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.     

超临界流体萃取用于水中有机污染物的富集

研究了用固相吸附与超临界流体萃取相结合富集水中有机污染物的方法。考察了萃取压力,温度,改性剂种类及其浓度,收集溶剂种类,流体流速,平衡时间,流体用量８种因素对样品萃取脱附效果的影响及吸附剂的吸附线性范围,并对标准水样的富集回收率进行了测定。     

Certified reference materials for inorganic and organic contaminants in environmental matrices

Chemical measurements often constitute the basis for informed decision-making at different levels in society; sound decision-making is possible only if the quality of the data used is uncompromised. To guarantee the reliability and comparability of analytical data an intricate system of quality-assurance measures has to be put into effect in a laboratory. Reference materials and, in particular, certified reference materials (CRMs) are essential for achieving traceability and comparability of measurement results between laboratories and over time. As in any other domain of analytical chemistry, techniques used to monitor the levels and fate of contaminants in the environment must be calibrated using appropriate calibration materials, and the methods must be properly validated using fit-for-purpose matrix-matched CRMs, to ensure confidence in the data produced. A sufficiently large number of matrix CRMs are available for analysis of most elements, and the group of chemicals known as persistent organic pollutants, in environmental compartments and biota. The wide variety of analyte/level/matrix/matrix property combinations available from several suppliers enables analysts to select CRMs which sufficiently match the properties of the samples they analyse routinely. Materials value-assigned for the so-called emerging pollutants are scarce at the moment, though an objective of current development programmes of CRM suppliers is to overcome this problem.     

Analysis of unknown organic pollutants in sewage by solid-phase extraction combined with gas chromatography-mass spectrometry

A rapid, simple, and reliable method of solid-phase extraction (SPE) combined with gas chromatography (GC)-mass spectrometry (MS) is developed for the analysis of a wide range of polarity of unknown organic pollutants in sewage. Wastewater samples are extracted by passing them through disposable C(18) cartridges, and the extracts are then analyzed by GC-MS. Different SPE parameters for ten organic compounds in the list of priority pollutants suggested by the China Environmental Protection Agency (EPA) are studied, and their breakthrough volumes are determined. Extraction recoveries for the tested compounds are greater than 60%, except the recovery of 1,2-dichloroethane is 48%. The relative standard deviations are less than 7.8% (n = 3). The developed approach is successfully applied for the identification of organic components in a sewage sample. Over 220 organic pollutants are identified, with 5 of these present in the list of priority pollutants suggested by the U.S. EPA and 4 from the list by the China EPA.     

Analysis and fate of surfactants in sludge and sludge-amended soils

Surfactants are among the most prevalent organic pollutants of anthropogenic origin with the potential to enter the environment through the discharge of wastewater and sewage sludge. We give an overview of analytical methods currently in use for the determination of different classes of surfactants in sewage sludge and soil. The main focus is on the application of liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), discussing various aspects of these two techniques, including sample preparation. We give an overview of data on the occurrence of sludge and sludge-amended soils, and we draw conclusions about the fate of surfactants and their metabolites in sludge-amended soils. Finally, we briefly discuss the current European legislation relating to the use of sludge in agriculture.     

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...     

Development of an analytical method for the determination of polybrominated diphenyl ethers in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry

