Flow injection electrochemical hydride generation inductively coupled plasma time-of-flight mass spectrometry for the simultaneous determination of hydride forming elements and its application to the analysis of fresh water samples

A flow injection (FI) method was developed using electrochemical hydride generation (EcHG) as a sample introduction system, coupled to an inductively coupled plasma time-of-flight mass spectrometer (ICP-TOFMS) for rapid and simultaneous determination of six elements forming hydrides (As, Bi, Ge, Hg, Sb and Se). A novel low volume electrolysis cell, especially suited for FI experiments was designed and the conditions for simultaneous electrochemical hydride generation (EcHG; electrolyte concentrations and flow rates, electrolysis voltage and current) as well as the ICP-TOFMS operational parameters (carrier gas flow rate, modulation pulse width (MPW)) for the simultaneous determination of 12 isotopes were optimized. The compromise operation parameters of the electrolysis were found to be 1.4 and 3 ml min⁻¹ for the anolyte and catholyte flow rates, respectively, using 2 M sulphuric acid. An optimum electrolysis current of 0.7 A (16 V) and an argon carrier gas flow rate of 0.91 l min⁻¹ were chosen. A modulation pulse width of 5 μs, which influences the sensitivity through the amount of ions being collected by the MS per single analytical cycle, provided optimum results for the detection of transient signals. The achieved detection limits were compared with those obtained by using FI in combination with conventional nebulization (FI-ICP-TOFMS); values for chemical hydride generation (FI-CHG-ICP-TOFMS) were taken from the literature. By using a 200 μl sample loop absolute detection limits (3σ) in the range of 10-160 pg for As, Bi, Ge, Hg, Sb and 1.1 ng for Se and a precision of 4-8% for seven replicate injections of 20-100 ng ml⁻¹ multielemental sample solutions were achieved. The analysis of a standard reference material (SRM) 1643d (NIST, “Trace Elements in Water”) showed good agreement with the certified values for As and Sb. Se showed a drastic difference, which is probably due to the presence of hydride-inactive Se species in the sample. Recoveries better than 93% for Ge and Hg and 83.9% for Se were achieved on a spiked SRM sample. The developed method was successfully applied to the simultaneous multielemental determination of hydride forming elements in spring water samples originating from two different regions in Hungary.     

Extraction and preconcentration of polychlorinated dibenzo-p-dioxins using the cloud-point methodology: Application to their determination in water samples by high-performance liquid chromatography

A new analytical method based on the cloud-point extraction (CPE) methodology combined with high-performance liquid chromatography is used in this study for the extraction and quantification of polychlorinated dibenzo-p-dioxins. These compounds are extracted by using the non-ionic surfactant polyoxyethylene 10 lauryl ether (POLE) from different aqueous systems: fresh, brackish and sea waters. After the cloud-point extraction, which also allowed a preconcentration of the PCDDs being studied, the samples were analysed using a HPLC–UV system under the optimum chromatographic conditions. The proposed method showed very satisfactory recovery percentages for the PCDDs under study and standard deviation values lower than 2%.

The results obtained were finally compared with those found using the traditional liquid–liquid extraction method.     

Evaluation of Cu–Ethylenediamine Metal Ion Buffers as Calibrants for Ion‐Selective Electrode Measurement of Copper in Fresh Water Systems

An investigation was made into the accuracy of cupric ion selective electrode (ISE) measurement of Cu in solutions approximating acidic freshwaters with Cu‐ethylenediamine buffers used as the calibrants. This method overestimates the free Cu compared with calibration using Cu(NO₃)₂ standards, the standard addition method, and speciation modelling calculations. Statistical tests showed a small, but significant, difference between the intercepts of the linear Nernstian regressions of the calibration plots of Cu‐en buffer standardisation and direct calibration with Cu(NO₃)₂ standards in matrix that matches the samples. The difference in the intercepts, which corresponds with E_o values of the electrode, is not well understood, but is possibly caused by potentially interfering cations such as Fe²⁺. The results of this study showed that down to 10^?8 M Cu²⁺, where a linear Nernstian response is possible, the Cu ISE is probably better calibrated using Cu standards prepared in the same matrix as the sample solutions to avoid potential matrix effects.     

