钢铁厂油泥堆场PAHs的污染特性研究

以某钢厂油泥堆放场的油泥为研究对象,油泥样品按照多环芳烃(PAHs)来源的不同分为石油源油泥样品和混合源油泥样品,通过高效液相色谱法对样品中PAHs进行测定.结果显示,油泥样品中PAHs主要来自于石油源.萘、苊烯、苊、芴和菲是油泥中PAHs的主要污染物.油泥样品中16种优控PAHs的总含量(∑PAHs)为0.973～1...     

索氏抽提-柱层析分离-高效液相色谱法测定煤沥青中多环芳烃

以甲苯为溶剂对煤沥青进行索氏抽提,抽提液经过有机滤膜过滤,过滤后的抽提液用二氯甲烷溶解,将样品溶液用硅胶柱分离,然后用体积比为1∶1的石油醚与甲苯混合液以5.0mL/min的流量进行淋洗,将淋洗液旋干后用乙腈定容至10mL,利用ZORBAX Eclipse PAH柱以不同体积比的乙腈-水体系为流动相对样品溶液进行梯度洗脱,建立了煤沥青中16种多环芳烃(PAHs)的高效液相色谱分离检测方法。结果表明,16种PAHs的线性范围为0.50~20mg/L,相关系数(r)不小于0.999,检出限为0.04~0.33μg/L,按照实验方法对湘钢煤沥青实际样品中16种PAHs进行测定,测得结果的相对标准偏差(RSD,n=6)为0.20%~3.5%,回收率为97%~109%。采用实验方法分别测定湘钢、涟钢两种不同煤沥青中16种PAHs的含量,测得结果与湘钢、涟钢两公司提供的推荐值基本一致。结果表明,每1kg湘钢煤沥青中16种致癌性PAHs质量为107.9g,即质量分数为10.79%;每1kg涟钢煤沥青中16种致癌性PAHs质量为104.1g,即质量分数为10.41%;其中苯并[a]芘分别为11.86g/kg和13.82g/kg,即质量分数为1.186%和1.382%。     

Solid-phase Microextraction with Benzoxy-calix[6]arene Fiber Coupled to Gas Chromatography for the Analysis of Polycyclic Aromatic Hydrocarbons in Water

Headspace solid-phase microextraction(HS-SPME) with sol-gel calix[6]arene-containing fiber followed by gas chromatography with a flame ionization detector was used to examine the composition and distribution of seven polycyclic aromatic hydrocarbons(PAHs) in water. The novel SPME fiber exhibited higher extraction efficiency to PAHs compared with poly(dimethylsiloxane) and other calixarene-containing fibers. Extraction/retention mechanism based on the interactions between calixarenes and PAHs was discussed. Owing to the good selectivity and high extraction capability of this calixarene fiber, low detection limits were obtained in a range of 0.34-6.50 ng/L and the relative standard deviation values were≤12.3% for all of the analytes. The linear ranges of the proposed method were five orders of magnitude for the tested compounds, with linear correlation coefficients(r) greater than 0.998. The method was applied to the determination of polycyclic aromatic hydrocarbons in nine water sources in Wuhan City, China. Standard addition method was selected for the quantification and the recovery values were in a satisfactory range. Total PAHs concentrations in the nine surface water samples were found to vary between undetectable and 8.840 μg/L with two-and three-ring PAHs predominating.     

Probability of Aluminum Toxicity from Bhandup Complex Water Treatment Plant, Mumbai: Case Study

Bhandup Complex water treatment plant located in Mumbai, India, supplies water to most of Mumbai. The plant receives raw water from Vehar Lake. Alum has been used as a coagulant in the treatment process for the past 27?years. The backwashed water from the plant is released into Vehar Lake, which carries a significant amount of suspended matter. Therefore, a layer of sludge was deposited on the meeting point of backwashed water and Vehar Lake. The status of aluminum (Al) concentration in sludge deposits, banks, water, and sediment samples of Vehar Lake and its comparison with Al concentration of soil in the area surrounding the plant is presented in this paper. The comparison showed that the surrounding soil samples had the least Al concentration (16,394–26,081??mg/kg), whereas the highest values of 53,882–73,382??mg/kg and 62,096–76,496??mg/kg were reported in upper and lower layers of sludge, respectively. This paper also discusses the detrimental effect of Al when it is available in toxic form at acidic pH.     

