Simultaneous preconcentration of a wide variety of organic pollutants in water samples: Comparison of stir bar sorptive extraction and membrane-assisted solvent extraction

Development of a stir bar sorptive extraction and thermal desorption–gas chromatography–mass spectrometry method for the simultaneous determination of several persistent organic pollutants in water samples

The European Water Framework Directive 2000/60 is one of the key legislations introduced for many years in water management and protection fields. The model of water management established by this directive is the river basin. There are a variety of indicators to define the good ecological and chemical status, including a list of priority and emerging pollutants to monitor. Compounds in the directive list are organic pollutants, e.g. hydrocarbons, organochlorine compounds, organic solvents, pesticides and chlorophenol, toxic metals (Hg, Ni, Cd and Pb) and one organometallic compound (tributyltin). Other chemical compounds such as pharmaceuticals, hormones and endocrine disruptor have also become important emerging contaminants due to their presence in environmental waters, the threat for drinking water sources and the concern about their possible estrogenic and other effects. For these reasons, some of them have been included as emerging pollutants in the directive. Although this directive does not specify the analytical methods and procedures to be used, the results should come to an agreement no matter which method is used and regardless in which lab the analysis is carried out. Therefore, a large effort to validate and harmonize analytical methods is very required to assure the quality of the results. Consequently, the implementation of robust analytical methods is still a challenging requirement. Among the different steps of the analytical procedure sample preparation is not only the a major source of uncertainties but also where the risk of artifacts and contamination is the highest. Different extraction techniques for the analysis of organic pollutants in water samples are being developed and optimized in order to automate and miniaturize the extraction step, using low volumes of solvents or even solventless procedures in order to pre-concentrate the analytes in the final acceptor phase. We review recent strategies for the analysis of organic pollutants in environmental water samples as alternative choices against the most classical liquid-liquid extraction or solid-phase extraction. Revised extraction techniques are classified in two main groups: (i) sorptive extractions and (ii) liquid-liquid microextraction. Among sorptive extractions, solid-phase microextraction, stir-bar sorptive extraction and microextraction by packed sorbent are described. Cloud point extraction, single drop microextraction, membrane liquid-phase microextraction and dispersive liquid-liquid microextraction are included in the group of liquid-liquid microextraction techniques. Among membrane liquid-phase microextraction the use of both porous and non-porous membranes is described. During the description of liquid-liquid microextraction techniques the use of ionic liquids is also mentioned due to the high number of applications found for both single drop microextraction and dispersive liquid-liquid microextraction. We discuss the basics, advantages, drawbacks and applications of the techniques for the analysis of organic pollutants in environmental water samples, including river, estuarine water, seawater or wastewater.

Determination of organic priority pollutants and emerging compounds in wastewater and snow samples using multiresidue protocols on the basis of microextraction by packed sorbents coupled to large volume injection gas chromatography–mass spectrometry analysis

This paper presents concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in marine water samples of Porto-Romano area. Porto-Romano is situated in Adriatic Sea, near city of Durres, in central Albania. It was considered Hot-spot area because before 90' there was located chemical plant for Lindane production. Landfill near Porto-Romano and elevated activity for industrial development of this area can be the main sources of water pollution in recent years. Water samples were taken in December 2018 and April 2019 in nine stations of Porto-Romano. Liquid-liquid extraction was used for isolate organic pollutants from water samples. Clean-up procedure for chlorinated pollutants was realized in a Florisil column. Qualitative and quantitative analyzes of pesticides and PCBs were performed in HP 6890 Series II, gas chromatograph equipped with p-ECD detector. For separation of organochlorine pollutants was used Rtx-5 capillary column. Analyzes of PAH were realized in Varian 450 GC, gas chromatograph equipped with FID detector and VF-1ms capillary column. The most frequent organic pollutants in water samples of Porto-Romano were found organochlorine pesticides because of ex-chemical plants impact in this area. Note, that Lindane and its isomers weren't found in high concentration. PCB 28, volatile congener, was found in higher concentrations because of their atmospheric origin. Presence of PCB 138 show terrestrial origin of PCBs in this area. PAH were found in higher concentrations inside of hydrocarbon port. Their concentrations were due to industrial activity and ship transport in this area. Mismanagement of Lindane plant wastes, urban pollution and recent industrial activity are factors of continues pollution in Porto-Romano area. Presence of organic pollutants in water samples of Porto-Romano indicates that monitoring of this Hot-spot should be continuous.