Feasibility of using direct determination of cadmium and lead in fresh meat by electrothermal atomic absorption spectrometry for screening purposes

A method for the direct determination of cadmium and lead in fresh meat for screening purposes is proposed using electrothermal atomic absorption spectrometry. The fresh meat samples were homogenized, weighed directly onto solid sampling platforms and introduced into a transversely heated solid sampling graphite tube. The main challenges associated with this procedure, such as weighing errors and optimization of the temperature program were investigated in detail. Calibration was performed against aqueous standards and two modifiers were investigated: 0.05% Pd + 0.03% Mg + 0.05% Triton X-100 and 0.01% Pd + 10% NH₄NO₃ + 0.05% Triton X-100. The former one is recommended due to the higher pyrolysis temperature obtained for cadmium and the better limits of detection of 1.9 μg kg^− 1 for lead and 0.13 μg kg^− 1 for cadmium, based on 10 mg of sample mass. The results obtained for cadmium and lead in two certified reference materials were statistically not different from the certified values on a 95% confidence level, indicating that calibration against aqueous standards is suitable for this application. In order to evaluate weighing errors the fresh samples were dried (at 60 °C) to constant weight; the results obtained with fresh and dried samples were in agreement, taking the loss of weight into consideration for the latter ones. The average relative standard deviation of 14% is in concordance with the results of others using fresh meat. Comparison with the digestion method adopted by the Brazilian Ministry of Agriculture shows no significant differences between the results at the 95% confidence level. This study shows that direct analysis of fresh meet can be applied as a rapid routine screening procedure for residue control in products of animal origin, helping the implementation and maintenance of sanitary control.     

A stationary flow of fresh and salt groundwater in a coastal aquifer with nonlinear darcy' law

We study an homogeneous aquifer where fresh and salt water are separated by an interface T. The flow is governed by a nonlinear Darcy' law. Using suitable approximated problems, we prove existence of a solution and establish some properties.     

Extraction and preconcentration of polychlorinated dibenzo-p-dioxins using the cloud-point methodology: Application to their determination in water samples by high-performance liquid chromatography

A new analytical method based on the cloud-point extraction (CPE) methodology combined with high-performance liquid chromatography is used in this study for the extraction and quantification of polychlorinated dibenzo-p-dioxins. These compounds are extracted by using the non-ionic surfactant polyoxyethylene 10 lauryl ether (POLE) from different aqueous systems: fresh, brackish and sea waters. After the cloud-point extraction, which also allowed a preconcentration of the PCDDs being studied, the samples were analysed using a HPLC-UV system under the optimum chromatographic conditions. The proposed method showed very satisfactory recovery percentages for the PCDDs under study and standard deviation values lower than 2%.The results obtained were finally compared with those found using the traditional liquid-liquid extraction method.     

Determination of labile Cu(2+) in fresh waters by chemiluminescence: interference by iron and other cations

Analysis of labile Cu²⁺ in fresh waters using the Cu²⁺-catalysed oxidation of 1,10-phenanthroline by superoxide anion radical has been investigated. It was found that certain metal ions, notably Fe³⁺, Fe²⁺ and Pb²⁺ enhance the chemiluminescence (CL) intensity of this reaction by up to an order of magnitude when present in the μM concentration range. This enhancement is considered to arise through coordination of the metal ion to 1,10-phenanthroline, which prevents free rotation of the benzene rings in the excited state intermediate thought to be responsible for light emission. This introduces a potential interference when analyzing fresh waters, which usually contain Fe³⁺ concentrations of this magnitude. However, the enhancement effect saturates at about 4 μM Fe³⁺, so that reliable results can be obtained if the water sample is supplemented with Fe³⁺ to reach this level. Application of the enhanced technique to a river water, and a reservoir to which CuSO₄ had been added to control algal growth, are described. In both cases, only a small fraction of total dissolved Cu²⁺ is labile with respect to the chemiluminesence method.     

An optimal method for the design of a robotic tracked vehicle to operate over fresh concrete under steering motion

The objective of this paper is to find an optimal method for the design of tracked base travel systems for special purpose vehicles and robotic machines that may be required to steer over a light bonded terrain composed of fresh concrete. For the case of a vehicle traveling on a weak fresh concrete during construction, the paper presents detailed comparative studies of the steering performances of a small model tracked test vehicle with alternative amount of steering ratio for various concrete slump values. For these studies a detailed simulation analytical method has been developed. From this work it is proven, in comparison to experiment, that the simulation analytical method is useful for predicting various steering performances of a test tracked vehicle running upon soft fresh concrete of various consistencies.     

