Risk analysis for groundwater intakes based on the example of neonicotinoids.

Neonicotinoids are a class of broad-spectrum insecticides that are dominant in the world market. They are widely distributed in the environment. Understanding the sources, distribution, and fate of these contaminants is critical to mitigating their effects and maintaining the health of aquatic ecosystems. Contamination of surface and groundwater by neonicotinoids has become a widespread problem worldwide, requiring comprehensive action to accurately determine the mechanisms behind the migration of these pesticides, their properties, and their adverse effects on the environment. A new approach to risk analysis for groundwater intake contamination with emerging contaminants was proposed. It was conducted on the example of four neonicotinoids (acetamiprid, clothianidin, thiamethoxam, and imidacloprid) in relation to groundwater accessed by a hypothetical groundwater intake, based on data obtained in laboratory tests using a dynamic method (column experiments). The results of the risk analysis conducted have shown that in this case study the use of acetamiprid and thiamethoxam for agricultural purposes poses an acceptable risk, and does not pose a risk to the quality of groundwater extracted from the intake for food purposes. Consequently, it does not pose a risk to the health and life of humans and other organisms depending on that water. The opposite situation is observed for clothianidin and imidacloprid, which pose a higher risk of groundwater contamination. For higher maximum concentration of neonicotinoids used in the risk analysis, the concentration of clothianidin and imidacloprid in the groundwater intake significantly (from several to several hundred thousand times) exceeds the maximum permissible levels for drinking water (<0.1 µg/L). This risk exists even if the insecticides containing these pesticides are used according to the information sheet provided by the manufacturer (lower maximum concentration), which results in exceeding the maximum permissible levels for drinking water from several to several hundred times.

Groundwater nitrate pollution risk assessment based on the potential impact of land use, nitrogen balance, and vulnerability.

The predicting groundwater nitrate pollution risk, especially in terms of changes in fertilizing, has not been fully investigated so far. In particular, there is no comprehensive method to assess this risk in areas of different land use type, and not only in agricultural areas. The aim of this study was to develop a novel multicriteria methodology for groundwater nitrate pollution risk assessment, which meets these issues. A further aim was to determine how much this risk would change if the amount of organic and synthetic fertilization was reduced. An assumption was that groundwater pollution risk is a combination of the potential adverse impacts of land use, fertilization, and intrinsic groundwater vulnerability to pollution. The impact of fertilization was holistically evaluated by balancing nitrogen from spatially differentiated the size of the breeding, species of livestock, manure and synthetic fertilizers input, and spatially differentiated topsoil, with nitrogen uptake by different crops. The nitrate concentration in the leachate was used as a measure of the impact of fertilization. This concentration was compared to the natural baseline nitrate concentration in groundwater. Three fertilization scenarios for groundwater pollution risk assessment in two study areas were discussed. Under typical agricultural, climatic, soil, and geological conditions in Europe for the current total fertilization level of 95-120 kg N ha-1 groundwater nitrate pollution risk is low and moderate, but for fertilization of 150-180 kg N ha-1, a reduction in the total fertilization (synthetic and manure) by 40 to 50% may be required to achieve low risk of degradation of natural groundwater quality. Predictive simulations of groundwater nitrate pollution risk confirmed that reducing synthetic and organic fertilization has an effect, especially in areas with intensive fertilization. This method may allow for a holistic and scenario-based assessment of groundwater pollution risk and may help decision-makers introduce solutions to manage this risk under conditions of climate change, preservation of groundwater quality, and food security.

Fate of selected neonicotinoid insecticides in soil-water systems: Current state of the art and knowledge gaps.

The occurrence of emerging contaminants, such as: personal care products, medicines, pharmaceuticals, pesticides, and their transformation products in the environment is of concern for human health and aquatic ecosystems due to their high persistence, toxicity and potential to bioaccumulation. Among pesticides, the main attention and thus our focus is on neonicotinoids: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam, which are widely used classes of insecticides in agriculture. Determining the associated risk to humans and ecosystems from neonicotinoid insecticides requires detailed understanding of their fate and transport in the environment which is complex and includes diverse pathways and processes depending on environmental compartments in which they occur. This paper critically reviews the current state of the art about processes, parameters and phenomena influencing the fate of neonicotinoid insecticides in soil-water systems (i.e. soil and groundwater), and reveals existing knowledge gaps. Sorption, biodegradation, chemical transformations of neonicotinoid insecticides in the soil and leaching to the groundwater, as well as groundwater/surface water interactions are highlighted, as they determine their further migration from sources, through soils to groundwater systems and then to other environmental compartments posing ecological and human risks. A number of key knowledge gaps in fate of neonicotinoid insecticides in soil-water systems are identified, that concern mostly processes and pathways occurring in the groundwater, and require further research to assess the associated risk to humans and ecosystems.

LC-MS/MS method validation for determination of selected neonicotinoids in groundwater for the purpose of a column experiment.

The work was carried out to develop and validate a method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous detection and quantification of five neonicotinoid insecticides: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam in groundwater samples for the purpose of a further column experiment. This experiment will be used to analyze breakthrough curves of neonicotinoids under a saturated water flow to set transport parameters, where the reliability of the results of chemical analysis plays an important role. The validation was performed in a concentration range from 0.09 µg L-1 to 100 µg L-1 using an Infinity 1290 (Agilent, USA) chromatograph coupled with a QTrap 5500 mass spectrometer (Sciex, Canada). The calibration curves were obtained on the basis of the results of six standard solution analyses. Linearity was not lower than 0.998. The limit of detection was set at the lowest concentration which can be determined with an acceptable accuracy and precision. All pesticides had recoveries in the range 85-109% with relative standard deviation values less than 8.1%. The estimated measurement uncertainty did not exceed 30%, so the LC-MS/MS method fits for the intended purpose.

Notes on the genera Antinia Pascoe, 1871 and Dermatodina Faust, 1895 with description of D. boroveci sp. nov. from Thailand (Coleoptera: Curculionidae: Entiminae).

The generic status of Dermatodina Faust, 1895 is restored and characters distinguishing this genus from Antinia Pascoe, 1871 are discussed. A new species, Dermatodina boroveci sp. nov., is described from Thailand. A checklist of species placed within the two genera is provided.