自制便携式振荡装置/间接竞争酶联免疫吸附法在水库微囊藻毒素-LR快速应急监测中的应用

应用自制便携式振荡装置,运用间接竞争酶联免疫吸附法(icELISA)建立快速测定水中微囊藻毒素(MC)-LR的现场初筛方法。结果表明:(1)自制便携式振荡装置的检测结果与手工振荡不存在差异,可用自制便携式振荡装置替代手工来进行振荡孵育操作。(2)icELISA建立了快速测定MC-LR的现场监测方法,MC-LR的标准曲线线性关系较好(r=-0.997 0),满足定性定量分析的要求,检出限为0.03μg/L,测定下限为0.12μg/L,空白溶液与实际水样加标回收率为96.2%～113.0%,方法精密度、准确度均较好。     

巢湖和太湖微囊藻毒素差异性研究

采用固相萃取高效液相色谱法检测巢湖和太湖水体中5种微囊藻毒素(MCs)——MC-RR、MC-YR、MC-LR、MC-LA、MC-LY的含量。结果表明,巢湖水体中的MCs以MC-RR、MC-LA、MC-LY为主,太湖水体主要以MC-RR、MC-LR、MC-LA为主,其中太湖MC-LR的最高质量浓度为2.558μg/L,超过《地表水环境质量标准》(GB 3838—2002)中对集中式生活饮用水地表水源地的限定值(1μg/L)。分析巢湖和太湖水体中MCs与水质指标之间的相关性,发现同种MCs与两湖环境因子的相关性存在明显差异。逐步回归拟合结果表明,氨氮和DO分别能与巢湖MC-LR、MC-LY进行拟合;Chl-a、TOC能与太湖MC-LR回归拟合,TOC能与太湖MC-YR进行拟合。由于多数MCs不能通过水质指标的拟合结果来预测,因此在未来研究中需结合环境因子和MCs的遗传机制来共同分析MCs在水中的分布规律。     

太子河水系印染行业重点污染河段优先控制污染物的确定

通过对太子河水系印染行业重点污染河段-海城河三期水样的采集以及水样中有机污染物的检测分析,获取了48种有机污染物的平均浓度水平,其中浓度较高的是苯酚(28.18μg/L)、邻苯二甲酸二(2-乙基己基)酯(22.30μg/L)和苯乙酮(8.818μg/L)。结合流域的实际污染状况,采用"改进潜在危害指数法",对海城河检测出的有机污染物进行加权综合评分计算,按照综合分数值大小,对其进行排序,提出了44种优先控制污染物名单,其中包括酯和酞酸酯类7种、含氮杂环类7种、胺及苯胺类5种、氯苯类6种、硝基苯类5种、苯酚类7种、苯及其他取代苯类5种、多环芳烃类2种,大部分污染物与印染行业废水排放有着密切关系。     

重庆市加油站周边浅层地下水中石油烃污染调查与特征分析

为了解加油站运营对周边浅层地下水环境质量的影响,随机选择了12个正常运营20年以上的加油站,在加油站上游和下游共布设了27口地下水监测井,对地下水中石油烃、苯系物、萘、1,2-二氯乙烷和甲基叔丁基醚开展了水质监测。结果表明,石油烃在地下水中的检出率较高,为96.3%,检出浓度为4.2~544.7μg/L,检出组分主要为柴油烃中的C26和C20,检出率分别达到了88.9%和77.8%;汽油烃的有效组分C6~C9未检出,作为汽油添加剂的1,2-二氯乙烷和甲基叔丁基醚在地下水中存在,检出率分别为96.3%和22.2%,检出浓度分别为1.7~30.9μg/L和3.8~30.9μg/L。其中,11.1%的监测井中甲基叔丁基醚浓度超过了EPA推荐的饮用水安全的浓度限值(20μg/L),3.7%的监测井中1,2-二氯乙烷浓度超过了《地表水环境质量标准》(GB 3838-2002)中"集中式生活饮用水地表水源地特定项目标准限值"规定的30μg/L。总体而言,石油烃、苯系物、1,2-二氯乙烷和甲基叔丁基醚的含量远低于油品渗(泄)漏导致的污染水平。     

微囊藻毒素-LR的全内反射荧光免疫传感器研究

在开发全内反射荧光免疫传感器的基础上,研究水中微囊藻毒素-LR(MC-LR)的检测方法。建立了基于MC-LR平面波导免疫芯片的制备方法,并结合流动分析和荧光检测开发检测系统,针对MC-LR的免疫检测条件进行优化。结果表明,全内反射荧光免疫传感器对MC-LR抗体的检测限为0.001μg/mL;在间接竞争免疫检测模式下,最优检测条件是预反应时间5min、预反应温度37℃、进样停留时间500s;在最优检测条件下,对MC-LR的检测限为0.100μg/L,线性区间为0.200~4.000μg/L;全内反射荧光免疫传感器检测MC-LR的加标回收率均在100.0%±20.0%,平行测定的相对标准偏差小于5%。     