Serum concentrations of polybrominated biphenyls (PBBs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the Michigan PBB Registry 40 years after the PBB contamination incident

Using an optimized relative response factor database to simplify a pyrolyzer/thermal desorption-gas chromatography-mass spectrometry method of screening for phthalate esters, polybrominated diphenyl ethers, and polybrominated biphenyls in polymers

Among the different organic pollutants, persistent organic pollutants and emerging organic contaminants (EOCs) are of particular concern due to their potentially dangerous effects on the ecosystems and on human health. In the framework of the analysis of some of these organic pollutants in water samples, sorptive extraction devices have proven to be adequate for their monitoring. The efficiency of four commercially available and low-cost polymeric materials [polypropylene, poly(ethylene terephthalate), Raffia, and polyethersulfone (PES)] for the simultaneous extraction of 16 organic compounds from five different families from environmental water samples was evaluated in this work. Firstly, the homogeneity of the sorbent materials was confirmed by means of Raman spectroscopy. After the optimization of the parameters affecting the extraction and the liquid desorption steps, it was found that PES showed the largest efficiencies for slightly polar analytes and, to a lesser extent, for nonpolar analytes. Additionally, Raffia rendered good extraction efficiencies for nonpolar compounds. Thus sorptive extraction methods followed by large volume injection-programmable temperature vaporizer-gas chromatography-mass spectrometry were validated using PES and Raffia as sorbent materials. The validation of the method provided good linearity (0.978 < r (2) < 0.999 for PES and 0.977 < r (2) < 0.999 for Raffia), adequate repeatability (below 19 % and 14 % for PES and Raffia, respectively), and low method detection limits (low ng · l(-1) level). Finally, these materials were applied to the analysis of contaminants in environmental water samples.

This study report data on physical-chemical parameters and on concentrations of organic pollutants in marine water samples of Albanian ports. Nutrients, PH, temperature, conductivity, TSS, DO, BOD, COD, chlorines, sulfates, magnesium and calcium ions were the indicators used for evaluation of water quality. Also, organic pollutants (organochlorine pesticides, PCBs, PAH and benzene) were determined in seawater samples. Albania is facing by Ionian and Adriatic seas in a coastline of more than 300 km. Several ports are in function in Albanian coastline. Ship transport and many activities (automobile transport, mechanical activities, deposits, etc.) are the main factors of water pollution in port areas. Water samples from seven ports (the main Albanian ports) starting from Saranda port in the South to Shengjini port in the North, were analyzed in this study. Sampling was realized in May 2023. Based on physical-chemical indicators the water in the port of Saranda was the cleanest water, while Porto-Romano, Petrolifera and the fishing port in Zvernec was the most polluted one. Organic pollutants were detected in all water samples. Presence of the degradation products of pesticides may be related with previous uses of them. Presence of PCBs can be because of atmospheric deposition (volatile congeners), water currents and mechanical businesses (heavy congeners). PAHs and Benzene were detected on more than 70% of the analyzed samples. Intense ship and automobile transport in the port areas, mechanical businesses discharge and hydrocarbon processing i(Petrolifera and Porto-Romano) can be main factor for their presence. Water currents and new arrivals from the rivers can influence the levels and profile of pollutants. The found levels of organic pollutants in water samples of Albanian ports were higher than reported levels in previous studies for the Adriatic Sea (Albania coastline).

A multi-determination method has been developed for the determination and confirmation of 68 organic pollutants in water samples by gas chromatography coupled to triple quadrupole mass spectrometry (GC-MS/MS). The following chemical families were determined in a chromatographic run of less than 26 min: polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenylethers (PBDEs), and pesticides (organochlorine, organophosphorus, triazine and others). The sample preparation involved a liquid-liquid extraction (LLE) procedure, obtaining recoveries ranging from 70 to 130% when dichloromethane was used as the extracting solvent. The detection limits of the proposed method were between 0.75 and 19.8 ng L−1. Samples from the Maipo River in central Chile were taken from 29 different points. Seven pesticides and two PAHs were detected in field collected samples with concentrations ranging from 10 to 95 ngL−1. Concentrations of benzo[a]pyrene in environmental samples ranged from 25 to 33 ngL−1 and were near the maximum levels established by the European Union Directives (50 ng L−1).

Polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), perfluorooctanoic acid (PFOA), perfluorooctyl sulfonates (PFOS), chlordecone and polybrominated dibenzo- p -dioxin and dibenzofurans (PBDD/Fs), as the new listed POPs in Stockholm Convention and emerging POPs, were increasingly concerned by environmental scientists. The research work about the residue’s characteristic, source analysis, trends evolution, transport, bioaccumulation, and toxic effects of these emerging chemicals depended on the development of the analytical methods. Analytical procedures of PBDEs and PBBs were similar to those of organochlorine pesticides (OCPs) and poly chlorinated biphenyls (PCBs), due to their similar physical and chemicalcharacteristics with “Dirty Dozen”. Many extraction methods, such as Soxhlet extraction, automatic Soxhlet extraction, supersonic extraction, microwave assisted extraction, pressurized fluid extraction, were applied for water, sediment, soil and particulate matter. Common clean-up steps were sulfuric acid silica gel cartridge, multiple layer chromatography column and GPC. Although HRGC/HRMS and GC/MS/MS were effective for environmental background samples, GC/MS-EI and GC/MS-NCI were most popular for determinations of the PBDEs and PBBs indicators or markers. HPLC/MS/MS with solid phase extraction was developed for the perfluorinated alkyl acids, sulfonates and their salts. HLB solid phase column was efficient for PFOA/PFOSs recoveries from water samples, as the weak anion exchange column could raise the recoveries of perfluorinated alkyl acids and sulfonates with the carbon chain ranging from 4 to 14. Acetone was necessary in the extraction because of the polarity of clordecone. The GC injector and capillary column needed cleaning carefully when clordecone was analyzed by GC/ECD and GC/MS, otherwise the strong tailing of chromatographic peak would make the exact qualitative and quantitative impossible. The analysis procedures for polybrominateddibenzo-p-dioxin and dibenzofurans (PBDD/Fs) were similar to those of PCDD/Fs. Florisil or active carbon-impregnated silica gel column were packed to separate PBDEs and PBDD/Fs. The instrumental conditions were optimized to prevent from the thermal degradation of higher brominated compounds. The application of the method was also depended on the improvement of PBDD/Fs reference materials.

