Simultaneous determination of brominated phenols in soils

Brominated phenols （BPs）, a widely used group of emerging flame retardants, are important environmental contaminants and exhibit endocrine disrupting potential. Method for simultaneous determination of tetrabromobisphenol A （TBBPA）, tribromophenol （TBP）, dibromophenols （DBPs） and monobromophenols （MBPs） in soils using gas chromatography-mass spectrometry analysis （GC/MS） was successfully developed. Cleanup methods for soil extracts including several solid-phase extraction cartridges and different elution solvents were compared and optimized. Florisil cartridge with dichloromethane as the elution reagent was selected for sample cleanup owing to its high and reproducible recoveries of the target analytes in soils. Derivatization conditions were tested and the optimal conditions were obtained with 20 μL silylation reagent at room temperature. The chromatographic separation was optimized with different columns and DB-XLB column was selected for its excellent separation of the analytes. The limits of detection for the target compounds were from 0.04 to 0.19 ng/g. Mean recoveries of the compounds from spiked soils exceeded 84% with a good reproducibility, excepting that the recovery of 2-bromophenol was relatively poor （lower than 55%） due to its instability. The developed method was applied to the determination of the BPs in the soils collected from e-waste sites. The contents of BPs in the soils were at ng/g levels with TBBPA and TBP the most frequently detected. To our knowledge, this is the first report for the simultaneous determination of TBBPA, TBP, DBPs and MBPs in soils.     

Cloud point extraction coupled with HPLC-UV for the determination of phthalate esters in environmental water samples

A method based on cloud point extraction was developed to determine phthalate esters including di-ethyl-phthalate （DEP）, di- （2-ethylhexyl）-phthalate （DEHP） and di-cyclohexyl-phthalate （DCP） in environmental water samples using high-performance liquid chromatography separation and ultraviolet detection （HPLC-UV）. The non-ionic surfactant Triton X-114 was chosen as extraction solvent. The parameters affecting extraction efficiency, such as concentrations of Triton X-114 and Na2SO4, equilibration temperature, equilibration time and centrifugation time were evaluated and optimized. Under the optimum conditions, the method can achieve preconcentration factors of 35, 88, 111 and detection of limits of 2.0, 3.8, 1.0 ng/ml for DEP, DEHP and DCP in 10-ml water sample, respectively. The proposed method was successfully applied to the determination of trace amount of phathalate esters in effluent water of the wastewater treatment plant and the lixivium of plastic fragments.     

Determination of arsenic in air particulates and diesel exhaust particulates by spectrophotometry

A method was developed for the determination of trace arsenic by spectrophotometry. The proposed method is rapid, simple,and inexpensive. This method can be used for sensitive determination of trace arsenic in environmental samples and especially in air particulates. The results obtained by this method as a proposed method were compared with those obtained by hydride generation atomic absorption spectrometry as a popular reported method for the determination of arsenic and an excellent agreement was found between them. The method was also used for determination of arsenic associated with airborne particulate matter and diesel exhaust particulates.The results showed that considerable amount of arsenic are associated with diesel engine particulates. The variation in concentration of arsenic was also investigated. The atmospheric concentration of arsenic was different in different sampling stations was dependent to the traffic density.     

Sensitized effect of β-cyclodextrin on the fluorescence in the determination of carbaryl

Based on the significant enhancement of fluorescence intensity of carbaryl in inclusion complex, a spetrofluorimetdc method with high sensitivity was developed for the determination of carbaryl in aqueous solution. Under the optimum conditions, the complex had excitation and emission maxima at 278 nm and 332 nm, respectively. The linear range of the method was 7.0 ng/ml-1500 ng/ml with a detection limit of 1.2 ng/ml. The proposed method was successfully used to determine quantitativelv of carbarvl in cottonseeds.     

