Pesticide water variability and prioritization: The first steps towards improving water management strategies in irrigation hydro-agriculture areas.

The presence of pesticides in aquatic ecosystems poses significant risks to non-target organisms, necessitating monitoring and environmental risk assessment. This study aimed to evaluate the dynamics and environmental risk of pesticides in a hydro-agricultural area with intensive agricultural practices, in the Mediterranean region (South of Portugal). Seasonality and location influenced pesticide numbers and concentrations, with the highest levels observed during the dry season. Triazines, phenylureas, and organophosphates were the predominant pesticide classes, with terbuthylazine, bentazone, terbutryn, diazinon, and metolachlor exhibiting the highest detection frequencies (68 % to 72 %). Notably, 44 % of the quantified pesticides are no longer authorized in Portugal, with 33 % posing a high environmental risk. Some insecticides, including imidacloprid, methiocarb, and malathion, were occasionally detected at concentrations that posed high risks to the aquatic ecosystem (RQ ≥ 1). Irgarol, an algicide used in irrigation canals, presented a high risk in 91 % of the analysed samples. The study's distribution profile of pesticides revealed a significant transportation of these compounds from reservoirs to irrigation hydrants, establishing them as a secondary source of crop and environmental contamination. Additionally, the assessment of spatial distribution and environmental risk allowed for the identification of specific pollutants in different locations, prioritizing them based on their ecotoxicological risk to aquatic ecosystems. These findings reinforce the importance of implementing management measures at the level of hydro-agricultural areas, helping to stop the cycle of pesticide contamination. Only this type of strategy will make it possible to protect water quality, biodiversity and the health of citizens, contributing to the European Union's objectives of improving the condition of freshwater bodies and promoting the sustainable use of pesticides.

Occurrence and risk assessment of pesticides in a Mediterranean Basin with strong agricultural pressure (Guadiana Basin: Southern of Portugal).

The study aimed to assess the occurrence and the environmental risk of a group of 51 selected pesticides in the Guadiana Basin (a biodiversity hotspot, in the Mediterranean). The most abundant pesticides were bentazone and 2,4-D, while terbuthylazine together with terbutryn constituted the most ubiquitous pesticides. Eighteen out of the 38 pesticides detected are no longer approved in Europe, and 5 of them are included in the list of priority substances. The risk assessment showed that azinphos ethyl, diflufenican, irganol, imidacloprid, and oxadiazon occurred occasionally, but always in concentrations above their respective ecotoxicological threshold value. Contrary, bentazone, terbuthylazine, and terbutryn presented a high risk in most of the sampled locations and periods. The site-specific risk assessment showed a spatial and temporal pattern, with a higher risk occurring mainly in intermittent streams, in the drought period. The presence of pesticides banned from the EU market since 2009 showed the importance of improving the monitoring process, to identify the main sources of pollution and the fate of these emerging compounds. The results showed the need of implementing actions to improve the sustainable use of pesticides in agricultural areas, working with farmers and management entities to reduce the contamination of aquatic ecosystems. Transboundary water governance is also required to solve potential transboundary contamination problems.

Ozonation of hospital raw wastewaters for cytostatic compounds removal. Kinetic modelling and economic assessment of the process.

The kinetics of the ozone consumption for the pretreatment of hospital wastewater has been analysed in order to determine the reaction rate coefficients between the ozone and the readily oxidisabled organic matter and cytostatic compounds. The wastewater from a medium size hospital was treated with ozone and peroxone methodologies, varying the ozone concentration, the reaction time and the hydrogen peroxide doses. The analysis shows that there are four cytostatic compounds, i.e. irinotecan, ifosfamide, cyclophosphamide and capecitabine, detected in the wastewaters and they are completely removed with reasonably short times after the ozone treatment. Considering the reactor geometry, the gas hydrodynamics, the mass transfer of ozone from gas to liquid and the reaction of all oxidisable compounds of the wastewater it is possible to determine the chemical ozone demand, COzD, of the sample as 256mgO3L(-1) and the kinetic rate coefficient with the dissolved organic matter as 8.4M(-1)s(-1). The kinetic rate coefficient between the ozone and the cyclophosphamide is in the order of 34.7M(-1)s(-1) and higher for the other cytostatics. The direct economic cost of the treatment was evaluated considering this reaction kinetics and it is below 0.3€/m(3) under given circumstances.

