UPLC-MS/MS测定地表水中总微囊藻毒素的快速前处理方法探究

为方便地表水中总微囊藻毒素(TMCs)的预警监测,探究提取MC-LR、MC-RR、MC-YR的不同快速前处理方法,建立同时测定3种TMCs的煮沸-过滤-UPLC-MS/MS法。该方法在0.006μg/L~50.0μg/L范围内线性良好,方法检出限为0.006μg/L~0.010μg/L,实际水样3个质量浓度水平的加标回收率为88.6%~108%,6次测定结果的RSD为2.6%~9.4%。     

超高效液相色谱 三重四极杆质谱法测定地表水和地下水中11种三嗪类农药

建立了针对地表水和地下水中11种三嗪类农药的超高效液相色谱三重四极杆质谱分析方法,并对前处理、仪器分析、方法特性指标等因素进行优化探讨。使用SB-C18色谱柱、乙腈水二元混合液流动相进行化合物分离,设置柱温为40℃、进样量为10μL,质谱采用正离子模式检测,内标法定量,采用平均相对响应因子法拟合标准曲线。结果表明,11种三嗪类农药的方法检出限为0.003~0.01μg/L,对3种质量浓度的基体加标样品分别进行6次平行分析,测定结果的相对标准偏差为2.1%~19%,平均加标回收率为80.0%~108%。采集地表水和地下水样品,经尼龙或聚四氟乙烯滤膜过滤后上机测定,在1种地表水样品中检出了阿特拉津和扑灭津,平均质量浓度分别为0.032和0.009μg/L。该方法具有准确度高、重复性好、检出限低等优点,能够满足现阶段地表水和地下水的环境管理监测要求。     

超高效液相色谱—串联质谱快速测定水中的溴氰菊酯

建立了超高效液相色谱-三重四级杆串联质谱(UPLC-MS/MS)快速测定地表水及饮用水中溴氰菊酯的方法,并应用于实际水样的检测分析。结果表明:水样经0.22μm滤膜过滤后可直接采用超高效液相色谱-三重四级杆串联质谱仪多重反应监测(MRM)模式定量检测水中溴氰菊酯;最优分析条件下,溴氰菊酯的检出限为0.30μg/L,其线性检测范围为0.30~20.0μg/L,相关系数为0.999 7;采用该方法检测水中的溴氰菊酯,不同水平(2.00、5.00μg/L和20.0μg/L)样品加标回收率为95.5%~98.5%,相对标准偏差为1.37%~3.59%。方法快速简便、灵敏度高、定性定量准确,适合日常批量水样的快速分析。     

地表水样品中10种卤代烃测定方法的优化

对地表水样品中10种卤代烃测定方法进行优化,找出空白偏高的原因。方法优化后的加标回收率为90.1%~104%,相对标准偏差为1.1%~6.9%,检出限为0.000 3μg/L~2.0μg/L,可满足地表水环境质量分析要求。     

气相色谱法测定地表水中百菌清和菊酯类农药

采用正己烷萃取地表水中的百菌清和6种菊酯类农药,通过毛细管气相色谱法-电子捕获检测器(GC-ECD)定性定量。供试农药的线性范围:百菌清为10.0μg/L～200μg/L,6种菊酯类为50.0μg/L～1 000μg/L;方法检出限分别为:百菌清0.054μg/L,甲氰菊酯0.62μg/L,三氟氯氰菊酯0.68μg/L,氯菊酯0.40μg/L,氯氰菊酯0.65μg/L,氰戊菊酯0.78μg/L,溴氰菊酯0.15μg/L;对地表水样品3个质量浓度水平的平均加标回收率为91.3%～118%,6次平行测定的RSD<5%。     

UPLC-串联质谱法快速测定地表水中多种农药残留

采用超高效液相色谱-串联质谱法测定地表水中21种氨基甲酸酯和有机磷农药,通过优化试验条件,使方法在0. 500μg/L～100μg/L范围内线性良好,方法检出限为0. 1μg/L～6. 2μg/L。对空白水样做3个质量浓度水平的加标回收试验,5次测定结果的RSD为0. 3%～9. 5%,回收率为82. 0%～113%。将该方法用于测定徐州某地表水样品,3个水样均为未检出。     

