固相萃取-超高效液相色谱-串联质谱法同时测定地表水中9种性激素

建立了地表水中9种性激素的固相萃取-超高效液相色谱-串联质谱检测方法。利用HLB固相萃取柱富集水体中痕量性激素,用甲醇洗脱并浓缩,再以1 mmol/L氟化铵-乙腈为流动相,经C_(18)柱分离,采用电喷雾离子源、质谱多反应监测模式,内标法定量,实现了地表水中9种性激素的同时检测。方法检出限为0. 1～1. 8 ng/L,在低、中、高3个加标水平下,性激素的平均回收率为69. 6%～115. 0%,相对标准偏差为3. 2%～17. 7%。该方法灵敏度高,定性准确,操作简单高效,适用于地表水中9种性激素的定性定量分析。     

固相萃取富集高效液相色谱法测定环境水样中的重金属元素

研究了用固相萃取富集高效液相色谱法测定环境水样中痕量重金属镍、铜、银、铅、镉和汞的方法。环境水样中的镍、铜、银、铅、镉和汞用四 -(对二甲氨基苯基 ) -卟啉 (T4 -DMAPP)柱前衍生 ,用C18固相萃取小柱萃取富集镍、铜、银、铅、镉和汞的T4 -DMAPP络合物 ,富集倍数为 1 0 0倍 ,然后用甲醇和四氢呋喃梯度洗脱为流动相 ,WatersXter raTMRP18( 3 9mm× 1 5 0mm)色谱柱为固定相分离 ,用二极管矩阵检测器检测。镍、铜、银、铅、镉和汞的检测限分别为3、2、4、3、1 5ng/L和 3ng/L。方法相对标准偏差为 1 8%— 3 2 % ,标准回收率为 92 %— 1 0 7%。该方法用于测定环境水样中的痕量重金属 ,结果令人满意     

盘式固相萃取-液相色谱-串联质谱法快速测定地表水中n-壬基酚、n-辛基酚和双酚A

建立了盘式固相萃取?超高效液相色谱?串联质谱快速测定地表水中n?壬基酚、双酚A、n?辛基酚的方法。1L水样经过Φ47 mm的C18盘式固相萃取膜盘萃取净化，用二氯甲烷／甲醇（体积比1∶1）洗脱、浓缩定容至1 mL。采用Waters BEH C18色谱小柱，以甲醇?0?1％氨水溶液为流动相，梯度洗脱分离后，UPLC?MS／MS多级监测模式（ MRM）下以外标法进行定性定量分析。该方法检出限：双酚A为1 ng／L，n?壬基酚为0?1 ng／L，n?辛基酚为0?1 ng／L。对同一环境样品进行了3种质量浓度（5、50、200 ng／L）的加标回收实验，平均回收率为84?6％～118?8％，相对标准偏差为1?8％～8?3％。基于该方法，对巢湖入湖河流水样进行了检测，质量浓度为13?2～42?3 ng／ L。     

固相萃取- GC/MS法测定水中有机氯农药

建立了固相萃取-气相色谱／质谱联用测定水中痕量六六六、滴滴涕和环氧七氯的方法。采用C18固相萃取柱富集水样，二氯甲烷／丙酮混合溶剂洗脱，加入菲-d10作为内标，利用气相色谱／质谱联用仪选择离子监测模式检测，内标法定量，定性、定量准确，线性响应良好，干扰小，按采样1 L计算，方法检出限为4．26ng／L～19、2ng／L，RSD在0、4％-6、3％之间，平均加标回收率在77．7％～118％之间，实际样品测定结果表明方法能满足环境水体中痕量有机氯农药的监测要求。     

固相微萃取-气相色谱法测定水中痕量有机氯农药

建立了固相微萃取-气相色谱联用快速测定水中14种痕量有机氯农药的方法,对比研究了浸入式直接固相微萃取与顶空固相微萃取两种方式对不同有机氯农药的富集效率,优化了试验条件.方法线性关系良好,检出限为0.1 ng/L～10 ng/L,定量下限为0.2 ng/L～40 ng/L,RSD＜8%,实际水样的加标回收率为67.0%～133%.     