Determination of total arsenic by photo-decomposition of organoarsenic compounds and hydride generation electrothermal atomic absorption spectrometry

A method was developed for the determination of total arsenic concentration in less than ng/ml level by decomposition of organoarsenicals using photo -oxidation combined with in situ trapping of arsenic hydride on a palladium coated graphite tube with subsequent atomization and detection by AAS. The organoarsenicals include monomethylarsenic, dimethylarsenic, arsenobetaine, arsenocholine, o -aminobenzenarsenate and p -aminobenzenarsenate. The method is simple and sensitive. Detection limit was obtained from different arsenic compounds over the range from 0. 058 to 0.063 ng/ml as As (based on three times of the standard deviation of 10 blank measurements) and the relative standard deviations for ten replicate measurements were from 2.0 to 3.8%. The calibration curves of arsenic compounds including inorganic and organic arsenicals were linear over the range from 0.1 to 3.0 ng/ml as As. The recommended method has been applied to the determination of total arsenic in tap and lake water samples at ng/ml leve     

Multiresidue determination and potential risks of emerging pesticides in aquatic products from Northeast China by LC–MS/MS

A simple method for determining 33 pesticides with a wide polarity range(log Kow0.6-4.5) in aquatic products was developed based on LC–MS/MS. The target analytes included three types of widely used pesticides: insecticides, fungicides and herbicides. Based on the optimization of ultrasonic assisted extraction and GPC clean-up procedures, the matrix effect, extraction recoveries and LOD were improved distinctively. LOQ of this method was below 0.5 ng/g for all pesticides, which is superior to values in the literature, and the matrix effect was reduced effectively(-14.7% to 7.5%). The method was successfully applied to investigate the pesticide residue levels of twenty-five samples including seven common kinds of fishes from Northeast China. The results showed that all targeted pesticides were present in the fish samples; however, their levels were low, except for atrazine, linuron,ethoprophos, tetrachlorvinphos, acetochlor and fenthion. Atrazine and linuron caught our attention because the concentrations of atrazine in fish samples from Liaoning province were in the range of 0.5-8 ng/g(w/w) with mean concentration of 2.3 ng/g, which were far above those of other pesticides. The levels of linuron were in the range of 0.6-6 ng/g(mean concentration 2.8 ng/g), which were the highest among all targeted pesticides in the Inner Mongolia. This is the first systematic investigation on the characteristics and levels of these pesticides in aquatic products from northeast China. Considering their toxicity and bioaccumulation, the potential risk of atrazine and linuron from consuming aquatic products should be paid more attention.     

TiO2 nanotubes as solid-phase extraction adsorbent for the determination of polycyclic aromatic hydrocarbons in environmental water samples

An analytical method based on TiO2 nanotubes solid-phase extraction (SPE) combined with gas chromatography (GC) was established for the analysis of seven polycyclic aromatic hydrocarbons (PAHs): acenaphtylene, acenaphthene, anthracene, fluorene, phenanthrene, fluoranthene and pyrene. Factors a ecting the extraction e ciency including the eluent type and its volume, adsorbent amount, sample volume, sample pH and sample flow rate were optimized. The characteristic data of analytical performance were determined to investigate the sensitivity and precision of the method. Under the optimized extraction conditions, the method showed good linearity in the range of 0.01–0.8 g/mL, repeatability of the extraction (RSD were between 6.7% and 13.5%, n = 5) and satisfactory detection limits (0.017–0.059 ng/mL). The developed method was successfully applied to the analysis of surface water (tap, river and dam) samples. The recoveries of PAHs spiked in environmental water samples ranged from 90% to 100%. All the results indicated the potential application of titanate nanotubes as solid-phase extraction adsorbents to pre-treat water samples.     

Analysis of α, β, γ-hexachlorocyclohexanes in water by novel activated carbon fiber-solid phase microextraction coupled with gas chromatography--mass spectrometry

A fast and simple method for determination of α, β,γ-hexachlorocyclohexanes (HCHs) in water using activated carbon fibersolid phase microextraction(ACF-SPME) were studied. Results showed the performance of adsorption and desorption of three HCHs on ACF were excellent. A wide linear range from 10 to 100 μg/L and detection limits of the ng/L level were obtained using ACF-SPME with GC-MS in selected ion monitoring(SIM) acquisition mode. The proposed method was also successfully applied for determination of three HCHs in tap water. Compared to commercial fibers, ACF showed some advantages such as better resistance to solvents, higher thermal stability, longer lifetime and lower cost. The data demonstrated that GC-MS with ACF-SPME is well suitable for the analysis of HCHs in water.     

