用四-(对氨基苯基)-卟啉柱前衍生的高效液相色谱法测定重金属

研究了用固相萃取富集、快速分离柱高效液相色谱法测定环境水样中镍、锡、铅、镉、汞5种重金属的方法。环境水样中的镍、锡、铅、镉、汞用四-(对氨基苯基)-卟啉(T4APP)柱前衍生,然后用ZORBAX RP18固相萃取小柱萃取富集镍、锡、铅、镉、汞的T4APP络合物,经富集后的络合物用甲醇-丙酮(体积比95∶5)为流动相,ZORBAX Stab le Bound(4.6 mm×50 mm,1.8μm)快速分离柱为固定相分离,用二极管矩阵检测器检测。镍、锡、铅、镉、汞的检测限分别为4,5,4,3,3 ng/L,分离5种重金属元素络合物的时间只需2.0 m in,相对标准偏差为2.2%~4.1%,加标回收率为88%~104%。用该法测定环境水样中的痕量镍、锡、铅、镉、汞,结果令人满意。     

固相萃取—微波衍生化—GC-MS法同时测定水中6种雌激素物质

建立了固相萃取—微波衍生化—气相色谱-质谱联用法快速同时测定水中雌酮（E1）、17α-雌二醇（α-E2）、17β-雌二醇（β-E2）、雌三醇（E3）、17α-乙炔基雌二醇（EE2）、双酚A（BPA）等6种雌激素物质的分析方法,对色谱柱升温程序、固相萃取及衍生化条件进行了优化。色谱柱最佳升温程序为：初始温度50 ℃,保持2 min;以20 ℃/min速率升至260 ℃,保持5 min;最后以10 ℃/min速率升至280 ℃,保持5 min。实验结果表明,在选取 HC-C18萃取小柱、添加双（三甲基硅烷基）三氟乙酰胺（BSTFA）+1%三甲基氯硅烷（TMCS）+吡啶作为衍生化试剂、微波315 W衍生化加热4 min的条件下,6种目标物标准曲线的相关系数均大于0.999,BPA、E1、EE2及E3的线性范围为3~300 ng/L,17α-E2及17β-E2的线性范围为5~300 ng/L,方法检出限为2.0~5.0 ng/L,加标回收率为76.45%~96.24%。     

固相萃取-气相色谱法检测水中的邻苯二甲酸酯

利用固相萃取技术富集了水中4种邻苯二甲酸酯类（PAEs）化合物：邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二乙酯（DEP）、邻苯二甲酸二丁酯（DBP）、邻苯二甲酸二（2-乙基己基）酯（DEHP）。借助均匀设计法及计算机回归建模优化技术对4种PAEs的固相萃取条件进行了设计与优化，得到的最佳固相萃取条件：洗脱剂配比（正己烷与丙酮的体积比）30：1，洗脱体积2mL，洗脱速率4mL／min，上样速率8mL／min。富集后的试样用带电子捕获器的毛细管气相色谱仪检测，方法的线性范围为1～1000μg／L（DMP，DEP），0．2—100μg／L（DBP，DEHP），线性回归方程的相关系数为0．9970～1．0000，检出限为0．02-0．4μg／L，4种PAEs的回收率为69％～117％，相对标准偏差为2．5％～9．5％。[关键词]     

二壬基萘磺酸反胶团萃取模拟废水中的铅

以二壬基萘磺酸（DNNSA）反胶团煤油溶液萃取模拟含铅废水中的铅。在萃取前水相中铅离子浓度为3×10-4 mol/L、DNNSA浓度为0.010 mol/L、油水比为1∶20、模拟含铅废水pH为6、萃取温度为303 K、萃取时间为40 min的条件下，萃取后水相中铅离子浓度为0.845×10-4 mol/L，有机相中铅离子浓度为4.517×10-3 mol/L，铅萃取率为71.83%。DNNSA反胶团萃取铅离子萃取容量为1 188.62 mg/g，热力学焓变为2.595 kJ/mol。     

