A novel method dependent only on the mixture information (MIM) for evaluating the toxicity of mixture

Compound contamination and toxicity interaction necessitate the development of models that have an insight into the combined toxicity of chemicals. In this paper, a novel and simple model dependent only on the mixture information (MIM), was developed. Firstly, the concentration-response data of seven groups of binary and multi-component (pseudo-binary) mixtures with different mixture ratios to Vibrio qinghaiensis sp.-Q67 were determined using the microplate toxicity analysis. Then, a desirable non-linear function was selected to fit the data. It was found that there are good linear correlations between the location parameter (α) and mixture ratio (p) of a component and between the steepness (β) and p. Based on the correlations, a mixture toxicity model independent of pure component toxicity profiles was built. The model can be used to accurately estimate the toxicities of the seven groups of mixtures, which greatly simplified the predictive procedure of the combined toxicity.     

Potential application of a semi-quantitative method for mercury determination in soils, sediments and gold mining residues

An alternative, low cost method for analyzing mercury in soil, sediment and gold mining residues was developed, optimized and applied to 30 real samples. It is semiquantitative, performed using an acid extraction pretreatment step, followed by mercury reduction and collection in a detecting paper containing cuprous iodide. A complex is formed with characteristic color whose intensity is proportional to mercury concentration in the original sample. The results are reported as range of concentration and the minimum detectable is 100 ng/g. Method quality assurance was performed by comparing results obtained using the alternative method and the Cold Vapor Atomic Absorption Spectrometry techniques. The average results from duplicate analysis by CVAAS were 100% coincident with alternative method results. The method is applicable for screening tests and can be used in regions where a preliminary diagnosis is necessary, at programs of environmental surveillance or by scientists interested in investigating mercury geochemistry.     

B/A法强化处理印染废水工艺条件研究

采用B/A法对印染废水处理工艺条件控制进行系列试验.探索了微生物种群与有机污染物降解率的关系.获得了提高水质达标率的数据:COD＜90 mg/L,BOD5＜20 mg/L,挥发酚＜0.5 mg/L,石油类＜0.5 mg/L,NH3-N＜15 mg/L;CN-＜0.5 mg/L,S2-＜1 mg/L,pH在6～9范围内,筛选优化B/A法处理印染废水的工艺设计.     

Comparison of the solution behaviour of a pyrite-calcite mixture in batch and unsaturated sand column

A successful application of reaction transport algorithms to calculate the chemical evolution of natural systems requires accurate methods to compute the rates of mineral/fluid surface reactions. Regarding the transport of radio-nuclides in mining dumps the dissolution of minerals is of special importance. Using a kinetic rate law of the mineral dissolution verified for unsaturated conditions will allow a realistic modelling of the mineral weathering in the environment. Dissolution rates of minerals in an aqueous solution are determined by several characteristics. These are surface reaction rates, morphology of the mineral's surface and, in case it is the unsaturated zone, the degree of the water saturation. For this process, the quantity of the particle surfaces which are in contact with percolating water is most decisive. In order to study the differences of mineral dissolution under saturated and unsaturated conditions batch and column experiments were carried out with a pyrite-calcite mixture. The experimental results were verified by calculations. Comparing the dissolution in batch with those in the column experiment, which was performed with a water flow velocity of 0.64 cm/day and was analyzed in the region of a water saturation of 0.11, one can conclude that only a small portion of about 5% of the grain surface is chemically reactive in this unsaturated flow.     

Ozonation of azo dye in a semi-batch reactor: a determination of the molecular and radical contributions

Azo dye ozonation was carried in a semi-batch reactor to evaluate both the molecular and radical contributions of ozone on the dye decay. From two mass balance equations, the simultaneous determination of mass transfer, self-decomposition and solubility parameters of ozone were determinated; thus establishing the steady state conditions in the experimental system. The results of kinetic studies showed that the decay of azo dye was a pseudo-first-order reaction with respect to dye concentration and the overall rate constant increased with an increase in the pH, however declined with an increase in the dye concentration. Furthermore, from the overall rate constants obtained at various pH values a mathematical analysis of dye decay was performed, which provides a practical new method to quantify the radical and molecular contributions in the ozonation of azo dyes.     