固相萃取-高效液相色谱法测定水中呋喃丹、甲萘威和阿特拉津

采用固相萃取-高效液相色谱(SPE - HPLC)二极管阵列检测器同时测定水中呋喃丹、甲萘威和阿特拉津,以甲醇-水为流动相,采用梯度洗脱方式,选择220 nm为检测波长,二氯甲烷为洗脱剂.呋喃丹在0.200 mg/L ～5.00 mg/L、甲萘威和阿特拉津在0.020 mg/L～5.00 mg/L范围内线性良好,检出限...     

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。     

固相萃取-高效液相色谱-质谱联用法用于地表水中类固醇激素测定

建立了固相萃取-高效液相色谱-质谱联用法对雌三醇、氟哌噻吨、炔雌醇、雄烯二酮、雌二醇、雌酚酮、睾酮共7种类固醇激素的检测方法。样品经C18萃取小柱富集净化,采用内标法定量时,方法的检出限为0.66～1.95 ng/L,R0.998,回收率为78.5%～94.6%,相对标准偏差为1.1%～7.7%。采用该方法对上海市地表水进行测定,在2个采样点中检出雌酚酮(1.88 ng/L)和雄烯二酮(1.48 ng/L)。     

动态固相微萃取-气相色谱质谱法测定水中多种异味有机物

采用动态固相微萃取技术富集水样中2-异丙基-3-甲氧基吡嗪、2-异丁基-3-甲氧基吡嗪、2-MIB、β-环柠檬醛、2,4,6-三氯苯甲醚、GSM、α-紫罗酮和β-紫罗酮等8种异味有机物,并用气相色谱质谱法测定。通过优化试验条件,使方法在2. 00 ng/L～100 ng/L范围内线性良好,方法检出限为1. 0 ng/L～4. 4 ng/L。空白水样3个质量浓度水平的加标回收率为81. 0%～121%,6次测定结果的RSD为1. 7%～8. 9%。将该方法用于一水库实际水样的测定,结果 2-MIB、β-环柠檬醛、α-紫罗酮和β-紫罗酮检出,其余均为未检出。     

污水处理厂废水中苯胺类化合物的测定及生态风险分析

本研究建立了固相萃取结合高效液相色谱-串联质谱法测定水样中苯胺类化合物的方法,水样前处理使用PCX固相萃取小柱吸附苯胺类化合物,以甲醇溶剂洗脱,采用ZORBAX Eclipse Plus C18色谱柱,电喷雾质谱正离子模式,以乙腈-0. 2%甲酸水为流动相,梯度洗脱,同时测定水样中12种苯胺类化合物。结果显示,进水中12种苯胺类化合物加标回收率62.3%～119%,日内精密度为2.55%～11.8%,日间精密度为4.17%～13.6%;出水中12种苯胺类化合物加标回收率为70.5%～115%,日内精密度为2.49%～10.5%,日间精密度为3.01%～15.5%;12种物质的检出限为0.25～1.97μg/L。该方法操作简单、结果准确,能够满足水样中12种苯胺类化合物的定性定量测定,可同时处理大批样品。用该方法对江苏省淮安市18家污水处理厂的进、出水样进行了测定,12种苯胺类化合物在18个采样点均能检出,其中N,N-二乙基间甲苯胺检出水平最高,平均值为15.29ng/L,2,6-二甲基苯胺同样检出水平最低,平均值为5.22 ng/L。采用风险商值法评估对12种苯胺类化合物进行了生态风险评估,结果表明二苯胺、苯胺和间甲苯胺为中等潜在生态风险,其他均为低生态风险。     

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.     

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.      

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.     

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.     

