Comparison of the presence of high production volume chemicals in farmed and wild fish highly consumed in catalonia and their risk assessment.

The decline in fish populations and the depletion of marine resources have sparked concerns about sustainable fish production, driving the innovation of new aquaculture methods. While some argue that wild fish are healthier than farmed fish due to less exposure to contaminants and pathogens, wild fish can accumulate contaminants from more contaminated water sources. The slower growth of wild fish and their longer exposure to the environment may contribute to higher pollutant levels in fish tissues. In this study, we focus on 25 contaminants considered as high production volume chemicals (HPVCs), such as organophosphate esters (OPEs), benzothiazoles (BTs), benzosulfonamides (BSAs) and phthalates (PAEs). The compounds were extracted from the edible part of the fish using the QuEChERS method and analysed by gas chromatography-tandem mass spectrometry. A total of 74 samples were analysed from three of the most commonly consumed species in Catalonia, Spain (turbot, sea bass and sea bream). Two samples of each species were collected each month, one form farmed and one from wild origin. In general, the compounds were found in all the samples in a wide concentrations range, although no significant differences were observed between the mean concentration of wild and farmed samples. Although similar mean concentrations for the OPEs, BTs and BSAs were found between farmed and wild origin samples, PAEs were more frequently detected in farmed samples. Di-n-octyl phthalate and diethyl phthalate showed the highest concentrations in all fish samples, with values up to 19505 and 17605 ng g-1 (d.w.), in sea bass and sea bream, respectively. Di-(2-ethylexyl)-adipate proved to be the most relevant carcinogenic compound, with no associated health risk. Despite the detection of the studied HPVCs, no health risk was associated with the consumption of these three fish species.

Wastewater-based epidemiology to assess pharmaceutical consumption. Spanish perspective.

Wastewater-based epidemiology (WBE) is a well-established approach that can provide objective and real-time data on the consumption of substances such as pharmaceuticals. However, most of the studies reported so far compares consumption data obtained using WBE with those derived from prescription data from public health systems, which is often incomplete and might represent a source of uncertainty. This study aims to compare the measured pharmaceutical consumption back calculated with the WBE approach with consumption derived from dispensed pharmaceuticals in two regions of Spain, managed by two different Health Systems. To do so, a group of 17 pharmaceuticals, including the most representative ones of every therapeutic family, were monitored in influent wastewater (IWW) samples collected over a week campaign in spring 2022 at four different wastewater treatment plants (WWTPs) in Spain: two WWTPs in Madrid city (center of Spain) and two WWTPs in Catalonia (Northeast of Spain). Population-normalized daily loads (PNDL) revealed that the patterns of pharmaceutical occurrence in the different WWTPs are very similar, being acetaminophen, 4-acetamidoantipyrine and valsartan the pharmaceuticals with the highest PNDL values: 17162 ± 1457 mg day-1 1000 inh-1 for acetaminophen, 2365 ± 696 and 2429 ± 263 mg day-1 1000 inh-1 for 4-acetamidoantipyrine, 2006 ± 541 and 2041 ± 352 mg day-1 1000 inh-1 for valsartan. Pharmaceutical PNLDs were then transformed into measured pharmaceutical consumption (MC) and compared with dispensed consumption (DC) data obtained from the pharmacies in the catchment area where the WWTPs are located. A ratio MC/DC within 0.8 to 1.2 was obtained for 11 out of the 17 studied pharmaceuticals. Highlighting a match in all the cardiovascular system pharmaceuticals, with the exception of losartan (1.29-1.39 ratio) and valsartan (1.35-1.43) in all WWTPs. In summary, the degree of correlation between MC/DC is higher than those previously reported comparing with the prescribed pharmaceutical consumption.

Occurrence and health risk assessment of PFAS and possible precursors: a case study in a drinking water treatment plant and bottled water (south Catalonia, Spain).