Headspace solid phase microextraction method for determination of triazine and organophosphorus pesticides in soil

A headspace solid phase microextraction method (HS-SPME) for simultaneous determination of five pesticides belonging to triazine and organophosphorus pesticide groups in soil samples was developed. Microextraction conditions, such as temperature, extraction time and sodium chloride (NaCl) content were investigated and optimized using 100 μ m polydimethyl-siloxane (PDMS) fiber. Detection and quantification were done by gas chromatography-mass spectrometry (GC-MS). Relative standard deviation (RSD) and recovery values for multiple analysis of soil samples fortified at 30 μ g kg^{? 1} of each pesticide were below 13 % and higher than 70 %, respectively. Limits of detection (LOD) for all the compounds studied were less than 3.2 μ g kg^{? 1}. The proposed method was applied in the analysis of some agricultural soil samples.     

Development and validation of a method for determination of trace levels of alkylphenols and bisphenol A in atmospheric samples

A method has been developed and validated in order to assess the occurrence of the alkylphenols tert-octylphenol and the isomers of technical nonylphenol as well as bisphenol A in gasphase and aerosol samples of a remote area. Gasphase samples were adsorbed to XAD2 resin, aerosol samples were taken on glass fiber filters. After ultrasonic extraction, clean-up by column chromatography and silylation of the analytes, ten nonylphenol peaks were quantified separately using a GC-MSD-SIM method. The absolute limits of detection and determination are in the range of a few pg per compound, which is a prerequisite for the quantification of the analytes in relatively unpolluted air. The precision of the whole analytical method is in the range of 1-17% and the recoveries range from 57% to 80%. Problems were encountered during method development due to the tendency of the analytes to sorb to glass surfaces. Silanisation of glassware was crucial to achieve acceptable recoveries. The widespread use of the analytes in plastic resins resulted in sample contamination. For this reason a careful choice of sampling material was necessary. Measured concentrations in gasphase samples (lower nanogram per m3 range) and aerosol samples (upper picogram per m3 range) are one to three orders of magnitude below already published concentrations.     

A sensitive and robust method for the determination of alkylphenol polyethoxylates and their carboxylic acids and their transformation in a trickling filter wastewater treatment plant

This paper presents a method for the determination of alkylphenols, alkylphenol polyethoxylates (APEO) and alkylphenol ethoxycarboxylates (APEC) in the aqueous and particulate phase of wastewater samples. Quantification was achieved by liquid chromatography-tandem mass spectrometry. The sensitivity of the method is demonstrated by low detection limits, in the dissolved phase 1.2-9.6ngl(-1) for alkylphenol, AP(1-3)EO and APEC and 0.1-4.1ngl(-1) for longer chain alkylphenol polyethoxylates. The method detection limit for particulate phase samples ranged from 6 to 60ngg(-1) for AP, AP(1-3)EO and APEC; with the longer chain APEO being from 0.5 to 20ngg(-1). Matrix effects were noted in complex matrix rich samples. There was a distinct change in the distribution of alkylphenol ethoxylates during biological treatment of the wastewater, with the major biotransformation products observed being carboxylated derivatives at concentrations of up to 1768ngl(-1). Shorter chain APEO were present in higher proportions in the suspended solids, due to their higher affinity to particulate matter compared to the long-chain oligomers.     

LC-MS/MS method validation for determination of selected neonicotinoids in groundwater for the purpose of a column experiment

The work was carried out to develop and validate a method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous detection and quantification of five neonicotinoid insecticides: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam in groundwater samples for the purpose of a further column experiment. This experiment will be used to analyze breakthrough curves of neonicotinoids under a saturated water flow to set transport parameters, where the reliability of the results of chemical analysis plays an important role. The validation was performed in a concentration range from 0.09?µg L^?1 to 100?µg L^?1 using an Infinity 1290 (Agilent, USA) chromatograph coupled with a QTrap 5500 mass spectrometer (Sciex, Canada). The calibration curves were obtained on the basis of the results of six standard solution analyses. Linearity was not lower than 0.998. The limit of detection was set at the lowest concentration which can be determined with an acceptable accuracy and precision. All pesticides had recoveries in the range 85–109% with relative standard deviation values less than 8.1%. The estimated measurement uncertainty did not exceed 30%, so the LC-MS/MS method fits for the intended purpose.     

