Determination of total organic chlorine and bromine in water samples by adsorption onto activated carbon and neutron activation analysis

A method was developed for the analysis of total organic chlorine and bromine compounds (TOCl, TOBr) in water samples. The method is based on the adsorption of organic compounds on specially prepared activated carbon. Neutron activation analysis (neutron flux 4·10¹² n cm⁻² s⁻¹) was used for the quantitative determination of chlorine and bromine.The factors investigated were the adsorption of organic chlorine and bromine compounds on activated carbon, the effect of pH on the adsorption, the removal of chlorine ions from activated carbon by nitrate washing, the amount of activated carbon required, the adsorption time, the potential number of successive adsorptions and the preservation of samples.The detection limits for TOC1 and TOBr were 5 and 0.5 μg 1⁻¹, respectively, when the sample size was 100 ml.     

A method for determining pyrene in mucus using synchronous fluorimetry with multiple standard additions

A new method was proposed to determine pyrene in mucus, which combined the synchronous fluorimetry with the multiple standard addition method (SFMSA). The method was used to determine pyrene in mucus directly without pretreatment. The method detection limit (MDL) for pyrene in mucus was measured as 0.47 ng/ml with a relative standard deviation of 12.7% (n = 7). The standard addition graph was linear in the range 0.05-50.00 ng/ml (r(2) = 0.9989). SFMSA was validated using a GC/MS method as a reference method, and nice agreement was found. The pyrene in mucus can be directly monitored by SFMSA without solvent extraction of samples. This indicates that SFMSA is more timesaving, less laborious and cheaper than the GC/MS method with solvent extraction. SFMSA has lower MDL and higher average recovery than the GC/MS method.     

Validation of an evacuated canister method for measuring part-per-billion levels of chemical warfare agent simulants

The National Institute for Occupational Safety and Health (NIOSH) research on direct-reading instruments (DRIs) needed an instantaneous sampling method to provide independent confirmation of the concentrations of chemical warfare agent (CWA) simulants. It was determined that evacuated canisters would be the method of choice. There is no method specifically validated for volatile organic compounds (VOCs) in the NIOSH Manual of Analytical Methods. The purpose of this study was to validate an evacuated canister method for sampling seven specific VOCs that can be used as a simulant for CWA agents (cyclohexane) or influence the DRI measurement of CWA agents (acetone, chloroform, methylene chloride, methyl ethyl ketone, hexane, and carbon tetrachloride [CCl4]). The method used 6-L evacuated stainless-steel fused silica-lined canisters to sample the atmosphere containing VOCs. The contents of the canisters were then introduced into an autosampler/preconcentrator using a microscale purge and trap (MPT) method. The MPT method trapped and concentrated the VOCs in the air sample and removed most of the carbon dioxide and water vapor. After preconcentration, the samples were analyzed using a gas chromatograph with a mass selective detector. The method was tested, evaluated, and validated using the NIOSH recommended guidelines. The evaluation consisted of determining the optimum concentration range for the method; the sample stability over 30 days; and the accuracy, precision, and bias of the method. This method meets the NIOSH guidelines for six of the seven compounds (excluding acetone) tested in the range of 2.3-50 parts per billion (ppb), making it suitable for sampling of these VOCs at the ppb level.     

生活污水中蛋白质测试方法研究

分别用Folin-酚改进法、考马斯亮兰法和紫外分光光度法等3种测试方法测试了上海市某小区生活污水中的蛋白质含量,对这3种测试方法进行了比较,并采用氨基酸仪分析了生活污水中蛋白质水解后的氨基酸化学组成.试验结果表明,Folin-酚改进法测试蛋白质浓度的准确性与精确性优于考马斯亮兰法和紫外分光光度法,可用于测定生活污水中蛋白质的浓度;氨基酸仪法测得该生活污水中含有17种氨基酸,其中最多的为谷氨酸(3.6 mg/L),含量最低的是脯氨酸(0.8 mg/L);所测生活污水中蛋白质COD占总COD的18.9%.     