The presence of PFAS in drinking water may pose a serious threat to human health. This study aims to determine the levels of these compounds and their precursors in water samples from a drinking water treatment plant (DWTP) located in l'Ampolla (Spain) and to assess their fate. Additionally, ten Spanish bottled waters were analyzed to compare the occurrence of PFAS in the mentioned matrices and in drinking water. Off-line solid phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was applied to determine 26 PFAS and PFAS precursors after a total oxidizable precursor assay. The analytical method presents low quantification limits (0.25-5 ng/L). A total PFAS concentration of up to 16 ng/L in all the DWTP samples was obtained, and 6:2 FTS was the only precursor detected. Results are close to the quantification limits, resulting in a high degree of uncertainty, and for this, it is difficult to evaluate the DWTP PFAS removal efficiency. Regarding bottled water, total PFAS concentration found was up to 12 ng/L in one of ten samples, with no precursors detected. Exposure assessment revealed that there is no risk associated with the ingestion of the samples analyzed. Moreover, there were no differences in terms of risk between drinking water from l'Ampolla DWTP and bottled water.

Passive sampling of high production volume chemicals and polycyclic aromatic hydrocarbons in urban atmospheres near petrochemical sites: Uptake rate determination and application.

This study describes the use of passive sampling followed by pressurised liquid extraction and gas chromatography-mass spectrometry for monitoring high production volume chemicals (HPVCs), such as benzothiazoles, benzesulfonamides, phthalate esters (PAEs), organophosphate esters, ultraviolet stabilizers, and phenolic antioxidants and polycyclic aromatic hydrocarbons (PAHs) in urban atmospheres close to a petrochemical area. To obtain accurate results when applying passive sampling, the uptake rates of each target compound for the sampling time applied must be known. Firstly, passive sampling was calibrated for two months and uptake rates of HPVCs and PAHs in an urban atmosphere determined using active sampling as the reference method. The obtained results showed experimental diffusive uptake rates between 1.6 m3 day-1 and 27 m3 day-1 for 32 of the target compounds that will allow enable cost-effective long-term monitoring campaigns of HPVCs to be performed. Secondly, the experimentally obtained uptake rates were used to monitor the concentrations of HPVCs and PAHs at six urban sampling sites close to the two petrochemicals parks in Tarragona (Spain) during a period the two months. Regardless of the sampling campaign, PAEs and PAHs were the families of compounds found at the highest concentration levels, with a sum of their mean values of 23 ng m-3 and 20 ng m-3, respectively.

Optimization of the ultrasound-assisted extraction method for determining high production volume chemicals in fish liver and skin samples.

The aquatic ecosystem is one of the most delicate environments, housing a diverse range of organisms, including fish, all of which are exposed to a wide variety of pollutants. The accumulation of these harmful substances in fish, which are part of the human diet, presents a significant health risk to humans. In our study, we have optimized an extraction technique to determine the presence of 25 high production volume chemicals in liver and skin samples taken from commonly consumed fish species. We have employed ultrasound-assisted extraction in conjunction with gas chromatography tandem mass spectrometry to achieve this goal. Apparent recoveries of the method ranged from 50% to 111% for both sample types with some exceptions such as most of the benzosulfonamides and benzothiazole. Additionally, the method's detection and quantification limits varied from 0.1 to 1.7 ng g-1 (dry weight, d.w) and 0.2-4.5 ng g-1 (d.w), respectively. Our investigation focused on three frequently consumed fish species in Tarragona: sea bass, sea bream, and turbot. Almost all of the samples we analysed contained traces of contaminants, with phthalates being the most commonly detected. The highest concentrations were observed for diethyl phthalate, with levels peaking at 8350 ng g-1 (d.w.). Organophosphate esters, such as triethyl phosphate and tributyl phosphate, also showed notable presence, with peak concentrations of 93.6 and 34.0 ng g-1 (d.w.), respectively.

Occurrence of high production volume chemicals and polycyclic aromatic hydrocarbons in urban sites close to industrial areas. Human exposure and risk assessment.