Polybrominated diphenyl ethers (PBDEs) are flame retardants. As a consequence of their widespread use, they have been released into the environment. PBDEs are lipophilic organic contaminants that enter wastewater treatment plants (WWTPs) from urban, agricultural and industrial discharges. Because of their low aqueous solubility and resistance to biodegradation, up to 90% of the PBDEs are accumulated in the sewage sludge during the wastewater treatment. To assess the possibilities for sludge re-use, a reliable determination of the concentrations of these PBDEs is of crucial importance. Six PBDE congeners (BDE 28, BDE 47, BDE 99, BDE 100, BDE 153 and BDE 154) are listed as priority substances under the EU Water Framework Directive. In the present work a simple analytical method with minimal sample-preparation steps was developed for a sensitive and reliable determination of the six PBDEs in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). For this purpose an extraction procedure was optimised. Different extracting agents (methanol (MeOH), acetic acid (AcOH)/MeOH mixture (3:1) and 0.1 mol L⁻¹ hydrochloric acid (HCl) in MeOH) followed by the addition of a Tris-citrate buffer (co-extracting agent) and iso-octane were applied under different modes of extraction (mechanical shaking, microwave- and ultrasound-assisted extraction). Mechanical shaking or the microwave-assisted extraction of sewage sludge with 0.1 mol L⁻¹ HCl in MeOH and the subsequent addition of the Tris-citrate buffer and the iso-octane extracted the PBDEs from the complex sludge matrix most effectively. However, due to easier sample manipulation during the extraction step, mechanical shaking was used. The PBDEs in the organic phase were quantified with GC-ICP-MS by applying a standard addition calibration method. The spike recovery test (recoveries between 95 and 104%) and comparative analyses with the species-specific isotope-dilution (ID) GC-ICP-MS confirmed the accuracy of the developed analytical procedure. The procedure is sensitive (limits of detection (LODs) for PBDEs congeners between 0.2 and 0.3 ng g⁻¹), repeatable and reproducible (RSDs 2.2–5.7%) and was applied for the determination of PBDEs in sewage sludge samples collected three times at the municipal WWTP over a period of 16 years.     

铁基金属-有机骨架及其复合物高级氧化降解水中新兴有机污染物

新兴有机污染物(Emerging organic contaminants,EOCs)是对人体健康及生态环境具有潜在或实质威胁的新型化学污染物.由于其被频繁使用且能在水生生态系统中持久性存在而对水生生物健康和安全造成严重威胁,故引起大众越来越多的关注.以活性污泥法为代表的传统水处理工艺通常不足以消除这些新兴有机污染物....     

Analysis of emerging organic contaminants in environmental solid samples

Spreading sewage sludge on agricultural lands has been actively promoted by national authorities as an economic way of recycling. However, as by-product of wastewater treatment, sewage sludge may contain toxic substances, which could be incorporated into agricultural products or be distributed in the environment. Moreover, sediments can be contaminated by the discharge of wastewater effluents into rivers. This article reviews the determination of emerging contaminants (surfactants, flame retardants, pharmaceuticals and personal care products) in environmental solid samples (sludge, soil and sediment). Sample preparation, including extraction and clean-up, as well as the subsequent instrumental determination of contaminants are discussed. Recent applications of extraction techniques, such as Soxhlet extraction, ultrasound assisted extraction, pressurised liquid extraction, microwave assisted extraction and matrix solid-phase dispersion to the analysis of emerging contaminants in environmental solid samples are reviewed. Determination of these contaminants, generally carried out by gas chromatography and liquid chromatography coupled with different detectors, especially mass spectrometry for the identification and quantification of residues, is also summarised and discussed.      

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.     

Quantitative determination of organic priority pollutants in the composts of sewage sludge with rice straw by gas chromatography coupled with mass spectrometry

In order to investigate the occurrence and distribution of organic contaminants in the compost of sewage sludge with rice straw, four different composting treatments at a low carbon/nitrogen (C/N) ratio (13:1) were conducted. Thirty semi-volatile organic compounds (SVOCs) listed as priority pollutants by both China and the US Environmental Protection Agency (EPA) were Soxhlet-extracted, separated and analyzed by gas chromatography coupled with mass spectrometry (GC-MS). The results showed that after composting (56 days) most of SVOCs were detected in the final composts. The total concentrations of polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters ranged from 1.8 to 10 mg/kg dry weight (d.w.) and from 9.8 to 18 mg/kg d.w., respectively, being significantly higher than those of chlorobenzenes and nitroaromatic compounds which were generally less than 1.0 mg/kg d.w. The concentrations and predominant compounds of organic contaminants in the different composts varied, and were affected by their physico-chemical properties and the composting processes. Concentrations of SVOCs in the static aerated composting processes especially intermittently aerated composting treatment were considerably lower than those in the manual-turned composting treatments. Concentrations of organic contaminants especially PAHs and di(2-ethylhexyl) phthalate in the final composts were in agreement with the maximum permissible limits for agricultural purposes proposed by the European Union and by the EPA.     