一种活性污泥总DNA提取方法的优化

对3种活性污泥DNA提取方法———传统蛋白酶K-SDS-氯仿异戊醇法(CPSCI法)、液氮研磨法和脱腐处理法进行了对比,并针对CPSCI法从污泥量、保温时间、裂解方式及沉淀时间等4个方面进行了优化。结果表明,优化的蛋白酶K-氯仿-异戊醇法(OPSCI法)采用污泥量0.10 g、37℃静置10 min,加SDS常温旋涡振荡及异丙醇直接离心等条件可获得长度在23.1 kb左右的DNA,OD260nm/OD280nm为1.86,稀释10倍后即可进行16S rDNA PCR。该方法重复性好,提取得率高,纯度好,操作简便,为常规实验室开展活性污泥微生物多样性研究提供了帮助。     

生活污水中糖类测试方法研究

分别用蒽酮比色、苯酚-硫酸及气相色谱法3种测试方法测试了上海市某生活小区生活污水的糖类组成.试验结果表明,蒽酮比色法测试糖类浓度的准确性与精确性优于苯酚-硫酸法,但不能得出污水中糖类的详细组成情况;与蒽酮比色法和苯酚-硫酸法相比,气相色谱法不仅能得出污水中糖类的详细组成,而且还具有较高的精密度.气相色谱法测得的生活污水中各种单糖,如木糖、甘露糖、葡萄糖、半乳糖、鼠李糖、核糖、岩藻糖的质量浓度分别为8.25、 6.02、5.52、4.80、4.44、4.41、2.66 mg/L.     

Determination of Nitrogen Oxides in Auto Exhaust

A new procedure for determining nitrogen oxides in automobile exhaust has been developed. The new procedure was included in a Bureau of Mines comparative study that aimed at evaluating various widely used methods for determining NO_x in auto exhaust. The methods included in the evaluation study follow: (1) Static oxidation in tank (ST method). The method involves oxidation of NO in residence with O₂ in a stainless steel tank. (2) Bureau of Mines method (BM method). The method involves application of the ST procedure in exhaust samples from which the hydrocarbons have been removed by combustion over catalyst. (3) Chevron Research method (CR method), as described in the literature. (4) Phenoldisulfonic acid method (PDS method), as described in the literature. The principal objective of this study was to generate experimental evidence which would lead to defining an optimum procedure for converting NO, present in exhaust gas, into NO₂; this conversion is desired so that the total of NO + NO₂ can be determined quantitatively in the form of NO₂. In pursuing this objective, the procedures prescribed by the foregoing methods were comparatively tested. The results indicated that all four methods are subject to error, the extent of which depends on the conditions employed. The BM method was superior from the standpoint of accuracy because it was less affected by interferences due to hydrocarbon-NO₂ reactions.     

Solid phase extraction with pyrenebutyric acid-bonded silica for analysis of polychlorinated biphenyls in sewage water by gas chromatography-mass spectrometry

A solid phase extraction (SPE) method using pyrenebutyric acid-bonded silica (PYB) as sorbent was developed to determine 23 polychlorinated biphenyls (PCBs) in sewage water by gas chromatography-mass spectrometry (GC-MS). Factors were optimized in SPE procedures including elution solvent, pH, and cartridge burden. The recoveries of 23 PCB congeners were 69.44-111.91% under optimized conditions. Comparisons were also conducted among PYB-SPE, C(18)-SPE and United States Environmental Protection Agency 608 (USEPA608) methods in the analysis of PCBs in sewage water samples. The results showed that the performance of PYB-SPE method was similar with USEPA608 method and better than C(18)-SPE method. Both PYB-SPE and USEPA608 methods were then employed to analyze PCBs in real spiked sewage water samples. The recoveries of PCB congeners determined by PYB-SPE method ranged from 70.6% to 92.4% in real spiked sewage water samples which were identified to be in accordance with USEPA608 method. Limits of detection (LOD) were in the range of 0.06-0.22ngL(-1) for PCB congeners. The optimized PYB-SPE method was successfully applied to the determination of PCBs in sewage water samples.     

