冷冻干燥技术在环境水样有机新污染物前处理中的应用进展

有机新污染物是一类在先进分析技术帮助下新鉴定的、现有法规未管制的、人为源的有机污染物。有机新污染物主要包括药品与个人护理、农药、全氟化合物、内分泌干扰物等,其会产生内分泌干扰效应、诱发抗性基因传播,还对人类和野生生物的生存与发展构成潜在威胁,因此检测环境样品中的有机新污染物浓度对生态环境和人体健康具有重大意义。由于环境样品中的有机新污染物浓度较低,为了达到检测仪器的检测要求,通常需要对环境样品进行前处理,包括样品的净化和浓缩。冷冻干燥技术是一种在真空干燥条件下通过升华方式去除水分的前处理技术,主要包括样品冷冻、初级干燥和再干燥3个阶段,常用于食品和药品行业。在药品行业中,冷冻干燥技术能维持药品的生物活性和化学活性,保持药品的物理化学特性。近年来,冷冻干燥技术逐步用于环境水样中有机新污染物的前处理。其主要的操作步骤包括水样预处理、冷冻干燥、洗脱、吹干、过滤、定容和上机检测。冷冻干燥技术具有操作简单、低成本、样品处理体积少、样品易保存和处理过程中样品损失少等优点,具有广泛应用于环境样品中有机新污染物监测的潜力。该文综述了环境样品中有机新污染物常见的种类,并重点介绍冷冻干燥技术的原理及其在环境样品前处理过程中的应用,提出了冷冻干燥技术在环境分析中的应用前景,为环境样品中有机新污染物的监测提供了参考。     

Retrospective LC-QTOF-MS analysis searching for pharmaceutical metabolites in urban wastewater

The presence of pharmaceuticals in the environment is a matter of major concern because of their wide consumption and their potential negative effect on the water quality and living organisms. After human and/or veterinary consumption, pharmaceuticals can be excreted in unchanged form as the parent compound and/or as free or conjugated metabolites. These compounds seem not to be completely removed during wastewater treatments and might finally arrive to surface and ground waters. Consequently, both parent pharmaceuticals and metabolites are target analytes to be considered in analytical methodologies. The satisfactory sensitivity in full-acquisition mode, high-resolution, exact mass measurements and MS/MS capabilities of hybrid quadrupole time-of-flight (QTOF) mass spectrometry make of this technique a powerful analytical tool for the identification of organic contaminants. In this study, the use of QTOF-MS with the aid of specialised processing-data application managers has allowed the retrospective analysis of pharmaceuticals metabolites in urban wastewater without the need for additional injection of sample extracts. Around 160 metabolites have been investigated in wastewater samples previously analysed only for parent compounds using LC-QTOF under MS(E) mode (simultaneous recording of two acquisition functions, at low and high collision energy). The retrospective analysis was applied to search for pharmaceutical metabolites in parent-positive effluent wastewaters from the Spanish Mediterranean region. Five metabolites, such as clopidogrel carboxylic acid or N-desmethyl clarithromycin, were identified in the samples.     

Application of strategically designed sample composition to the rapid analytical screening of milk samples for polychlorinated biphenyls

Strategically designed sample composition (SSC) is a new technique that decreases the number of analytical determinations needed in routine screening to as few as the number of original sample specimens while providing information that is specific to them. Although this new technique has been applied to environmental studies, this paper describes its first application to food safety studies. Contamination of milk samples with polychlorinated biphenyls (PCBs) was chosen as a case study to show the usefulness and potential of the SSC technique with a fast analytical procedure that involves saponification of the samples and solid-phase microextraction of the PCBs. A total of 20 sample specimens can be analyzed in 11 determinations with excellent predictions of the positive samples and the concentration levels of the contaminants. The robustness of the strategy was investigated and demonstrated.     