Alamine336对低浓度模拟含硝酸废水的萃取分离

以模拟低浓度含硝酸废水为研究对象,以煤油为稀释剂,考察了工艺条件对硝酸萃取和反萃效果的影响,并对萃取机理进行了探讨。实验结果表明：以10.0%（φ）Alamine336为萃取剂,在有机相与水相的体积比为1∶2、萃取温度为298 K的条件下,对初始硝酸质量浓度为2.00 g/L的含硝酸废水进行两级逆流萃取操作后,理论上水相硝酸质量浓度低于15 mg/L,达到GB 8987—1996中的一级标准;以0.05 mol/L氢氧化钠溶液为反萃剂,在有机相与水相的体积比为1∶2、反萃温度为298 K的条件下,对硝酸负载量为1.50 g/L的有机相进行两级反萃后,理论上有机相硝酸残余量小于0.005 g/L。机理研究表明Alamine336通过与硝酸形成离子对络合物来萃取硝酸。     

碘化钾-维多利亚蓝B光度法测定塑料浸出液中痕量镉

在聚乙烯醇存在下,镉(Ⅱ)与碘化钾、维多利亚蓝 B 形成三元离子络合物。摩尔吸光系数为3.7×10~5摩尔~(1-)·厘米~(-1)·升,最大吸收波长在580纳米处,镉量在0—4微克/25毫升范围内符合比尔定律。用本方法可直接在水相中测定塑料浸出液中的痕量镉,结果令人满意。     

芳香胺测定中试样制备技术的研究进展

介绍了目前应用在环境芳香胺测定中的固相微萃取(SPME)、柱内固相微萃取(INSPME)、搅动棒吸附萃取(SBSE)、液相微萃取(LPME)、离子液体分散液液微萃取(IL - DLLME)等试样的提取、富集、浓缩技术.     

废水和大气中痕量己二胺的气相色谱分析

本文研究了萃取-衍生-气相色谱法分析工业废水和大气中的痕量己二胺。以甲苯为萃取剂,七氟丁酸酐为衍生化试剂,色谱分析以SE-30为固定相,电子捕获检测器测定。可检测水中0.02ppm及大气中0.001毫克/米~3的己二胺,相对标准偏差为11.4％,回收率为98—105％。     

铋电极差分脉冲伏安法测定水中痕量2,4-二硝基苯肼

以自制铋电极作为工作电极，建立了铋电极差分脉冲伏安法测定2，4-二硝基苯肼的分析方法。实验结果表明：以0.1 mol/L NaOH+0.1 mol/L KCl混合溶液（pH=13.0）配制测定底液，在扫描速率为100 mV/s的条件下，2，4-二硝基苯肼于-0.53 V处产生灵敏的氧化峰;在2，4-二硝基苯肼浓度为3.0×10-8~1.0×10-5 mol/L范围内，空白和试样的氧化峰电流强度差值与对应2，4-二硝基苯肼浓度的对数呈良好的线性关系，检出限达8.37×10-9 mol/L;将该方法应用于工业废水中痕量2，4-二硝基苯肼的检测，回收率为95.6%~103.1%，相对标准偏差小于3%。     

分光光度法测定废水中的二甲胺

1 前言二甲胺的定量测定报道最多的是气相色谱法。以2.4-二硝基氯苯、顺丁烯二酸酐-氯乙烯共聚物、二硫化碳-铜氨试剂及碱性条件下次氯酸钠-碘化钾作为显色剂的分光光度法也有报道。我们进行了次氯酸钠-碘化钾作显色剂的分光光度法测定废水中二甲胺的试验,在碱性介质下,使次氯酸钠与二甲胺反应生成氯胺,用加入亚硝酸钠的方法除去过量的次氯酸钠,氯胺与淀粉-碘化钾试剂形成蓝色络合物,其摩尔吸光系数达2.4×10~4。二甲胺含量在0.2-1.6mg/L范围内符合比尔定律。相对     

Programs assessing implementation and effectiveness of state forest practice rules and BMPs in the West

The major forest nonpoint source control programs in the West are largely regulatory, either under forest practices acts (California, Idaho, New Mexico, Nevada, Oregon, and Washington) or a streamside management act (Montana). These programs and the specific rules they enforce continue to undergo intensive scrutiny. Still, the questions are the same for these regulatory programs as for states that base nonpoint source control on voluntary BMPs (Arizona, Colorado, Utah, Wyoming). Are the rules or BMPs being applied, and are they effective in reducing nonpoint source pollution to levels that protect beneficial uses of water? The level of debate about forestry in the West has resulted in detailed monitoring and research to answer these questions. In the past, state agencies have assumed levels of BMP compliance based on the percent of operations without enforcement actions. These estimates are being replaced by statistically valid and reproducible monitoring of forest practices rules and BMP compliance levels. BMP effectiveness is being assessed using both qualitative and quantitative methods. This can involve field assessments, process-based research, and control watershed studies. Some trend monitoring is also beginning. With the regional implementation rate for forestry BMPs at about 94% and rising, it is likely that effectiveness testing will continue to be a priority and consume the majority of assessment resources for this region.     

