Organic pollutants in indoor dust from Ecuadorian Amazonia areas affected by oil extractivism.

Fifty-five household dust samples collected within six settlements surrounding oil production complexes along the Ecuadorian Amazonia were analysed to evaluate the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs), phthalates, alkylphenols (APs), bisphenol A (BPA), nicotine, organophosphorus flame retardants (OPFRs), polychlorinated biphenyls (PCBs), legacy organochlorine pesticides (OCs) and organophosphorus pesticides. Studied areas are mainly affected by gas flares emissions and oil spilling coming from extractivist operations and pesticides used in agriculture. Median ΣPAHs values ranged from 739 to 1182 ng g-1 and up to 52% of the PAH dust concentrations were associated to petrogenic activities from crude oil extraction, according to diagnostic ratios. ΣPAHs and toxic equivalents based on benzo[a]pyrene concentration (ΣTEQBaP, ng g-1) suggested similar toxicities among the different areas. Individual lifetime cancer risk (ILCRdust) was calculated for ingestion and dermal contact exposure routes and a non-acceptable total carcinogenic risk of up to 10-4 (one case per ten thousand people) was found for newborns from 0 to 3 years-old in Pimampiro area. Plasticisers and OPFRs were present in dust at maximum median concentrations of 332,507 ng g-1 (DEHP), 5,249 ng g-1 (DBP), 1,885 ng g-1 (BPA), 871 ng g-1 (TBOEP) and 122 ng g-1 (TEHP). Some dust samples from Ecuadorian houses had high maximum levels of legacy and modern pesticides such as chlorpyrifos (up to 44,176 ng g-1), 4,4'-DDT (12,958 ng g-1), malathion (34,748 ng g-1) and α+ß-endosulfan (10,660 ng g-1) attributed to inappropriate use and storage of the pesticides. Finally, nicotine was seldom detected (36 ng g-1). The sources and risks of these compounds are discussed based on the activities carried out in the study areas and attending to an additional non-cancer risk assessment which showed high hazard quotients (HQ) and hazard indexes (HI) for DEHP, DBP, 4,4'-DDT, malathion, chlorpyrifos, naphthalene and benzo[a]pyrene in newborns and children up to 16 years-old.

Variation in scale cortisol concentrations of a wild freshwater fish: Habitat quality or seasonal influences?

A significant body of literature suggests that aquatic pollutants can interfere with the physiological function of the fish hypothalamic-pituitary-interrenal (HPI) axis, and eventually impair the ability to cope with subsequent stressors. For this reason, development of accurate techniques to assess fish stress responses have become of growing interest. Fish scales have been recently recognized as a biomaterial that accumulates cortisol, hence it can be potentially used to assess chronic stress in laboratory conditions. We, therefore, aimed to evaluate the applicability of this novel method for cortisol assessment in fish within their natural environment. Catalan chub (Squalius laietanus) were sampled from two sites; a highly polluted and a less polluted (reference) site, in order to examine if habitat quality could potentially influence the cortisol deposition in scales. We also evaluated the seasonal variation in scale cortisol levels by sampling fish at three different time points during spring-summer 2014. In each sampling, blood was collected to complement the information provided by the scales. Our results demonstrated that blood and scale cortisol levels from individuals inhabiting the reference site were significantly correlated, therefore increasing the applicability of the method as a sensitive-individual measure of fish HPI axis activity, at least in non-polluted habitats. Since different environmental conditions could potentially alter the usefulness of the technique, results highlight that further validation is required to better interpret hormone fluctuations in fish scales. Scale cortisol concentrations were unaffected by habitat quality although fish from the polluted environment presented lower circulating cortisol levels. We detected a seasonal increase in scale cortisol values concurring with an energetically costly period for the species, supporting the idea that the analysis of cortisol in scales reveals changes in the HPI axis activity. Taken together, the present study suggests that cortisol levels in scales are more likely to be influenced by mid-term, intense energetically demanding periods rather than by long-term stressors. Measurement of cortisol in fish scales can open the possibility to study novel spatio-temporal contexts of interest, yet further research is required to better understand its biological relevance.