Evaluating the occurrence of high production volume chemicals (HPVCs) and polycyclic aromatic hydrocarbons (PAHs) in the air is important because they carry a carcinogenic risk and can lead to respiratory or endocrine problems. Examples of HPVCs are organophosphate esters, benzosulfonamides, benzothiazoles, phthalate esters (PAEs), phenolic antioxidants and ultraviolet stabilizers. In this paper we develop a multi-residue method for determining HPVCs and PAHs in air samples via pressurized liquid extraction followed by gas chromatography-mass spectrometry. Air samples were collected by active sampling with high volume samplers using quartz fiber filter for the particulate matter (PM10) and polyurethane foams for gas phase. The compounds found at the highest concentrations were PAEs, with a concentration of up to 24 ng m-3 of DEHP in gas phase and up to 109 ng m-3 of DEHA in PM10. Non-carcinogenic risk assessment results ranged from 9.7E-05 to 9.5E-03 for most of the compounds studied. On the other hand, the results for carcinogenic risk showed that PAHs made the highest contribution.

Selective determination of 2-aminobenzothiazole in environmental water and organic extracts from fish and dust samples.

In the present study, a homemade mixed-mode ion-exchange sorbent based on silica with embedded graphene microparticles is applied for the selective extraction of 2-aminobenzothiazole (NH2BT) followed by determination through liquid chromatography coupled to high-resolution mass spectrometry. The sorbent was evaluated for the solid-phase extraction of NH2BT from environmental water samples (river, effluent wastewater, and influent wastewater), and NH2BT was strongly retained through the selective cation-exchange interactions. Therefore, the inclusion of a clean-up step of 7 mL of methanol provided good selectivity for the extraction of NH2BT. The apparent recoveries obtained for environmental water samples ranged from 62 to 69% and the matrix effect from -1 to -14%. The sorbent was also evaluated in the clean-up step of the organic extract for the extraction of NH2BT from organic extracts of indoor dust samples (10 mL of ethyl acetate from pressurized liquid extraction) and fish (10 mL of acetonitrile from QuEChERS extraction). The organic extracts were acidified (adding a 0.1% of formic acid) to promote the cation-exchange interactions between the sorbent and the analyte. The apparent recoveries for fish samples ranged from 22 to 36% depending on the species. In the case of indoor dust samples, the recovery was 41%. It should be highlighted the low matrix effect encountered in such complex samples, with values ranging from -7 to 5% for fish and dust samples. Finally, various samples were analyzed. The concentration in river samples ranged from 31 to 136 ng/L; in effluent wastewater samples, from 55 to 191 ng/L; in influent wastewater samples, from 131 to 549 ng/L; in fish samples, from 14 to 57 ng/g dried weight; and in indoor dust samples, from

Evaluation of ceramic passive samplers using a mixed-mode strong cation-exchange sorbent to monitor polar contaminants in river water.

Although most of the analytical methods developed for the monitoring of contaminants in environmental waters are based on discrete grab sampling, an alternative of increasing interest is the use of passive sampling. Methods based on passive sampling provide the sampling and pre-concentration of the analytes in-situ, which makes the sample treatment less time consuming and costly than using discrete grab sampling. In this study, ceramic passive samplers (CPSs) using mixed-mode strong cation-exchange sorbent (Oasis MCX) as retention phase were evaluated for the determination of a group of 21 therapeutic and illicit drugs and some of their metabolites in river water samples that were determined by liquid chromatography-tandem mass spectrometry. After assessing the stability of the analytes, the CPSs were calibrated for 9 days with bottled water and river water, obtaining, for the 19 stable compounds, sample rates (Rs) ranging between 0.180 and 1.767 mL/day and diffusion coefficients (De) between 2.02E-8 and 2.81E-7 cm2/s. Once calibrated, CPSs were deployed for the determination of contaminants in the Ebre River, with good reproducibility, and some of the analytes were determined, including amongst others, gabapentin at 76 ng/L, caffeine at 203 ng/L or diclofenac amine at 57 ng/L. The passive sampling method herein presented is simple and feasible and allows the time-integrated analysis of pharmaceuticals and drugs at trace levels in river water. This study opens the possibility of using other mixed-mode sorbents or other types of sorbents as retaining phase on CPSs for the determination of very polar contaminants in water.