Development of a comprehensive analytical method for the determination of chlorinated paraffins in spruce needles applied in passive air sampling

Conifer needles are used for the monitoring of atmospheric persistent organic pollutants. The objective of the present study was to develop a method for the detection of airborne chlorinated paraffins (CPs) using spruce needles as a passive sampler. The method is based on liquid extraction of the cuticular wax layer followed by chromatographic fractionation and detection of CPs using two different GCMS techniques. Total CP concentrations (sum of short (SCCP), medium (MCCP) and long chain CPs (LCCP)) were determined by EI-MS/MS. SCCP and MCCP levels as well as congener group patterns (n-alkane chain length, chlorine content) could be evaluated using ECNI-LRMS. For the first time, data on environmental airborne CPs on spruce needles taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) are presented providing evidence that spruce needles are a suitable passive sampling system for the monitoring of atmospheric CPs.     

污水中溶解游离氨基酸和结合氨基酸测定方法研究

采用邻苯二甲醛作为柱前衍生化试剂,结合反相高效液相色谱,对污水中溶解游离氨基酸（dissolvedfreeami．nOacid,DFAA）进行定性和定量分析,探讨了污水样品有无前处理对DFAA分析的影响,并采用气相酸水解方法对污水中总溶解氨基酸（dissolvedtotalaminoacid,DTAA）进行了分析。结果表明,污水经过pH调节和N,流清洗后,可以明显去除氨和挥发性胺的干扰,色谱峰更加清晰;前处理后的水样经RP—HPLC分析,能够快速检测出14种氨基酸,各氨基酸在一定线性范围内呈现良好的线性关系,相应的线性相关系数（R^2）均大于0．99,加标回收率为92％～102％。污水处理厂进水和出水中氨基酸主要以溶解结合氨基酸（dissolvedcombinedaminoacid,DCAA）为主,与进水相比,出水中DFAA含量减少了0．22μmol／L,DTAA由5．68μmol／L降至3．08μmol／L。     

Adaptation and validation of QuEChERS method for the analysis of trifluralin in wind-eroded soil

This study was carried out to develop and validate a reliable analytical procedure for trifluralin analysis in wind-eroded sediments. Soil sediments trapped in BEST sediment traps were subjected to QuEChERS extraction method, incorporating a simple simultaneous cleanup step, followed by trifluralin analysis with GC-ECD. Results revealed that QuEChERS method offered a potential alternative technique for pesticide extraction from soil samples. The validity of analytical method was performed by the method-performance criteria such as, recovery, LOD, LOQ repeatability, precision, and all found to be within the required limits. It was also observed in this study that herbicide concentrations in the wind-eroded sediment did not vary with the time and trap height. Trifluralin concentrations of surface soil after four erosion events were higher (626.05 μg/kg) than wind-eroded soil (450.08 μg/kg).     

Validation of a pressurized solvent extraction and GC-NCI-MS method for the low level determination of 40 polybrominated diphenyl ethers in mothers' milk

This study reports an efficient method for the determination of 40 PBDEs from mono- to hepta-brominated in human milk. Pressurized liquid extraction (PLE) was optimized to recover PBDEs in a quantitative way using 1g of freeze dried milk. Due to the great amount of coextracted compounds, the clean-up step was optimized using alumina SPE disposable cartridges of 2 and 5g. Whereas 2g alumina SPE failed in providing good extraction yields, all PBDEs were satisfactorily recovered using 5g alumina SPE cartridges. Detection was performed with gas chromatography coupled to mass spectrometry with negative chemical ionization and method detection limits ranged from 0.01 to 0.05mugkg(-1) wet weight (ww) with a good intra and inter-day variation (coefficient of variation lower than 13.4%). This method was validated by participating in an interlaboratory exercise from Quasimeme (United Kingdom), where a standard solution containing seven congeners and a certified unspiked mothers' milk were analyzed. In the standard mixture, levels between 96.915 and 570.172mugl(-1) were quantified, whereas in certified mothers' milk, BDEs 47, 99, 100 and 154 were detected at levels from 0.010 and 0.061mugkg(-1) ww, with an error <30%. The applicability of the method was tested experimentally in five mothers' milk samples, where only BDE 47 was detected at a maximum concentration of 10.45mugkg(-1) lipid weight (lw). PLE succeeded in extracting all PBDEs from the sample with good reproducibility although the clean-up step had to be severely performed to eliminate sample interferences such as milk lipids and proteins.     