Pesticide residue analyses and biomarker responses of native Costa Rican fish of the Poeciliidae and Cichlidae families to assess environmental impacts of pesticides in Palo Verde National Park.

Pesticide chemical residues in water samples and biomarker responses in transplanted fish were used to monitor environmental hazards of pesticides in Palo Verde National Park (Costa Rica). The Costarican fish, Parachromis dovii (Ciclhidae) and Poecilia gillii (Poecillidae), were selected as sentinel species. Contaminant analyses detected up to 15 different pesticide residues in water with hexachlobenzene (2261 ng l(-1)), phorate (473 ng l(-1)), epoxiconazole (314) and bromacil (117 ng l(-1)) being the compounds found in higher concentrations. Biomarker responses evidenced impacts on cholinesterase activities in transplanted fish at Barbudal site probably due to the presence of organophosphate insecticides such as phorate. High enzyme activities of glutathione S-transferase and catalase and elevated levels of lipid peroxides were also observed at a site impacted by rice fields (Cabuyo); those effects could be associated with the presence of hexachloro benzene and triazole fungicides. In general, P. dovii biomarkers were affected to a greater extent than those of P. gillii in fish transplanted to sites associated with agriculture, which suggests the former species is a good candidate for future surveys.

Nasal lavage technique reveals regular inhalation exposure of microplastics, not associated from face mask use.

During the COVID-19 pandemic, the use of face masks has been a worldwide primary protection measure to contain the spread of the virus. However, very little information is known about the possible inhalation of microplastics (MP) from wearing masks. This pilot study evaluates the presence of MP accumulated in nasal cavities through the nasal lavages technique. Six different commercial face masks were tested in 18 participants during five working days (8 h use/day). Eight different polymers (polystyrene, polyamide, poly(ethylene - propylene) diene monomer, polyester, polyethylene, polyvinylidene fluoride, polypropylene, and polyvinyl chloride) predominantly within the 20-300 µm size were detected in nasal lavages, with an average concentration of 28.3 ± 15.6 MP/5 mL nasal solution. Results demonstrate that MP in the nasal cavity are not associated to face mask use but rather to general exposure to airborne MP. We highlight the use of nasal lavages to evaluate human inhalation of MP and associate it to potential sources and risks.

Target and untargeted screening of perfluoroalkyl substances in biota using liquid chromatography coupled to quadrupole time of flight mass spectrometry.

Perfluoroalkyl substances (PFAS) are known to bioaccumulate and trigger adverse effects in marine birds. This study develops an extraction and analytical methodology for the target/untargeted analysis of PFAS in eggs of Yellow-legged gull (Larus michahellis) and Audouin's gull (Larus audouinii) and blood of Greater flamingo (Phoenicopterus roseus), which are used as bioindicators of organic chemical pollution. Samples were extracted by ultrasonication with acetonitrile and cleaned-up with activated carbon, and analysis was performed by ultra-high-performance liquid chromatography coupled to a quadrupole-time of flight mass spectrometer (UHPLC-Q-TOF) with negative electrospray ionization. Data-independent acquisition (DIA) was performed through full-scan acquisition to obtain MS1 at 6 eV and MS2 at 30 eV. In a first step, quantitative analysis of 25 PFAS was performed using 9 mass-labelled internal standard PFAS and quality parameters of the method developed are provided. Then, an untargeted screening workflow is proposed using the high-resolution PFAS library database from NORMAN to identify new chemicals through accurate mass measurement of MS1 and MS2 signals. The method permitted to detect several PFAS at concentrations ranging from 0.45 to 55.2 ng/g wet weight in gull eggs and from 0.75 to 125 ng/mL wet weight in flamingos' blood, with PFOS, PFOA, PFNA, PFUdA, PFTrDA, PFDoA, PFHxS and PFHpA the main compounds detected. In addition, perfluoro-p-ethylcyclohexylsulfonic acid (PFECHS, CAS number 646-83-3) and 2-(perfluorohexyl)ethanol (6:2 FTOH, CAS number 647-42-7) were tentatively identified. The developed UHPLC-Q-TOF target/untargeted analytical approach increases the scope of PFAS analysis, enabling a better assessment on contaminant exposure and promoting the use of bird species as bioindicators of chemical pollution.