Development of a solid phase microextraction-gas chromatography-mass spectrometry method for the determination of pentachlorophenol in human plasma using experimental design

A new method, headspace solid-phase microextraction (HS-SPME) with in situ derivatization and gas chromatography-mass spectrometry (GC-MS), which was used for the determination of trace amount of pentachlorophenol (PCP) in human plasma was presented. The acetylation derivatization reaction was firstly optimized using a Doehlert design. Then a series of parameters relevant to the headspace SPME procedure, including fiber coating, extraction temperature, extraction time and salt addition, were optimized using a two-level full factorial design expanded further to a central composite design. The validation of method showed that the optimized method had good linearity (R(2)=0.999) within the concentration ranges 0.1-50.0ngml(-1), and was sensitive with the limit of detection of 0.02ngml(-1). Intra- and inter-day precision for pentachlorophenol in human plasma samples were not greater than 11.9% and 12.6%, respectively. The proposed method, to our knowledge, describes the first application of HS-SPME with GC-MS for analysis of PCP in blood plasma sample. Application of the method to real human plasma samples, PCP was successfully detected in some cases at concentration levels 1.2-6.3ngml(-1).     

Comparison of GC-MS and FTIR methods for quantifying naphthenic acids in water samples

The extraction of bitumen from the oil sands in Canada releases toxic naphthenic acids into the process-affected waters. The development of an ideal analytical method for quantifying naphthenic acids (general formula C(n)H(2n+Z)O(2)) has been impeded by the complexity of these mixtures and the challenges of differentiating naphthenic acids from other naturally-occurring organic acids. The oil sands industry standard FTIR method was compared with a newly-developed GC-MS method. Naphthenic acids concentrations were measured in extracts of surface and ground waters from locations within the vicinity of and away from the oil sands deposits and in extracts of process-affected waters. In all but one case, FTIR measurements of naphthenic acids concentrations were greater than those determined by GC-MS. The detection limit of the GC-MS method was 0.01 mg L(-1) compared to 1 mg L(-1) for the FTIR method. The results indicated that the GC-MS method is more selective for naphthenic acids, and that the FTIR method overestimates their concentrations.     

Studies of selenium in environmental samples and synthetic mixtures by spectrophotometry

A rapid, highly sensitive and selective spectrophotometric method for the determination of traces of selenium(IV) is described. The method is based on oxidation of p-nitroaniline by selenium(IV) followed by coupling reaction with N-(1-naphthalene-1-yl)ethane-1,2-diamine dihydrochloride (NEDA) in neutral medium to give red colored derivative with lambda(max) 515 nm and is stable for more than 10 days at 35 degrees C. Beer's law is obeyed for selenium(IV) in the concentration range of 0.02-3.2 microg ml(-1) at the wavelength of maximum absorption. The optimum reaction conditions and other analytical parameters were investigated to enhance the sensitivity of the present method. The detailed study of various interferences made the method more selective. The proposed method was successfully applied to the analysis of selenium in polluted water, natural water samples, plant material, soil samples, and synthetic mixtures. The results obtained were agreed with the reported methods at the 95% confidence level. The performance of proposed method was evaluated in terms of Student's t-test and Variance ratio f-test which indicates the significance of proposed method over reported method.     

Preconcentration of trace arsenite and arsenate with titanium dioxide nanoparticles and subsequent determination by silver diethyldithiocarbamate spectrophotometric method.

A novel method of preconcentration of trace arsenite and arsenate by using titanium dioxide nanoparticles as adsorbent was described. The concentrations of preconcentrated arsenite and arsenate were determined by a silver diethyldithiocarbamate spectrophotometric method without desorption. Batch adsorption experiments were carried out as a function of the pH, contact time, amount of titanium dioxide nanoparticles, and solution volume. In the pH range 5 to 6, adsorption rates of arsenite and arsenate were higher than 98%. The calibration coefficient was 0.9991, and the linear range was 0 to 100 microg/L. The developed method was precise, with the relative standard deviation <5% at concentration level of 10 microg/L, with a detection limit (3sigma, n=6) of 0.44 microg/L. The accuracy of the method for total arsenic was validated by standard reference materials (SRM 3103a) (National Institute of Standards and Technology, Gaithersburg, Maryland). The method was also applied to the analysis of arsenite and arsenate in natural water samples to verify the accuracy. The recovery values remained in a narrow range, from 95 to 103%.     