Kinetic-spectrophotometric determination of free cyanide by stopped-flow reversed flow injection analysis

A stopped-flow reversed flow injection method for the determination of free cyanide is proposed. Pyridine-barbituric acid mixture is injected in the flow system as reagent to form the colour species with cyanide. The flow is stopped when the reagent zone comes in the flow cell, where absorbance-time data are collected at 580nm wavelength. The linear range of the determination is 0.1 -10μg/ml CN-. The sampling rate is 60h-1 and the relative standard deviation is 1.6% (n=16) at 5.0 μg/ml CN-1 level. With satisfactory results, the proposed method was applied to the determination of free cyanide in wastewater without sample pretreatment.     

Rapid detection of multiple class pharmaceuticals in both municipal wastewater and sludge with ultra high performance liquid chromatography tandem mass spectrometry

This work described the development, optimization and validation of an analytical method for rapid detection of multiple-class pharmaceuticals in both municipal wastewater and sludge samples based on ultrasonic solvent extraction, solid-phase extraction, and ultra high performance liquid chromatography-tandem mass spectrometry quantification. The results indicated that the developed method could effectively extract all the target pharmaceuticals （25） in a single process and analyze them within 24 min. The recoveries of the target pharmaceuticals were in the range of 69%-131% for wastewater and 54%-130% for sludge at different spiked concentration levels. The method quantification limits in wastewater and sludge ranged from 0.02 to 0.73 ng/L and from 0.02 to 1.00μg/kg, respectively. Subsequently, this method was validated and applied for residual pharma- ceutical analysis in a wastewater treatment plant located in Beijing, China. All the target pharmaceuticals were detected in the influent samples with concentrations varying from 0.09 ng/L （tiamulin） to 15.24 μg/L （caffeine）; meanwhile, up to 23 pharmaceuticals were detected in sludge samples with concentrations varying from 60 ng/kg （sulfamethizole） to 8.55 mg/kg （ofloxacin）. The developed method demonstrated its selectivity, sensitivity, and reliability for detecting multiple-class pharmaceuticals in complex matrices such as municipal wastewater and sludge.     

富氧空气—乙炔火焰原子吸收法测定水样中锶

研究了富氧空气-乙炔火焰原子吸收光谱法测定锶的方法,优化了实验条件,选择了最佳的观察高度、氧气流量和乙炔流量,研究了有机试剂的增感作用,0.5%的磺基水杨酸可以提高测定的灵敏度约40%,并可很好的抑制共存离子的干扰,方法的检出限为4ng/mL,该法快速、简便、准确,适合一般水样中痕量锶的测定。     

Simultaneous preconcentration of cadmium and lead in water samples with silica gel and determination by flame atomic absorption spectrometry

A new method that utilizes pretreated silica gel as an adsorbent has been developed for simultaneous preconcentration of trace Cd(II) and Pb(II) prior to the measurement by flame atomic absorption spectrometry. The effects of pH, the shaking time, the elution condition and the coexisting ions on the separation/preconcentration conditions of analytes were investigated. Under optimized conditions, the static adsorption capacity of Cd(II) and Pb(II) were 45.5 and 27.1mg/g, the relative standard deviations were 3.2% and 1.7% (for n = 11), and the limits of detection obtained were 4.25 and 0.60 ng/mL, respectively. The method was validated by analyzing the certified reference materials GBW 07304a (stream sediment) and successfully applied to the analysis of various treated wastewater samples with satisfactory results.     

利用正交试验法优化原子吸收测定镉的仪器参数研究

镉对人类和动物是一种毒性极强的污染物,由于工业化发展和人类活动范围扩大,导致环境镉污染越来越严重.环境监测站用火焰原子吸收光谱法测定镉,但影响镉准确测定的因素较多.为了优化原子吸收测定镉的仪器参数,利用正交试验法,对原子吸收分析过程中需要设置的原素灯工作电流、燃气流量和燃烧器高度三个主要因素进行无交互作用试验,优化仪器参数：原素灯工作电流4mA、燃气流量1 200 ml/min、燃烧器高度5.0 mm,其中燃气流量影响最显著.     