Airborne microplastic particle concentrations and characterization in indoor urban microenvironments.

Airborne microplastics (MPs) have recently drawn the attention of the scientific community due to their possible human inhalation risk. Indoor environments are of relevance as people spend about 90% of their time indoors. This study evaluated MPs concentrations in three indoor environments: houses, public transport and working places, which are representative of urban life. Sampling involved the collection of airborne particulate matter on nylon 20 µm pore size filters. Samples were first visually inspected, and particles were characterized (colour, length or area). Polymer identification was performed through µFTIR analysis. Working conditions were controlled to guarantee quality assurance and avoid background contamination. Limits of detection, recovery tests and repeatability were performed with home-made polyethylene (PE), polypropylene (PP), and polystyrene (PS) standards. The highest average MP concentrations were found in buses (17.3 ± 2.4 MPs/m3) followed by 5.8 ± 1.9 MPs/m3 in subways, 4.8 ± 1.6 MPs/m3 in houses, and 4.2 ± 1.6 MPs/m3 in the workplaces. Polyamide, PA (51%), polyester PES (48%) and PP (1%) were the polymers identified and most common in personal care products and synthetic textiles. Most of these polymers were below 100 µm in size for both fibres (64 ± 8%) and fragments (78 ± 11%). The frequency of MP particles in our study decreased with increasing size, which points to their potential as an inhalation hazard.

Exhaustive characterization of (semi-)volatile organic contaminants in car dust using comprehensive two-dimensional gas chromatography ‒ Time-of-flight mass spectrometry.

This work represents the first reported effort to build an extensive database of the organic volatile and semi-volatile contaminants present in car dust as a result of migration from materials used in auto-manufacturing. Untargeted analysis of car dust samples has been performed using comprehensive two-dimensional gas chromatography combined with time-of-fight mass spectrometry (GC×GC ‒ToF MS) after generic sample preparation. The enhanced separation power and structural confirmation capabilities provided by this technique have been used for the either positive or tentative identification of 245 GC-amenable compounds, a number of them being identified for the first time in this type of matrix. Information concerning 5 compounds remaining unidentified has also been provided. Results have been summarised in a searchable database containing chromatographic, mass spectral and normalised abundances calculated for the detected analytes in the ten investigated car dusts used to discuss the main findings of the study. Results are expected to serve other researcher to take decisions concerning priority analytes for further evaluation in this research field and for car manufacturers who might search for safer materials.

Overview on the occurrence of microplastics in air and implications from the use of face masks during the COVID-19 pandemic.

Environmental pollution from microplastics (MPs) in air is a matter of growing concern because of human health implications. Airborne MPs can be directly and continuously inhaled in air environments. Especially high MPs contributions can be found in indoor air due to the erosion and breakage of consumer, domestic and construction products, although there is little information available on their sources and concentrations and the risks they might pose. This is in part due to the fact that sampling and analysis of airborne MPs is a complex and multistep procedure where techniques used are not yet standardized. In this study, we provide an overview on the presence of MPs in indoor air, potential health impacts, the available methods for their sampling and detection and implications from the use of face masks during the COVID-19 pandemic.

Differential occurrence, profiles and uptake of dust contaminants in the Barcelona urban area.

Dust is a complex but increasingly used matrix to assess human exposure to organic contaminants both in indoor and outdoor environments. Knowledge concerning the effects of organic pollution towards health outcome is crucial. This study is aimed to determine the presence of legacy compounds (DDTs and polychlorinated biphenyls, PCBs), compounds used in recent times (organophosphorous flame retardants, organophosphorous pesticides, BPA, phthalates and alkylphenols) and compounds originated from combustion processes (polycyclic aromatic hydrocarbons, PAHs) as well as nicotine in indoor environments along the metropolitan area of Barcelona. Monitored sites include public areas with high turnout (high schools, museums samples) and libraries and private spaces (houses and cars). Almost all compounds (57 over the 59 targeted) were found in each dust sample and libraries and schools were the most contaminated, with concentrations of ∑phthalates and ∑OPFRs up to 15 and 10 mg g-1, respectively. One-way ANOVA tests, Tukey contrasts and principal component analysis (PCA) revealed that sampling place influenced the observed contamination profiles and public and private environments were clearly differentiated. Finally, based on the concentrations detected, a deterministic calculation was performed to estimate the total daily intakes of each compound via dust. This information was used to evaluate the human exposure for toddlers, teenagers and adult workers. Consistently, the highest concentrations coming from plasticisers and flame retardants gave the major exposure rates. As expected, toddlers were the most affected group followed by museum and library workers, although the levels were below the reference doses.

