M. López de Alda

Risk assessment of representative and priority pesticides, in surface water of the Alqueva reservoir (South of Portugal) using on-line solid phase extraction-liquid chromatography-tandem mass spectrometry.

Surface waters located in intensive agricultural areas are more vulnerable to the pesticides contamination, which is a major concern if the water is intended to be used for human consumption. The aim of this study was to evaluate the presence and the distribution of pesticides in the Alqueva reservoir, an important source of water supply (South of Portugal), considering their representativeness in the agricultural practice of the area. For the analysis of pesticides risk impact we used the environmental quality standards in the field of water policy proposed recently by the European Commission. The pesticides belonging to the classes of phenylureas, triazines, chloroacetanilides, organophosphorous and thiocarbamates were analysed by on-line solid phase extraction-liquid chromatography-tandem mass spectrometry. The pesticides more frequently detected were atrazine, simazine, diuron and terbuthylazine. The highest levels of these pesticides were registered in spring, after pesticides treatment, namely in olive-tree and vine crops. The priority pesticides atrazine and diuron reached values above the annual average proposed in the European Union Legislation. The herbicide atrazine reached values that surpassed the proposed maximum allowable concentration (2,000 ng L(-1)). The sampling stations most affected by these pesticides were Sra. Ajuda, Lucefecit and Alcarrache, located in the northern part of the reservoir, closer to Spain where the agricultural activity is more intensive.

Analysis of phytoestrogens, progestogens and estrogens in environmental waters from Rio de Janeiro (Brazil).

The environment is currently exposed to a large variety of man-made chemicals (e.g. for industrial, medicinal use) which have potential adverse effects to its ecological status. In addition, the densely populated areas represent local high emissions of those chemicals leading to more aggravating consequences. Estrogenic compounds that end-up in environmental water directly affect living organisms by interfering with their endocrine metabolism. The assessment of their presence in the environment requires sensitive and selective analytical methods. Nineteen estrogenic compounds belonging to different classes (5 free estrogens, 6 conjugated estrogens, 3 progestogens and 5 phytoestrogens) have been studied. The analytical methodology developed is based on solid phase extraction followed by liquid chromatography tandem mass spectrometry and has been applied to study the occurrence of the above mentioned analytes in environmental waters from the state of Rio de Janeiro (Brazil). Due to insufficient infra-structure in this region, waste waters are released onto the environment without or with incomplete previous treatment. The results show that high levels of the phytoestrogens daidzein, coumestrol and genistein of up to 366 ng/L and progesterone of up to 47 ng/L could be found in river water. Estrogens and their conjugated derivatives were detected in the lower ng/L range up to 7 ng/L. The main estrogens estrone, estradiol and the synthetic ethinyl estradiol could not be detected. The developed method showed overall good performance with recoveries above 80% (with one exception), limits of detection < or =2 ng/L, good linearity and reproducibility.

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.

Pharmaceuticals and iodinated contrast media in a hospital wastewater: A case study to analyse their presence and characterise their environmental risk and hazard

This work analyses the presence of twenty-five pharmaceutical compounds belonging to seven different therapeutic groups and one iodinated contrast media (ICM) in a Spanish medium-size hospital located in the Valencia Region. Analysis of the target compounds in the hospital wastewater was performed by means of solid phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry analysis (HPLC-MS/MS). A screening level risk assessment combining the measured environmental concentrations (MECs) with dose-response data based on Predicted No Effect Concentration (PNEC) was also applied to estimate Hazard Quotients (HQs) for the compounds investigated. Additionally, the environmental hazard associated to the various compounds measured was assessed through the calculation of the Persistence, Bioaccumulation and Toxicity (PBT) Index, which categorizes compounds according to their environmentally damaging characteristics. The results of the study showed the presence of twenty-four out of the twenty-six compounds analysed at individual concentrations ranging from 5 ng L(-1) to 2 mg L(-1). The highest concentrations corresponded to the ICM iomeprol, found at levels between 424 and 2093 μg L(-1), the analgesic acetaminophen (15-44 μg L(-1)), the diuretic (DIU) furosemide (6-15 μg L(-1)), and the antibiotics (ABIs) ofloxacin and trimethoprim (2-5 μg L(-1)). The lowest levels corresponded to the anti-inflammatory propyphenazone, found at concentrations between 5 and 44 ng L(-1). Differences in terms of concentrations of the analysed compounds have been observed in all the therapeutic groups when comparing the results obtained in this and other recent studies carried out in hospitals with different characteristics from different geographical areas and in different seasons. The screening level risk assessment performed in raw water from the hospital effluent showed that the analgesics and anti-inflammatories (AAFs) acetaminophen, diclofenac, ibuprofen and naproxen, the antibiotics (ABIs) clarithromycin, ofloxacin and trimethoprim, and the β-blocker (BBL) propranolol were present at concentrations leading to HQ values higher than 10, thus indicating high risk. When applying a factor to take into account potential dilution and degradation processes, only the compound ibuprofen showed a HQ higher than 1. Likewise, the cumulative HQ or Toxic Units (TUs) calculated in the raw water for each of the therapeutic groups studied showed that these three classes of drugs were at concentrations high enough to potentially generate high risk to aquatic organisms while taking into account possible dilution and degradation processes only one of them, the AAFs can be considered to represent high risk. Finally, the environmental hazard assessment performed showed that the AAFs diclofenac and ibuprofen and the ABI clarithromycin have the highest, maximum value of 9 of PBT Index due to their inherent environmentally damaging characteristics of persistence, bioaccumulation and toxicity. The methodology followed in the present case study can be taken as a novel approach to classify and categorize pharmaceuticals on the basis of their occurrence in hospital effluents, their derived environmental risks, and their associated environmental hazard. This classification becomes important because it can be used as a model or orientation for hospitals in the process of developing environmentally sustainable policies and as an argument to justify the adoption of advanced, specific treatments for hospital effluents before being discharged into the public sewage system.