Occurrence and potential risk of currently used pesticides in sediments of the Alqueva reservoir (Guadiana Basin).

The evaluation of sediments, concerning to pesticides, constitutes an important step for the understanding of the principal sources of contamination of the surface water. Hence, the purpose of this study was to evaluate for the first time the occurrence, distribution and risk of pesticides in sediments of the Alqueva reservoir, the largest reservoir in the Europe. For this purpose, the occurrence of 22 pesticides and some of their degradation products was determined in surficial sediments of the Alqueva reservoir. To assess the potential risk on ecosystem, the measured concentrations of pesticides were compared with regulatory and toxicological benchmarks. Of the 22 pesticides analysed, only 8 were detected. Diuron was the pesticide detected in greater concentration, followed by terbuthylazine and chlortoluron. The sediments most polluted by pesticides were from Lucefécit, constituted totally by fine particles (<0.063 mm) and with high values of organic matter, and are located nearby large agricultural fields. The risk assessment allowed us to conclude that the sediments from the Alqueva reservoir presented low risk, concerning to pesticides, for the various communities that integrate the aquatic ecosystems. However, some of the compounds detected present a high potential for bioaccumulation that may lead to their bioamplification in the trophic chain, reaching concentrations higher than their acceptable daily intake, putting, in this way the populations at risk.

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.

Analysis of bisphenol A in natural waters by means of an optical immunosensor.

This work describes a very simple, fast and sensitive method based on the use of the optical immunosensor "RIver ANAlyser" (RIANA) to the determination of bisphenol A in a waters. RIANA is based on a rapid solid-phase indirect inhibition immunoassay that takes place at an optical transducer chip chemically modified with an analyte derivative. Fluorescence produced by labelled antibodies bound to the transducer is detected by photodiodes and can be correlated with the analyte concentration. The sensor surface can be regenerated thus allowing the performance of several measurements (around 300) with the same transducer. Each test cycle, including one regeneration step, is accomplished in 15 min. The detection limit achieved in the direct determination of bisphenol A in water with this system was 0.014 microg/L. Satisfactory repeatability, with relative standard deviations (RSD) ranging between 1.48% and 6.93% were obtained. The immunosensor method developed was applied to the monitoring of bisphenol A in various types of water collected in a waterworks (from the river water source to the finished drinking water) and validated against the results obtained in the same approach by a more traditional method, based on solid-phase extraction followed by liquid chromatography-mass spectrometry. Results obtained by both techniques were in general good agreement (considering the typical overestimation bias of immunoassays), and served to prove the satisfactory removal efficiency of the overall purification process applied in the waterworks and, in particular, of the sand filtration step.

Simultaneous multi-analyte determination of estrone, isoproturon and atrazine in natural waters by the RIver ANAlyser (RIANA), an optical immunosensor.

In most medical and environmental applications of biosensors, only single analytes are determined. However, the monitoring of several analytes is obviously preferable in order to gather more information about the sample under analysis. In line with this, different technologies are being developed to obtain multi-analyte sensors. In this paper, an analytical method for the simultaneous determination of three different contaminants-atrazine, isoproturon, and estrone-in natural waters by using an optical immunosensor prototype, the so-called "RIver ANAlyser" (RIANA), is described. RIANA is based on a rapid solid-phase fluoroimmunoassay that takes place at an optical transducer chip. The transducer surface is chemically modified with three analytes derivatives placed in different discrete locations. The sensor surface can be regenerated thus allowing the performance of several measurements with the same transducer. Each test cycle, including one regeneration step, is accomplished in 15 min. Detection limits achieved were 0.155, 0.046, and 0.084 microg/l, for atrazine, isoproturon, and estrone, respectively. Satisfactory repetition, with relative standard deviations between 1.06 and 6.98%, was obtained. Excluding a minor non-specifical binding of the isoproturon antibodies, no cross-reactivity effects were observed. Matrix effects were significant only in the case of wastewater samples. Biosensor measurements were validated using conventional liquid chromatography-mass spectrometry. The results obtained with both techniques were in good agreement.