过硫酸钠/钴离子/超声波协同降解酸性橙7

以酸性橙7(AO7)为目标污染物,研究了过硫酸钠(Na_2S_2O_8)/钴离子(Co~(2+))/超声波(US)协同降解水体中AO7的过程及其降解机理,并分别考察了Na_2S_2O_8初始浓度、AO7初始浓度、催化剂投加量和超声波功率对AO7降解率的影响。实验结果表明,过硫酸钠/钴离子/超声波协同工艺能有效的降解水中的酸性橙7。初始AO7浓度越低降解效果越好。超声功率在200~450 W之间时,AO7的降解率随着超声波功率的增大同样先升高后降低。在体系中加入乙醇和叔丁醇后明显抑制AO7的降解,证明该体系中主要氧化物种为硫酸根自由基(SO-4·)和羟基自由基(·OH)。     

施氏矿物/H2O2 体系对废水中甲基橙的降解性能及机理

为了考察施氏矿物/H2O2体系对废水中甲基橙的氧化降解性能,通过化学法合成施氏矿物,分析了溶液初始pH、施氏矿物和H2O2投加量、共存阴离子等因素对甲基橙降解的影响,并对降解机理进行了初步探讨。结果表明:当溶液初始pH为3.0～5.0、甲基橙浓度为10 mg·L-1、施氏矿物和H2O2投加量分别为1.0 g·L-1和800 mg·L-1时,经过12 h反应后,废水中甲基橙降解率可达97.0%;而当初始溶液pH=6.0时,甲基橙的降解被抑制,降解率仅为52.4%。无机阴离子对甲基橙降解率的影响微弱,在Cl-、NO3-、SO24-共存条件下,12 h反应后,甲基橙降解率仍可达90.0%以上。施氏矿物重复利用性能良好,在经6个反应周期后,甲基橙的降解率仍可达93.4%。施氏矿物/H2O2体系可有效拓宽传统Fenton反应的pH范围,该体系对甲基橙具有良好的降解性能,降解过程遵循羟基自由基机理。     

零价铁与双氧水异相Fenton降解活性艳橙X-GN

采用Fe0与H2O2构成异相Fenton体系降解偶氮染料活性艳橙X-GN,考察了初始pH、H2O2和Fe0投加量、温度等对反应过程的影响。实验结果表明,在初始pH值为3.0、Fe0投加量为0.8 g/L、H2O2投加量为5 mmol/L和反应温度30℃的条件下,反应60 min后活性艳橙降解率达到96.2%。Fe0与H2O2投加量都存在一个最佳范围,当Fe0与H2O2浓度大于0.8 g/L和5 mmol/L时,羟基自由基会通过其他方式消耗,致使活性艳橙降解率下降。酸性条件和提高温度均有利于反应的进行。反应符合准一级动力学,表观反应速率常数k为0.064 min-1(30℃),反应活化能为80.62 kJ/mol。UV-Vis光谱扫描表明,反应过程中活性艳橙的发色基团及苯环结构均被破坏。     

铁电极活化过硫酸盐对金橙G的降解

研究了铁电极活化过硫酸盐(EC/PDS)产生的具有强氧化性的硫酸根自由基(SO_4~-·)对溶液中金橙G(orange G,OG)的氧化降解行为。重点考察了电流强度、PDS投加量、金橙G初始浓度、溶液初始pH值以及共存阴离子对金橙G降解速率的影响。实验结果表明:相比单独絮凝(EC)和投加过硫酸盐(PDS),EC/PDS体系能够有效地去除金橙G;金橙G的去除效率随着电流强度的增大而增大,随着PDS投加量的增大而增大,随着金橙G初始浓度增大而减小;较低的溶液pH值更利于OG的降解。水中共存阴离子对金橙G的降解存在着不同程度的抑制作用:PO_4~(3-)CO_3~(2-)Cl~-。此外,通过加入不同的淬灭剂(甲醇和叔丁醇),确定了体系中主要存在的自由基。     

PVA-I修饰介孔TiO2光催化剂对盐酸四环素的光降解

水热法制备了PVA-I修饰的介孔TiO2催化剂,利用XRD、UV-Vis、BET和Zeta电位等手段对所制备的催化剂进行了表征。研究了改性的介孔TiO2在模拟太阳光下对盐酸四环素的光催化降解,考察了盐酸四环素的初始浓度、溶液的初始pH、共存离子对盐酸四环素光催化降解去除率的影响。实验结果表明,PVA-I修饰的TiO2催化剂为锐钛矿的介孔TiO2,比表面积190.22 m2/g,催化剂的等电点为3.92。PVA-I修饰的介孔TiO2催化剂在模拟太阳光下对TC光催化降解效率可达96.7%,比P25的催化效率提高1.23倍。NO3-、SO2-4和PO3-4对盐酸四环素的光降解有明显的抑制作用。     

