高效液相色谱串联质谱法分析土壤中多溴联苯醚类化合物

建立了一种超高效液相色谱串联质谱法(UPLC-MS/MS)同时测定土壤中8种多溴联苯醚化合物(PBDEs)的方法,采用快速溶剂萃取(ASE)和凝胶净化色谱(GPC),经BEH反相C₁₈色谱柱分离,10 min内完成分离,使用含0.1%氨水的甲醇和水进行梯度洗脱,采用液相色谱-负离子-大气压化学电离(APCI)串联质谱,多反应监测模式(MRM),加入 ¹³C₁₂-BDE-139和¹³C₁₂-BDE-209内标作定量分析。结果表明:在优化的分析条件下,PBDEs的线性相关系数为0.998 8～0.999 5,方法检出限为0.22～0.59 μg/kg,在2个添加水平下,平均回收率为71%～126%,标准偏差为3%～18%,土壤实际质控样测定结果均在允许范围内。适合于土壤中PBDEs的快速分析,特别对于高溴代PBDEs,相比气相色谱质谱方法具有更快的分析速度和更好的稳定性。     

固相萃取-超高效液相色谱/三重四极杆质谱法同时测定地表水中8种亚硝胺类化合物

建立了固相萃取（SPE）-超高效液相色谱/三重四极杆串联质谱（UPLC-MS/MS）同时测定地表水中8种亚硝胺类化合物的方法。水样中目标物经椰壳活性炭固相萃取小柱吸附富集，小柱经氮气吹干后采用二氯甲烷洗脱。待测样品采用Atlantis T₃柱，以水-甲醇作为流动相进行梯度洗脱，大气压力化学电离源（APCI）正离子模式多反应监测方式（MRM）进行检测，内标法定量分析。8种目标物在相关线性范围内线性良好(r≥0.9950)，地表水加标回收率为55.4%~90.4%，相对标准偏差为3.1%~14.3%，方法检出限为1.1 ~1.8 ng/L。本方法准确度和灵敏度高，适用于快速测定地表水中8种亚硝胺类化合物含量。     

气相色谱法同时测定指甲油中的苯系物和邻苯二甲酸酯类化合物

建立指甲油中苯系物、邻苯二甲酸酯类化合物(DMP,DEP,DBP,BBP,DEHP,DNOP)多种有毒有害成分同时检测技术: 用毛细管柱气相色谱分离,外标法定量,苯系物的线性范围为1×10^-2~100μg,邻苯二甲酸酯类为5×10^-2~20μg;苯系物的回收率为90%~102%,相对标准偏差(RSD)的范围为0.13%~0.92%;邻苯二甲酸酯类的回收率为92%~109%,相对标准偏差(RSD)的范围为0.44%~2.54%。结果表明,该方法简便、快速、灵敏、精密度好。     

高效离子色谱柱后衍生法测定环境水体中过渡金属离子含量

建立了可同时分析饮用水中铁、铜、镍、锌、钴、镉、锰等过渡金属离子的方法。优化后的离子色谱条件:选用 Dionex IonPac CS5A色谱柱(4 mm×250 mm),以7.0 mmol/L 吡啶-2,6-二羧酸＋66 mmol/L KOH＋74 mmol/L HCOOH＋5.6 mmol/L K₂SO₄为淋洗液,流速为1.2 mL/min,柱温为30 ℃;以0.5 mmol/L 4-(2-吡啶偶氮)间苯二酚＋1.0 mol/L 2-二甲醇胺＋0.5 mol/L氨水＋0.3 mol/L NaHCO₃为衍生液,流速为0.7 mL/min,紫外检测器波长为520 nm。结果表明,该离子色谱柱对以上过渡金属具有很好的保留和分离效果,衍生后的紫外检测手段具有优异的灵敏度和选择性。该方法稳定性良好,连续进样5针的相对标准偏差均小于0.79%;标准曲线线性关系良好,r≥0.998 8;方法检出限低,Fe³⁺为0.8 μg/L,Fe²⁺为4 μg/L,Cu²⁺为0.8 μg/L,Ni²⁺为3 μg/L,Zn²⁺为2 μg/L,Co²⁺为0.9 μg/L,Cd²⁺为16 μg/L,Mn²⁺为6 μg/L;检测结果准确,低、中、高3个水平的加标回收率均大于91.5%。该方法适用于环境水体中过渡金属离子的定量分析。     