Ceramic passive samplers for determining pharmaceuticals and drugs of abuse in river and drinking water.

An important challenge today is to efficiently monitor the presence of polar pharmaceuticals and drugs in surface and drinking waters to ensure its safeness. Most studies rely on grab sampling techniques, which enable the determination of contaminants at a given point and given time. In this study, we propose the use of ceramic passive samplers (CPSs) to increase the representativeness and efficiency of organic contaminant monitoring in waters. Firstly, we have assayed the stability of 32 pharmaceuticals and drugs and found that five of those compounds were unstable. Moreover, we evaluated the retention capabilities of three sorbents (Sepra ZT, Sepra SBD-L, and PoraPak Rxn RP) in solid-phase extraction (SPE) mode and found no differences in terms of recoveries for all three sorbents. We then calibrated CPSs using the three sorbents for the 27 stable compounds over 13 days, with a suitable uptake for 22 compounds with sampling rates between 0.4 and 17.6 mL/day, which indicates high uptake efficiency. CPSs with the Sepra ZT sorbent were deployed in river water (n = 5) and drinking water (n = 5) for 13 days. Some of the studied compounds occurred with a time-weighted concentration, for instance, of 43 ng/L for caffeine, 223 ng/L for tramadol or 175 ng/L for cotinine in river water.

Seafood consumption as a source of exposure to high production volume chemicals: A comparison between Catalonia and the Canary Islands.

Seafood plays an important role in diet because of its health benefits. However, the fact that chemical compounds such as high production volume chemicals may be present in seafood means that its consumption can be a potential risk for population. To assess the occurrence of HPVs and estimate the exposure and risk associated with their consumption, specimens of the most consumed seafood species in Catalonia and the Canary Islands, Spain, were collected and analysed. Results showed higher levels of HPVs in samples from Catalonia and a prevalence of phthalate esters and benzenesulfonamides over the other target compounds in samples from both locations. Multivariate analysis showed spatial differences between the mean concentration profiles of HPVs for the samples from Catalonia and the Canary Islands. Exposures were higher for the samples from Catalonia, although the intake of HPVs via seafood was not of any real concern in either of the locations.

Extraction of selected benzothiazoles, benzotriazoles and benzenesulfonamides from environmental water samples using a home-made sol-gel silica-based mixed-mode zwitterionic sorbent modified with graphene.

A novel sol-gel silica-based mixed-mode zwitterionic sorbent modified with graphene microparticles was synthesized. Thanks to the inclusion of multiple functional groups and graphene microparticles to exert a wide range of intermolecular/interionic interactions including dipole-dipole interactions, ion-exchange interactions and π-π interactions, the sorbent showed high retention in the solid-phase extraction (SPE) of benzothiazoles, benzotriazoles and benzenesulfonamides. The SPE protocol was optimized in terms of pH, sample loading volume and elution conditions using liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). The method based on SPE followed by LC-HRMS was validated. Apparent recoveries at two levels of concentration were in the range from 48 to 85% (in most cases) in matrices such as influent wastewater, matrix effect was lower than ±30% in most cases, method detection and quantification limits being lower than 20 ng/L and repeatability and reproducibility between days were lower than 18% (n = 4). River, effluent and influent wastewaters samples were analyzed, obtaining concentrations ranging from 3 to 175 ng/L in river samples, from 12 to 499 ng/L in effluent samples and from 15 to 632 ng/L in influent samples, when the compounds were above the method quantification limits.

Determination of benzothiazoles, benzotriazoles and benzenesulfonamides in seafood using quick, easy, cheap, effective, rugged and safe extraction followed by gas chromatography - tandem mass spectrometry: Method development and risk assessment.