As(V)在金红石TiO_2颗粒表面吸附特性及机理

通过静态动力学和热力学吸附实验,研究了温度、共存离子以及溶质的初始浓度对As(V)在金红石TiO2颗粒表面吸附的影响,探讨了As(V)在金红石TiO2颗粒表面吸附特性及机理。结果表明,在As(V)初始浓度为10 mg/L,pH为7的条件下,25℃时的吸附量0.41 mg/g高于30℃时的吸附量0.31 mg/g,As(V)在金红石TiO2上的吸附为放热过程。CaCl2和MgCl2的添加对As(V)在金红石TiO2表面吸附起到明显的促进作用。T=25℃,Ca2+或Mg2+浓度为10 mmol/L时,As(V)吸附量分别为0.64和0.56 mg/g,Ca2+比Mg2+对As(V)吸附促进作用强。As(V)在金红石TiO2的吸附等温线符合Frendlich方程,Lagergren二级动力学方程能较好地描述As(V)在金红石TiO2颗粒表面吸附的动力学过程。     

负载TiO2的活性炭纤维改性电极电吸附除氟

采用溶胶-凝胶法制备TiO2凝胶,将TiO2凝胶涂覆在活性炭纤维表面并进行热处理制备改性电极(TiO2/ACF),利用扫描电子显微镜(SEM)、X射线衍射光谱仪(XRD)、比表面和孔隙度分析仪对负载前后电极的表面特性进行表征,并探讨了其对NaF溶液的电吸附效果。结果表明,电极负载TiO2后表面变得粗糙,比表面积和总孔体积减小,而介孔体积和平均孔径增大。此外,表面的TiO2同时以金红石和锐钛矿的晶型存在。电吸附实验结果显示,加电可以提高吸附容量,而且电压、pH和初始氟离子浓度均对电吸附容量产生影响:电压增大,吸附容量增加,当施加电压为2 V时,电吸附容量为1.03 mg/g,比开路电位时提高40%;pH可以通过影响氟离子在溶液中的存在形态和TiO2/ACF电极表面的羟基基团对电吸附容量产生影响;初始氟离子浓度升高,电极吸附容量增大,但是去除率降低。在处理初始氟离子浓度为4 mg/L的NaF溶液时,在2 V电压、中性pH和12 h的吸附时间下,改性ACF为电极的吸附量为1.32 mg/g。     

负载TiO_2的活性炭纤维改性电极电吸附除氟

采用溶胶-凝胶法制备TiO2凝胶,将TiO2凝胶涂覆在活性炭纤维表面并进行热处理制备改性电极（TiO2/ACF）,利用扫描电子显微镜（SEM）、X射线衍射光谱仪（XRD）、比表面和孔隙度分析仪对负载前后电极的表面特性进行表征,并探讨了其对NaF溶液的电吸附效果。结果表明,电极负载TiO2后表面变得粗糙,比表面积和总孔体积减小,而介孔体积和平均孔径增大。此外,表面的TiO2同时以金红石和锐钛矿的晶型存在。电吸附实验结果显示,加电可以提高吸附容量,而且电压、pH和初始氟离子浓度均对电吸附容量产生影响：电压增大,吸附容量增加,当施加电压为2 V时,电吸附容量为1.03 mg/g,比开路电位时提高40%;pH可以通过影响氟离子在溶液中的存在形态和TiO2/ACF电极表面的羟基基团对电吸附容量产生影响;初始氟离子浓度升高,电极吸附容量增大,但是去除率降低。在处理初始氟离子浓度为4 mg/L的NaF溶液时,在2 V电压、中性pH和12 h的吸附时间下,改性ACF为电极的吸附量为1.32 mg/g。     

As（V）在金红石TiO2颗粒表面吸附特性及机理

通过静态动力学和热力学吸附实验,研究了温度、共存离子以及溶质的初始浓度对As（V）在金红石TiO2颗粒表面吸附的影响,探讨了As（V）在金红石TiO2颗粒表面吸附特性及机理。结果表明,在As（V）初始浓度为10mg／L,pH为7的条件下,25℃时的吸附量0．41mg／g高于30℃时的吸附量0．31mg／g,As（V）在金红石TiO,上的吸附为放热过程。CaCl2和MgCl2的添加对As（V）在金红石TiO2表面吸附起到明显的促进作用。T=25℃,Ca2＋或Mg2＋浓度为10mmol／L时,As（V）吸附量分别为0．64和0．56mg／g,Ca2＋比Mg2＋对As（V）吸附促进作用强。As（V）在金红石TiO2的吸附等温线符合Frendlich方程,Lagergren二级动力学方程能较好地描述As（V）在金红石TiO2颗粒表面吸附的动力学过程。     

光催化降解水体异味物质2-MIB的机理

以水体异味物质2-甲基异莰醇(2-methylisoborneol,2-MIB)为研究对象,在紫外光(λ<380 nm)照射下,探讨TiO2(P25)对2-MIB的光催化降解特性及光化学作用机理。结果表明,UV/TiO2光催化体系可以有效去除水体异味物质2-MIB,紫外光照射60 min,对2-MIB的降解率达95%。同时研究了光催化降解体系介质pH,共存腐殖酸(HA)和过硫酸钾(K2S2O8)对UV/TiO2光催化体系降解2-MIB的影响,发现低浓度HA([HA]≤0.5 mg/L)可以提高2-MIB降解速率,当HA浓度高于0.5 mg/L,2-MIB降解反应受到抑制;同时当加入电子受体K2S2O8后,降解体系中活性物种羟基自由基(.OH)明显增加,提高了TiO2对2-MIB的降解能力。利用苯甲酸荧光光度法和POD-DPD显色法跟踪测定降解过程中羟基自由基(·OH)和过氧化氢(H2O2)的变化,表明光催化反应涉及·OH机理。     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.