超高效液相色谱串联质谱法测定水体中17种抗生素

建立了一种超高效液相色谱串联质谱法同时测定饮用水源中17种超痕量水平抗生素的分析方法。采用Oasis HLB柱对500 mL pH=5含目标物的水样进行富集，干燥15 min后，用5%氨水甲醇洗脱，氮吹后定容至1 mL。用C₁₈柱吸附目标物，并用0.1%甲酸水和甲醇对目标物进行分离，采用正离子电喷雾电离模式在多反应监测通道中对目标物同时进行分析。该方法检出限为0.07~0.78 ng/L，超痕量水平下回收率范围为75.8%~108%。该方法灵敏度高，精密度为1.8%~15.0%，适用于同时测定饮用水源等水体中的抗生素。     

便携式气相色谱-氢火焰离子化检测器法测定低浓度总烃的氧气干扰特征研究

研究了采用便携式气相色谱-氢火焰离子化检测器法测定气体中的总烃浓度时,氧气浓度对测定结果的影响,并采用多元线性回归模型对总烃的测定结果进行了校准。当总烃的实际浓度不低于9 mg/m³时,氧气的干扰较小(相对标准偏差≤2%)。在试验的所有总烃实际浓度下(1~200 mg/m³),当氧气浓度为1%~7%时,也无需考虑氧气干扰的影响(相对标准偏差≤2%)。当总烃的实际浓度低于9 mg/m³且氧气浓度为9%~21%时,需依据多元线性回归分析原理并采用模型对测得的总烃浓度进行校准。线性回归方程分析结果显示,模型拟合情况良好(R²=0.999),可以用来修正测试结果,从而得到更加准确的总烃实际浓度。     

超高效液相色谱-串联质谱法同时检测溴代阻燃剂

采用Acquity BEH C18色谱柱,以甲醇-乙腈混合液和水为流动相,辅以电喷雾正离子模式多反应监测(MRM)进行定性定量分析,建立了一种同位素稀释超高效液相色谱-串联质谱(UPLC-MS/MS)同时检测四溴双酚A(TBBPA)、三-(2,3-二溴丙基)异氰脲酸酯(TBC)和3种六溴环十二烷(HBCD)异构体的方法。水样通过固相萃取进行净化,回收率达到85.3%~96.1%。土壤和底泥样品经加速溶剂萃取后,采用酸性硅胶和中性硅胶柱进行净化,回收率达到81.5%~102.7%。该方法对TBBPA、TBC、α-HBCD、β-HBCD、γ-HBCD在水和土壤中的检测限分别为1.0、1.2、2.0、0.8、1.2 ng/L和0.10、0.12、0.20、0.08、0.12 ng/g。     

离子色谱-柱后衍生可见光检测环境空气中六价铬和废气中铬酸雾

以硫酸铵-氨水溶液为淋洗液，二苯碳酰二肼为柱后显色剂，采用离子色谱-柱后衍生可见光检测环境空气中六价铬和废气中铬酸雾的含量。通过对分析条件的优化，建立了简便、灵敏、选择性好、准确性高和重现性好的分析气体中六价铬的方法。该方法在Cr⁶⁺浓度1.00~600 μg/L之间线性良好，当采集50 L有组织废气和20 L无组织废气时，铬酸雾分析的检出限分别为2.2×10^-5和1.1×10^-5 mg/m³，采集64 m³环境空气时，Cr⁶⁺分析的检出限为7.8×10^-9 mg/m³，以浸提后的样品水溶液连续进样得到其相对标准偏差为1.42%（n=8）。利用该法进行环境空气中六价铬和废气中铬酸雾的测定，回收率在80%~105%之间。监测结果显示：环境空气中六价铬含量处于极低状态；五金厂厂界废气中铬酸雾含量极低，约为5 μg/m³；五金厂废气排气筒监测的气体中则含有较高浓度的铬酸雾，其含量已经超过GB 21900—2008中规定的排放限值。     