Comparison of the MURA and an improved single-receptor (SIRA) trajectory source apportionment (TSA) method using artificial sources

Two trajectory source apportionment methods were tested using an artificially generated data set to determine their ability to detect the known sources. The forward-looking step from the multi-receptor trajectory analysis (MURA) method was added to the conditional probability (CP)method of Ashbaugh et al. [1985. A residence time probability analysis of sulfur concentrations at Grand Canyon National Park. Atmospheric Environment 19(8), 1263–1270] to develop the single-receptor forward CP (SIRA) method. The multi-receptor (MURA) and the SIRA methods were tested with three simulations using artificially generated sources. The ability of the methods to detect the sources was quantified for each simulation. The first simulation showed that the SIRA method is an improvement over the original CP method. The MURA trajectory method proved to be superior at identifying sources for the simulation located in the west and comparable to the SIRA method for the two simulations located in the east.     

Method development for determination of fluroxypyr in soil

Four methods were developed for the analysis of fluroxypyr in soil samples from oil palm plantations. The first method involved the extraction of the herbicide with 0.05 M NaOH in methanol followed by purification using acid base partition. The concentrated material was subjected to derivatization and then cleaning process using a florisil column and finally analyzed by gas chromatography (GC) equipped with electron capture detector (ECD). By this method, the recovery of fluroxypyr from the spiked soil ranged from 70 to 104% with the minimum detection limit at 5 microg/kg. The second method involved solid liquid extraction of fluroxypyr using a horizontal shaker followed by quantification using high performance liquid chromatography (HPLC) equipped with UV detector. The recovery of fluroxypyr using this method, ranged from 80 to 120% when the soil was spiked with fluroxypyr at 0.1-0.2 microg/g soil. In the third method, the recovery of fluroxypyr was determined by solid liquid extraction using an ultrasonic bath. The recovery of fluroxypyr at spiking levels of 4-50 microg/L ranged from 88 to 98% with relative standard deviations of 3.0-5.8% with a minimum detection limit of 4 microg/kg. In the fourth method, fluroxypyr was extracted using the solid liquid extraction method followed by the cleaning up step with OASIS HLB (polyvinyl dibenzene). The recovery of fluroxypyr was between 91 and 95% with relative standard deviations of 4.2-6.2%, respectively. The limit of detection in method 4 was further improved to 1 pg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1-50 microg/kg ranged from 82-107% with relative standard deviations of 0.5-4.7%.     

Molecularly imprinted polymer for analysis of trace atrazine herbicide in water

A molecularly imprinted polymer (MIP) for atrazine was synthesized by non-covalent method. The binding capacity of MIP was 1.00 mg g^{? 1} polymer. The selectivity and recovery were investigated with various pesticides which are mostly, found in the environment, for both similar and different chemical structure of atrazine. The competitive recognition between atrazine and structurally similar compounds was evaluated and it was found that the system provided highest recovery and selectivity for atrazine while low recovery and selectivity were obtained for the other compounds. The highest recovery was obtained from MIP compared with non-imprinted polymer (NIP), a commercial C₁₈ and a granular activated carbon (GAC) sorbent. The method provided high recoveries ranged from 94 to 99% at two spiked levels with relative standard deviations less than 2%. The lower detection limit of the method was 80 ng L^{? 1}. This method was successfully applied for analysis of environmental water samples.     

