改进GC/FID法连续观测大气中CO浓度

改进装配有氢火焰离子化检测器(即FID)的气相色谱仪(GC),可连续监测大气中痕量气体CO浓度.本系统采用单阀双柱反吹进样技术,优选前置柱能更有效地剔除杂质,提高了分析柱效率,保持色谱基线平稳,提高分辨率和定量分析的准确率.优化后的气路设计与色谱柱的改进,使GC/FID对CO的最低检出限达到10×10-9、精密度误差小于2%,准确度在±2%之内.将气相色谱与动态气体稀释仪耦合使系统能够自动进行工作曲线校准,系统自动采样、分析和标定,无需人员职守.对北京大气CO连续观测结果表明,北京大气CO浓度变化受气象要素与排放源双重控制.     

大气中过氧乙酰硝酸酯在线监测技术研究与应用

基于低温气相色谱分离技术、电子捕获检测技术和光化学合成技术,搭建了大气过氧乙酰硝酸酯(PAN)在线监测及校准装置,实现对大气中PAN的在线监测及自动校准。通过参数优化实验,确定了系统最佳运行条件为:柱箱温度12℃、柱前压18k Pa、电子捕获检测器温度50℃、尾吹气流量25 m L/min。测得该条件下基线平稳、噪声小,峰响应最佳;PAN保留时间为1.75 min,线性相关系数(R2)为0.999,检出限为0.026 nmol/mol,定量重复性为1.57%,24 h稳定性为0.74%。将该系统用于现场测试,结果表明系统能够自动运行,并实现定期自动校准。     

紫外—荧光检测器高效液相色谱法测定PM2.5中16种多环芳烃

建立了一种利用高效液相色谱(HPLC)同时分离和测定大气颗粒物中16种优控多环芳烃(PAHs)的方法。样品经二氯甲烷超声提取,浓缩后经乙腈定容,以乙腈和水作为流动相进行反相HPLC梯度淋洗分离后,由紫外检测器串联程序波长荧光检测器检测。通过实验条件的优化,实现了16种PAHs组分基线完全分离和高灵敏度检测。16种PAHs检测限为0.05～1.20μg/L,回收率在75.0%～106.0%,相对标准偏差在0.27%～7.42%,均符合方法学的要求。将该方法用于测定贵阳市不同功能区PM2.5中PAHs的含量,具有快速简便、准确灵敏、重现性好等优点,适合大批量样品的分析。     

毛细管柱气相色谱法测定大气污染源氯苯类化合物

建立了毛细管柱-ECD检测器气相色谱测定大气污染源中氯苯类污染物的检测方法,当采样量为30 L时,方法检测限：氯苯0.03μg/m^3、1.2-二氯苯0.10μg/m^3、1.4-二氯苯0.08μg/m^3、1.2.4-三氯苯0.20μg/m^3,加标回收率在78.9%-90.6%之间,相对标准偏差为2.7%-3.3%。方法简单、灵敏、分离度好、检出限低。     

夏季降雨对大气污染物的清除影响

从南昌市环境监测站获取大气中主要污染物浓度,降雨量由APS-3A型降雨降尘自动采样器实际监测得到,分析了南昌市新城区2014年夏季降雨对大气污染物浓度的影响。结果表明:(1)中强降雨(日降雨量≥10 mm)对大气中的SO_2、PM_(10)和PM_(2.5)都有明显的清除效果,对SO_2、PM_(10)和PM_(2.5)的清除效率分别为14.3%~50.0%、20.2%~68.8%、20.0%~74.0%;1~10mm的降雨对SO_2、PM_(10)和PM_(2.5)也有一定的清除效果;≤1mm的降雨,对PM_(10)具有清除作用,但清除效率较低(2.3%~23.2%),而对SO_2和PM_(2.5)清除效果不明显。降雨量对NO_2的浓度变化影响不大。(2)降雨对大气污染物的清除效率受降雨前污染物本底浓度的影响,污染物本底浓度很低时甚至会出现反弹现象。(3)降雨对污染物的清除效率除了受降雨量的影响外,其降雨场数和降雨累积时间对其也有一定的影响。     