Advanced mass spectrometric methods applied to the study of fate and removal of pharmaceuticals in wastewater treatment

This overview is of analytical methodologies based on gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry, applied in environmental monitoring of pharmaceutical residues and their known degradation products. We also consider the ability of time-of-flight (TOF) and quadrupole-TOF instruments to provide sufficiently accurate-mass measurements and full-scan spectra for unequivocal confirmation of target compounds and investigation of their degradation products, which are either known or unknown.

We focus attention on the fate and the behavior of pharmaceutical residues during conventional and advanced wastewater treatments. Wastewater-treatment plants are designed to remove conventional pollutants (e.g., suspended solids and biodegradable organic compounds), but not low concentrations of synthetic pollutants (e.g., pharmaceutically active compounds).

Membrane bioreactor systems represent a new generation of processes that have proved to outperform conventional activated sludge treatment in terms of sludge production and effluent quality. In the past few years, there has been much attention paid to their capability for removing trace organic contaminants from sewage. This review highlights their improved performance in removing pharmaceutical residues from wastewater compared to conventional treatment.     

Carbon-based materials applied to the development of chemically modified sensors: Trends to environmental applications**

Nowadays, carbon-based materials applied to the development of chemically modified sensors have been highlighted once they can generate methods with high sensitivity, stability, conductivity, accuracy and low cost. Hence, these sensors have been used in environmental monitoring in aneco-friendlyy, sensitive, fast, efficient, inexpensive and robust way. In this review, firstly we described about carbon-based materials and their derivatives, followed by the chemically modified carbon-based sensors manufacturing overview and their applications in environmental analytical chemistry related to inorganic and organic compounds determinations. Future perspectives on trends of the carbon-based materials applications in the sensor modifications are also described.     

HF-LPME as a green alternative for the preconcentration of nickel in natural waters

In the last years, some analytical methodologies have been identified as a source of pollution, receiving increasing attention to decrease their impact on the environment. In this sense, the so-called solvent-less methodologies appear as a green alternative to reduce the volume of solvents used in many sample treatment procedures and, consequently, the volume of toxic wastes produced. Among these techniques, analytical methodologies based on liquid-phase microextraction are being continuously developed, although most applications are focused on organic compounds. In this work, a three-phase hollow-fibre liquid-phase microextraction (HF-LPME) system has been developed for the preconcentration of nickel in natural waters, prior to the analysis by atomic absorption spectrometry. Under optimum conditions, the new system allowed an enrichment factor of 29.80 to be obtained after 60 min of experiment, and it was successfully applied to the determination of nickel in both saline and non-saline water samples, at ppb and ppt levels. The results were compared with those obtained using a well-established methodology based on liquid solvent extraction showing no significant differences (α = 0.05) between both values. In addition, the new HF-LPME presents the advantages of a green analytical technique, as its greenness profile shows, with the additional reduction of sample manipulation and time cost.     

纳米铁及铁基纳米复合粒子在环境修复中的研究进展

由于纳米零价铁及铁基纳米复合粒子对大多数常见的环境污染物,如重金属离子、卤代有机物等均具有转化和降低毒性的作用,因此,在环境修复领域,它们已成为研究的热点之一。 纳米零价铁及铁基纳米复合粒子的比表面积大,反应活性高,应用灵活,为大多数具有挑战性的环境污染问题提供了一个有效的解决方法。 本文主要阐述了近些年来纳米零价铁及铁基纳米复合粒子在环境修复中的具体应用,同时也评估了其对环境微生物的潜在毒理效应,为以后进一步研究工作奠定一定的理论基础。     

Recent trends in the liquid chromatography–mass spectrometry analysis of organic contaminants in environmental samples

An overview of liquid chromatography–mass spectrometry methods used for the determination of trace organic contaminants in environmental samples is presented. Among the organic contaminants the focus is given on five groups of emerging contaminants that raised most concern as environmental contaminants and therefore attracted attention of a research community: pharmaceuticals, drugs of abuse, polar pesticides, perfluorinated compounds and nanoparticles. Various aspects of current LC–MS methodology, using tandem and hybrid MS instruments, including sample preparation, are discussed.     

