The environmental condition of an estuarine ecosystem disturbed by pesticides.

Knowledge regarding the concentration levels resulting from the use of agricultural pesticides may indicate the nature of the controls necessary to reduce environmental and human health risks to an acceptable level. Therefore, the main goal of the present work was to assess the spatial and temporal occurrence of 35 pesticides in the River Sado estuary (Portugal) in 2017 and evaluate its environmental condition, as data for estuarine ecosystems is scarce. Since pesticides are very susceptible to matrix effects promoted by environmental samples, to attain the main goal, we developed a fast and almost solvent-free environmentally friendly method with a good performance for both estuarine surface water and sediment samples. Quantified residues were determined mostly during summer, in line with the pesticide application period. Five herbicides (alachlor, bentazon, metobromuron, metribuzin and triclopyr) were measured in the water before and after the production season, suggesting a long-term aquatic exposure. Sediment samples were less contaminated, since a lower number of quantified pesticides were found in the study area, in lower frequencies and lower concentrations. No potential high adverse effects of the use of agricultural pesticides were expected on the aquatic organisms of the Sado estuary, even considering the potential combination effect of pesticide mixtures.

Environmental and human health risk indicators for agricultural pesticides in estuaries.

The present study aims to contribute to a better assessment of pesticide environmental and human health (here evaluated in the context of human exposure via food items) risks for the estuarine system by comprehensively studying the spatial and temporal occurrence of the pesticides atrazine, azoxystrobin, bentazon, λ-cyhalothrin, penoxsulam and terbuthylazine in the River Mondego estuary (Portugal). Pesticide quantification was performed in surface water, sediment, macroalgae (Ulva spp., Gracilaria gracilis, Fucus vesiculosus), aquatic plants (Zostera noltii, Spartina maritime, Scirpus maritimus) and bivalves (Scrobicularia plana). Since intense precipitation could promote the runoff of pesticides from the surrounding agricultural fields, a single long-duration flood event was also studied in this estuarine system. Under normal flow conditions, quantified concentrations were determined mostly during summer in agreement with the pesticide application period. Azoxystrobin presented the highest detection frequency and atrazine (an herbicide used globally but banned in the EU) presented the second highest frequency, thus highlighting the need to include legacy pesticides in monitoring programmes. Pesticide concentrations in surface water determined in the present study suggest low risk to estuarine organisms. However, all the pesticides were bioaccumulated by S. plana, leading us to consider that pesticides may not only cause adverse effects on the aquatic organism itself, but should also be an alert for human exposure, for this is an edible species and is considered of economic interest. Concern is also expressed about edible seaweeds, since s-triazine pesticides were found in Ulva spp. and G. gracilis. Acknowledging these concerns, developing and establishing allowable pesticide safety values for edible seaweeds and bivalves is recommended, as well as monitoring bivalve pesticide levels, using the whole animal, as a human health exposure indicator for estuarine systems. During the studied flood event, it appears that no serious pesticide contamination has occurred in the River Mondego estuary.

A single-step pesticide extraction and clean-up multi-residue analytical method by selective pressurized liquid extraction followed by on-line solid phase extraction and ultra-high-performance liquid chromatography-tandem mass spectrometry for complex matrices.

Pesticides, a group of compounds linked to human activity, may, when in toxic levels, have a profound effect on water quality, and hence result in adverse consequences to aquatic life and ultimately to human health. Analytical challenges arise when successfully trying to determine these levels in environmental complex matrices. Therefore, fast, simple, sensitive and selective analytical methodologies for multi-residue determination of pesticides (atrazine, azoxystrobin, bentazon, λ-cyhalothrin, penoxsulam and terbuthylazine) in sediment, macrophytes (algae and aquatic plants) and aquatic animals were developed and validated. The established methods were matrix-dependent and were based on Selective Pressurized Liquid Extraction (SPLE) followed by on-line Solid Phase Extraction and Ultra Performance Liquid Chromatography-tandem Mass Spectrometry (on-line SPE-UPLC-ESI-MS/MS). This cutting-edge research methodology uses a small amount of sample, is time saving and reduces the use of organic solvents in compliance with Green Chemistry principles. The analytical features were adequate for all compounds in all studied matrices. The established methodology was applied on real marine samples and no pesticide concentrations above their respective method quantification limits were measured in sediments or aquatic plants. However, terbuthylazine was found in the macroalgae Ulva spp. (108ngg(-1)dw) and all the prospected pesticides were measured above their respective method quantification limits in the bivalve Scrobicularia plana (atrazine: 48ngg(-1)dw, azoxystrobin: 64ngg(-1)dw, bentazon: 33ngg(-1)dw, λ-cyhalothrin: 2531ngg(-1)dw, penoxsulam: 50ngg(-1)dw, and terbuthylazine: 44ngg(-1)dw).

Evaluation of the phototransformation of the antiviral zanamivir in surface waters through identification of transformation products.

The antiviral zanamivir has been recently reported to occur in surface waters where its presence may lead to the selection of resistant strains of virus in aquatic fauna. In order to evaluate the fate of zanamivir in surface waters, its susceptibility to phototransformation was evaluated using simulated and natural sunlight. Upon exposure of aqueous solutions (20µgL(-1)) to simulated sunlight, zanamivir in surface water degraded at t1/23.6h. Under natural sunlight in surface water about 30% of the initial concentration of the antiviral disappeared within 18 days. The experiments with surface water showed similar effect as humic acid addition with expected decreasing effect on degradation while nitrate addition showed increasing effect. In the experiments with artificial sunlight at high concentrations of zanamivir, four photoproducts were tentatively identified by hydrophilic interaction chromatography-LTQ-Orbitrap-MS, showing [M+H](+) ions at m/z 112 (TP111), m/z 275 (TP274), m/z 323 (TP322), and m/z 333 (TP332). However at 20µgL(-1) only the formation of the recalcitrant TP111 was observed. The proposed structures were rationalized by photolysis mechanisms. Photoproduct TP111 was confirmed with a commercially available standard (isocytosine). In summary, the findings suggest that the photodegradation of zanamivir in surface waters proceeds with slow kinetics.