Extraction of selected rare earth elements from anthracite acid mine drainage using supercritical CO_2 via coagulation and complexation

Rare earth elements(REEs) are valuable raw materials which are in great demand in modern high technology industries.Developing methods to produce/recover REEs from waste is significant to the national security of any developed country.This study was focused on investigating the use of supercritical CO2(sCO_2) to extract REEs from anthracite acid mine drainage(AMD).Four different mine drainage water source locations at Blaschak Coal Corp.in Pennsylvania,USA were selected for sample collection.An extraction process was developed and demonstrated for two of those water sources containing the highest concentration of REEs.A method involving metal ion coagulation,their dissolution from the sludge into a concentrated aqueous HNO_3 solution,complexation with organic ligands and sCO_2 extraction was developed to recover REEs from AMD.Specifically,sodium aluminate(NaAlO_2) was used as the coagulant to concentrate REEs from the AMD into a solid precipitate.Consequently,over 99%of the REEs in AMD is concentrated in the remaining sludge.During the coagulation process,the effects of pH and NaAlO_2 concentration on REE precipitation were investigated.Fuming nitric acid(HNO_3) was used to digest the pre-concentrated sludge and tributyl phosphate(TBP) was used to form REE/TBP/HNO_3,a non-polar complex with selected REEs,specifically,cerium(Ce),lanthanum(La) and neodymium(Nd).HNO_3 concentration and organic/aqueous phase ratio were considered as the variables to improve complexation efficiency.Dynamic extraction experiments using sCO_2 and REE/TBP/HNO_3 solutions were then conducted at optimal conditions of 60℃ and 20 MPa.The overall REE extraction efficiencies are found to increase with the atomic number of the REE.As a result,the average overall REE extraction efficiencies of 41.8%,40.1% and 58.2% for Ce,La and Nd,respectively,are obtained.The potential improvements in the overall extraction efficiency are also discussed.     

Validation of a high-performance liquid chromatographic assay method for pharmacokinetic evaluation of busulfan

The development and validation of a high-performance liquid chromatographic (HPLC) assay for determination of busulfan concentrations in human plasma for pharmacokinetic studies is described. Plasma samples containing busulfan and 1,6-bis(methanesulfonyloxy)hexane, and internal standard, were prepared by derivatization with sodium diethyldithiocarbamate (DDTC) followed by addition of methanol and extraction with ethyl acetate. The extract was dried under nitrogen and the samples reconstituted with 100 microl of methanol prior to HPLC determination. Chromatography was accomplished using a Waters NovaPak octadecylsilyl (ODS) (150 x 3.9 mm I.D.) analytical column, NovaPak ODS guard column, and mobile phase of methanol-water (80:20, v/v) at a flow-rate of 0.8 ml/min with UV detection at 251 nm. The limit of detection was 0.0200 microg/ml (signal-to-noise ratio of 6) with a limit of quantitation (LOQ) of 0.0600 microg/ml for busulfan in plasma. Calibration curves were linear from 0.0600 to 3.00 microg/ml in plasma (500 microl) using a 1/y weighting scheme. Precision of the assay, as represented by C.V. of the observed peak area ratio values, ranged from 4.41 to 13.5% (13.5% at LOQ). No day-to-day variability was observed in predicted concentration values and the bias was low for all concentrations evaluated (bias: 0 to 4.76%; LOQ: 2.91%). The mean derivatization and extraction yield observed for busulfan in plasma at 0.200, 1.20 and 2.00 microg/ml was 98.5% (range 93.4 to 107%). Plasma samples containing potential busulfan metabolites and co-administered drugs, which may be present in clinical samples, provided no response indicating this assay procedure is selective for busulfan. This method was used to analyze plasma concentrations following administration of a 1 mg/kg oral busulfan dose.     

Determination of oxfendazole in cow milk by reversed-phase high-performance liquid chromatography

A specific and sensitive high-performance liquid chromatographic method for the analysis of oxfendazole in cow milk is described. Oxfendazole was extracted from milk using a mixture of acetone and chloroform under alkaline conditions. The solvents were evaporated, and the oily residue was purified by hexane-acetonitrile partition and acid-base extraction. The residue obtained after cleanup was redissolved in methanol for chromatographic analysis. Chromatography was performed on a reversed-phase column with acetonitrile-water as the mobile phase. As low as 0.005 microgram of oxfendazole/g can be measured by this method using 50 g of milk. The method was applied to measure oxfendazole in the milk of a cow given an oral 5-mg/kg dose.     

电感耦合等离子体原子发射光谱法测定污泥废料中铬

污泥废料中铬含量很低,通常采用分光光度法测定铬的含量,该方法操作繁杂,周期较长.使用电感耦合等离子体原子发射光谱法(IC P-A ES)测定污泥废料中的铬,快速高效.采用硝酸、氢氟酸和高氯酸溶解样品,选择C r267.716 nm波长的光谱线作为铬的分析线.在选择最佳实验条件下测定,污泥废料中硅、碳和铁等杂质元素对测定...     