How chronic administration of benzodiazepines leads to unexplained chronic illnesses: A hypothesis.

It is thought that an ill defined biochemical cascade may lead to protracted withdrawal symptoms subsequent to discontinuance of routine use of benzodiazepine class drugs and establish chronic illness in some patients. In this review, published findings are presented that support the novel concept that withdrawal from benzodiazepine class drugs can trigger elevated and sustained levels of a potent oxidant called peroxynitrite via potentiation of the L-type voltage-gated calcium channels, and in the later stages of withdrawal, via excessive N-methyl-D-aspartate receptor activity, as well. Potentiation of L-type voltage-gated calcium channels and excessive N-methyl-D-aspartate receptor activity both result in calcium influx into the cell that triggers nitric oxide synthesis. In pathophysiological conditions, such increased nitric oxide synthesis leads to peroxynitrite formation. The downstream effects of peroxynitrite formation that may occur during withdrawal ultimately lead to further peroxynitrite production in a system of overlapping vicious cycles collectively referred to as the NO/ONOO(-) cycle. Once triggered, the elements of the NO/ONOO(-) cycle perpetuate pathophysiology, perhaps including reduced GABAA receptor functioning, that may explain protracted withdrawal associated symptoms while the vicious cycle nature of the NO/ONOO(-) cycle may explain how withdrawal becomes a chronic state. Suboptimal levels of tetrahydrobiopterin may be one risk factor for the development of the protracted withdrawal syndrome as this will lead to partial nitric oxide uncoupling and resultant peroxynitrite formation. Nitric oxide uncoupling results in superoxide production as calcium-dependent nitric oxide synthases attempt to produce nitric oxide in response to L-type voltage-gated calcium channel-mediated calcium influx that is known to occur during withdrawal. The combination of nitric oxide and superoxide produced, as when partial uncoupling occurs, react together in a very rapid, diffusion limited reaction to form peroxynitrite and thereby trigger the NO/ONOO(-) cycle. The NO/ONOO(-) cycle may explain the nature of the protracted withdrawal syndrome and the related constellation of symptoms that are also common in other illnesses characterized as NO/ONOO(-) disorders such as myalgic encephalomyelitis/chronic fatigue syndrome and fibromyalgia.

Comprehensive method for the analysis of multi-class organic micropollutants in indoor dust.

In the last decades, there has been an increasing concern about the human exposure to indoor dust because it has been observed that its contact or ingestion represents an important exposure source to several contaminants. The principal aim of this study was to evaluate the presence of multi pollutants in indoor dust. Therefore, an efficient multi-residue analytical method based on gas chromatography-electron ionisation-tandem mass spectrometry (GC-EI-MS/MS) was developed for the quantitative determination of 59 pollutants in house dust. The studied compounds belong to different families which have been reported as dangerous due to their possible effects for human health (endocrine disruption, neurotoxicity, mucosa-irritating effects, etc.). They are plasticisers, pesticides, flame retardants or polycyclic aromatic hydrocarbons, and reflect compounds used in construction materials, domestic goods or coming from outdoor air accumulation in indoor environments. The optimised methodology was simple, reliable and sensitive and was tested to evaluate the presence of contaminants in house dust samples collected in the area of Barcelona (Spain). Among all compounds studied, 54 contaminants were detected, being phthalates the group of compounds encountered at the highest concentrations, followed by organophosphorus flame retardants and bisphenol A.

Pilot survey monitoring pharmaceuticals and related compounds in a sewage treatment plant located on the Mediterranean coast.

