Metabolism of pharmaceuticals in plants is important to evaluate their fate and accumulation in vegetables, and subsequently the risks to human health. However, limited knowledge is available to evaluate metabolism of pharmaceuticals in plants due to the lack of appropriate research approaches. In this study, radish was selected as a model plant to investigate metabolism of pharmaceuticals in intact plants (in vivo) growing in hydroponic solution and in plant tissue enzyme extracts (in vitro). For caffeine, six phase-I demethylation metabolites identified in the intact radish plant were also found in the plant enzyme extracts. After 7 days of in vivo exposure, the amount of the identified metabolites was about 5.4 times greater than the parent compound caffeine in radish roots. Furthermore, the metabolism potential of fifteen pharmaceuticals in radish was evaluated on the basis of mass balance. After 7 days of hydroponic exposure, oxytetracycline, trimethoprim, carbamazepine, lincomycin, monensin and tylosin manifested relatively less extent of metabolism with the mass recoveries ranging from 52.3 to 78.2%. In contrast, 17 β-estradiol, sulfamethoxazole, sulfadiazine, estrone, triclosan, acetaminophen, caffeine, carbadox and lamotrigine underwent extensive metabolism with only 3.0 to 32.1% of the parent compound recovered. In the in vitro system, 17 β-estradiol, estrone, triclosan, oxytetracycline, acetaminophen, sulfadiazine and sulfamethoxazole were readily metabolized in radish root enzyme extracts with 1.8 to 34.0% remaining after 96-h exposure. While in the leaf enzyme extracts, only triclosan was rapidly metabolized with 49.2% remaining, and others pharmaceuticals were ≥60%, indicating that the varying extents of metabolism occurred in different plant parts. This study highlights the importance of pharmaceutical metabolism in plants, and suggests that plant tissue enzyme extracts could serve as an alternative tool to assess pharmaceutical metabolism in plants.

This study reports the development of a multi-residue method for determining 48 compounds of emerging concern (CEC) including three diclofenac transformation products (TP) in Slovenian wastewater (WW) and surface water (SW). For solid-phase extraction (SPE), Oasis™ Prime cartridges were favoured over Oasis HLB™. The validated method was then applied to 43 SW and 52 WW samples collected at nine locations. Ten bisphenols in WW and 14 bisphenols in SW were traced in Europe for the first time. Among all of the 48 targeted CEC, 21 were >LOQ in the influents and 20 in the effluents. One diclofenac TP was also quantified in WWs (3.04–78.1 ng L⁻¹) for the first time. As expected, based on mass loads in the wastewater treatment plant influents, caffeine is consumed in high amounts (105,000 mg day⁻¹ 1000 inhab.⁻¹) in Slovenia, while active pharmaceutical ingredients (APIs) are consumed in lower amounts compared to other European countries. Removal was lower in winter in the case of four bisphenols (17–78%), one preservative (36%) and four APIs (-14–91%), but remained constant for caffeine, one API, two UV-filters and three preservatives (all >85.5%). Overall, a constructed wetland showed the lowest (0–80%) and most inconsistent removal efficiencies (SD > 40% for some CECs) of CECs including caffeine, two UV-filters, two preservatives and two APIs compared to other treatment technologies. The method was also able to quantify Bisphenol S in SW (<36.2 ng L⁻¹). Environmental risk was assessed via risk quotients (RQs) based on WW and SW data. Two UV-filters (oxybenzone and dioxybenzone), estrone and triclosan, despite their low abundance posed a medium to high environmental risk with RQs between 0.282 (for HM-BP) and 15.5 (for E1).

Eragrostis plana Nees leaves, abundant lignocellulosic biomass, was used as carbon source for preparation of activated carbon, by using microwave-assisted pyrolysis and chemical activation. The novel activated carbon (MWEPN) was characterised by FTIR, CHN elemental analysis, Boehm’s titration method, TGA, SEM, N₂ adsorption/desorption curves and pH of the point of zero charge (pHₚzc). Afterwards, the adsorbent was successfully employed for adsorption of the two emerging contaminants (caffeine and 2-nitrophenol). The results indicated that MWEPN had a predominantly mesoporous structure with a high surface area of 1250 m² g⁻¹. FTIR analysis indicated the presence of carbonyl, hydroxyl and carboxylic groups on the surface of MWEPN. The Boehm analysis showed the existence of the high amount of acid moieties on the surface of activated carbon. Adsorption kinetic indicated that the system followed the Avrami fractional order at the optimal pH of 7. The equilibrium time was attained at 30 min. The Liu isotherm model better described the isothermal data. Based on the Liu isotherm, the maximum sorption capacities (Qₘₐₓ) of caffeine and 2-nitrophenol adsorbed onto activated carbon at 25 °C were 235.5 and 255.8 mg g⁻¹, respectively.

