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.

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.

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.

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.

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.

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.