A one-year monitoring study was performed to evaluate the occurrence, persistence and fate of a group of 14 organic compounds in a sewage treatment plant (STP) located in the south of Spain. These results are part of a more extensive study, financed by the Spanish Ministry of Research with the aim to evaluate the traceability of new pollutants on the Mediterranean coast and to determine the removal efficiency of sewage treatment plants (STP) for these pollutants. The compounds which have been analyzed include pharmaceuticals of various therapeutic categories (ibuprofen, acetaminophen, dipyrone, diclofenac, carbamazepine and codeine), pesticides (chlorfenvinfos and permethrin), caffeine, triclosan, bisphenol A and three of their more relevant metabolites (1,7-dimethylxanthine, carbamazepine 10,11-epoxide and 2,7/2,8-dichlorodibenzo-p-dioxin). An SPE/GC-MS multi-residue analytical method was developed and validated to facilitate simultaneous determination of these compounds in both influent and effluent wastewater. The method provided mean recoveries higher than 75%, with the exception of 2,7/2,8-dichlorodibenzo-p-dioxin, dipyrone and permethrin which exhibited recoveries lower than 22%. The overall variability of the method was below 14%. The method detection limit (LOD) was between 1 and 100 ng l(-1) and precision, which was calculated as relative standard deviation (RSD), ranged from 1.8% to 11.2%. The application of the proposed method has allowed the identification of all the target compounds at mean concentrations which ranged from 0.12 to 134 microg l(-1) in the influent and from 0.09 to 18.0 microg l(-1) in the effluent. The removal efficiencies of the STP for these compounds varied from 20% (carbamazepine) to 99% (acetaminophen), but in all cases resulted insufficient in order to avoid their presence in treated water and subsequently in the environment.

Spatial distribution of heavy hydrocarbons, PAHs and metals in polluted areas. The case of "Galicia", Spain.

The aim of this work is to verify the impact of anthropogenic activities and the effects of accidental events, e.g. oil spills, on the marine environment. For this reason, marine sediments and soil samples were collected in the inner part of Vigo and Pontevedra bays, in the Galicia region, northwest Spain, an area interested by many events of oil spills and also characterized by coastal areas with intense anthropic activities; also Cíes Islands, a natural protected area facing the Vigo bay, was investigated, as background site. PAHs, heavy hydrocarbons and metals were analyzed according to standard methods, in order to satisfy quality assurance and quality check constraints. Total PAHs concentration (Σ16 compounds) were in the range of 25-4000ng/g, and 30-800ng/g for marine sediments and soil samples, respectively. Even some samples from the Cíes Islands, show a contamination with values achieving >200ng/g of PAHs. Although contamination levels have been shown to be strong at several locations in the study area, their ranges are those typical of other estuarine sites, with PAHs and hydrocarbons primarily of pyrolytic origin. This observation was further confirmed by enrichment factors of some metals (Cd, Cu, Pb and Zn) that match to those of harbor and shipyard zones of the main industrial and commercial maritime areas.

Relationships between lines of evidence of pollution in estuarine areas: Linking contaminant levels with biomarker responses in mussels and with structure of macroinvertebrate benthic communities.

Data obtained in a pollution survey performed in estuarine areas were integrated using multivariate statistics. The sites selected for the study were areas affected by treated and untreated urban discharges, harbours or industrial activities as well as reference sites. Mussels were transplanted to each site and after different times of exposure, samples of water, sediments and mussels were collected. Biomarkers were analysed on mussels after 3 and 21 days of transplant whereas concentrations of contaminants were measured in water, sediments and mussels after 21 days of transplant. The structure of macroinvertebrate benthic communities was studied in sediment samples. Studied variables were organised into 5 datasets, each one constituting a line of evidence (LOE): contaminants in water, contaminants in sediments, contaminants accumulated by transplanted mussels, biomarkers in transplanted mussels and changes in the structure of macroinvertebrate benthic communities of each sampling site. Principal Component Analysis (PCA) identified the variables of each LOE best explaining variability among sites. In order to know how LOEs relate to each other, Pearson's correlations were performed. Contaminants in sediments were not correlated with the rest of LOEs. Contaminants in water were significantly correlated with contaminants and biomarkers in mussels and with structure of macroinvertebrate benthic communities. Similarly, significant correlations were found between contaminants and biomarkers in mussels and between biomarkers in mussels and structure of macroinvertebrate benthic communities. In conclusion, biomarker responses give relevant information on pollution in estuarine areas and provide a link between chemical and ecological statuses of water bodies in the context of the Water Framework Directive.