Radionuclide Concentrations in Benthic Invertebrates from Amchitka and Kiska Islands in the Aleutian Chain, Alaska

Concentrations of 13 radionuclides (¹³⁷Cs, ¹²⁹I, ⁶⁰Co, ¹⁵²Eu, ⁹⁰Sr, ⁹⁹Tc, ²⁴¹Am, ²³⁸Pu, ^239,249Pu, ²³⁴U, ²³⁵U, ²³⁶U, ²³⁸U were examined in seven species of invertebrates from Amchitka and Kiska Islands, in the Aleutian Chain of Alaska, using gamma spectroscopy, inductively coupled plasma mass spectroscopy, and alpha spectroscopy. Amchitka Island was the site of three underground nuclear test (1965–1971), and we tested the null hypotheses that there were no differences in radionuclide concentrations between Amchitka and the reference site (Kiska) and there were no differences among species. The only radionuclides where composite samples were above the Minimum Detectable Activity (MDA) were ¹³⁷Cs, ²⁴¹Am, ^239,249Pu, ²³⁴U, ²³⁵U, ²³⁶U, and ²³⁸U. Green sea urchin (Strongylocentrotus polyacanthus), giant chiton (Cryptochiton stelleri), plate limpets (Tectura scutum) and giant Pacific octopus (Enteroctopus dofleini) were only tested for ¹³⁷Cs; octopus was the only species with detectable levels of ¹³⁷Cs (0.262 ± 0.029 Bq/kg, wet weight). Only rock jingle (Pododesmus macroschisma), blue mussel (Mytilus trossulus) and horse mussel (Modiolus modiolus) were analyzed for the actinides. There were no interspecific differences in ²⁴¹Am and ^239,240Pu, and almost no samples above the MDA for ²³⁸Pu and ²³⁶U. Horse mussels had significantly higher concentrations of ²³⁴U (0.844 ± 0.804 Bq/kg) and ²³⁸U (0.730 ± 0.646) than the other species (both isotopes are naturally occurring). There were no differences in actinide concentrations between Amchitka and Kiska. In general, radionuclides in invertebrates from Amchitka were similar to those from uncontaminated sites in the Northern Hemisphere, and below those from the contaminated Irish Sea. There is a clear research need for authors to report the concentrations of radionuclides by species, rather than simply as ‘shellfish’, for comparative purposes in determining geographical patterns, understanding possible effects, and for estimating risk to humans from consuming different biota.     

Kelp as a Bioindicator: Does it Matter Which Part of 5 M Long Plant is Used for Metal Analysis?

Kelp may be useful as a bioindicator because they are primary producers that are eaten by higher trophic level organisms, including people and livestock. Often when kelp or other algae species are used as bioindicators, the whole organism is homogenized. However, some kelp can be over 25 m long from their holdfast to the tip of the blade, making it important to understand how contaminant levels vary throughout the plant. We compared the levels of arsenic, cadmium, chromium, lead, manganese, mercury and selenium in five different parts of the kelp Alaria nana to examine the variability of metal distribution. To be useful as a bioindicator, it is critical to know whether levels are constant throughout the kelp, or which part is the highest accumulator. Kelp were collected on Adak Island in the Aleutian Chain of Alaska from the Adak Harbor and Clam Cove, which opens onto the Bering Sea. In addition to determining if the levels differ in different parts of the kelp, we wanted to determine whether there were locational or size-related differences. Regression models indicated that between 14% and 43% of the variation in the levels of arsenic, cadmium, chromium, manganese, mercury, and selenium was explained by total length, part of the plant, and location (but not for lead). The main contributors to variability were length (for arsenic and selenium), location (mercury), and part of the plant (for arsenic, cadmium, chromium and manganese). The higher levels of selenium occurred at Clam Cove, while mercury was higher at the harbor. Where there was a significant difference among parts, the holdfast had the highest levels, although the differences were not great. These data indicate that consistency should be applied in selecting the part of kelp (and the length) to be used as a bioindicator. While any part of Alaria could be collected for some metals, for arsenic, cadmium, chromium, and manganese a conversion should be made among parts. In the Aleutians the holdfast can be perennial while the blade, whipped to pieces by winter wave action, is regrown each year. Thus the holdfast may be used for longer-term exposure for arsenic, cadmium, chromium and manganese, while the blade can be used for short-term exposure for all metals. Cadmium, lead and selenium were at levels that suggest that predators, including people, may be at risk from consuming Alaria. More attention should be devoted to heavy metal levels in kelp and other algae from Adak, particularly where they may play a role in a subsistence diets.     

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。