Determination of organochlorine pesticide and polychlorinated biphenyl residues in fatty fish by tandem solid-phase extraction cleanup

A rapid, multiresidue solid-phase extraction (SPE) technique for determination of organochlorine pesticide and polychlorinated biphenyl (PCB) residues in nonfatty fish was modified for use with fatty fish. In the modified procedures, samples are extracted with acetonitrile, and the extract is cleaned up with both C18 and Florisil SPE columns. Residues are determined by gas chromatography with electron capture detection. The original method was modified for use with fatty fish by reducing the amount of tissue extracted and by using an improved Florisil SPE cleanup. Recovery data are presented for 24 fortified organochlorine pesticide residues (0.12 ppm) and 3 fortified PCB residues (0.80 ppm) from flounder, bluefish, and shad samples, which contained 0.8, 5.4, and 22.6% fat, respectively. For the 3 types of fish, recoveries of 23 of 24 fortified organochlorine pesticide residues ranged from 55 to 129%, and recoveries of 3 fortified PCB residues ranged from 55 to 104%. There were no significant differences in recovery based on fish species and/or fat content for the majority of residues studied. This SPE method and the official AOAC method yielded comparable results for fish containing incurred organochlorine residues.     

Sequence capture-PCR improves detection of mycobacterial DNA in clinical specimens

The rapid identification of mycobacterial DNA in clinical samples by PCR can be useful in the diagnosis of tuberculous infections, but several large studies have found that the sensitivity of this approach is not better than that of culture. In order to improve the sensitivity of detection of mycobacterial DNA in clinical specimens from patients with paucibacillary forms of tuberculosis, we have developed a procedure permitting the specific capture of mycobacterial DNA in crude samples prior to amplification, thereby concentrating the target sequences and removing irrelevant DNA and other potential inhibitors of the amplification reaction (sequence capture-PCR). By using this approach to capture and amplify two different sequences specific for organisms of the Mycobacterium tuberculosis complex (IS6110 and the direct repeat region), it was possible to detect as little as one genome of mycobacterial DNA in samples containing up to 750 micrograms of total DNA, representing a 10- to 100-fold increase in sensitivity compared with that obtained by purifying total DNA prior to amplification. Detection of the IS6110 sequence in pleural fluid samples from patients with tuberculous pleurisy by sequence capture-PCR gave positive results in 13 of 17 cases, including 3 of 3 culture-positive samples and 10 of 14 culture-negative samples. In contrast, when total DNA was purified from these samples by adsorption to a silica matrix prior to amplification, only the three culture-positive samples were positive by PCR. The sensitivity of detection of the direct repeat sequence in these samples by sequence capture-PCR was similar to that of IS6110 and, in addition, permitted immediate typing of the strains from some patients. We conclude that sequence capture-PCR improves the sensitivity of detection of mycobacterial DNA in paucibacillary samples. This approach should be useful in detecting rare target sequences from organisms implicated in other pathologic processes.     

Simultaneous determination of epirubicin, doxorubicin and their principal metabolites in human plasma by high-performance liquid chromatography and electrochemical detection

A method is described which permits the trace analysis of 10 chlorobenzenes in aqueous samples. Chlorobenzenes were extracted from water samples by solid-phase extraction with a C18 cartridge and analysis was carried out by gas chromatography-mass spectrometry in the selected-ion monitoring mode. The recovery and precision of the method were evaluated by extraction of spiked reagent-grade water at concentration levels of 0.1, 1.0 and 10.0 micrograms/l. This method was applied to the determination of chlorobenzenes in tap, ground and river water. By preparing 200 ml of environmental water samples, the detection limits of the compounds studied were in the range of 0.010-0.042 microgram/l.     

Multiresidue determination of pesticides in apples and pears by gas chromatography-mass spectrometry

This paper describes a rapid, specific and sensitive multiresidue method for the routine analysis of several classes of pesticides used for the treatment of apples and pears, involving a rapid extraction procedure at pH 4.5 with a mixture of acetone-dichloromethane-hexane (50:20:30, v/v/v) and gas chromatography coupled to mass-selective detection, in order to achieve quantitative analysis down to their respective maximum residue limit. Extraction recoveries were between 55 and 98%. Limits of detection and limits of quantitation ranged respectively, from 0.01 to 0.05 mg/kg and from 0.02 to 0.1 mg/kg. Intra-assay relative standard deviation was less than 19% for all compounds. An excellent linearity was observed from these LOQs up to 500 mg/kg. Intermediate (inter-assay) precision and accuracy were satisfactory. The method has been applied to many fruit samples intended for commercialisation.     