磺胺类制药废水中苯系物的快速同步检测

磺胺类制药废水是一类难降解有机废水,其中含有苯磺酰胺、苯磺酸、苯酚等苯系物,对这些物质的快速检测十分必要,针对这3种物质建立了基于高效液相色谱的快速同步检测方法。采用C18柱为分离柱,比较了乙腈/水、甲醇/水和甲醇/缓冲盐3种流动相体系的分离效果,优化了230、240、250和260 nm 4种检测波长等条件。结果表明,V甲醇∶V磷酸二氢铵溶液(0.5%,p H=3.5)=50∶50作为流动相时,基线稳定,峰形较好,3种目标物在11 min内即可实现有效分离,且浓度为5～100 mg·L~(-1)时,3种目标物峰面积与质量浓度的线性关系良好(R20.999),检出限为15.0～29.4μg·L~(-1),相对偏差为0.05%～1.56%(n=5),该方法能同时检测苯磺酸、苯酚和苯磺酰胺,具有简便、灵敏、准确等优点,可为制药废水的快速检测和磺胺类药物降解机理的分析提供便利。     

大气细粒子的快速捕集及化学成分在线分析方法研究

本文介绍了一种新型的大气细粒子快速捕集及其化学成分在线分析方法。该方法中大气细粒子与过饱和水蒸气绝热混和而增长成大粒子 ,并在气流的带动下惯性撞击到一垂直玻璃板上 ,一含有内标物的去离子水流自上而下将撞击到玻璃板上的粒子收集 ,收集液被直接输送到离子色谱、总有机碳分析仪 ,在线分析其中的化学成分。该方法每 12min可完成单个样品分析 ,每小时可连续采集分析 5个样品。离子色谱最低检测限约为 0 .0 5 μg/m3(NH+4 )到 0 .2 0 μg/m3(SO2 -4 ) ,不确定度约为 3 % ,TOC最低检测限为 5× 10 -5μg/m3,不确定度约为 3 %。真实的大气细粒子观测结果表明 ,该方法快速、简捷、灵敏度高 ,是实时监测大气中细粒子化学成分的有效工具     

高效液相色谱法测定南昌市环境空气PM10中16种多环芳烃

建立了以二极管阵列检测器和荧光检测器串联的高效液相色谱分析方法,在标样未完全分离的情况下,采用双激发波长有效地改善了色谱分离条件.在设定的色谱条件下,各种多环芳烃(PAHs)的检出限为0.11～39.83μg/L,平均回收率为76.7%～98.3%,相对标准偏差为3.6%～12.6%.在南昌市布设4个环境空气采样点,测定PM10中PAHs含量.结果表明,八一广场、南昌市区二中老校区和罗家集区苯并(a)芘日均质量浓度最大值均超过<环境空气质量标准>(GB 3095-1996)的限值,PAHs污染状况较严重.     

气相色谱法测定环境空气中的正丁醇

以活性炭吸附环境空气中的正丁醇,2%异丙醇的二硫化碳溶液洗脱,用DB-WAX毛细管柱分离,氢火焰离子化检测器检测,保留时间定性,峰面积定量,方法分离度较好,分析灵敏度高,当采样15 L时,检测限为0.002 mg/m^3,满足环境分析要求。     

环境中金属有机化合物形态分析方法近期进展

本文综合了环境中金属有机化合物形态分析方法的近期进展。在分离方面,高效液相色谱法(HPLC)的应用逐渐增加;等离子体激发的原子发射光谱作为检测器其应用也不断增长;HPLC与炉式原子吸收在接口上的困难已经解决;新的衍生技术已用于非挥发性物质的衍生以便于气相色谱分离;序列分析系统如GC/HPLC—AAS、GC/HPLC—AED、GC/HPLC—MS等的应用逐渐增多,所有这些联用系统都是相当灵敏的,而且很特效。     

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.     

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.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.