonding forms between PAHs and exchangeable cations at mineral surfaces and affects PAH sorption to hydrated mineral surfaces.     

超微气泡富氧+生物活化技术在黑臭水体治理中的工程应用

针对当前黑臭河道治理工作中出现的黑臭反复,长效性难保持问题,以某内源污染严重的重度黑臭河道为例实施原位生态修复。第1阶段采用超微气泡富氧（移动式曝气船+定点式曝气设备）和生物活化技术进行水体和底质修复,削减内源污染,改善生境;第2阶段应用定点式曝气设备、生态浮岛、水生植物净化、水生动物多样性调控进行生态修复,营造健康稳定的生态系统。经过近4个月的治理,治理区水质由重度黑臭稳定达到GB 3838—2002《地表水环境质量标准》Ⅴ类水标准,水体COD、NH₃-N和TP含量分别为28.79,0.36,0.19 mg/L,去除率分别达到45%、98%和85%以上,治理后水体澄清,可见多种水生动物和沉水植物,河道底质呈现自然泥土色泽,在未进行清淤处理的情况下即达到了泥水共治的效果,水环境质量得到显著提升,实现了长效治理。     

Integrated bioremediation of soil and groundwater at a superfund site

The soil and two aquifers under an active lumber mill in Libby, Montana, had been contaminated from 1946 to 1969 by uncontrolled releases of creosote and pentachlorophenol (PCP). In 1983, because the contaminated surface soil and the shallower aquifer posed immediate risks to human health and the natural environment, the U.S. Environmental Protection Agency placed the site on its National Priorities List. Feasibility studies in 1987 and 1988 determined that in situ bioremediation would help clean up this aquifer and that biological treatment would help clean up the contaminated soils. This article outlines the studies that led to a 1988 EPA record of decision and details the EPA-approved remedial plan implemented starting in 1989; EPA estimates a total cost of about $15 million (in 1988 dollars). The plan involves extensive excavation and biological treatment of shallow contaminated soils in two lined and bermed land treatment units, extraction of heavily contaminated groundwater, an aboveground bioreactor treatment system, and injection of oxygenated water to the contaminant source area, as well as to other on-site areas affected by the shallower aquifer's contaminant plume.     

Amendment of hydroxyapatite in reduction of tetrachloroethylene by zero-valent zinc: its rate enhancing effect and removal of Zn(II)

The effects of hydroxyapatite (HAP) on dechlorination of tetrachloroethylene (PCE) by zero-valent zinc (ZVZ) were examined in batch systems. PCE was primarily transformed to trichloroethylene by ZVZ, with 1,2-trans-dichloroethylene representing a minor product. Dechlorination of PCE was accelerated by the presence of HAP, and the pseudo-first order rate constants increased with increasing amount of HAP. Zn(II), mostly generated from oxidative dissolution of ZVZ by PCE, was effectively removed from the solution by HAP. Ion substitution, coprecipitation, and adsorption are proposed as the possible mechanisms for Zn(II) removal. These reactions appeared to occur simultaneously and the contribution of each reaction to overall removal of Zn(II) was primarily dependent on HAP loading at constant ZVZ loading. The results indicate that the use of HAP in combination with conventional zero-valent metals is promising in that it can achieve both degradation of organic contaminants and stabilization of inorganic contaminants.