Cost minimization analysis and utility of pretreatment and posttreatment total body iodine-131 scans in patients with thyroid carcinoma

An on-line immunoaffinity extraction with liquid chromatography/membrane introduction mass spectrometry (IAE/LC/MIMS) method for the determination of BTEX compounds in complex sample matrixes is described. This method uses an immunoaffinity column (1 mm i.d. x 20 mm) for on-line sample cleanup and enrichment, a 5-micron C18 trapping column (2 mm i.d. x 20 mm) for analyte focusing, a 3-micron C18 analytical column (3.2 mm i.d. x 100 mm) for separation, and a membrane introduction mass spectrometer for quantitation. The immunoaffinity column was evaluated in terms of binding capacity, recovery, and enrichment factor. The method was optimized for the determination of BTEX compounds in a mixture of 30 volatile organic compounds, which showed no matrix interference and a dramatic improvement of the detection limit over that of the LC/MIMS method (up to 474-fold). This method was also used for the determination of BTEX compounds in several gasoline-contaminated water samples, and the results were compared with the EPA reference methods.     

Gas-liquid chromatographic determination of azinphos ethyl in human plasma and in mouse plasma, tissue, and fat

A new method for the determination of azinphos ethyl (O,O-diethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl) phosphorodithioate) in human plasma and in mouse plasma, tissue, and fat has been developed. The method is based on extraction with benzene or hexane and cleanup of fat and tissue samples by a minicolumn containing Florisil and sodium sulfate. Azinphos ethyl is eluted from the column with 10% acetonitrile in benzene and is concentrated to an appropriate volume for gas-liquid chromatographic analysis, using a 63Ni electron capture detector and a glass column containing 3% OV-1 on Gas-Chrom Q. The method is sensitive to 0.005 ppm in human plasma, 0.01 ppm in mouse plasma, 0.08 ppm in mouse liver, 0.05 ppm in mouse brain, and 0.10 ppm in mouse fat. The limit of detection is 2 pg; mean recoveries ranged from 96 to 98%.     

Determination of cyanide in whole blood by capillary gas chromatography with cryogenic oven trapping

Cyanide, one of the most important toxic substances, has been found measurable with high sensitivity by capillary gas chromatography (GC) with cryogenic oven trapping upon injection of headspace (HS) vapor samples. The entire amount of cyanide in the HS sample could be cryogenically trapped prior to on-line GC analysis. A 0.5-mL volume of blood in the presence or absence of cyanide and propionitrile (internal standard, IS) was added to a vial containing 0.25 mL of distilled water, 0.3 g of Na2-SO4, 0.2 mL of 50% H3PO4, and 0.1 g of ascorbic acid (when needed), and the mixture was heated at 70 degrees C for 15 min. A 5-mL volume of the HS vapor was introduced into a GC capillary column in the splitless mode at -30 degrees C oven temperature that was programmed up to 160 degrees C for GC analysis with nitrogen-phosphorus detection. A sharp peak was obtained for cyanide under the present conditions, and backgrounds were very clean. The extraction efficiencies of cyanide and IS were 2.89-3.22 (100 or 500 ng/mL) and 2.42%, respectively. The calibration curve showed good linearity in the range of 25-1000 ng/mL and the detection limit was approximately 2 ng/mL. The coefficients of intraday and interday variations were 2.9 and 11.8%, respectively. The mean blood cyanide level measured for actual fire victims was 687 +/- 597 ng/mL (mean +/- SD, n = 9). Endogenous blood cyanide concentration for healthy subjects was 8.41 +/- 3.09 ng/mL (mean +/- SD, n = 6).     

微波消解-氢化物发生原子荧光光谱法测定污泥中汞和砷

利用高压密闭微波消解技术消解样品, 建立了氧化物发生原子荧光光谱法测定污水处理厂污泥中汞和砷的方法。对消解酸和消解程序进行了优化, 同时讨论了硼氢化钾浓度对测定的影响。结果表明, 选用10 mL 硝酸-盐酸(4+6)可将0.25 g污泥样品消解完全;确定消解程序如下:消解功率为850 W, 发射率为80%, 第1步采用5 min内从室温升温至110 ℃, 保持5 min, 第2步采用10 min内继续升温至180 ℃, 保持20 min;在硼氢化钾浓度为20 g/L时进行测定, 效果最佳。汞和砷的方法检出限分别为0.001 6 mg/kg和0.002 2 mg/kg。方法应用于污泥样品中汞和砷的测定, 相对标准偏差(RSD, n=6)分别为2.7 %～3.8%和1.1%～2.0%, 汞和砷的加标回收率分别为96%～102%和98%～104%。方法应用于土壤标准样品GSS-25和GSS-26中汞和砷的测定, 结果与认定值一致, 汞和砷的RSD(n=6)分别为4.5%～7.4%和2.2%～2.4%。     