Hysteresis in Reversal of Central European Mountain Lakes from Atmospheric Acidification

Extremely high emissions of S and N compounds in Central Europe (both 280 mmol m^-2 yr^-1) declined by 70and 35%, respectively, during the last decade. Decreaseddeposition rates of SO₄ ^-2, NO₃ ^-, and NH₄ ⁺ in the region paralleled emission declines. The reduction in atmospheric inputs of S and N to mountain ecosystemshas resulted in a pronounced reversal of acidification in the Tatra Mountains and Bohemian Forest lakes. Between the 1987–1990and 1997–1999 periods, concentrations of SO₄ ^-2 and NO₃ ^- decreased (average ± standard deviation) by 22±7 and 12±7 mol L^-1, respectively, in theTatra Mountains, and by 19±7 and 15±10 mol L^-1, respectively, in the Bohemian Forest. Their decrease was compensated in part (1) by a decrease in Ca²⁺ + Mg²⁺ (17±7 mol L^-1) and H⁺ (4±6 mol L^-1), and an increase in HCO₃ ^-(10±10 mol L^-1) in the Tatra Mountains lakes, and (2) by a decrease in Al (7±4 mol L^-1), Ca²⁺ + Mg²⁺ (9±6 mol L^-1), and H⁺ (6±5 mol L^-1), in Bohemian Forest lakes. Despite the rapid decline in lake water concentrations of SO₄ ^-2 and NO₃ ^- in response to reduced S and N emissions, their present concentrations in some lakes are higher than predictionsbased on observed concentrations at comparable emission rates during development of acidification. This hysteresis in chemical reversal from acidification has delayed biological recovery of the lakes. The only unequivocal sign of biological recovery hasbeen observed in erné Lake (Bohemian Forest) where a cladoceran species Ceriodaphnia quadrangular has recentlyreached its pre-acidification abundance.     

Reconstruction of Long-Term Changes in Lake water Chemistry,Zooplankton and Benthos of a Small,Acidified High-Mountain Lake: Magic Modelling and Palaeolimnogical Analysis

Starolesnianske pleso is a small and shallow acid lake in the High Tatra Mountains, situated at 2000 m above sea level, on granitic bedrock, with sparse and thin soil cover. When detailed measurements began in the 1980s Starolesnianske pleso had pH below 5 and only one species of cladoceran zooplankton, the ubiquitous Chydorus sphaericusPalaeolimnological investigations show changes in cladoceran zooplankton and chironomid zoobenthic assemblages since about 1920 and a major change in 1970–1980. The dynamic acidification model MAGIC was used to reconstruct changes in water chemistry over the past 150 years. The results from MAGIC agree well with the sediment record; pH levels gradually decreased from 6.5 in the mid-1800s to about 5.6 in 1920 (first response in biota) to below 5.0 by 1970, and concentrations of inorganic aluminium rose dramatically beginning about 1960. In the 1990s the lake water chemistry showed clear signs of reversal in acidification brought about by a major decline in S deposition.     

Heavy Metals Removal by Biosorption and Flotation

The removal of a mixture of heavy (toxic) metal cations (copper, nickeland zinc) from liquid effluents was investigated in this study at pilotscale, using counter-current contact mode. The innovative processinvolved the abstraction of metal ions onto fungal biosorbents, followedby the application of flotation for the subsequent solid/liquid separationof biomass particles. The ability of microorganisms to remove metal ionsfrom aqueous solutions is a well-known phenomenon. Nevertheless,engineering considerations are very important in decisions, concerningthe commercial future of biosorption and practical solutions are neededfor certain problems, such as the efficient post-separation ofmetal-loaded biomass. The two processes (flotation and biosorption) caneffectively operate in combination, in what it was termed biosorptiveflotation process. The sorbents may be recycled, after appropriate elutionof metals, as well as the treated (clean) water.     