石墨探针采样/石墨探针炉原子吸收光谱测定APM中痕量铜

采用一定规格的石墨探针可直接收集大气微料物质（ＡＰＭ）。然后,立即采用石墨探针炉原子吸收光谱测定收集在探针上的ＡＰＭ中痕量铜。方法简便,快速。在０－５５０ｎｇ／ｍＬ范围内,铜的浓度与峰面积吸光度呈良好的线性关系。铜的特征量为２２．０ｐｇ,检出限为６．６ｎｇ／ｍＬ。分析标准参比材料,铜的回收率达９８％,相对标准偏差为３．３％。     

Preparation, characterization and application of thiosemicarbazide grafted multiwalled carbon nanotubes for solid-phase extraction of Cd(Ⅱ), Cu(Ⅱ) and Pb(Ⅱ) in environmental samples

Thiosemicarbazide-grafted multi-walled carbon nanotubes were prepared and employed to investigate the pre-concentration of Cd（Ⅱ）, Cu（Ⅱ） and Pb（Ⅱ） from aqueous solution prior to their determination by ICP-OES. The resulting material was characterized by FT-IR, TGA and SEM. Various factors influencing the separation and pre-concentration were investigated. The enrichment factor typically is 60. Under optimized experimental conditions, the maximum adsorption capacities of Cd（Ⅱ）, Cu（Ⅱ） and Pb（Ⅱ） were found to be 1.98, 10.94, 3.69 mg/g, and the relative standard deviations are 〈 3.5% （n = 6）. The new adsorbent shows superior reusability and stability. The procedure was successfully applied to the determination of trace quantities of Cd（Ⅱ）, Cu（Ⅱ） and Pb（Ⅱ） in water samples.     

流动注射在线离子交换富集-原子荧光光谱法测定环境水样中痕量汞

提出了一种流动注射在线离子交换富集一氢化物发生原子荧光光谱法测定水样中总汞的分析方法。设计了双柱并联富集，串联洗脱的在线离子交换流路及操作程序，优化了各项化学条件及流路参数。方法操作简便快速，灵敏度高，干扰少。富集倍数达25倍以上，采样频率为30次／h，回收率达90％－105％。应用于环境水样中痕量汞的测定，获得了满意的结果。     

交联壳聚糖富集分离火焰原子吸收法测定环境样品中微量锰

提出了交联壳聚糖 (CCTS)分离富集火焰原子吸收法测定环境样品中微量锰的新方法。研究了富集的最佳条件及洗脱方法 ;考察了共存元素的影响。方法的检出限为 2 .6μg/L ,RSD为 2 .9% ,用于牡蛎和人发标样中微量锰的测定 ,结果满意。     

在线分离富集FI分光光度法直接测定铜

本文针对ＡＡＳ法测定痕量铜时，大量铁存在表现干扰，研究并建立了流动注射（ＦＩ）在线螯合树脂分离富集光度法直接测定痕量铜的新方法，具有灵敏度高、选择性强；因此，已成功地用于水样中痕量铜的测定，该法在水质检验和环境监测中有一定的适用性．     

微波消解－ICP－MS法测定土壤中稀土元素的研究

建立了电感耦合等离子体质谱（ ICP－MS）测定土壤中稀土元素的分析方法。采用HNO3＋HF酸体系用微波消解对土壤样品进行处理,以混合内标（ In、Bi）校正基体干扰和信号漂移,用ICP－MS对其中的16种稀土元素进行了测定。在优化的实验条件下,16种稀土元素标准曲线的相关系数r＞0．9999,检出限为0.012 ng／ml～0.069 ng／ml,加标回收率为84.0％～110％,相对标准偏差（n＝6）RSD均小于3.5％。该方法可用于四种不同类型土壤中稀土元素含量的测定。