超高效液相色谱/串联质谱法测定饮用水源水中多种藻毒素

饮用水源水样品经过直接进样或固相微萃取法净化后,用超高效液相色谱/串联质谱测定水中11种藻毒素。通过试验优化测定条件,使该方法在0.500μg/L~50.0μg/L范围内线性良好,检出限为0.01μg/L~0.05μg/L。对同一实际环境样品做3个质量浓度水平加标回收试验,6次测定结果的RSD为2.2%~9.3%,回收率为76.1%~108%。将该方法用于测定环巢湖湖面12个监测断面水样,结果 3组样品中MC-YR、MC-LR和MC-RR值为0.3μg/L~0.8μg/L。     

地表水中SVOCs和氨基甲酸酯类农药同步萃取技术的探讨

采用大体积固相萃取富集地表水中SVOCs和氨基甲酸酯类农药,再以气相色谱-质谱和超高效液相色谱-串联质谱联用对目标物定性定量。通过优化固相萃取条件,使SVOCs在0.500 mg/L~10.0 mg/L之间,氨基甲酸酯类农药在1.00μg/L~100μg/L之间线性良好,方法检出限为0.002μg/L~0.009μg/L,加标回收率分别为70.5%~105%和78.5%~124%。用该方法测定某流域地表水,结果邻苯二甲酸酯类物质、多环芳烃类、酚类、硝基苯环类化合物等SVOCs,以及克百威、仲丁威等氨基甲酸酯类农药检出。     

固相萃取-GC/MS法测定地表水中3-甲基吲哚

采用微球硅胶键合C_(18)固相萃取柱萃取水样中的3-甲基吲哚,并用气质联用法测定,方法在0 mg/L~10.0 mg/L范围内线性良好,方法检出限为0.2μg/L。空白水样3个质量浓度水平的加标回收率为89%~94%,7次测定结果的RSD为2.3%~6.9%。用该方法测定7个实际地表水样品,其中4个地表水样品检出3-甲基吲哚,地表水样的加标回收率为81.5%~97.0%。     

土壤中挥发性有机物的快速测定方法

本文建立了用便携式气相色谱-质谱仪快速测定土壤中VOCs的方法。该方法能够快速对土壤样品中VOCs进行定性分析和定量测定。当采样量达到5 g时,方法检出限0.02~2.11μg/L,相对标准偏差2.0%~13.5%;加标20μg/L时,回收率63%~123%。采用该方法测定北京地区5个土壤样品,总体质量浓度为0~873μg/kg。     

A New Mathematical Approach in Environmental and Life Sciences: Gene–Environment Networks and Their Dynamics

An important research area in life sciences is devoted to modeling, prediction, and dynamics of gene-expression patterns. As clearly understood in these days, this enterprise cannot become satisfactory without acknowledging the role of the environment. To a representation of past, present, and most likely future states, we also encounter measurement errors and uncertainties. This paper surveys and improves recent advances in understanding the foundations and interdisciplinary implications of the newly introduced gene–environment networks, and it integrates the important theme of carbon dioxide emission reduction into the networks and dynamics. We also introduce some operational and managerial issues of practical working and decision making, expressed in terms of sliding windows, quadrants (modules) of parametric effects, and navigating (controlling) between such effects and directing them. Given data from DNA microarray experiments and environmental records, we extract nonlinear ordinary differential equations that contain parameters that have to be determined. For this, we employ modern (Chebychevian) approximation and (generalized semi-infinite) optimization. After this is provided, time- discretized dynamical systems are studied. A combinatorial algorithm with polyhedra sequences allows to detect the region of parametric stability. Finally, we analyze the topological landscape of gene–environment networks with its structural (in)stability. By embedding as a module and investigating CO₂ emission control and figuring out game theoretical aspects, we conclude. This pioneering work is theoretically elaborated, practically devoted to health care, medicine, education, living conditions, and environmental protection, and it invites the readers to future research.      