Selection of Autochthonous Plant Species from SE Spain for Soil Lead Phytoremediation Purposes

Mining activity in SE of Spain, in the west Mediterranean coast, originated more than two millenniums ago. It has generated huge areas affected by heavy metals contamination, especially of lead, which is possibly one of the most important. Investigations related to the selection of autochthonous plant taxa from a typical Spanish Mediterranean area, useful for phytoextraction and phytostabilization purposes in these polluted areas are shown. Under these edaphoclimatic conditions 12 interesting species were considered, from them six taxa were chosen for further studies. Some plant species have been proposed either for phytoextraction or phytostabilization purposes. Recommendations for further research have been discussed.     

Concentrations and Pools of Heavy Metals in Urban Soils in Stockholm,Sweden

The concentrations of heavy metals (Cd, Cr, Cu, Hg, Ni, Pb andZn) and arsenic (As) were surveyed and the metal pools estimatedin soils in Stockholm Municipality. The sampling sites were distributed all over the entire municipality with a higher sampling density in the city centre. Soils were sampled to a maximum depth of 25 to 60 cm. Soil texture, total-C content, electrical conductivity and pH were analysed. Heavy metal concentrations were determined after wet digestion with boiling7 M HNO₃.The results showed a wide range in heavy metal concentrations, as well as in other soil properties. The city centre soils constituted a rather homogeneous group whereas outside this areano geographical zones could be distinguished. These soils were grouped based on present land use, i.e. undisturbed soils, public parks, wasteland (mainly former industrial areas), and roadside soils. The city centre and wasteland soils generally hadenhanced heavy metal concentrations to at least 30 cm depth compared to park soils outside the city centre and rural (arable)soils in the region, which were used to estimate background levels. For example, the mean Hg concentration was 0.9 (max 3.3)mg kg^-1 soil at 0–5 cm and 1.0 (max 2.9) at 30 cm depth in the city centre soils, while the background level was 0,04 mg kg^-1. Corresponding values for Pb were 104 (max 444) and135 (max 339) mg kg^-1, at 0–5 and 30 cm, respectively, while the background level was 17 mg kg^-1.The average soil pools (0–30 cm depth) of Cu, Pb and Zn were 21,38 and 58 g m^-2 respectively, which for Pb was 3–4 timeshigher and for Cu and Zn 1.5–2 times higher than the backgroundlevel. The total amount of accumulated metals (down to 30 cm)in the city centre soils (4.5^*10 ⁶ m² public gardens and green areas) was estimated at 80, 1.1, 120 and 40 t for Cu, Hg, Pb and Zn, respectively. The study showed (1) thatfrom a metal contamination point of view, more homogeneous soilgroups were obtained based on present land use than on geographicdistance to the city centre, (2) the importance of establishing a background level in order to quantify the degree of contamination, and (3) soil samples has to be taken below the surface layer (and deeper than 30 cm) in order to quantify theaccumulated metal pools in urban soils.     

Effect of Coconut, Sisal and Jute Fibers on the Properties of Starch/Gluten/Glycerol Matrix

Coconut, sisal and jute fibers were added as reinforcement materials in a biodegradable polymer matrix comprised of starch/gluten/glycerol. The content of fibers used in the composites varied from 5% to 30% by weight of the total polymers (starch and gluten). Materials were processed in a Haake torque rheometer (120 °C, 50 rpm) for 6 min. The mixtures obtained were molded by heat compression and further characterized. Addition of lignocellulosic fibers in the matrix decreased the water absorption at equilibrium. The diffusion coefficient decreased sharply around 5% fiber concentration, and further fiber additions caused only small variations. The thermogravimetric (TG) analysis revealed improved thermal stability of matrix upon addition of fibers. The Young’s modulus and ultimate tensile strength increased with fiber content in the matrix. The storage modulus increased with increasing fiber content, whereas tanδ curves decreased, confirming the reinforcing effect of the fibers. Morphology of the composites analyzed under the scanning electron microscope (SEM) exhibited good interfacial adhesion between the matrix and the added fibers. Matrix degraded rapidly in compost, and addition of increased amounts of coconut fiber in the matrix caused a slowdown the biodegradability of the matrix. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may be suitable.     