不同来源废水COD、TOC与Cl-的关系

通过对含盐化工废水(A)、受潮汐影响的河流水(B)、城市生活污水处理厂排水(C)、采油废水(D)4种不同来源废水进行为期15 d的采样监测,测定了其COD、TOC和Cl-浓度,分析比较了3种废水指标之间的关系,其中COD分别使用重铬酸钾法、氯气校正法和碘化钾碱性高锰酸钾法3种方法进行测定.实验结果表明,4种废水Cl-浓...     

Novel method for determining pyrene biodegradation using synchronous fluorimetry

To study the biodegradation rate of pyrene dissolved in liquid medium supplemented with mineral salts, a synchronous fluorimetry (SF) method was established. The limit of detection for pyrene dissolved in mineral salts medium (MSM) was determined as 0.19 ng/ml with a relative standard deviation of less than 1.3% (n = 9). The pyrene degrading rates of four bacterial strains were investigated using this method under the same experimental conditions. The degradation rates of the three active strains ranged from 76% to 87% after a 14-h incubation. The results were confirmed by the gas chromatography with a flame ionized detector (GC/FID) method. This implies that pyrene degradation can be directly monitored by the SF method without the solvent extraction of samples. The advantages of SF are that it is less laborious, faster, and less expensive than the GC/FID determination method with solvent extraction. The SF method provides a new tool for studying the degradation of polynuclear aromatic hydrocarbons (PAHs) in the natural environment and under experimental conditions.     

Analysis method for PCBs in reclaimed oil using a fast-GC triple stage quadrupole mass spectrometer with the 13-component quantitation method

It is necessary for companies supplying reclaimed oil to analyze polychlorinated biphenyls (PCBs), because there is a possibility of the presence of contaminants due to trace-level PCBs in the reclaimed oil. However, common analysis methods of PCBs are time-consuming and complicated. Fast-GC triple stage quadrupole mass spectrometer with the 13-component quantitation method is an official method for analyzing PCBs in insulating oil in Japan. This method is extremely fast and simplified. The purpose of this study involves an investigation of the aforementioned fast and simple method for potential use in the analysis of reclaimed oil. Furthermore, it was attempted to combine the method with sample preparation involving only hexane dilution. The effect of sample dilutions corresponding to 100, 300, and 500 times was evaluated for reducing the matrix effect. The matrix effect was suppressed at a dilution ratio equal to or exceeding 300 times. Calibration curves of four points, namely 0.01, 0.05, 0.1, and 0.5 ng/mL, (ignored origin) by using an internal standard method were prepared for the 13 components. The square of regression coefficient (R²) values of all calibration curves exceeded 0.997. This method was adopted for the analysis of reclaimed oil containing 0.5 μg/mL PCBs, which corresponds to the judgment criteria, and accurate quantitation (accuracy value, 94.0–102%) and good repeatability (%RSD, 3.6%) were obtained. Furthermore, the required sensitivity was maintained even when 800 samples were analyzed without a cleaning ion source and an exchanging analysis column.     

Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

Simultaneous gas chromatographic determination of chlorpyrifos and its impurity sulfotep in liquid pesticide formulations

An analytical method for simultaneous determination of the active substance (chlorpyrifos) and its relevant impurity (sulfotep) in commercial pesticide formulations has been developed and validated. The proposed method entails extraction of the analytes from samples by sonication with acetone and analysis by gas chromatography-flame ionization detection (GC-FID). The proposed method was characterized by satisfactory accuracy and precision. The repeatability expressed as relative standard deviation (RSD) was lower than the acceptable values calculated from the modified Horwitz equation whereas individual recoveries were in the range of 98–102% and 80–120% for chlorpyrifos and sulfotep, respectively. The limit of quantification (LOQ) for the impurity (sulfotep) was 0.003 mg mL^?1 corresponding to the maximum permitted level according to Food and Agricultural Organization of the United Nations (FAO) specifications for the active substance (chlorpyrifos) being 3 g kg^?1 of the chlorpyrifos content found. The main advantage of the proposed method was a considerable reduction in the analysis time since both analytes were determined based on a single injection into the GC-FID. Analysis of real samples of commercial pesticide formulations confirmed fitness-for-purpose of the proposed method.