A simple spectrophotometric method for the determination of cobalt in industrial, environmental, biological and soil samples using bis(salicylaldehyde)orthophenylenediamine

Bis(salicylaldehyde)orthophenylenediamine (BSOPD) has been proposed as new analytical reagent for the direct non-extractive spectrophotometric determination of cobalt. It reacts with cobalt in slightly acidic (0.0002-0.001 M H(2)SO(4)) 50% 1,4-dioxanic medium to form a red-orange chelate with a molar ratio 1:1. The reaction is instantaneous and the maximum absorbance was obtained at 458 nm and remains constant for over 24h. The average molar absorption coefficient and Sandell's sensitivity were found to be 1.109 x 10(4)l mol(-1)cm(-1) and 20 ng cm(-2) of Co(II), respectively. Linear calibration graph was obtained for 0.1-15 mg l(-1) of Co(II) with a correlation coefficient value of 0.995 for Co-BSOPD complex. Large excess of 44 cations, anions and complexing agents do not interfere in the determination. The method was successfully used in the determination of cobalt(II) from synthetic mixture and certified reference materials for the purpose of validating the method and the results of analyses were found to be excellent agreement with those of actual values. This developed method was also used for determination of cobalt in some environmental waters (potable and polluted), biological (blood and urine) and soil samples and solution containing both cobalt(II) and cobalt(III). The results of the proposed method for biological samples were comparable with AAS and were found to be in good agreement. The method has high precision and accuracy (s=+/-0.01 for 0.5 mg l(-1)).     

Development,validation of QuEChERS-based method for simultaneous determination of multiclass pesticide residue in milk,and evaluation of the matrix effect

Extraction and quantification of pesticide residue from the milk matrix at or below the established maximum residue limit (MRL) is a challenging task for both analytical chemists and the regulatory institutions to take corrective actions for the human health and safety. The main aim of the study is to develop a simple rapid and less expensive QuEChERS extraction and cleanup method for simultaneous analysis of 41 multiclass pesticide residue in milk by gas chromatography-electron capture detector (GC-ECD), followed by confirmation of the residues with gas chromatography-mass spectrometer (GC-MS). Effect of sorbent type, temperature, spiking concentration, matrix effect (ME), measurement uncertainty (MU), inter- and intra-assay repeatability, reproducibility of recovery, and trueness of the results were investigated to validate the effectiveness of the method. Limit of determination (LOD) and limit of quantitation (LOQ) for all the analytes ranged within 0.001–0.02 and 0.002–0.05 µg mL^?1, respectively. The % recovery of all the pesticides ranged between 91.38 and 117.56% with relative standard deviation (RSD) below 2.79%. The MU for all the analytes was ≤29% of respective LOQs, and except for few pesticides, the ME was largely negative. The method fulfilled all the SANTE guidelines and thus can be extended for routine analysis of multiclass pesticide residue in milk.     

A multi-residue method for the analysis of organophosphorus residues in cooked and polished rice using accelerated solvent extraction and dispersive-solid phase extraction (D-SPE) technique and uncertainty measurement

Quick, simple and efficient multi-residue analytical methods were developed and validated for the determination of organophosphorous insecticides from polished and cooked rice. Polished rice was extracted using a simple, automated technique namely accelerated solvent extraction (ASE) using dichloromethane as the extraction solvent. Cooked rice was extracted with acetone and cleaned up using dispersive-solid phase extraction (D-SPE) technique. The single step extraction method adopted for polished rice using accelerated solvent extractor provided satisfactory recovery for eight organophosphorus pesticides (OPPs) which ranged from 85.5–116.7%; 90.0–110.3% and 93.5–118.8% at 1, 5 and 10 limit of quantification (LOQ) levels, respectively. The recovery of cooked rice was in the range of 74–124%; from 75–100% and from 73–87% for 1, 5 and 10 level of fortification, respectively. The total uncertainty was evaluated, taking four main independent sources viz., weighing, purity of the standard, GC calibration curve and repeatability under consideration. The expanded uncertainty was found to be in the range of 5–20%.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