Analytical methodologies for the determination of nitroimidazole residues in biological and environmental liquid samples: A review

Nitroimidazoles (NDZs) are antiprotozoal drugs that are typically used in veterinary and human medicine. NDZs and their metabolites are believed to possess genotoxic, carcinogenic and mutagenic properties, and this is (one reason) why their use has been banned within the European Union. Hence, the determination of trace residues of these substances in edible animal tissues has been of growing concern over the past few years. Even, though there has been a need to develop sensitive and reliable analytical methods to study the residues of these compounds in different matrices, available methodologies in environmental samples are rather limited. These and other pharmaceutical compounds have become one of the most important new classes of environmental pollutants that have been detected in wastewater-treatment-plant (WWTP) effluents, receiving waters, drinking water and groundwater. A compilation of the most representative analytical methodologies for the determination of NDZ residues during the last decade is presented in this paper. Its scope is the two main areas which require their determination, namely biological and environmental matrices. A detailed explanation of both areas, including sample treatment and detection systems, and future trends is presented, focusing on the difficulties of confirming analytes at low concentration levels.     

Perspectives of analysis of carcinogenic and mutagenic metals in biological samples

There is a continuing need to assess the status of exposure to humans of the carcinogenic and/or mutagenic metals in both biological and environmental samples to better ensure that current or past exposures do not entail unacceptable health risks or to detect potentially excessive exposure before the appearance of adverse health effects. In order to more readily evaluate both the extent of exposure and trends of human exposure as well as the bioavailability, bioaccumulation and transport of these elements and their compounds, sensitive analytical procedures are required for their determination of the various oxidative states (as well as their organic derivatives) in complex matrices such as those found in both environmental and biological samples. The major objective of this overview is to highlight the more recent trends and state-of-the-art methodologies for the determination and speciation of arsenic, selenium, cadmium, chromium and nickel in human and animal tissues while concomitantly noting germane aspects of their bioavailability and interactions. Aspects of biological monitoring of the above elements will be stressed due to their potential utility in augmenting diverse epidemiologic and occupational health studies.     

Application of ultrasound-assisted extraction to the determination of contaminants in food and soil samples

The application of ultrasound-assisted extraction (UAE) to the sample preparation of environmental and food samples has increased in the last years. This technique has been used in the development of methods for the analysis of numerous contaminants, including organic compounds (pesticides, pharmaceuticals, polycyclic aromatic hydrocarbons, polyhalogenated flame retardants, etc.) and heavy metals. The aim of this work is to review the application of this extraction procedure to the analysis of contaminants in food and soil and the comparison of its use with other well-established extraction procedures. The advantages and disadvantages of this technique together with the possibility of coupling UAE with other analytical techniques will be also discussed.     

Contributions of Flow Analysis for Quality Control of Automotive Fuels: A Review

Automotive fuels require strict quality control to assure best energy use with minimal environmental pollution. Fuels can be modified before consumption by inadequate transport, storage, and handling, as well as illegal adulteration. Continuous monitoring is of paramount importance to reduce such irregularities, thus requiring reliable analytical methods, which should be simple, fast, and minimize both reagent consumption and waste generation. The potential for in-situ monitoring is also highly desirable. Flow analysis plays an important role in this sense, by means of automated sample processing in closed systems, under highly reproducible conditions. In spite of this potential, application for routine fuel analysis is yet limited and wide dissemination is desirable. This review focuses on analytical approaches for in-line sample pretreatment and determination of organic and inorganic contaminants in automotive fuels by flow analysis. Applications in gasoline, diesel oil, biodiesel, and ethanol fuels are critically discussed.     