Determination of nonylphenol and octylphenol in paper by microwave-assisted extraction coupled to headspace solid-phase microextraction and gas chromatography-mass spectrometry.

A novel and simple method for the determination of active endocrine disrupter compounds (octylphenol OP, and nonylphenol NP) in paper using microwave-assisted extraction (MAE) and headspace solid-phase microextraction, coupled with gas chromatography-mass spectrometry has been developed. Parameters affecting the efficiency in the MAE process such as exposure time and extraction solvent were studied in order to determine operating conditions. The optimised method was linear over the range studied (1.25-125 microg kg(-1) for OP and 9.50-950 microg kg(-1) for NP) and showed good level of precision, with a RSD lower than 10% and detection limits at 0.10 and 4.56 microg kg(-1) for OP and NP, respectively. The results obtained from six different types of paper revealed the presence of the target compounds in all samples analysed, at levels ranging between 3 and 211 microg kg(-1).

Sorption behaviour of nonylphenol and nonylphenol monoethoxylate in soils.

Sorption behaviour of two alkylphenolic compounds (APCs), nonylphenol (NP) and nonylphenol monoethoxylate (NP1EO), was studied in five soils with contrasting characteristics. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions containing different initial concentrations of NP or NP1EO. Linear fitting was generally appropriate for describing the sorption behaviour of NP and NP1EO in the soils, with the exception of two cases, for which the Freundlich model was more suitable for describing the sorption pattern of NP1EO. Solid-liquid distribution coefficients derived from sorption isotherms (Kd) varied from 24 to 1059 mL g(-1) for NP and from 51 to 740 mL g(-1) for NP1EO. For most soils, sorption Kd values were higher for NP than for NP1EO due to the higher hydrophobicity of NP. Sorption reversibility of NP and NP1EO was also tested from desorption isotherms. Desorption solid-liquid distribution coefficients (Kd,des), obtained from linear fitting, were between 130 and 1467 mL g(-1) for NP and between 24 and 1285 mL g(-1) for NP1EO. Kd,des values were higher than Kd values, which demonstrated that target compounds were irreversibly sorbed into soils, with the exception of the high desorption yield (45%) of NP1EO in the soil with the lowest content of organic matter. The fraction of soil organic carbon (FOC) was a key parameter that influenced the sorption of NP and NP1EO in soils, with logKOC values of 4.0 and 3.8, respectively.

Broad spectrum analysis of 109 priority compounds listed in the 76/464/CEE Council Directive using solid-phase extraction and GC/EI/MS

A single multiresidue method was developed to determine 109 priority organic compounds included in the 76/464/EEC Council Directive on Pollution of the European Union. Such Directive includes 132 priority pollutants with a broad spectrum of polarities to be analyzed in drinking and surface waters, with the aim to protect water quality. From this list, the compounds analyzed included benzidines, chloroanilines, chloronitrobenzenes, chloronitrotoluenes, chlorophenols, chloronitrotoluidines, PAHs, PCBs, pesticides, phenylurea, and triazine herbicides. The method was developed in four steps. First, automated off-line solid-phase extraction using polymeric sorbent Oasis 60 mg cartridges was optimized to trap 109 compounds. Second, gas chromatography coupled to mass spectrometry with electron impact ionization (GC/EI/MS) was used in selected ion monitoring (SIM) mode for tentative identification of target analytes. Third, GC/EI/MS under full scan conditions was used for spectrum identification and analyte confirmation. Last, quantification was performed from SIM chromatogram using surrogates and internal standard. This method offered excellent sensitivity and selectivity, and the preconcentration of 200 mL permitted the achievement of limits of detection at the low nanogram/liter level and recoveries between 70 and 120%. Such methodology was applied to determine 109 organic compounds in French surface waters, and several pollutants were detected at levels from ppt to ppb. This multiresidue method developed was highly reproducible and robust and permitted a high sample throughput.