Wastewater treatment plants (WWTPs) are considered to be a source of environmental contamination by micropollutants, especially from pharmaceuticals and personal care products (PCPs). The pathway of those compounds during sewage treatment has been investigated, but data from real-scale WWTPs is still missing (for example, the values of the solid-liquid coefficient (Kd) during treatment). This paper uses the Kd values for some pharmaceuticals and PCPs (fenofibrate, gemfibrozil, propranolol, metoprolol, salicylic acid, acetylsalicylic acid, ibuprofen, diclofenac, naproxen, fenoprofen, caffeine, triclosan, methylparaben, ethylparaben, propylparaben, butylparaben, and benzylparaben) to describe the micropollutants’ behavior in the treatment process. In order to attain this data, an aerobic wastewater treatment plant located in Brazil was studied. Six samplings were carried out and a mass balance was performed, associating the concentrations of the micropollutants in the liquid phase with the solid phase (sludge and suspended solids). Of all the compounds analyzed, caffeine was the most biodegradable pollutant, as almost 98% of its mass was biodegraded. In contrast, triclosan had the highest load in sludge (median of 163.0 mg day⁻¹) and adsorbed in SS (median of 0.593 mg day⁻¹) at the output. Summing up, each micropollutant had a specific way to be removed during wastewater treatment.

A chromatographic procedure (HPLC-DAD) using a relatively rapid gradient has been combined with a chemometric curve deconvolution method, multivariate curve resolution-alternating least squares (MCR-ALS), in order to quantify caffeine and chlorogenic acid in green coffee beans. Despite that the HPLC analysis (at these specific operating conditions) presents some coeluting peaks, MCR-ALS allowed their resolution and, consequently, the creation of a calibration curve to be used for the quantification of the analytes of interest; this procedure led to a high accuracy in the quantification of caffeine and chlorogenic acid present in the samples. In a second part of this study, the possibility of classifying the green coffee beans on the basis of their cultivar (Arabica or Robusta), by partial least squares discriminant analysis (PLS-DA) and soft independent modeling of class analogies (SIMCA), has been explored. SIMCA resulted in 100% of sensitivity and specificity for the Arabica class, while for the Robusta, it reached 66.7% of sensitivity and 100% of specificity, or 100% of sensitivity and 100% of specificity, depending on the extraction procedure followed prior to the chromatographic analysis; PLS-DA achieved 100% of correct classification independently of the procedure used for the extraction.

Having in mind that there is a general lack of monitoring plans and precaution measures in the developing countries and that the Danube is the second longest river in Europe, the estimation of the relevant concentration levels of unregulated xenobiotics is a topic of interest both on local and international level. The selected pharmaceuticals, caffeine, and benzotriazole presented in the collected water samples from seven representative locations around the territory of Novi Sad, Serbia, during 1-year period, were analyzed with the use of solid-phase extraction followed by the liquid chromatography coupled with triple quad tandem mass spectrometry. The most frequently detected compounds were caffeine and carbamazepine in the concentrations up to 621 and 22.2 ng/L, respectively, while the maximum concentration of the analyzed pharmaceuticals was obtained for ibuprofen (60.1 ng/L). The presence of benzotriazole along the analyzed section of the river was confirmed in the concentration levels up to 26.7 ng/L. Although sulfamethoxazole and desmethyldiazepam were detected at trace levels (0.22 and 3.41 ng/L, respectively); the presence of these pharmaceuticals in complex mixtures should not be neglected. Due to the frequent detection caffeine, carbamazepine, ibuprofen, and benzotriazole could be proper candidate for hydrophilic anthropogenic markers for quantification of wastewater contamination in surface water in the analyzed Danube section.

Pharmaceuticals and personal care products (PPCPs) have attracted increasing concern during the last decade because of their widespread uses and continuous release to the aquatic environment. This work aimed to study the distribution of caffeine (CAF), oxybenzone (MBPh), and triclosan (TCS) when they arrive in salt marsh areas and to assess their remediation potential by two different species of salt marsh plants: Spartina maritima and Halimione portulacoides. Experiments were carried out in the laboratory either in hydroponics (sediment elutriate) or in sediment soaked in elutriate, for 10 days. Controls without plants were also carried out. CAF, MBPh, and TCS were added to the media. In unvegetated sediment soaked in elutriate, CAF was mainly in the liquid phase (83%), whereas MBPh and TCS were in the solid phase (90% and 56%, respectively); the highest remediation was achieved for TCS (40%) and mainly attributed to bioremediation. The presence of plants in sediment soaked in elutriate-enhanced PPCPs remediation, decreasing CAF and TCS levels between approximately 20-30% and MBPh by 40%.. Plant uptake, adsorption to plant roots/sediments, and bio/rhizoremediation are strong hypothesis to explain the decrease of contaminants either in water or sediment fractions, according to PPCPs characteristics.

