Pesticides and pharmaceuticals data collected during two consecutive years in a Mediterranean micro-estuary.

The Alexander micro-estuary, located at the eastern edge of the Mediterranean Sea, is a typical example of small water bodies that suffer from a combination of urban and agricultural pollution, and overuse of its natural water sources. It is∼6.5 km long, with maximum depth of 3 m and maximum width of 45 m. To evaluate the anthropogenic stress on the system and its ability to mitigate pollution, water samples were collected within the framework of Ruppin's Estuarine and Coastal Observatory [1]. Water samples were collected from the estuary head, which drains about 510 km2, and at a point 300 m upstream from the estuary mouth before water flows into the Mediterranean Sea. A total of 236 stormwater and 44 base-flow water samples between December 2016 and December 2018. Stormwater samples were collected every 0.25 - 4 h along the entire course of the flow events using an automated samplers (Sigma 900, Hach Company, Loveland CO, USA; and ISCO 3700 Full-Size Portable Sampler, Teledyne, Lincoln, NE, USA). Base-flow samples were taken once a month using a horizontal grab sampler (5 L, model 110B, OceanTest Equipment, Fort Lauderdale, FL, USA). All samples were filtered using 90mmGF/F filters (nominal pore size of 0.7 µm, MGF, Sartorius, Göttingen, Germany) and immediately frozen (-20°C) before chemical analysis. Chemical analysis was performed using liquid chromatography with high-resolution mass spectrometry (LC-HRMS) analysis using a QExactive Plus hybrid FT mass spectrometer coupled with a Dionex Ultimate 3000 RS UPLC (Thermo Fisher Scientific, Waltham, MA, USA). The targeted analysis, which included 15 fungicides, 25 herbicides, 18 Insecticides, and 19 pharmaceuticals, concluded with a total of 21,142 entries. All entries are organized in a worksheet, along with location, date, flood section duration, discharge rate, and the total water volume discharged during the relevant period. The provided data offers an opportunity to explore the sources, transport, and impact of a large mixture of organic pollutants in a confined aquatic system located in an urbanized coastal environment.

Ecological Risk Dynamics of Pharmaceuticals in Micro-Estuary Environments.

Micro-estuarine ecosystems have a surface area <1 km2 and are abundant in Mediterranean regions. As a result of their small size, these systems are particularly vulnerable to the effects of chemical pollution. Due to the fluctuating flow conditions of base flow dominated by treated wastewater effluents and flood events transporting rural and urban non-point-source pollution, micro-estuaries are under a dynamic risk regime, consequently struggling to provide ecological services. This 2 year study explored the occurrence and risks of pharmaceutical contamination in the Alexander micro-estuary in Israel. Pharmaceuticals were detected in all samples (n = 280) at as high as 18 µg L-1 in flood events and 14 µg L-1 in base flow. The pharmaceutical mixture composition was affected by flow conditions with carbamazepine dominating the base flow and caffeine dominating flood events. The median annual risk quotients for fish, crustaceans, and algae were 19.6, 5.2, and 4.5, respectively, indicating that pharmaceuticals pose a high risk to the ecosystem. Ibuprofen, carbamazepine, and caffeine contributed most to the risk quotients. The current work highlights that micro-estuary ecosystems, like the Alexander estuary, are continuously exposed to pharmaceuticals and most likely to other pollutants, placing these ecologically important systems under an elevated risk in comparison to the more frequently studied large estuarine systems.

Environmental risk dynamics of pesticides toxicity in a Mediterranean micro-estuary.

Pesticides are potentially toxic to aquatic systems, even at low concentration, depending on their individual ecotoxicological properties and their mixture composition. Thus, to evaluate possible ecological stress due to pesticide load, a thorough assessment of the potential toxicity of pesticide mixtures is required. Here we report water discharge and quality data of an eastern Mediterranean micro-estuary (Alexander stream), targeting the temporal distribution of a pesticide mixture. Over 150 water samples were collected during 2 hydrological years representing base-flow and flood conditions. On average, each water sample contained 34 and 45 different pesticides with peak concentrations of 1.4 µg L-1 of Imidacloprid and 55 µg L-1 of Diuron during base-flow and flood events, respectively. Pesticide mixtures were potentially toxic to benthic invertebrates and algae during flood events, surpassing the toxicity benchmark with medians of 110% and 155%, respectively. The herbicide Diuron and the insecticide Imidacloprid were the main pesticides responsible for the high potential toxicity during flood events. The falling limb of the flood hydrographs was found to inflict the highest stress on the estuarine environment due to elevated toxicity combined with prolonged residence time of the water. Examination of the potential chronic toxicity of single compounds showed continuous stress for plants, algae, amphibians, crustaceans, insects and fish from nine pesticides. Our data show that the ecosystem of the Alexander micro-estuary is under a continuous chronic stress with acute peaks in potential toxicity during flood events and the period that follows them. We propose that analyzing a small set of flood-tail samples is needed for the evaluation of small estuarine ecosystems risk during the rainy season. From a management perspective, we suggest better control of application practices for Diuron in the watershed to minimize the stress to the estuarine ecosystem.

Pesticide load dynamics during stormwater flow events in Mediterranean coastal streams: Alexander stream case study.

Cultivated land is a major source of pesticides, which are transported with the runoff water and eroded soil during rainfall events and pollute riverine and estuarine environments. Common ecotoxicological assessments of riverine systems are mainly based on water sampling and analysis of only the dissolved phase, and address a single pesticide's toxicological impact under laboratory conditions. A clear overview of mixtures of pesticides in the adsorbed and dissolved phases is missing, and therefore the full ecotoxicological impact is not fully addressed. The aim of this study was to characterize and quantify pesticide concentrations in both suspended sediment and dissolved phases, to provide a better understanding of pesticide-load dynamics during storm events in coastal streams in a Mediterranean climate. High-resolution sampling campaigns of seven flood events were conducted during two rainy seasons in Alexander stream, Israel. Samples of suspended sediments were separated from the solution and both media were analyzed separately for 250 pesticides. A total of 63 pesticides were detected; 18 and 16 pesticides were found solely in the suspended sediments and solution, respectively. Significant differences were observed among the pesticide groups: only 7% of herbicide, 20% of fungicide and 42% of insecticide load was transported with the suspended sediments. However, in both dissolved and adsorbed phases, a mix of pesticides was found which were graded from "mobile" to "non-mobile" with varied distribution coefficients. Diuron, and tebuconazole were frequently found in large quantities in both phases. Whereas insecticide and fungicide transport is likely governed by application time and method, the governing factor for herbicide load was the magnitude of the stream discharge. The results show a complex dynamic of pesticide load affected by excessive use of pesticides, which should be taken into consideration when designing projects to monitor riverine and estuarine water quality.