高效液相色谱-二极管阵列检测器测定邻苯二甲酸酯色谱条件优化

采用高效液相色谱-二极管阵列检测器对6种PAEs类物质进行测定,并对梯度洗脱条件、流速、检测波长等影响化合物色谱响应的关键参数进行优化。综合考虑样品测试效率、分析精度、实际样品中存在杂质干扰等因素,确定以乙腈-水为流动相进行梯度洗脱,洗脱0~11 min流动相乙腈-水梯度比例为50∶50,11 min后流动相调整为100%乙腈,各化合物均能完全分离;色谱分析流速为0.8 m L/min;PAEs的最佳吸收波长为225 nm。在优化的色谱条件下,6种PAEs的线性良好,相关系数均大于0.999 8,仪器检出限为0.08~0.12 mg/L,保留时间、峰面积的相对标准偏差分别为0.02%~0.60%、0.13%~0.86%。方法灵敏度较高,适合土壤等邻苯二甲酸酯含量较高基质样品的快速分析。     

水环境中26种类固醇激素的分析方法研究

建立了固相萃取-超高效液相-串联质谱法同时测定水环境中26种类固醇激素的分析方法。明确了取样体积为500 m L,Cleanert PEP为富集柱,乙酸乙酯为洗脱剂,甲醇为溶剂进行提取操作。选择了正离子模式,以0. 1%甲酸/甲醇-水为流动相,负离子模式以0. 1%氨水/乙腈-水为流动相,试样经AcquityTMUPLC BEH C18色谱柱分离后,选用质谱检测模式进行定性、定量分析。通过方法验证,26种类固醇激素的方法检出限为0. 3～1. 5 ng/L,测定下限为1. 2～6. 0 ng/L,代表性样品测定结果的相对标准偏差为2. 6%～13. 7%(n=6),加标回收率为71. 2%～121%。该方法操作便捷,灵敏度高,精密度和准确度良好,可适用于水环境中多种痕量、超痕量类固醇激素的定性定量分析。     

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.      

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。     

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.     

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.     

Comparative studies on accumulation of Cr from metal solution and tannery effluent under repeated metal exposure by aquatic plants: its toxic effects

The present study demonstrates comparison of Cr accumulatingpotential by the plants of Najas indica Cham. (submerged),Vallisneria spiralis L. (rooted submerged) and Alternanthera sessilis R. Br. (rooted emergent) under repeatedmetal exposure and its effect on chlorophyll and protein concentrations. These plants were treated with different concentrations of Cr under repeated exposure in controlled laboratory conditions to assess the maximum metal accumulationpotential. The plants of V. spiralis accumulated significantly high amount of Cr under laboratory conditions incomparison to N. indica and A. sessilis. The maximumaccumulation of 1378, 458 and 201 g g^-1 dw Cr was found in the leaves of V. spiralis, N. indica and A. sessilis, respectively at 8 mg L^-1 after 9 day of Cr exposure. These plants have shown a decrease in chlorophyll andprotein concentrations with increase in Cr concentrations. In view of high accumulation of Cr in V. spiralis, the plantswere treated with different concentrations of tannery effluent collected from Common Effluent Treatment Plant, Unnao (UP). Theplants of V. spiralis treated with 100% tannery wastewatershowed the maximum accumulation (57.5 g g^-1 dw) of Cr in the roots after 10 days of exposure. The plants were foundeffective in removing Cr from solution and tannery effluent.     

Assessment of Air Quality After the Implementation of Compressed Natural Gas (CNG) as Fuel in Public Transport in Delhi, India

Public transport in Delhi was amended by the Supreme Court of India to use Compressed Natural Gas (CNG) instead of diesel or petrol. After the implementation of CNG since April 2001, Delhi has the highest fraction of CNG-run public vehicles in the world and most of them were introduced within 20 months. In the present study, the concentrations of various criteria air pollutants (SPM, PM₁₀, CO, SO₂ and NO_x) and organic pollutants such as benzene, toluene, xylene (BTX) and polycyclic aromatic hydrocarbons (PAHs) were assessed before and after the implementation of CNG. A decreasing trend was found for PAHs, SO₂ and CO concentrations, while the NO_x level was increased in comparison to those before the implementation of CNG. Further, SPM, PM₁₀, and BTX concentrations showed no significant change after the implementation of CNG. However, the BTX concentration demonstrated a clear relation with the benzene content of gasoline. In addition to the impact of the introduction of CNG the daily variation in PAHs levels was also studied and the PAHs concentrations were observed to be relatively high between 10 pm to 6 am, which gives a proof of a relation with the limited day entry and movement of heavy vehicles in Delhi.