The common use of benzothiazoles, benzotriazoles and benzenesulfonamides has led to widespread ubiquity in several environmental matrices. Their occurrence in edible fish could represent an additional exposure route for the population. The present study aims to develop a method for the simultaneous determination of these three compound families in seafood samples. Based on QuEChERS extraction, different salt combinations and clean-up strategies have been evaluated to achieve the highest recoveries while reducing the matrix effect in low and high lipidic content species. The best results were obtained with the original method salts and the lipid-selective push-through clean-up, which combined with gas chromatography-tandem mass spectrometry led to recoveries between 50 and 112% with negligible matrix effects and method detection limits between 0.15-9.50 ng g-1 dw. The application of the method to commercially available samples confirmed the presence of BTs as well as BSAs, with the latter being determined in seafood for the first time. Exposure and risk assessment calculations indicated a minor risk for the population when consuming fish.

High production volume chemicals in the most consumed seafood species in Tarragona area (Spain): Occurrence, exposure, and risk assessment.

Seafood consumption has become a potential exposure route towards high production volume chemicals (HPVs) due to the pathway of these compounds reaching the aquatic environment via industrial and domestic discharges. The present study focuses on the determination of phthalate esters (PAEs), organophosphate esters (OPEs), benzothiazoles (BTs), benzotriazoles (BTRs) and benzenesulfonamides (BSAs) in the ten most consumed fish species in Catalonia. A total of 120 commercially available seafood specimens were purchased throughout February 2019-February 2020 in three different stores (supermarket, local market, and local fishmonger) of the city of Tarragona, Spain, to cover the most typical places where seafood can be obtained. ΣOPEs, ΣBTs, ΣBSAs and ΣPAEs concentrations ranged between 5.99 and 139.45 ng g-1 w.w., 8.41-54.08 ng g-1 w.w., 8.38-304.47 ng g-1 w.w and 2.86-323.80 ng g-1 w.w., respectively. BTRs were not detected in any of the samples. PAEs and BSAs had similar contributions which combined represented nearly the 70% of detected compounds and sardine resulted as the species with the higher HPVs mean concentration. No considerable threat was posed due to the individual intake of these compounds via seafood consumption.

Development of a Liquid Chromatography-Tandem Mass Spectrometry Method for the Simultaneous Determination of 40 Drugs of Abuse in Human Urine: Application to Real Cases.

Drugs of abuse are constantly evolving, while new synthetized substances are constantly emerging to avoid regulations. However, traditional drugs such as cocaine and amphetamine are still two of the most consumed drugs in the world. It is important, therefore, to provide suitable multiresidue methods for determining a wide range of drugs for use in toxicological and forensic analyses. The aim of this study is to develop a method for determining several families of drugs of abuse, including classic drugs, new psychoactive substances and some of their metabolites, in urine by liquid chromatography-tandem mass spectrometry. Urine is one of the most common biological matrices used in drug analysis because of its easy collection and a wide window of detection. In this study, we used solid-phase extraction to remove interferences and extract analytes from urine. Four different mixed-mode cation-exchange commercial sorbents were evaluated. The best results, in terms of apparent recoveries, were achieved with one of the strong cationic sorbents, ExtraBond SCX. The method achieved detection limits from 0.003 to 0.500 ng/mL and quantification limits from 0.050 to 1.500 ng/mL, which are suitable for determining these compounds at the usual levels found in the urine of drug users. The applicability of this method was demonstrated by analyzing real urine specimens from women following a detoxification program. Our results showed that the drug most consumed was cocaine, since it was detected in most urine specimens together with its main metabolite, benzoylecgonine. The polyconsumption of drugs from different families was also observed in some urine samples analyzed.

Determination of Organophosphate Ester Metabolites in Seafood Species by QuEChERS-SPE Followed by LC-HRMS.