Optimization of congener-specific analysis of 40 polybrominated diphenyl ethers by gas chromatography/mass spectrometry.

The analysis by gas chromatography coupled with mass spectrometry (GC/MS) of 40 different congeners of polybrominated diphenyl ethers (PBDEs) containing 1-7 bromine atoms is described. Two different MS approaches were used, negative chemical ionization (NCI-MS) and electron ionization (EI-MS). Operating parameters such as electron energy and source temperature were optimized in order to obtain the maximum sensitivity in the EI-MS study. For NCI-MS analyses, the effects of the moderating gas (methane or ammonia), source temperature and system pressure were studied. The quality parameters of the two approaches tested were compared. NCI-MS gave detection limits between 30 fg and 1.72 pg, whereas EI-MS gave detection limits between 0.53 and 32.09 pg. The main advantage of EI-MS is that it provides better structural information. Moreover, the use of EI-MS allowed the use of an isotope dilution method for quantification, making the analysis more reliable at trace levels.

Direct determination of resin and fatty acids in process waters of paper industries by liquid chromatography/mass spectrometry.

Liquid chromatography/mass spectrometry (LC/MS)-based methods were developed for the analysis of 10 resin acids and five fatty acids in process waters of paper industries. No fragmentation of target compounds was observed using atmospheric pressure chemical ionization (APCI) with negative ionization. The [M - H](-) ion permitted the individual quantification of fatty and aromatic resin acids, whereas the non-aromatic resin acids presented a single and common ion at m/z 301. Separation with two columns of different polarity permitted peak confirmation. The method that used a C(8) column with 2-propanol in the mobile phase allowed a certain separation and identification of the non-aromatic resin acids, whereas the method using a C(18) column provided detection limits 10-fold lower for fatty acids. Limits of detection were 0.10 ng for all compounds. Direct sample introduction was compared with liquid-liquid extraction, with similar recoveries (70-101%). Whereas slightly lower detection limits were obtained with liquid-liquid extraction, better reproducibility was observed for direct sample introduction. Resin and fatty acids were determined in process waters of several paper industries. Palmitic, dehydroabietic and non-aromatic resin acids were encountered in most water samples, at levels between 22 and 403 micro g l(-1). LC/MS with direct sample introduction was found to be a good alternative to traditional liquid-liquid extraction and gas chromatography for the analysis of such compounds since no derivatization was required and sample manipulation was minimal.

Determination of organophosphorus pesticides and their transformation products in river waters by automated on-line solid-phase extraction followed by thermospray liquid chromatography-mass spectrometry.

The trace-level determination of ten priority organophosphorus (OP) pesticides (e.g., chlorpyrifos-methyl, diazinon, disulfoton, fenthion, fenamiphos) and various transformation products (TPs; e.g., disulfoton sulfoxide, fenthion sulfoxide etc.) using automated on-line solid-phase extraction (SPE) with C18 precolumns followed by LC-MS and thermospray interface with time-scheduled selected-ion monitoring (SIM) was developed. Two main ions (usually [M+H]+ and [M+NH4]+ or [M+CH3CN]+) were used for each pesticide in the positive ion (PI) detection mode, while [M-H]- and [M+HCOO]- ions were used in the negative ion (NI) mode. The proposed method requires 100 ml of sample for a limit of detection (LOD) of 0.01-0.1 microgram/l. Calibration graphs were constructed by preconcentrating 100 ml of water spiked with the pesticide mixture at various concentrations (from 0.025 to 2 microgram/l). Good linearity was observed for most of the analytes studied. The experimental setup described in this paper was applied to study the kinetics of degradation of ten organophosphorus pesticides in spiked river water samples. The different samples were first analyzed by an automated on-line precolumn exchange system (OSP-2) followed by LC with diode array detection. To confirm the identity of the organophosphorus pesticides detected, the samples were then analyzed by automated on-line SPE-LC-MS. The method permitted unequivocal identification of many of the TPs formed during the experiments, e.g., the oxo-derivatives of chlorpyrifos-methyl, temephos and pyridafenthion, fenamiphos sulfoxide. Many of these TPs are here reported for the first time since previously used MS-based techniques were not sensitive enough.