An investigation on biological stability of product water generated by lab-scale and pilot-scale distillation systems

Material Disposal Area G is the primary low-levelradioactive waste disposal site at Los Alamos NationalLaboratory, New Mexico, and is adjacent to Pueblo of SanIldefonso lands. Pueblo residents and Los Alamos scientists areconcerned about radiological doses resulting from uptake of AreaG radionuclides by mule deer (Odocoileus hemionus) andRocky Mountain elk (Cervus elaphus), then consumption ofdeer and elk meat by humans. Tissue samples were collected fromdeer and elk accidentally killed near Area G and were analyzedfor ³H, ⁹⁰Sr, total U, ²³⁸Pu, ^{239, 240}Pu,²⁴¹Am, and ¹³⁷Cs. These data were used to estimatehuman doses based on meat consumption of 23 kg y^-1. Humandoses were also modeled using RESRAD, and dose rates to deer andelk were estimated with a screening model. Dose estimates tohumans from tissue consumption were 2.9 × 10^-3 mSv y^-1and 1.6 × 10^-3 mSv y^-1 from deer and elk, respectively,and RESRAD dose estimates were of the same order of magnitude. Estimated dose rates to deer and elk were 2.1 × 10^-4 mGyd^-1 and 4.7 × 10^-4 mGy d^-1, respectively. Allestimated doses were significantly less than established exposurelimits or guidelines.     

Assessing health consequences in an environmental impact assessment: The case of Amsterdam Airport Schiphol

In this article a comprehensive approach for the evaluation of possible health effects in an environmental impact assessment (EIA) is described, illustrated with the example of Amsterdam Airport Schiphol. Unlike many EIAs, we estimated quantitatively the impact of aircraft-related pollution in terms of the number of affected people for aircraft noise annoyance, odour annoyance and hypertension. In addition, an analysis of health registry data on cardiovascular and respiratory diseases and a short survey on annoyance and risk perception were carried out. The scope of a health impact assessment depends on the situation, available knowledge and data, concern in the population about the impact and the number of people concerned. It is important to pay attention to the perception of risks and concerns from all parties involved. Moreover, the results demonstrate that far more people outside the area for which standards apply were affected than inside.     

Contaminant Profiles of Two Species of Shorebirds Foraging Together at Two Neighboring Sites in South San Francisco Bay, California

The San Francisco Bay estuary isused by over one million shorebirds during springmigration and is home to several hundred thousandduring the winter. Most shorebird use occurs in thesouthern reach of the estuary (South Bay). Thereduced water circulation and discharge fromindustrial sources in the South Bay are responsiblefor the highest levels of some trace elements in theestuary. Wintering shorebirds have been found to havestrong site fidelity to areas as small as a fewkilometers in the South Bay, which may increase theirexposure to contaminants near local point sources. Inaddition, different shorebird species foraging at thesame site have been shown to have differentcontaminant burdens. Thus, our objectives were totest whether contaminant burdens differed by species,or whether contaminant burdens differed in shorebirdscollected at adjacent sites. We examined thecontaminant profiles of two species of shorebirds,long-billed dowitchers (Limnodromus scolopaceus)and western sandpipers (Calidris mauri) thatforage together at two sites, Hayward and Newark,separated by 8 km in the South Bay. We usedmultivariate analysis of variance tests to compare thecomposition of 14 elemental analytes in their livertissues and estimated their molar ratios of Hg and Se. Composite samples were used for contaminant analysesbecause of the small body size of the shorebirds. Seven elemental analytes (Ag, Ba, Be, Cr, Ni, Pb, V)were below detection limits in a majority of thesamples so statistical analyses were precluded. Inthe measurable analytes (As, Cd, Cu, Hg, Mn, Se, Zn),we found no significant intra-site differences ofcontaminant profiles for the two species. We pooledthe samples to examine inter-site differences andfound significant differences in contaminant profilesbetween shorebirds at the neighboring sites (P = 0.03). Shorebirds at Newark had higher (P < 0.05) concentrations of As, Cd, and Se than those at Hayward. Dowitchers at Newark had concentrations of Hg and Se which were highly correlated (P < 0.003) in a mean molar ratio of 1:19, similar tothat reported in other birds. In the larger dowitcherspecies, we also examined exposure to 20organochlorine compounds. Organic analyses showedthat the dowitchers had been exposed to DDE, PCBs,dieldrin and trans-nonachlor, but with no significantdifferences in concentrations between Hayward andNewark (P > 0.05).     

