气相色谱-串联质谱法测定沉积物中多环芳烃

采用ASE法提取沉积物中16种多环芳烃,以固相萃取法净化提取液,用气相色谱-串联质谱法测定。通过优化测定条件,使方法在5.00μg/L~1 600μg/L范围内线性良好,方法检出限为0.15μg/kg~0.66μg/kg。空白石英砂的加标回收率为61.9%~121%,7次测定结果的RSD为2.6%~11.1%。     

顶空气相色谱质谱法测定土壤中挥发性卤代烃方法研究

采用顶空气相色谱质谱法(HS/GC-MS)对土壤中挥发性卤代烃进行了测定,优化了分析的顶空条件、气相色谱质谱分离条件。在优化条件下成功实现了24种挥发性卤代烃的分离,确定了分析方法的检出限、测定下限、精密度及回收率等质量控制参数。方法的检出限为0.8~4.4μg/kg,测定下限为3.2~17.6μg/kg。当加标量为100μg/kg和250μg/kg时,相对标准偏差分别为1.3%~12.6%和2.6%~8.7%,加标回收率分别为71.4%~126%和63.1%~121%。     

快速溶剂萃取-气相色谱/串联质谱法测定农作物中的有机氯农药

建立快速溶剂萃取,固相萃取柱净化,气相色谱/串联四极杆质谱检测分析农作物中23种有机氯农药残留的方法。以油菜为样品,加标浓度为5、10、25、50μg/kg时,平均回收率在72%~101%之间,相对标准偏差3%~14%(n=5)。8种农作物(莴笋、黄瓜、蒜苗、辣椒、油菜、茄子、玉米和水稻)加标浓度为25μg/kg时的平均回收率在71%~113%之间,相对标准偏差3%~16%(n=5)。方法检出限0.75~1.76μg/kg之间。     

顶空-便携式气相色谱法测定土壤中的苯系物

建立了顶空-便携式气相色谱快速测定土壤中苯、甲苯、乙苯、间对二甲苯、邻二甲苯的方法,并讨论了无机盐及振荡时间等因素对顶空分析灵敏度的影响。结果表明,方法回收率为87.2%~105.1%,相对标准偏差(RSD)5.3%~7.8%,最低检出限为0.1~0.8μg/kg;苯、甲苯、乙苯、间对二甲苯、邻二甲苯的线性范围分别为0.8~160μg/kg、1.6~320μg/kg、2.0~400μg/kg、2.0~400μg/kg和3.2~800μg/kg。方法回收率、RSD与标准方法相比没有显著性差异,较之标准方法其更能满足现场快速监测的需要。     

加速溶剂萃取-固相萃取/超高效液相色谱-串联质谱法测定沉积物中5种微囊藻毒素

建立了加速溶剂萃取-固相萃取/超高效液相色谱-串联质谱法同时测定沉积物中5种微囊藻毒素(MC-LR、MC-RR、MC-LW、MC-LF、MC-YR)的方法。选择甲醇-水(1∶4,V/V)为ASE萃取溶剂,萃取温度和萃取压力分别为80℃和13.1 MPa,固相萃取过程以HLB小柱为萃取柱,采用液相色谱-串联质谱分析。方法在5种微囊藻毒素质量浓度5~100μg/L内线性良好(r0.995),回收率为76.0%~118%,相对标准偏差为1.9%~12.0%,检出限为2~3μg/kg,定量下限为8~12μg/kg。该方法已用于西太湖沉积物的检测,具有较好的方法适用性。     

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。     

QuEChERS-气相色谱法快速测定土壤中8种有机氯农药

建立QuEChERS-气相色谱法同时检测土壤中8种有机氯农药的方法,优化分散固相萃取剂用量。土壤样品通过分散固相萃取净化技术,氮吹浓缩后用正己烷定容,最后通过气相色谱测定。结果表明,在2.0~100μg/L质量浓度范围内呈线性,相关系数r为0.9895~0.9991。空白样品在0.5,5和20μg/kg加标浓度下的回收率为75.3%~92.3%,相对标准偏差为3.2%~5.6%(n=5),方法检出限为0.053~0.064μg/kg,测定下限为0.21~0.26μg/kg。该方法操作简单、结果准确、有机试剂用量少、分析成本低,适用于土壤中有机氯农药的残留检测与分析。     

固相萃取-液相色谱-串联质谱法测定水中5种雌激素

建立了固相萃取-液相色谱-串联质谱组合联用技术同时测定地表水、饮用水和污水处理厂出厂水中的5种雌激素(17β-雌二醇、雌三醇、雌酮、17α-炔雌醇、己烯雌酚)的方法。水样经过全自动固相萃取仪富集,以OASIS HLB柱为萃取柱,甲醇为洗脱剂,用液相色谱-串联四极杆质谱联用仪分析定量。分别在0.5~8、5~80μg/L范围内线性良好,相关系数为0.995~0.998。17β-雌二醇、雌三醇、17α-炔雌醇的检出限均为5μg/L,雌酮与己烯雌酚的检出限为0.5μg/L。5种雌激素的纯水加标回收率为63.6%~120.2%,地表水加标回收率为59.8%~91.5%,自来水加标回收率为55.3%~92.1%,精密度为3.7%~10.7%,该方法简单、可靠,可用于水中雌激素类污染物的同时测定。     

QuEChERS-超高效液相色谱-串联质谱法测定鱼肉中六溴环十二烷

建立了一种测定鱼肉中六溴环十二烷（HBCD）的QuEChERS-超高效液相色谱-串联质谱方法。方法采用QuEChERS法进行样品前处理,采用C18色谱柱分离,以水为流动相A,以甲醇-乙腈（V∶V=50∶50）为流动相B进行梯度洗脱;采用超高效液相色谱-串联质谱法在负离子模式下以多反应监测方式检测,用同位素稀释法定量。该方法在 0.5~50μg/L范围内具有良好的线性关系（相关系数≥0.999）,检出限为0.05~0.27 μg/kg,3个加标质量分数（2.5,125,25 μg/kg）的回收率范围为99.3%~107%,相对标准偏差为0.4%~8.4%。该方法简便准确、灵敏度高,可满足鱼肉中HBCD的检测要求。     

加速溶剂萃取-高效液相色谱法测定固体废物中多环芳烃

建立了固体废物中多环芳烃的快速溶剂萃取(ASE)-高效液相色谱(HPLC)检测方法。加速溶剂萃取仪在温度100℃、压强1.05 MPa条件下,以体积比1:1的丙酮和二氯甲烷为萃取剂,萃取5 min,萃取液采用固相萃取柱或凝胶色谱净化。灰渣和污泥中的PAHs的方法检出限分别为1.03~1.96 μg/kg和4.71~7.04 μg/kg,相对标准偏差分别为4.0%~13.8%和3.3%~13%,加标回收率分别为73.2%~89.8%和67.7%~90.5%。     

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.