Organophosphate triesters are compounds widely used in industries and are ubiquitous in the environment, where they can be transformed into organophosphate diesters. Some organophosphate diesters are also used by industry. Several studies suggest organophosphate diesters can have toxic effects for reproduction, and hazardous and mutagenic properties. Due to the impact these compounds can have on marine biota and human beings through the consumption of fish and shellfish, it is necessary to study their presence in widely consumed seafood species. We therefore developed an analytical method for determining six of the most common organophosphate diesters in seafood. The procedure is based on the Quick, Easy, Cheap, Effective, Rugged and Safe extraction method and a solid phase extraction clean-up, followed by liquid chromatography coupled to high-resolution mass spectrometry. The method was optimised and validated for seafood with different lipid content, providing satisfactory relative recoveries (from 89 to 138%) and limits of detection (1.0-50 ng g-1 dry weight), as well as repeatability values (RSD% (n = 5, 100 ng g-1 (dry weight)) lower than 15%. Eight seafood species were analysed using this method and two organophosphate diesters were detected and quantified in all the samples, demonstrating the suitability of the method.

Occurrence of organic contaminants bonded to the particulate matter from outdoor air influenced by industrial activities.

This paper discusses the occurrence of organic contaminants bonded to particulate matter (PM) in ambient air. We describe the presence and concentration levels of contaminants mainly reported in atmospheres close to factories or at locations influenced by them, and the relationship between factory emissions and the type of organic contaminants found in PM samples from the surrounding air. Many organic contaminants have been found in these types of samples, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs). Their sources, fates and distributions in the ambient atmosphere are therefore well known. However, in addition to these most studied compounds, others are also of concern nowadays due to their detection and toxic effects on the environment. The continuous updating of regulations on these contaminants and the appearance of new air pollutants make it important to be aware of their occurrence. This will help to either establish new guidelines for the newer contaminants or reassess existing limitations for known ones. Moreover, if we know their occurrence, we can analyse their sources, destinations and distributions in the outdoor air.

Development of sol-gel silica-based mixed-mode zwitterionic sorbents for determining drugs in environmental water samples.

Four novel mixed-mode zwitterionic silica-based functionalized with strong moieties sorbents were synthesized and evaluated through solid-phase extraction (SPE) to determine acidic and basic drugs in environmental water samples. All sorbents had the same functionalization: quaternary amine and sulfonic groups and C18 chains so that hydrophobic and strong cationic exchange (SCX) and strong anionic exchange (SAX) interactions could be exploited, in addition, two of them had carbon microparticles embedded. All sorbents retained both acidic and basic compounds in the preliminary assays but only the basic compounds were retained selectively through ionic exchange interactions when a clean-up step was introduced. The SPE method was therefore optimized to promote the selective retention of the basic compounds, initially with the two best-performing sorbents. After optimization of the SPE protocol, these sorbents were evaluated for the analysis of environmental water samples using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method with the best-performing sorbent was then validated with 100 mL of river samples and 50 mL of effluent wastewater samples in terms of apparent recoveries (%Rapp) spiking samples at 50 ng/L (river) and 200 ng/L (river and effluent), matrix effect, linear range, method quantification and detection limits, repeatability, and reproducibility. It should be highlighted that %Rapp ranged from 40 to 85% and matrix effects ranged from -17 to -4% for spiked river samples. When the method was applied to river and effluent wastewater samples, most compounds were found in the range from 24 to 1233 ng/L with detection limits from 1 to 5 ng/L.

Evaluation of air quality in indoor and outdoor environments: Impact of anti-COVID-19 measures.