填料添加方式对MBR运行稳定性及膜污染特征的影响

为提高MBR的去除性能并延缓膜污染,采用复合型悬浮生物膜强化膜生物反应器(hybrid suspended biofilm enhanced membrane bioreactor, HSBE-MBR)处理生物制药废水,考察了填料添加方式对HSBE-MBR中典型污染物的去除特征、运行稳定性及膜污染特征的影响,并分析了膜污染机理。结果表明：缺氧区和好氧区添加填料时(工况1),TCOD、${{\rm{NH}}_4^ + }$-N和TN平均去除率分别为91.61%、97.08%和79.40%;缺氧区、好氧区及膜区添加填料时(工况2),TCOD、${{\rm{NH}}_4^ + }$-N和TN平均去除率分别为91.09%、97.24%和83.66%。在上述2种工况下,HSBE-MBR对TCOD、${{\rm{NH}}_4^ +} $-N和TN均具有良好的去除性能,且运行稳定性良好,工况2中TN去除率提高了4.26%。在工况1下,膜运行时间为0.02~8.17 d;在工况2下,膜运行时间为0.26~138 d。2种工况下的膜污染机理均以滤饼层污染为主,滤饼层阻力占比分别为94.7%和90.1%;膜区添加填料能够减缓膜表面滤饼层的形成,使滤饼层阻力降低8.07%;同时,混合液中溶解性微生物代谢产物(soluble microbial products, SMP)、松散结合EPS (loosely bound-EPS, LB-EPS)和紧密结合EPS (tightly bound-EPS, TB-EPS)浓度分别由(63.70±12.95)、(13.97±2.03)和(153.82±12.64) mg·g⁻¹(工况1)降低为(31.77±3.17)、(9.11±0.40)和(78.12±18.92) mg·g⁻¹(工况2)。粒度分布测定结果表明,膜区添加填料后,污泥平均粒径从31.35 μm(工况1)增大至34.71 μm(工况2)。根据污染物去除特征及膜污染特征,确定最优添加方式为在缺氧区、好氧区和膜区添加填料。上述研究结果可为提高MBR运行稳定性并改善膜污染提供参考。     

Polycyclic aromatic hydrocarbons in crude oil-contaminated soil: A two-step method for the isolation and characterization of PAHs

A two-step analytical method is developed for the isolation and characterization of polycyclic aromatic hydrocarbons (PAHs) in crude oil contaminated soil. In the first step, those crude oil components were isolated which are easily mobilized with water from the contaminated soil (determination of groundwater pollution potential). In the second step, the fraction containing the remaining crude oil compounds was extracted using toluene. After the cleanup of the fractions, both fractions were analyzed using high-performance liquid chromatography (HPLC). The HPLC of the toluene extracted fraction shows that along with the sixteen priority pollutants from the US-EPA list, many other polycyclic aromatic hydrocarbons (PAHs) are present as well. It is evident from the chromatograms that a significant amount of PAHs are present as is also the case in the fractions eluted by water. The described method allows the determination of total organic pollutants from crude oil, some of them being potential groundwater contaminants. The major part of the total pollutants could not be mobilized by water and therefore remains in the soil, which was extracted in the second step.     

Validation of QuEChERS method for the determination of 36 pesticide residues in fruits and vegetables from Ghana,using gas chromatography with electron capture and pulsed flame photometric detectors

In this study, “Quick, Easy, Cheap, Effective, Rugged and Safe” ‘QuEChERS’ method was modified for the determination of 36 pesticides fortified at (0.01–1.0) mg kg^?1 in three vegetables and a fruit (lettuce, carrot, tomatoes and pineapples respectively) from Ghana. The method involved extraction with acetonitrile, phase separation with primary secondary amine and magnesium sulfate; the final injection solution was reconstituted in ethyl acetate. Organochlorine and synthetic pyrethroids residues were detected with electron capture detector whereas organophosphorus, pulsed flame photometric detector was used. The recoveries at different concentration levels (0.01, 0.1 and 1.0 mg kg^?1) were in the range of 83% and 93% with relative standard deviation ranging from 2% to 10% (n = 5) and the coefficient of determination (R²) was greater than 0.99 for all the 36 pesticides. The method was successfully tested on 120 real samples from Accra markets and this proved to be useful for monitoring purposes particularly in laboratories that have no gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry.