Phthalate occurrence in rivers and tap water from central Spain.

The aim of this study is to evaluate the presence and concentrations of the main phthalates in water from the Jarama and Manzanares rivers in the region of Madrid (RM, Central Spain), the most densely populated region of Spain, and to determine the possible oestrogenic activity based on found phthalate concentration. The presence of phthalates in major supply drinking water areas of the RM was also analysed, thus allowing a preliminary assessment of the health risks resulting from the concentrations obtained. The results of this study show the presence of the three (dimethyl phthalate (DMP), diethyl phthalate (DEP) di-n-butyl phthalate (DBP)) of five phthalates studied (dimethyl phthalate (DMP), diethyl phthalate (DEP), di-(2-ethylhexyl) phthalate (DEHP), benzyl-butyl phthalate (BBP) and di-n-butyl phthalate (DBP)). The DBP was found in both river and tap water samplers, whereas DMP and DEP were found in only drinking water samples. The DBP was found to make the highest average contribution to pollution in both river and tap water. The DEHP was not found in both the river and tap water because it is one of the most regulated phthalates. The highest phthalate contamination was found in the Manzanares river and in those areas that receive treated water from the Tagus river. The phthalates found in river and tap water in the RM do not represent a potential oestrogenic risk for the aquatic environment or humans. A preliminary risk assessment suggested that the risk of exposure to phthalates from tap water in this study is acceptable, although continuous monitoring of the presence of these substances in both drinking and river water should be undertaken to detect possible increases in their concentrations. This is the first study to analyse the presence of phthalates in both rivers and drinking water of the centre of Spain.

Drugs of abuse and benzodiazepines in the Madrid Region (Central Spain): seasonal variation in river waters, occurrence in tap water and potential environmental and human risk.

This work analyzes the seasonal variation (winter and summer) of ten drugs of abuse, six metabolites and three benzodiazepines in surface waters from the Jarama and Manzanares Rivers in the Madrid Region, the most densely populated area in Spain. The occurrence of these compounds in tap water in this region is also investigated and a preliminary human health risk characterization performed for those substances found in tap water. Finally, a screening level risk assessment that combines the measured environmental concentrations (MECs) with dose-response data to estimate Hazard Quotients (HQs) for the compounds studied is also presented. The results of this study show the presence of fourteen out of the nineteen compounds analyzed in winter and twelve of them in summer. The most ubiquitous compounds, with a frequency of detection of 100% in both seasons, were the cocaine metabolite benzoylecgonine (BE), the amphetamine-type stimulant (ATS) ephedrine (EPH), the opioid methadone (METH), the METH metabolite 2-ethylene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), and the three benzodiazepines investigated, namely alprazolam (ALP), diazepam (DIA) and lorazepam (LOR). The highest concentrations observed corresponded to EPH (1020ngL(-1) in winter and 250ngL(-1) in summer). The only compounds not detected in both seasons were heroin (HER) and its metabolite 6-acetylmorphine (6ACM), lysergic acid diethylamide (LSD) and its metabolite 2-oxo-3-hydroxy-LSD (O-H-LSD), and Δ(9)-tetrahydrocannabinol (THC). In terms of overall concentration, all sampling points presented higher concentrations in winter than in summer. Statistical analyses performed to gather evidence concerning occasional seasonal differences in the concentrations of individual substances between summer and winter showed statistically significantly higher concentrations (p<0.05) of BE, EPH and the opioid morphine (MOR) in winter than in summer. Two out of the nineteen compounds studied, namely cocaine (CO) and EPH, were detected in tap water from one sampling point at concentrations of 1.61 and 0.29ngL(-1), respectively. The preliminary human health risk characterization showed that no toxic effects could be expected at the detected concentration level in tap water. The screening level risk assessment showed that MOR, EDDP and the THC metabolite 11-nor-9-carboxy-Δ(9)-tetrahydrocannabinol (THC-COOH) were present in at least one of the sampling sites in a concentration leading to a Hazard Quotient (HQ) value between 1.0 and 10.0, thus indicating some possible adverse effects. The cumulative HQ or Toxic units (TUs) calculated for each of the groups studied showed that opioids and cannabinoids were present at concentrations high enough to potentially generate some adverse effects on at least one sampling point.

Monitoring endocrine disrupting compounds and estrogenic activity in tap water from Central Spain.

The aims of this study are to investigate the presence of 30 substances known or thought to act as endocrine disrupting compounds in tap water from the main water supply areas for region of Madrid, to determine the total estrogenic activity of the samples analysed and to estimate the health risk for the population resulting from those compounds found at detectable concentrations. To this end, a one-off composite sampling was performed in August 2012 in which six tap water samples were collected from private residences in the drinking water supply network of the region of Madrid. A total of 14 of the 30 endocrine disruptors analysed were found at concentrations ranging from 0.3 to 165 ng/L. The organophosphorus flame retardants were detected at the highest concentrations followed by the plasticizer bisphenol A, alkylphenols, anticorrosion agents and preservatives. Tap water in the region of Madrid is contaminated with traces (ng/L) of compounds with endocrine disrupting properties. Although the concentrations of endocrine disrupting compounds obtained are too low to be able to confirm a public health risk, and no risk has been detected upon evaluation, it should be remembered that these compounds act at very low doses and that their effects may only appear in the long term.

Occurrence of drugs of abuse and benzodiazepines in river waters from the Madrid Region (Central Spain).

This work investigates, for the first time, the occurrence of 10 drugs of abuse, six metabolites, and three benzodiazepines in surface waters from the Jarama and Manzanares Rivers in the Madrid Region, the most densely populated area in Spain and one of the most densely populated in Europe. The results of this study have shown the presence of 14 out of the 19 compounds analyzed at concentrations ranging from 1.45 to 1020 ng L(-1). The most ubiquitous compounds, found in 100% of the samples, were the cocaine metabolite benzoylecgonine (BE), the amphetamine-like compound ephedrine (EPH), the opioids morphine (MOR), methadone (METH), and the METH metabolite 2-ethylene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), and the three investigated benzodiazepines alprazolam (ALP), diazepam (DIA) and lorazepam (LOR). Meanwhile, the largest concentrations observed corresponded to EPH (up to 1020 ng L(-1)), BE (823 ng L(-1)), EDDP (151 ng L(-1)), and LOR (167 ng L(-1)). The only not detected compounds were heroin (HER) and its metabolite 6-acetylmorphine (6ACM), lysergic acid diethylamide (LSD) and its metabolite 2-oxo-3-hydroxy-LSD (OH-LSD), and Δ(9)-tetrahydrocannabinol (THC). Overall, the levels measured are comparatively higher than those previously reported in Europe. Comparison of the results obtained for samples collected on different days (Thursday and Sunday) did not show meaningful differences between weekdays and weekends. The lack of (eco)toxicological data does not permit to predict or disregard potential adverse effects on wildlife. Risk assessment in humans would require further knowledge, not currently available, on exposure to these compounds through other routes like drinking water and/or food.

Analysis and occurrence of endocrine-disrupting compounds and estrogenic activity in the surface waters of Central Spain.

Endocrine-disrupting compounds (EDCs) are chemical compounds with the ability to alter the hormonal systems of organisms. Such compounds are used in several industrial and domestic activities and reach the aquatic environment via wastewater discharge. The aim of this study is to assess the occurrence of 30 EDCs and related compounds in the surface waters of central Spain and to determine the overall estrogenic activity of environmental samples. This study analyzed a large number of EDCs and other emergent or suspected compounds with endocrine-disrupting activity. The results have shown the presence of 19 EDCs at concentrations ranging from 2 to 5928 ng L(-1). Organophosphorus-based flame retardants, alkylphenolic compounds and anticorrosives were found at the highest concentrations. Furthermore, although insufficient data are available to calculate an average over time, these preliminary results show the need to monitor the waters in both rivers studied. Alkylphenolic compounds, particularly nonylphenol, were the main contributors to overall estrogenicity. A higher concentration of the compounds studied was detected in the river Jarama, although the estrogenicity expressed as estradiol equivalents (EEQs) was higher in the river Manzanares due to a higher concentration of nonylphenol. However, the total estrogenicity did not exceed 1 ng L(-1) (EEQ), which is the level that may cause estrogenic effects in aquatic organisms, in any of the samples. In conclusion, the potential estrogenic risk in both rivers is low, although organophosphorus-based flame retardants may increase this risk as they were found at high levels in all samples. Unfortunately, these compounds could not be taken into account when calculating the estrogenic activity due to the lack of activity data for them. For future investigations, it will be important to assess the estrogenicity provided by these flame retardants. Due to the significant concentrations of EDCs detected in both rivers, further studies in this region are required.

Drugs of abuse in surface and tap waters of the Tagus River basin: heterogeneous photo-Fenton process is effective in their degradation.

This work investigates for the first time the occurrence of drugs of abuse and metabolites in surface waters from the Tagus River on its way through the province of Toledo (downstream Madrid metropolitan area) and in drinking waters in two nearby cities. Some of the studied drugs are used for therapeutic purposes but they can also be consumed as illicit drugs. The results of this preliminary study have revealed the presence of 12 out of 22 drugs of abuse analyzed in fluvial water at concentrations ranging from 1.14 to 40.9 ng/L. The largest concentrations corresponded to the anxiolytics diazepam and lorazepam, the cocaine metabolite benzoilecgonine, the amphetamine-like compound ephedrine, and the methadone metabolite EDDP. All these substances, except for lorazepam, were detected in all the sampling points. Traces of methadone and ephedrine were detected in some samples of tap water. Despite the low concentrations of these pollutants, effects on wildlife or human health cannot be disregarded, especially on vulnerable population. Thus, the treatment of these substances using a heterogeneous photo-Fenton process has been evaluated, rendering a remarkable effectiveness for their degradation.

Nicotine occurrence in bottled mineral water: analysis of 10 brands of water in Spain.

The presence of pharmaceuticals in surface and drinking water has been evidenced in numerous studies. Despite representing one of the most common consumption sources, to the best of our knowledge, this is the first report on the presence of pharmaceutical compounds in bottled mineral water. Pollution of these sources not only could pose a serious human health risk, but would also warn about the quality of the water in our aquifers, a vital and vulnerable source of water, essential for the future water supply. Fifty eight pharmaceutically active compounds (PhACs) belonging to the 12 main therapeutic groups were analyzed in 10 bottled mineral water brands produced in Spain. Nicotine was detected in concentrations ranging from 7ngL(-1) to 15ngL(-1) in 5 of 10 bottled mineral waters. Despite the low nicotine concentration measured, the presence of this compound in bottled water still raises concern. Health risk assessment researchers have postulated that the risk to adult healthy humans from oral intake of nicotine at low levels is negligible. However, no studies have been conducted to assess the human health risk of vulnerable populations such as pregnant women and newborns. This population is the target of advertising on the purity and quality characteristics of bottled mineral water.

Detection of pharmaceutically active compounds in the rivers and tap water of the Madrid Region (Spain) and potential ecotoxicological risk.

Concentrations of pharmaceutically active compounds (PhACs) in the order of ng L(-1) to µg L(-1) have been reported worldwide in waste, fluvial and even drinking water, raising concern about the efficacy of the currently employed waste water treatments in the elimination of this kind of compounds. Despite ranking 29th in terms of population, Spain is currently the 8th country on pharmaceutical prescription with an expense of 14×10(9) euros in 2008. In this context, the aim of this study was to determine the presence of 33 pharmaceutically active compounds in specific points of the main rivers of the Madrid Region (MR) as well as tap water samples from the metropolitan area of Madrid. Additionally, a screening level risk characterization by means of the Hazard Quotient (HQ) method was applied. A total of 25 pharmaceutical compounds and metabolites were detected in the 10 sampling points downstream the outlet of the major STPs of the MR. The highest concentrations were detected for the anticonvulsant carbamazepine and the stimulant caffeine. Concentrations for most of the analyzed compounds exceed levels previously reported in the literature. Moreover, we report the highest concentration of the cytostatic ifosfamide, detected for the first time in Spain in surface water. Preliminary risk characterization shows that a total of 16 compounds represent at least a low potential hazard based on their scored HQs, with five of them present in a concentration that exceeds the predicted no effect concentration (PNEC). Toxic Units calculation indicates that for all the selected sampling points high hazard is anticipated from the presence of the analyzed compounds in the measured concentrations (TUs>10). Caffeine and cotinine were detected in all (10) the analyzed tap water samples. Carbamazepine and nicotine were detected in six and venlafaxine in two samples. No studies venlafaxine in drinking water have been reported. These results clearly pinpoint the need for water quality monitoring and research in urban rivers, as well as the need for improved water treatment techniques able to eliminate this kind of compounds from the effluent waters as well as from drinking water sources.