This study monitors the presence of 88 volatile organic compounds (VOCs) and semi-volatile organic compounds (semi-VOCs) at the gas phase of seven indoor settings in a school in the city of Tarragona, Spain, and five outdoor locations around the city. The VOCs and semi-VOCs monitored were solvents (∑Solvents), aldehydes (∑Aldehydes), emerging organic compounds (∑EOCs), and other VOCs and semi-VOCs (∑Others). Passive sampling campaigns were performed using Carbopack X tubes followed by thermal desorption coupled to gas chromatography with mass spectrometry (TD-GC-MS). Overall, 70 of the target compounds included in the method were determined in the indoor air samples analysed, and 42 VOCs and semi-VOCs in the outdoor air samples. Our results showed that solvents were ubiquitous throughout the school at concentrations ranging from 272 µg m-3 to 423 µg m-3 and representing 68%-83% of total target compounds (∑Total). The values of ∑Total in 2021 were three times as high as those observed at the same indoor settings in 2019, with solvents experiencing the greatest increase. A plausible explanation for these observations is the implementation of anti-COVID-19 measures in the indoor settings, such as the intensification of cleaning activities and the use of hydroalcoholic gels as personal hygiene. The ∑Total values observed in the indoor settings evaluated were twenty times higher than those found outdoors. ∑Solvents were the most representative compounds found indoors (74% of the ∑Total). The concentrations of VOCs and semi-VOCs observed in the outdoors were strictly related to combustion processes from automobile traffic and industrial activities, with ∑Others contributing 58%, ∑Solvents 31%, and ∑Aldehydes 11% of the ∑Total. EOCs, on the other hand, were not detected in any outdoor sample.

Multiresidue analytical method for high production volume chemicals in dust samples, occurrence and human exposure assessment.

A multiresidue analytical method based on pressurised liquid extraction and gas-chromatography mass spectrometry was developed to determine 22 compounds belonging to different chemical families in indoor dust.: Seven organophosphate esters, six phthalate esters, three benzotriazoles, five benzothiazoles and four benzenesulfonamides were included in the present study, all of them belonging to the category of high production volume chemicals (HPVCs). Apparent recoveries ranged between 45% and 123% and method quantification limits ranged from 0.03 µg/g to 3.8 µg/g. The occurrence of the selected HPVCs was evaluated in indoor dust from different locations in the Tarragona (Catalonia, Spain) region. Two benzenesulfonamides, ortho-toluenesulfonamide and para-toluenesulfonamide, were detected in dust samples for the first time. Phthalate esters and organophosphate esters were the most abundant compounds found, and di-(2-ethylhexyl) phthalate (DEHP) was determined at the highest concentrations. With the data obtained, human exposure was assessed by calculating the estimated daily intakes (EDI) via ingestion and dermal contact. Non-carcinogenic and carcinogenic risk assessments found no risks in any of the scenarios tested, which included two age classes (children and adults) and two possible exposure scenarios (median and worst-case scenario), except for the evaluation of carcinogen risk due to ingestion of DEHP in the worst-case scenario.

Comparison of different chiral selectors for the enantiomeric determination of amphetamine-type substances in human urine by solid-phase extraction followed by capillary electrophoresis-tandem mass spectrometry.

The present study develops a method for the enantioseparation of a group of amphetamines and their metabolites in urine by CE coupled to MS/MS (CE-MS/MS). Amphetamines present a chiral center and thus two enantiomers, which is important from a toxicological point of view because they may have different pharmacokinetic and pharmacological properties. It is therefore essential to find suitable methods to distinguish both enantiomers. Today the use of CE is becoming more important in this field since, with the simple addition of a chiral selector to the background electrolyte, the enantioseparation can easily be achieved. However, when CE is coupled to MS, the use of volatile chiral selectors and compatible background electrolytes or other strategies such as the countercurrent migration approach are required to avoid contamination of the ion source from nonvolatile species. In the present study, we use the latter strategy to evaluate six different chiral selectors using CE-MS/MS. As a sample pre-treatment, two cationic-exchange sorbents-Oasis WCX and Oasis MCX-are compared for the urine pre-treatment. Using this method, it was possible to achieve the complete chiral separation of the amphetamines under study with detection limits ranging between 0.8 and 1.5 ng/mL and method quantification limits between 2.0 and 8.0 ng/mL. Matrix-matched calibration curves up to 150 ng/mL were used to cover the usual concentration ranges at which amphetamines have generally been found in toxicological and forensic analyses.