基于生物光子的小麦新陈度快速无损检测

小麦籽粒作为一种活的生命体,在正常储藏过程中,会不断消耗自身的营养物质来维持其生命活动。随着储藏时间的推移,小麦籽粒内部各种酶的活性减弱或丧失,自身呼吸强度逐步降低,原生质胶体结构松弛,籽粒的物理和化学状态发生改变,进而导致其后续食用和加工品质变劣。因此,对小麦新陈度的准确判定,是保证储藏小麦数量和质量的前提,对指导我国粮食储存具有重要的经济和社会意义。目前常用的小麦新陈度鉴定方法主要包括感官判定法和各种生化类方法;前者主要依赖操作者个人的主观经验,容易受到外界因素的干扰,可重复性较差,判定结果因人而异,只适合作小麦新陈度鉴定的辅助方法。后者虽然判定精度较高,但整个检测过程耗时过长,一般需要对待测样品进行复杂预处理,且检测过程中用到的多种化学试剂会对环境造成一定的污染。因此,迫切需要研究出一套快速、准确、绿色的小麦新陈度鉴定方法。利用生物光子仪器分别测试了5种不同储藏年份小麦样品的生物光子信号,并结合改进多尺度排列熵算法对2015年-2018年四种小麦样品的光子信号进行特征分析,最后借助反向传播神经网络对这4种不同储藏年份的小麦进行分类验证。实验结果表明,不同储藏年份小麦的自发光子量存在一定的差异,其中2019年小麦样品产生的光子数量明显高于其他年份的小麦样品,其余年份小麦样品光子数量的排列熵值随着储藏年限的增加而增大。对比实验结果显示,改进多尺度排列熵算法在很大程度上解决了由多尺度排列熵算法引起的信号抖动和突变问题,可以作为一种明显的特征来标识小麦的新陈度。最后借助BP神经网络进行分类测试,输出结果证明新构建的分类模型的准确度可以达到95%,能够实现对不同年份小麦新陈度的准确鉴别。     

Effects of ultrasound-assisted low-concentration chlorine washing on ready-to-eat winter jujube (Zizyphus jujuba Mill. cv. Dongzao): Cross-contamination prevention,decontamination efficacy,and fruit quality

Wash water is circulated for use in the minimal processing industry, and inefficient disinfection methods can lead to pathogen cross-contamination. Moreover, few disinfection strategies are available for ready-to-eat fruits that do not need to be cut. In this study, the use of chlorine and ultrasound, two low-cost disinfection methods, were evaluated to disinfect winter jujube, a delicious, nutritious, and widely sold fruit in China. Ultrasound treatment (28 kHz) alone could not decrease the cross-contamination incidence of Escherichia coli O157:H7, non-O157 E. coli, and Salmonella Typhimurium, and free chlorine treatment at 10 ppm decreased the incidence from 55.00% to 5.00% for E. coli O157:H7, 65.00% to 6.67% for non-157 E. coli, and 70.00% to 6.67% for S. Typhimurium. The cross-contamination incidence was completely reduced (pathogens were not detected in sample) when the treatments were combined. The counts of aerobic mesophiles, aerobic psychrophiles, molds, yeasts, and three pathogens in the group subjected to combination treatment (28 kHz ultrasound + 10 ppm free chlorine) were significantly lower than those in the control, chlorine-treated, and ultrasound-treated groups during storage (0–7 d at 4 °C). Analysis of weight loss, sensory quality (crispness, color, and flavor), instrument color (a*/b*), soluble matter contents (total soluble solids, reducing sugar, total soluble sugar, and titratable acid), and nutritional properties (ascorbic acid and polyphenolic contents) indicated that treatment with ultrasound, chlorine, and their combination did not lead to additional quality loss compared with properties of the control. Additionally, the activities of phenylalanine ammonia-lyase and polyphenol oxidase were not significantly increased in the treatment group, consistent with the quality analysis results. These findings provide insights into disinfection of uncut ready-to-eat fruits using a minimum dose of disinfectant for cross-contamination prevention under ultrasonication. The use of ultrasound alone to decontaminate fresh produce is accompanied by a high risk of pathogen contamination, and the use of sanitizers to decrease cross-contamination incidence is recommended.