Pharmaceuticals and personal care products in biosolids/sewage sludge: the interface between analytical chemistry and regulation

Modern sanitary practices result in large volumes of human waste, as well as domestic and industrial sewage, being collected and treated at common collection points, wastewater treatment plants (WWTPs). In recognition of the growing use of sewage sludge as fertilizers and soil amendments, and the scarcity of current data regarding the chemical constituents in sewage sludge, the US National Research Council (NRC) in 2002 produced a report on sewage sludge. Among the NRC’s recommendations was the need for investigating the occurrence of pharmaceuticals and personal care products (PPCPs) in sewage sludge. PPCPs are a diverse array of non-regulated contaminants that had not been studied in previous sewage sludge surveys but which are likely to be present. The focus of this paper will be to review the current analytical methodologies available for investigating whether pharmaceuticals are present in WWTP-produced sewage sludge, to summarize current regulatory practices regarding sewage sludge, and to report on the presence of pharmaceuticals in sewage sludge.     

Analysis of industrial contaminants in indoor air: Part 1. Volatile organic compounds,carbonyl compounds,polycyclic aromatic hydrocarbons and polychlorinated biphenyls

This article reviews recent literature on the analysis of industrial contaminants in indoor air in the framework of the REACH project, which is mainly intended to improve protection of human health and the environment from the risks of more than 34 millions of chemical substances. Industrial pollutants that can be found in indoor air may be of very different types and origin, belonging to the volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) categories. Several compounds have been classified into the priority organic pollutants (POPs) class such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/PCDFs) and related polychlorinated compounds, and polycyclic aromatic hydrocarbons (PAHs). Many of these compounds are partially associated to the air gas phase, but also to the suspended particulate matter. Furthermore, settled dust can act as a concentrator for the less volatile pollutants and has become a matrix of great concern for indoors contamination. Main literature considered in this review are papers from the last 10 years reporting analytical developments and applications regarding VOCs, aldehydes and other carbonyls, PCBs, PCDDs, PCDFs, and PAHs in the indoor environment. Sample collection and pretreatment, analyte extraction, clean-up procedures, determination techniques, performance results, as well as compound concentrations in indoor samples, are summarized and discussed. Emergent contaminants and pesticides related to the industrial development that can be found in indoor air are reviewed in a second part in this volume.     

Using Bismuth Vanadate/Copper Oxide Nanocomposite as Photoelectrochemical Sensor for Naproxen Determination in Sewage

Conventional sewage treatment plants are not usually designed to remove emerging contaminants, and this shortcoming leads to the discharge of pharmaceuticals, among other emerging pollutants, into the environment. The present work reports the development of BiVO₄/CuO‐based photoelectrochemical sensor for the determination of naproxen in sewage samples. Morphological characterizations were carried out by X‐ray diffraction and Scanning electron microscopy. The band gap energy of the nanocomposite material was calculated by Tauc plots using the data obtained from diffuse reflectance spectroscopy analysis. The sensor presented analytical signal during the photocurrent generation simultaneously with the oxidation of naproxen on the working electrode. The sensor responses were found to be proportional to the increase in naproxen concentration in the linear range of 5 nmol L^?1 to 480 nmol L^?1, R²=0.996, with a limit of detection of 5 nmol L^?1. The presence of naproxen in sewage samples was successfully determined with recovery percentages above 95 %.     

Recent advances in persulfate-based advanced oxidation processes for organic wastewater treatment

In recent years, with the emergence of new pollutants, the effective treatment of wastewater has become very important. Persulfate-based advanced oxidation processes have been successfully applied to the treatment of wastewater, such as wastewater containing antibiotics, pharmaceuticals and personal care products, dyes, endocrine-disrupting chemicals, chlorinated organic pollutants, and phenolics, for the degradation of refractory organic contaminants. This paper summarizes the production of sulfate radicals, which can be generated by the activation of persulfate via conventional and emerging approaches. The existing problems of persulfate-based advanced oxidation processes were analyzed in detail, including residual sulfates, coexisting factors (coexisting inorganic anions and natural organic matter), and energy consumption. This paper proposes corresponding possible solutions to the problems mentioned above, and this paper could provide a reference for the application of persulfate-based advanced oxidation processes in actual wastewater treatment.     