Molecularly imprinted polymers—potential and challenges in analytical chemistry

Among the variety of biomimetic recognition schemes utilizing supramolecular approaches molecularly imprinted polymers (MIPs) have proven their potential as synthetic receptors in numerous applications ranging from liquid chromatography to assays and sensor technology. Their inherent advantages compared to biochemical/biological recognition systems include robustness, storage endurance and lower costs. However, until recently only few contributions throughout the relevant literature describe quantitative analytical applications of MIPs for practically relevant analyte molecules and real-world samples. Increased motivation to thoroughly evaluate the true potential of MIP technology is clearly attributed to the demands of modern analytical chemistry, which include enhanced sensitivity, selectivity and applicability of molecular recognition building blocks at decreasing costs. In particular, the areas of environmental monitoring, food and beverage analysis and industrial process surveillance require analytical tools capable of discriminating chemicals with high molecular specificity considering increasing numbers of complex environmental contaminants, pollution of raw products and rigorous quality control requested by legislation and consumer protection. Furthermore, efficient product improvement and development of new products requires precise qualitative and quantitative analytical methods. Finally, environmental, food and process safety control issues favor the application of on-line in situ analytical methods with high molecular selectivity. While biorecognition schemes frequently suffer from degrading bioactivity and long-term stability when applied in real-world sample environments, MIPs serving as synthetic antibodies have successfully been applied as stationary phase separation matrix (e.g. HPLC and SPE), recognition component in bioassays (e.g. ELISA) or biomimetic recognition layer in chemical sensor systems. Examples such as MIP-based selective analysis of flavones/flavonoids in wine, the determination of mycotoxins in beverages and analysis of organic contaminants in environment samples will elucidate the perspectives of this technology and will be contrasted with the challenges of rational MIP design providing control on binding site density, receptor capacity and selectivity.     

Congener-specific determination of dioxins and related compounds by gas chromatography coupled to LRMS,HRMS, MS/MS and TOFMS

Their characteristics as persistent organic pollutant and their toxicity (2,3,7,8-TCDD is named as a known human carcinogen) make the dioxins and related compounds a focus of interest in environmental analytical chemistry. In view of the widespread distribution of dioxins in the environment, these compounds must be monitored in several matrices, such as air, effluents, soil, sludge and biological samples. The analytical methodologies are especially difficult owing to the complexity of the mixtures of congeners (210 PCDD/Fs and 209 PCBs) and to the low detection limits required (ppb to ppq). Moreover, time-consuming sample preparation steps are needed owing to the presence of a large number of interfering compounds. The different toxicity of each congener requires the development of congener specific methods. This review of trace dioxin determination by mass spectrometry (MS) includes sample preparation and chromatographic separation. In this Special Feature, the use of different MS techniques such as low-resolution MS (LRMS) and high-resolution MS (HRMS) is discussed in terms of selectivity and sensitivity. The performances of other MS techniques, such as tandem MS (MS/MS) and time-of-flight MS (ToFMS), are compared. Quantification techniques, especially the isotopic dilution method, are also discussed. Conclusions and future perspectives are outlined.     

Analysis of industrial contaminants in indoor air. Part 2. Emergent contaminants and pesticides

This article reviews recent literature on the analysis of several contaminants related to the industrial development in indoor air in the framework of the REACH project. In this second part, the attention is focused on emergent contaminants and biocides. Among these chemicals, phthalates, polybrominated and phosphate flame retardants, fragrances, pesticides, as well as other emerging pollutants, are increasing their environmental and health concern and are extensively found in indoor air. Some of them are suspected to behave as priority organic pollutants (POPs) and/or endocrine disrupting compounds (EDC), and can be found both in air and associated to the suspended particulate matter (PM) and settled dust. Main literature considered for this review is from the last ten years, reporting analytical developments and applications regarding the considered contaminants in the indoor environment. Sample collection and pretreatment, analyte extraction or desorption, clean-up procedures, determination techniques, and performance results are summarized and discussed.     