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.

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.

Drugs of abuse in airborne particulates in urban environments

The presence of cocaine, heroin, cannabinoids and amphetamines, among other drugs of abuse, was detected in airborne particulates in urban environments in Spain. The levels of these compounds were determined at air quality monitoring sites by the application of a novel and specifically targeted analytical methodology, by which mean daily concentrations of cocaine (204-480 pg/m(3), up to one order of magnitude higher than in Italy and Portugal), cannabinoids (THC, 27-44 pg/m(3)), amphetamine (1.4-2.3 pg/m(3)) and heroin (9-143 pg/m(3)) were determined in the atmosphere. Results allowed detecting common temporal consumption patterns between cocaine and cannabis (with week-end maxima), but markedly distinct consumer groups. Personal exposure to the levels of all the drugs detected may be considered negligible, posing no harm for human health. Given the worldwide scarcity of data on drug levels in atmospheric particulates, we present this methodology as a fast, economic and reliable tool to obtain high quality data for the monitoring of drug abuse and drug dealing in cities. Applications include the detection of changes in drug consumption trends, the mapping of drug consumption and/or dealing areas in cities, and the identification of new emerging drugs.

Cocaine and other illicit drugs in airborne particulates in urban environments: a reflection of social conduct and population size

Levels of cocaine and other psychoactive substances in atmospheric particulate matter (PM) were determined in urban environments representing distinct social behaviours with regard to drug abuse: night-life, university and residential areas. Three cities (with population>1 million and <0.3 million inhabitants) were selected. Mean daily levels of drugs in PM were 11-336 pg/m3 for cocaine, 23-34 pg/m3 for cannabinoids, and 5-90 pg/m3 for heroin. The highest levels were recorded on weekends, with factors with respect to weekdays of 1-3 for cocaine, 1-2 for cannabinoids and 1.1-1.7 for heroin. Higher levels were detected in the night-life areas, pointing towards consumption and trafficking as major emission sources, and possibly ruling out drug manufacture. The similarities in temporal trends at all sites suggested a city-scale transport of psychoactive substances. Correlations were detected between cocaine and amphetamine consumption (r2=0.98), and between heroin and cannabinoids (r2>0.82).

Elimination of drugs of abuse and their toxicity from natural waters by photo-Fenton treatment

This paper investigates the elimination of drugs of abuse from six different chemical classes and their metabolites in natural fluvial waters (nearby the output of a sewage system). Mineralization of these substances and toxicological characterization before and after treatment by a heterogeneous photo-Fenton system has been evaluated. This advanced oxidation technology was able to significantly reduce the concentration of the drugs of abuse in all the tested conditions (different hydrogen peroxide and catalyst loadings). However, toxicological analyses measured as inhibition of fern spore mitochondrial activity, showed only a complete elimination of acute and chronic toxicity when a higher solid catalyst loading was used (0.6 g/L). A lower catalyst loading of 0.2 g/L was not enough for toxicity elimination. These results evidence the need for combining toxicological tests and chemical analyses in order to establish the effectiveness of the water treatment technologies based on advanced oxidation processes.

Evaluation of the aquatic passive sampler Chemcatcher for the monitoring of highly hydrophobic compounds in water.

The Chemcatcher passive sampler was primarily developed for the detection and quantification of priority organic pollutants (e.g., polycyclic aromatic hydrocarbons) in water. In the present study, this prototype was evaluated for highly hydrophobic compounds such as the tetrabrominated diphenyl ether BDE-47, the hexabrominated diphenyl ether BDE-153, and the historic pesticide DDT with its main metabolites (DDE and DDD). The sampling device consists basically of a receiving phase with high affinity for organic chemicals which is separated from the environment by a diffusion limiting membrane, both placed in a rigid PTFE body. C18 Empore disks were evaluated as receiving phase, obtaining a better accumulation when impregnated until saturation with n-octanol. As diffusion membrane, low density polyethylene was chosen over polyethersulphone. Once optimized its accumulation capacity for the target compounds, the linear behaviour of this accumulation was investigated and shown to be satisfactory in a period of 15 days. Preliminary uptake rates calculated from that accumulation anticipate the utility of this device for the detection of DDXs and the PBDEs, as calculated limits of detection are lower than usually reported environmental concentrations.