Sampling and analytical framework for routine environmental monitoring of organic pollutants

Dubious data would lead to incorrect interpretations and consequently faulty conclusions. Environmental monitoring results therefore have to be unambiguous to avoid misunderstanding the problems under investigation. Representative sampling and appropriate laboratory procedures are keys to acquiring quality data in order to draw unbiased conclusions.Although a large number of studies on organic pollutants have been published, few efforts have been directed towards instituting a systematic framework from sampling design to instrumental analysis. Generally, the main components in such a framework should include sampling design, sample preparation, sample extraction, extract purification and fractionation, and quantification (including qualitative and quantitative analyses).This review outlines the sampling and analytical framework appropriate for routine monitoring of organic pollutants, particularly persistent organic pollutants widely occurring in the environment. We emphasize statistically-based sampling schemes and quality-assurance and quality-control measures desirable for environmental monitoring programs.By way of demonstrating their importance, we especially review procedures for collecting unconventional environmental samples (e.g., human blood, breast milk, human hair, fish and bird tissues, and ice and snow) and analytical methods for typical emerging organic chemicals.     

New challenges in environmental analytical chemistry: Identification of toxic compounds in complex mixtures

Toxic effects evidenced in the environment are most often caused by mixtures of known and unknown pollutants. One of the key challenges in environmental chemistry and ecotoxicology is to characterize and identify those toxicants in relation with the effect. However, many of the current bottlenecks in the assessment of organic contaminants in our environment are related to the difficulty of evaluating various chemical classes and biological effects within complex mixtures and more precisely to link both approaches. To tackle these analytical challenges, the bioanalytical concept has emerged during the last decade. In this article, we describe through some outstanding examples the current limitations in the chemical-driven approach such as problems encountered for a correct evaluation of water quality when the continuous introduction of new chemicals has to be taken into account in monitoring for correct evaluation of this quality and could led to tremendous analytical costs or some of the integrated bioanalytical approaches as promising powerful tools to improve environmental risk assessment by taking into account the link presence/effect.     

钴催化过一硫酸氢盐降解水中有机污染物:机理及应用研究

钴/过一硫酸氢盐(Co/PMS)是为了克服Fenton技术的诸多缺陷而基于类Fenton思路(过氧化物+过渡金属)建立起来的一种高级氧化技术。该体系具有Co用量少(μg/L数量级),产生的SO₄^-·氧化还原电位高,能够在广泛的pH范围(2-9)降解有机污染物,反应后不产生污泥等优点,在环境污染治理领域具有广阔的应用前景。本文从自由基链式反应、溶液pH、阴离子效应、光照条件、反应气氛及固液两相交换六个方面分析了Co/PMS体系降解水中有机污染物的机理,并在此基础上综述了Co/PMS (黑暗条件)、UV/Co/PMS、Vis/Co/PMS三类均相Co/PMS体系以及Co氧化物催化、Co负载催化两类非均相Co/PMS体系降解水中有机污染物的国内外研究进展,并就存在的问题提出了展望。     

GC-MS analysis of organic compounds in wastewater and sewage sludge

A multimethod based on liquid-liquid extraction and solid-liquid extraction for the analysis of persistent organic pollutants in water and sludge from sewage treatment plants has been established. Traces of 22 organic compounds used in industry and personal care products (PCPs) were analyzed by GC/MS. The LODs for the analytes were less than 2.3 ng/L for wastewater and 31 microg/kg (dry weight matter) for sewage sludge. Satisfactory recoveries (70-130%) were achieved. The validated method permits the analysis of water and sludge samples at various stages of the treatment from different sewage treatment plants. Thus, the distribution between water and sludge as well as the dissipation of the compounds analyzed were balanced. By this means, the efficiency of different wastewater treatment plants (WWTPs) can be evaluated and measures can be taken to optimize the treatment process at different stages.