Pressurized hot water extraction (PHWE)

Pressurized hot water extraction (PHWE) has become a popular green extraction method for different classes of compounds present in numerous kinds of matrices such as environmental, food and botanical samples. PHWE is also used in sample preparation to extract organic contaminants from foodstuff for food safety analysis and soils/sediments for environmental monitoring purposes. The main parameters which influence its extraction efficiency are namely the temperature, extraction time, flow rates and addition of modifiers/additives. Among these different parameters studied, temperature is described as the most important one. It is reported that the extraction of certain compounds is rather dependent on pressurized water with different applied temperature. Thus, the stability and reduced solubilities of certain compounds at elevated temperatures are highlighted in this review. With some modifications, a scaled-up PHWE could extract a higher amount of desirable compounds from solid and powdered samples such as plant and food materials. The PHWE extracts from plants are rich in chemical compounds or metabolites which can be a potential lead for drug discovery or development of disease-resistant food crops.     

Methods for determination of polybrominated diphenyl ethers in environmental samples - review

Polybrominated diphenyl ethers (PBDEs) are a group of persistent organic pollutants. They are used as flame retardants in plastics, paints, varnishes and textile materials. PBDEs pose great risk to the environment because of their high persistence and ability to get into the environment easily due to the lack of chemical bonds with the matrix of materials, to which they are added. Global research studies confirmed the occurrence of those compounds in the majority of elements of water and land environment. Analysis of PBDEs in environmental samples is one of the specific analytical methods of criteria that comprise low detection limits and high selectivity. The analysis of PBDEs in environmental samples is one of the specific analytical methods, in which the main criteria are low detection limits and high selectivity. In this article, a literature review of methods for environmental sample preparation and analysis of the PBDE content was presented. The article discusses the potential of modern extraction techniques such as: solid-phase microextraction, single-drop microextraction, dispersive liquid-liquid microextraction, microwave-assisted extraction, cloud point extraction, hollow fibre-liquid phase microextraction and others for the separation of PBDEs from environmental samples with a complex matrix. Among the methods for qualitative and quantitative determination of PBDEs, a particular focus was put on gas chromatography/mass spectrometry with various injection techniques and different types of sample ionisation.     

Recent developments in headspace microextraction techniques for the analysis of environmental contaminants in different matrices

Headspace microextraction procedures such as solid-phase microextraction (SPME) and single drop microextraction (SDME) or liquid-phase microextraction (LPME) are increasingly used for the extraction of environmental organic pollutants from a variety of aqueous, viscous, semisolid and solid environmental and biological matrices. In this article, recent analytical applications of these methodologies when used as an isolation and trace enrichment step prior to the analysis of organic pollutants (pesticides, polycyclic aromatic hydrocarbons, polychlorinated compounds, organotin compounds, phenolic derivatives, aromatic amines, phthalates, etc.) by gas and liquid chromatography are reviewed. The applicability and inherent limitations of headspace microextraction are also discussed. The future direction of research in this field and general trends toward commercial applications are considered.     

Microextraction methods for the determination of phthalate esters in liquid samples: A review

1,2‐Benzenedicarboxylic acid esters, commonly referred to as phthalate esters, form a group of compounds that are mainly used as plasticizers in polymers. Because phthalate esters are not chemically bound to the plastics, they can be released easily from products and migrate into the food or water that comes into direct contact. Due to their widespread use, they are considered as ubiquitous environmental pollutants. Phthalate esters are regarded as endocrine disrupting compounds by means of their carcinogenic effect. Phthalate esters can be analyzed by gas chromatography or high‐performance liquid chromatography, however, their sensitivity and selectivity limit their direct use for determination of phthalates at very low level of concentrations exist in environmental samples with complex matrices. Therefore a sample pretreatment prior to their analysis is necessary. In this review, the historical development and overview of sample preparation methodologies have briefly been discussed and a comprehensive application of these methods in combination with different analytical techniques for preconcentration and determination of phthalate esters in various matrices have been summarized. Finally, a critical comparison of the different approaches in terms of enrichment factors achieved, extraction efficiency, precision, selectivity and simplicity of operation is provided.