The presence of caffeine in environmental water samples is almost entirely human-related, given that there are virtually no industrial or agricultural releases. Caffeine has already been proposed as an anthropogenic marker for wastewater contamination of surface waters. The aim of this study was to evaluate if caffeine concentrations in water can be a predictor of virological and bacteriological contamination. Water samples were taken at three sampling sites from urban water streams from the hydrographic basin of the Sinos River (Brazil) monthly in the period of May 9th, 2016 to April 11th, 2017 (n = 36). Concentrations of Human mastadenovirus (HAdV-F and HAdV-C), fecal coliforms, and caffeine were measured in all collected samples. Concentrations of caffeine in water were strongly correlated with HAdV-F (rₛ = 0.704, p = 0.000). This study, for the first time, characterized caffeine concentrations in water as predictors of virus presence, with cut-off values presenting 92.9% specificity and 95.5% sensitivity for HAdV-F and 66.7% specificity and 80% sensitivity for HAdV-C. Considering its marked chemical stability and ease of quantification, caffeine concentrations can be used as a comprehensive marker of human contamination of water resources, also being predictive of bacteriological and virological concentrations.

The occurrence, partitioning, and spatio-temporal distribution of seven pharmaceuticals for human use, three steroid hormones and one personal care product were determined in surface water, suspended particulate matter (SPM), and sediment of Piraí Creek and Jundiaí River (Jundiaí River Basin, São Paulo, Brazil). The maximum average detected concentrations of the compounds in the Piraí River samples were < 30 ng L⁻¹, except for caffeine (222 ng L⁻¹). In Jundiaí River samples, most of the compounds were frequently detected, wherein caffeine had the highest concentration, with maximum average concentrations of 14,050 ng L⁻¹, followed by atenolol (431 ng L⁻¹), ibuprofen (268 ng L⁻¹) and diclofenac (214 ng L⁻¹). Atenolol, propranolol, estrone, and triclosan were the contaminants most frequently detected in sediment and SPM samples. Triclosan had the highest average proportion of SPM as opposed to in the aqueous phase (> 75%). Contaminants with acid functional groups showed, in general, a lower tendency to bind to particulate matter and sediments. In addition, hydrophobicity had an important effect on their environmental partitioning. The spatial distribution of contaminants along the Jundiaí River was mainly affected by the higher concentration of contaminants in water samples collected downstream from a sewage treatment plant (STP). The results obtained here clearly showed the importance of the analysis of some contaminants in the whole water, meaning both dissolved and particulate compartments in the water, and that the partitioning is ruled by a set of parameters associated to the physicochemical characteristics of contaminants and the matrix properties of the studied, which need be considered in an integrated approach to understand the fate of emerging chemical contaminants in aquatic environments.

The rapid increase in the number and volume of chemical substances being used in modern society has been accompanied by a large number of potentially hazardous chemicals being found in environmental samples. In Vietnam, the monitoring of chemical substances is mainly limited to a small number of known pollutants in spite of rapid economic growth and urbanization, and there is an urgent need to examine a large number of chemicals to prevent impacts from expanding environmental pollution. However, it is difficult to analyze a large number of chemicals using existing methods, because they are time consuming and expensive. In the present study, we determined 1153 substances to grasp a pollution picture of microcontaminants in the aquatic environment. To achieve this objective, we have used two comprehensive analytical methods: (1) solid-phase extraction (SPE) and LC-TOF-MS analysis, and (2) SPE and GC-MS analysis. We collected 42 samples from northern (the Red River and Hanoi), central (Hue and Danang), and southern (Ho Chi Minh City and Saigon-Dongnai River) Vietnam. One hundred and sixty-five compounds were detected at least once. The compounds detected most frequently (>40 % samples) at μg/L concentrations were sterols (cholesterol, beta-sitosterol, stigmasterol, coprostanol), phthalates (bis(2-ethylhexyl) phthalate and di-n-butyl phthalate), and pharmaceutical and personal care products (caffeine, metformin). These contaminants were detected at almost the same detection frequency as in developed countries. The results reveal that surface waters in Vietnam, particularly in the center of large cities, are polluted by a large number of organic micropollutants, with households and business activities as the major sources. In addition, risk quotients (MEC/PNEC values) for nonylphenol, sulfamethoxazole, ampicillin, acetaminophen, erythromycin and clarithromycin were higher than 1, which indicates a possibility of adverse effects on aquatic ecosystems.