This study was undertaken to investigate the current contamination status of polyhalogenated aromatic hydrocarbons (PHAHs) in sediments from large reservoirs located in Hebei and Hubei provinces in China. The concentrations of 21 polybrominated biphenyl (PBB) congeners, seven polybrominated diphenyl ether (PBDE) congeners, and 27 polychlorinated biphenyl (PCB) congeners in sediments were measured using the GC-MS/MS technique. Low-brominated PBBs (including 1, 3, 4, 10, 30, 31 and 53) were the most abundant PBB congeners and PBDEs 28, 47 and 99 were the most prevalent PBDE congeners in these samples. Among the three subfamilies of PHAHs, PCBs were the most predominant pollutants detected. The measured levels of PHAHs were compared with recent results reported in the literature and their respective sediment quality guidelines recommended by USEPA. The levels of PHAHs in the present study were generally lower than their respective threshold-effect levels, or were comparable to those reported in relatively uncontaminated freshwaters from other regions. This suggests that, in these reservoirs, toxic biological effects on aquatic biota—due to PHAH contamination of sediments—can be expected to be negligible. Thus, in terms of PHAHs, the sediments in the selected reservoirs are relatively uncontaminated.

A long-term sampling system, called the Adsorption Method for Sampling of Dioxins and Furans (AMESA), was used for long-term sampling (up to 168 hours) of an electric arc furnace (EAF) to obtain the representative flue gas samples. In order to have a comprehensive view of the emissions of persistent organic pollutants (POPs) from EAFs, six POPs, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs), were investigated. Tests showed the breakthroughs of PBDD/Fs and PBDEs are much larger (8.9%–43%), while the others are less than 3%. A significant increase in breakthrough with the increase in halogen numbers is observed, because highly halogen-substituted POPs tend to partition to the particulate-phase. Except for PCBs and PCDEs, whose percentages of the POPs in the rinses to the total POPs collected from the long-term samples (cartridges + rinses) are less than 7%, those of the other POPs are all greater than 30%. Therefore, the solvents from the rinses of the sampling probe and other components need to be combined with an XAD-2 cartridge for analyses. The PCBs and PBDEs are the most abundant pollutants in the stack flue gases of the EAF, and their mass concentrations are one to three orders higher than those of the other POPs. With regard to POPs with dioxin-like toxicity, the percentages of the contributed toxicities by PCDD/Fs, PCBs and PBBD/Fs are 87.1%, 11.7% and 1.2%. The close association that PBDEs and PBDD/Fs have with the concentrations and congener profiles is not present for PCDEs and PCDD/Fs, suggesting the need for further studies of the formation mechanisms of these analogues.

A method for the determination of polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) in water samples is proposed. The method involving stir bar sorptive extraction (SBSE) and thermal desorption followed by gas chromatography coupled with mass spectrometry was optimised using statistical design of experiments. In the first place, the influence of different polydimethylsiloxane stir bars was studied. A Plackett-Burman design was chosen to estimate the influence of five factors on the efficiency of the SBSE process: desorption time (5-10 min), desorption temperature (250-300 degrees C), desorption flow (50-100 mL min(-1)), cryofocusing temperature (-130 to 40 degrees C) and vent pressure (0-12.8 psi). Afterwards, two central composite designs were used to find the optimal process settings that were applied to the optimisation of both desorption and extraction efficiency. In the case of the desorption parameters, long desorption times (10 min) and desorption flows lower than 70 mL min(-1) yielded the best signals for the majority of compounds. However, different behaviour among the analytes was observed for the vent pressure and we decided to fix it at an intermediate value (7 psi). In the case of extraction parameters, the sample volume and the addition of NaCl did not have a significant effect, while the addition of methanol yielded better extraction responses. Remarkable recovery (82-106%) and repeatability (less than 18%) were attained. Furthermore, excellent regression coefficients (r2 = 0.991-0.999) and low detection limits (1.1-6.0 ng L(-1)) were also achieved for the congeners studied. The proposed method was applied to the analyses of PBDEs and PBBs in waters from the Basque Country, Spain.

Associations of concurrent PCB and PBDE serum concentrations with executive functioning in adolescents

MultiSimplex optimisation of the solid-phase microextraction-gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and phthalates from water samples.