土壤和底泥中砷、铬、锰测定的前处理技术

试验了土壤和底泥中砷的前处理技术，其目的是能对土壤、底泥中砷、铬、锰在一次前处理中制备成试液，比色法分析。试验表明，用Ｈ２ＳＯ４－Ｈ３ＰＯ４－Ｈ２Ｏ２进行前处理是可行的。方法简单、挥发酸雾少，用标准参考物质检验证明，分解完全，数据准确，有粒较好一致性。     

Metal concentrations in deciduous tree leaves from urban areas in Poland

Accumulation of metals in deciduous tree foliage fromurban areas in western-south Poland was monitored duringthe vegetation season of 2000 year. Concentrations of Al,Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr, Ti and Znwere measured in birch, willow, linden and maple leavesusing the ICP-AES method. Seasonal variations of metalconcentrations and their relations with sampling sitewere investigated. The most dynamic accumulation of Al,Cd, Cr, Ni and Pb was observed for examined species. Thehighest differences in element concentrations forinvestigated sites were found for Ba, Cd, Mn and Ni.Interelement correlations were investigated. In allfoliar samples synergistic relationships between Al–Crand Ca-Sr were found. Statistically significant negativecorrelations were observed only for Cd and Ti in birch leaves.     

Geochemical assessment of metal transport in glacial till during electrokinetic remediation

This paper presents the chemical speciation and retention behavior of chromium (Cr), nickel (Ni), and cadmium (Cd) prior to and after the electrokinetic remediation in glacial till soil. The speciation of the metals was predicted using the chemical speciation program MINEQL⁺. The simulations were performed for single-contaminant with only Cr(VI) or Ni, and multi-contaminants consisting of: (1) Cr(VI), Ni, and Cd; (2) Cr(III), Ni and Cd; (3) Cr(VI), Cr(III), Ni and Cd; (4) Cr(VI), Ni, and Cd with reducing agents; and (5) Cr(III), Ni, and Cd with oxidizing agent (Mn). The results showed that the speciation and distribution of cationic metals [Ni, Cd, and Cr(III)] in glacial till soil remain unaffected or slightly affected during electrokinetics. This is attributed to the high pH buffering capacity of the glacial till, leading the metals to precipitate in the soil prior to and after electrokinetics. This study showed that during electrokinetics, Cr(VI) existed as anionic complex and migrated towards the anode and the migration is maximum in case of a single-contaminant system. The study also showed that near the anode in the absence of any reducing and oxidizing agent, Cr(VI) mostly adsorbed, and some of Cr(VI) reduced to Cr(III) and migrated towards the cathode and finally precipitated due to high pH conditions. Ni and Cd remain adsorbed or precipitated due to the high pH conditions throughout the soil. Among the reducing agents, the sulfide had significant effect on the migration of metals compared to ferrous ions. While in the presence of oxidizing agent (Mn), no noticeable Cr(VI) was found in the soil sample indicating the reduction of Cr(VI) to Cr(III) and the predominance of reducing conditions due to the presence of naturally occurring iron in the glacial till soil. Overall, this study provides a reasonable explanation of the speciation and distribution of chromium, nickel and cadmium during the electrokinetic remediation of glacial till soil.     

Biomonitoring of Lead, Zinc, and Cadmium in Streams Draining Lead-Mining and Non-Mining Areas, Southeast Missouri, USA

We evaluated exposure of aquatic biota to lead (Pb), zinc (Zn), and cadmium (Cd) in streams draining a Pb-mining district in southeast Missouri. Samples of plant biomass (detritus, periphyton, and filamentous algae), invertebrates (snails, crayfish, and riffle benthos), and two taxa of fish were collected from seven sites closest to mining areas (mining sites), four sites further downstream from mining (downstream sites), and eight reference sites in fall 2001. Samples of plant biomass from mining sites had highest metal concentrations, with means 10- to 60-times greater than those for reference sites. Mean metal concentrations in over 90% of samples of plant biomass from mining sites were significantly greater than those from reference sites. Mean concentrations of Pb, Zn, and Cd in most invertebrate samples from mining sites, and mean Pb concentrations in most fish samples from mining sites, were also significantly greater than those from reference sites. Concentrations of all three metals were lower in samples from downstream sites, but several samples of plant biomass from downstream sites had metal concentrations significantly greater than those from reference sites. Analysis of supplemental samples collected in the fall of 2002, a year of above-average stream discharge, had lower Pb concentrations and higher Cd concentrations than samples collected in 2001, near the end of a multi-year drought. Concentrations of Pb measured in fish and invertebrates collected from mining sites during 2001 and 2002 were similar to those measured at nearby sites in the 1970s, during the early years of mining in the Viburnum Trend. Results of this study demonstrate that long-term Pb mining activity in southeast Missouri has resulted in significantly elevated concentrations of Pb, Cd, and Zn in biota of receiving streams, compared to biota of similar streams without direct influence of mining. Our results also demonstrate that metal exposure in the study area differed significantly among sample types, habitats, and years, and that these factors should be carefully considered in the design of biomonitoring studies.     