SPE-HPLC法检测环境水样中的痕量三氯卡班

建立了环境水样中三氯卡班(TCC)的预处理和测定方法。考察了3种固相萃取(SPE)小柱、5种洗脱液对TCC回收率的影响。结果表明,采用ENVI-18 SPE小柱、以乙酸乙酯/乙腈(1∶1)为洗脱液、高效液相色谱仪-紫外检测器(HPLC-UV)检测,以蒸馏水为背景溶液TCC的加标回收率高达95%,仪器检出限与定量限分别为2.37与7.89μg/L。该方法用于实际环境水样,TCC加标浓度1~10μg/L,污水厂进水、出水与地表水中TCC的加标回收率分别在89.38%~96.90%、87.74%~94.34%与83.64%~94.61%之间,表明所建立的SPE-HPLC法适合城市生活污水和地表水中痕量TCC的检测。运用该方法测定实际环境水样中的TCC含量,集美污水处理厂进水与出水中TCC浓度分别为1.35与0.22μg/L;华大污水厂进水与出水中TCC浓度分别为1.05与0.53μg/L;白鹭湖水样中的TCC浓度为1.11μg/L。     

微囊藻毒素的酶联免疫法分析影响因素探讨

考察样品与抗微囊藻毒素(MC)-LR的单克隆抗体(单抗)加入间隔时间、温育温度、检测时间、pH、H2O2、Fe2+等不同因素对酶联免疫法(ELISA)测定MC-LR的影响。结果表明:(1)随着样品与单抗加入间隔时间延长,MC-LR测定值逐渐降低。(2)25、37℃下,MC-LR测定值几乎没有差别,测定结果与取用标准样品具有很好的一致性。(3)不同检测时间下,无论是低浓度还是高浓度标准样品,MC-LR测定值均有一定变化,虽然幅度均不大,但仍然建议终止反应后尽快比色。(4)当pH为7～9时,MC-LR测定值变化不大。(5)当H2O2摩尔浓度为0.1、1.0、10.0mmol/L时,均会对ELISA产生干扰。通过水浴去除H2O2后,H2O2初始摩尔浓度分别为0.1、1.0mmol/L时,MC-LR回收率分别达到87%及81%。(6)Fe2+对酶有显著的抑制作用,可通过沉淀过滤的方式消除干扰。     

京郊灌渠水体和底泥中多环芳烃污染特征

以美国环境保护署(USEPA)公布的16种优先控制多环芳烃(PAHs)作为目标污染物,对通州区和大兴区灌渠水体和底泥中PAHs种类、浓度进行研究,并进行源解析,以了解京郊灌渠水体和底泥中PAHs的污染现状和主要污染来源,为农业环境保护和农产品质量安全提供科学依据和数据支持。结果表明:通州区灌渠水体和底泥中16种PAHs全部检出,水体和底泥中总PAHs分别为2.19~83.02 ng/L、52.61~785.22μg/kg;大兴区灌渠水体中检出15种PAHs,底泥中检出13种PAHs,水体和底泥中总PAHs分别为2.72~36.56 ng/L、2.69~39.20μg/kg。灌渠水体中以2~3环PAHs为主,底泥中以4~6环PAHs为主。     

木炭填料生物反应器对微囊藻毒素的去除

为了研究自然水体中产毒藻细胞和微囊藻毒素(MC)的迁移转化机理,以经济实用的木炭为填料的柱状反应器对含微囊藻和MC的自然水进行了分阶段连续性去除实验。结果表明,当进水叶绿素a(chl-a)浓度为94.9~203.4μg/L,MC浓度为4.5~24.7μg/L时,藻细胞(以chl-a浓度为指标)的去除率高于77.1%,MC的去除率高于66.2%。不同阶段的结果比较发现,HRT为6.8 h时去除效果最佳。反应器中,原生动物和后生动物大量存在,以钟型虫(Vorticella sp.)、草履虫(Paramecrum sp.)、旋轮虫(Philodina sp.)和腔轮虫(Lecane sp.)为主要物种。实时荧光定量PCR分析结果表明,可降解MC细菌的特异性基因(mlr A)被检出。由此说明,除木炭填料的物理吸附外,微型浮游动物的捕食及细菌降解对水中藻细胞和MC的去除也起重要作用。     

北方某城市饮用水中多环芳烃的来源及其在水处理过程中的行为研究

采用固相萃取(SPE)样品富集前处理技术和气相色谱/质联联用(GC/MS)分析方法,对北方某工业城市给水系统中的多环芳烃类化合物的含量水平进行了研究.结果表明,该城市多环芳烃污染水平较高,但总浓度均未超过城市供水水质标准(CJ/T206-2005)中限值(2μg/L).近郊水库由于受到燃料燃烧产生的多环芳烃的污染,成为该市饮用水中多环芳烃污染的主要来源.传统的混凝-砂滤工艺对多环芳烃有较好的去除效果,总去除率可达55.9%.     

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.     

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.     

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.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.