Quantification of Polymerisation Processes During The Oxidative Degradation of 14C-Labelled Chlorophenols

In experiments employing the lignocellulose-decaying basidiomycetes Trametes versicolor and Stropharia rugosoannulata degrading uniformly¹⁴C-labelled 2,4-dichlorophenol and pentachlorophenol, acombination of size exclusion chromatography (SEC),fractionation, and -scintillation counting wasapplied to quantify polymerisation products formed duringchlorophenol degradation. Time-dependent mass balances weregenerated by analysis of ¹⁴C in polymerisation products,CO₂, as well as monomer non-polar and polar metabolites.Approximately 30% of the chlorophenols were found to bepolymerised. A major fraction of the polymerised productscorresponded to a molecular weight range from 0.24 – 40 kDa.Only a minor fraction could be attributed to a molecularweight >40 kDa. This method proved to be useful inquantification of polymerisation products and kinetics of thepolymerisation processes, whereas UV/Vis detection ofpolymerisation products separated by SEC led to false positiveresults. The SEC-¹⁴C method could also be applied forother complex processes where polymerisation ordepolymerisation occurs (humification, degradation oflignocellulose, formation of bound residues from xenobioticssuch as polycyclic aromatic hydrocarbons or 2,4,6-trinitrotoluene) and where spectrophotometric determinationsare difficult or impossible.     

The Relative Influences of Primary and Secondary Particulates to Urban Air Quality in the United Kingdom

This study uses a combination of data from U.K. monitoringstations and from modelling undertaken with the U.K.Meteorological Office's NAME Model to investigate therelative influences of primary and secondary particulateson total PM₁₀ levels at sites in the United Kingdom. Co-located PM₁₀ and sulphate aerosol measurementsindicate that sulphate has a disproportionately largeinfluence on the variation of PM₁₀ levels incomparison to its contribution to their total mass.Comparisons of measured PM₁₀ at urban centre, roadsideand rural sites suggest that local primary sources havevery little influence on daily mean levels. NAME has beenused to model both primary particles and sulphate aerosolfrom sources across the whole of Europe. The discrepanciesbetween modelled and observed PM₁₀ suggest that coarseparticles, such as windblown dust and resuspended roaddust,may comprise a very large, if not dominant, proportion ofobserved PM₁₀ levels. The apparently minor role ofprimary particles (especially locally-sourced ones) raisesa number of issues regarding the suitability of current U.K.and European legislation to addressing the particle problem.     

Changes in Extractability of Cr and Pb in a Polycontaminated Soil After Bioaugmentation With Microbial Producers of Biosurfactants, Organic Acids and Siderophores

Partly because of the low bioavailability of metals, the soil cleaning-up using phytoremediation is usually time-consuming. In order to enhance the amount of metals at the plant's disposal, the soil bioaugmentation coupled together with phytoextraction is an emerging technology. In this preliminary work, two agricultural soils which mainly differed in their Cr, Hg and Pb contents (LC, low-contaminated soil; HC, high-contaminated soil) were bioaugmented in laboratory conditions by either bacterial (Bacillus subtilis, Pseudomonas aeruginosa, Pseudomonas fluorescens or Ralstonia metallidurans) or fungal inocula (Aspergillus niger or Penicillium simplicissimum) and incubated during three weeks. The LC soil pots bioaugmented with A. niger and P. aeruginosa contained higher concentrations of Cr (0.08 and 0.25 mg.kg⁻¹ dw soil) and Pb (0.25 and 0.3 mg.kg⁻¹ dw soil) in the exchangeable fraction F1 (extraction with MgCl₂) by comparison with the non-bioaugmented soil where neither Cr nor Pb was detected. Conversely, immobilization of Cr and Pb in the soil were observed with the other microorganisms. The soil bioaugmentation not only modified the metal speciation for the most easily extractable fractions but also modified the distribution of metals in the other fractions, to a lesser extent nevertheless. The difference in microbial concentrations between the bioaugmented or not HC soils reached up to 1.8 log units. Thus the microorganisms that we chose for the soil bioaugmentation were competitive towards the indigenous microflora. The PCA analysis showed close positive relationships between the microorganisms which potentially produced siderophores in the soil and the amount of Cr and Pb in the fraction F1.