Histones and DNA ultrastructural distribution in plant cell nucleus: a combination of immunogold and cytochemical methods

Test samples were collected at a range of sites using the MDHS 68 sampler, a 7-hole sampler, and a cyclone respirable-dust sampler. Glass fibre, Zefluor, Fluoropore and silver (0.8 and 5 microns) filters were compared for weighing error, handling characteristics, and amount collected. The effects of a carbon back-up, of extraction solvent, and of analytical method were studied. The current HSE method for the sampling and analysis of coal tar pitch volatiles, MDHS 68 has been reviewed. It is recommended that the MDHS 68 sampler be replaced by a 7-hole head containing a silver or PTFE filter (approximately 1 micron pore size), with a graphitized carbon back-up if efficient collection of 2 to 4-ring PAHs is required. Cyclohexane is recommended as the extraction solvent. Methods of analysis which quantify the fume as a whole (MDHS 68, u.v., ELSD) were shown to give a response which varied according to the type of CTPV generating process. Therefore analysis of specific PAHs of occupational interest, by GC-MS or HPLC is recommended.     

利用高盐水氧化提取高脉石矿物难处理金矿中金

针对矿区所在地的地表水和地下水盐度高、淡化水生产成本高、影响难处理金矿资源的利用问题,采用矿山含氯高盐水,对高碱性脉石难处理金矿进行次氯酸钠氧化—氰化提金试验,考查了次氯酸钠用量、氧化时间、氰化工艺等对金浸出率的影响。次氯酸钠用量94.5kg/t以上氧化处理2~4h后,金浸出率从直接氰化浸出的26.8%升高至88.1%~97.6%,氰化尾渣金品位降至0.07~0.36g/t。     

Simultaneous Nitrogen and Phosphorus Removal from High-Strength Industrial Wastewater Using Aerobic Granular Sludge

Aerobic granular sludge technology was applied to the simultaneous nitrogen and phosphorus removal from livestock wastewater that contains high concentrations of nitrogen and phosphorus (TN: 650?mg/L; TP: 125?mg/L). A lab-scale sequencing batch reactor was operated in an alternating anaerobic/oxic/anoxic denitrification mode. Granular sludge was first formed using synthetic wastewater. When livestock wastewater was diluted with tap water, the shape and settleability of aerobic granular sludge were maintained even though livestock wastewater contained suspended solids. Simultaneous nitrification, denitrification, and phosphate uptake were observed under an aerobic condition. However, when nondiluted livestock wastewater was used, the diameter of granular sludge and the denitrification efficiency under an oxic condition decreased. When the concentrations of nitrogen and phosphorus in wastewater increased, hydraulic retention time (HRT) increased resulting in a decrease in selection pressure for granular sludge. Therefore, the sustainment of granular sludge was difficult in livestock wastewater treatment. However, by applying a new excess sludge discharge method based on Stokes’ law, the shape of granular sludge was maintained in spite of the long HRT (7.5?days). To select large granular sludge particles, excess sludge was discharged from the upper part of settled sludge because small particles localized there after settling. Finally, excellent nitrogen and phosphorus removal was accomplished in practical livestock wastewater treatment. The effluent concentrations of NH4–N, NOx–N, and PO4–P were <0.1, 1.4, and 1.2?mg/L, respectively.     

Mitochondrial DNA mutations in multiple symmetric lipomatosis

We describe an analytical technique for measuring residues of imidacloprid, a relatively new and highly active insecticide, in water and soil using high-performance liquid chromatography (HPLC). All analyses were performed on reversed-phase HPLC with UV detection at 270 nm using a mobile phase of acetonitrile-water (20:80, v/v). Fortified water samples were extracted with either solid-phase extraction (SPE) or liquid-liquid extraction methods. A detection limit of 0.5 microgram/l was achieved using the SPE method. The imidacloprid residues in soils were extracted with acetonitrile-water (80:20, v/v), and the extract was then evaporated using a rotary evaporator. The concentrated extract was redissolved in 1 ml of acetonitrile-water (20:80, v/v) prior to analysis by reversed-phase HPLC. A detection limit of 5 micrograms/kg was obtained by this method which is suitable for analysis of environmental samples. Accuracy and precision at 10 and 25 micrograms/kg soil samples were 85 +/- 6% and 82 +/- 4%, respectively.