Varying Stable Nitrogen Isotope Ratios of Different Coastal Marsh Plants and Their Relationships with Wastewater Nitrogen and Land Use in New England, USA

The stable nitrogen isotope ratios of some biota have been used as indicators of sources of anthropogenic nitrogen. In this study the relationships of the stable nitrogen isotope ratios of marsh plants, Iva frutescens (L.), Phragmites australis (Cav.) Trin ex Steud, Spartina patens (Ait.) Muhl, Spartina alterniflora Loisel, Ulva lactuca (L.), and Enteromorpha intestinalis (L.) with wastewater nitrogen and land development in New England are described. Five of the six plant species (all but U. lactuca) showed significant relationships of increasing δ ¹⁵N values with increasing wastewater nitrogen. There was a significant (P < 0.0001) downward shift in the δ ¹⁵N of S. patens (6.0 ± 0.48‰) which is mycorrhizal compared with S. alterniflora (8.5 ± 0.41‰). The downward shift in δ ¹⁵N may be caused by the assimilation of fixed nitrogen in the roots of S. patens. P. australis within sites had wide ranges of δ ¹⁵N values, evidently influenced by the type of shoreline development or buffer at the upland border. In residential areas, the presence of a vegetated buffer (n = 24 locations) significantly (P < 0.001) reduced the δ ¹⁵N (mean = 7.4 ± 0.43‰) of the P. australis compared to stands where there was no buffer (mean = 10.9 ± 1.0‰; n = 15). Among the plant species, I. frutescens located near the upland border showed the most significant (R ² = 0.64; P = 0.006) inverse relationship with the percent agricultural land in the watershed. The δ ¹⁵N of P. australis and I. frustescens is apparently an indicator of local inputs near the upland border, while the δ ¹⁵N of Spartina relates with the integrated, watershed-sea nitrogen inputs.     

Effect of heavy metal contaminated shooting range soils on mycorrhizal colonization of roots and metal uptake by leek

We grew leek (Allium porrum) in soils of two shooting ranges heavily contaminated with heavy metals in the towns of Zuchwil and Oberuzwil in Switzerland as a bioassay to test theactivity of arbuscular mycorrhizal (AM) fungi in these soils.Soil samples were taken from (1) front of the shooting house(HOUSE), (2) the area between house and target (FIELD) and (3) the berm (BACKSTOP). Samples of Ribwort plantain (Plantagolanceolata) growing naturally within the shooting ranges werealso collected and the colonization of its roots by mycorrhizalfungi was measured. The number of AM spores in the soils wassignificantly reduced concomitant with the increase in thedegree of soil contamination with metals. In Zuchwil,mycorrhizal fungi equally colonized roots of Ribwort plantainsampled from BACKSTOP and HOUSE. In Oberuzwil, however, plantsfrom BACKSTOP had lower colonization when compared with thosesampled from HOUSE. Colonization of leek was strongly reducedin the BACKSTOP soil of Zuchwil and slightly reduced in theBACKSTOP soil of Oberuzwil when compared with plants grown inrespective HOUSE soil. Concentrations of Cd, Cr, Cu, Ni, Pb andZn in the leaves of leek grown in the BACKSTOP soil was withinthe range considered toxic for human consumption. This pointsto the high degree of bio-availability of these metal in thesesoils. Significant decrease in the number of mycorrhizal sporesin the BACKSTOP soils in Zuchwil and the low colonization ofleek roots grown in these soils point to possible changes inthe species diversity of mycorrhizal fungi in these soils.