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.

Assessing health risks in bottled water: chemical compounds and their impact on human health.

Bottled mineral and spring water constitute one of the main sources of drinking water. Relevant legal acts in each country individually regulate the highest permitted concentrations of harmful substances in these waters. However, current regulations do not take into account newly emerging contaminants such as BPA. Analysis of the chemical composition of 72 bottled waters from the Polish market showed that undesirable elements occur in quantities that do not exceed the maximum permissible concentrations. Special attention should be paid to bottled therapeutic water, which may contain elevated concentrations of some micronutrients, such as Al, B, Ba, Fe, Mn, or Sr contributing to the pattern of health risk with excessive consumption of this type of water. The presence of BPA was confirmed in 25 tested waters. The calculated hazard index values showed that the most exposed group are children up to 12 years of age. The greatest attention should be paid to waters with high mineralisation, for which the calculated risk values are the highest.

Spent sulfuric acid plant catalyst: valuable resource of vanadium or risky residue? Process comparison for environmental implications.

The enormous amount of spent catalysts generated worldwide may pose a risk to the environment because of their high load of metals, including vanadium. The latter may be mobilized and released to the environment if managed improperly. Moreover, the catalysts could be considered as secondary resources rather than waste. This study aimed at the efficient extraction of vanadium from spent desulfurization catalyst (SDC) from a sulfuric acid production plant. The raw SDC and the post-extraction residues were characterized in terms of their chemical and phase composition. The metal mobility from the materials was examined with both single-step and multi-step extractions. The environmental risk assessment was performed using sequential extraction. The study revealed that both tested methods (citric acid leaching and bioleaching with Acidithiobacillus thiooxidans) enable the extraction of nearly 96% of V from SDC with a simultaneous reduction of metal mobility. However, the bacterial treatment was found more suitable. The leached residue was mostly (> 90%) composed of SiO2, which makes it a potential candidate for application in construction (e.g., concrete mixtures) after additional examinations. The study highlights the need to develop a metal extraction process for SDC in a way that metal-free residue could be a final product.

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.

Redox potential research in the field of balneochemistry: case study on equilibrium approach to bioactive elements in therapeutic waters.

In some countries (e.g. Poland, Czechia, Slovakia, Russia, Germany), oxidation-reduction potential (ORP) measurements are required to document the quality of groundwater which are planned to be used as therapeutic waters. ORP is still rarely studied and not fully availed in therapeutic water research. Studies of ORP in various types of therapeutic, mineral and thermal waters in sites of Poland integrated with geochemical equilibrium approach were employed to characterize two redox-sensitive and bioactive elements, i.e. iron and sulphur. Studied waters present reducing conditions (EH between - 406 and - 41 mV) at outflow or extraction sites; however, they significantly differ in terms of total dissolved solids, temperature, and iron, sulphur(II) and sulphate concentrations. These result in recognizable differences, e.g. in terms of saturation state with respect to aquifer rock minerals and the dominating forms of occurrence of elements studied disclosed on the stability field diagrams. Considering the methodological determinants, ORP orchestrated with geochemical modelling tools might be successfully applied for studying natural linkages between various groundwater in natural systems, protecting the therapeutic water resource, and identifying the changes of water quality both at exploitation sites (springs, wells) and treatment places.

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.

Bacterial leaching of critical metal values from Polish copper metallurgical slags using Acidithiobacillus thiooxidans.

Global economy faces an increasing problem of the supply risk of critical raw materials, therefore the search for secondary resources has become an urgent issue. Copper orebodies in Poland contain substantial amounts of metals deemed critical (e.g. Co, Mo, rare earth elements (REE) or V), which are not recovered during processing. The metals of interest are concentrated in metallurgical waste residues that should be classified as a secondary resource rather than as a waste. Bioleaching is a frontier technology promising for environment-friendly treatment of slags. Therefore, the objective of this work was to study the feasibility of metal (Co, Mo, REE, V) bioleaching from copper metallurgical wastes employing Acidithiobacillus thiooxidans bacterial strain as the leaching agent. The effect of particle size (fractions <0.25 mm and 0.25-0.5 mm) and pulp density (1%, 2%) was studied using three different slag samples (lead slag - LS, shaft furnace slag - SFS and granulated slag - GS). The bioleaching experiment was set up for 28 days under acidic conditions (pH t0 = 2.5). The results revealed that the microorganisms can catalyze metal extraction from slags as compared to leaching achieved under abiotic conditions. The optimal bioleaching yield was achieved under conditions at 0.25-0.5 mm particle size and 1% pulp density, regardless of used type of slag. After 28 days, the extracted amounts of metals were: 88% Co, 40% Mo, 83% REE and 55% V from LS, 100% Co, 44% Mo, 70% REE and 70% V from SFS and 95% Co, 70% Mo, 99% REE and 93% V from GS. All examined slags showed good potential for bioleaching of valuable elements. However, optimization of initial parameters is still needed for further efficiency improvement, especially in terms of the process duration.

Geotechnical properties of products of alternative fuel combustion and co-firing with hard coal in the context of their use as solidifying dense mixtures.

Efforts directed to reduction of greenhouse gas emissions have led to the introduction of new firing/co-firing technologies and alternative fuels in the coal-based power industry. This has resulted in the formation of combustion products with new properties that can affect the reuse of these wastes and/or pose a hazard to the environment. One of the power-plant fly ash (FA) reuse options is its application as a solidifying dense mixture with water for backfilling mine workings or in engineering constructions. In this comparative study, geotechnical properties of three groups of FA were evaluated: (i) weathered and freshly generated ash from hard coal combustion in conventional pulverized coal boilers without (C-PCA, C-PFA) and with selective non-catalytic reduction installations for NO x reduction (NC-PFA); (ii) FA from hard coal co-firing with alternative fuels: off gases (GC-PFA) or biomass (BC-PFA) in pulverized coal boilers; (iii) FA from coal (C-FFA) or biomass combustion (B-FFA) in fluidized-bed boilers. The transportability, bonding and solidification properties, uniaxial compression strength, and rewetting of dense mixtures were evaluated by measurements of volumetric density, fluidity, water retention capacity, bonding time, solidification time, uniaxial compression test, and slakeability at the background of the FA chemical composition. Calcareous C-FFA > B-FFA displayed the best geotechnical properties. Other materials showed poorer geotechnical properties than FFA and could be aligned in the order BC-PFA > GC-PFA > NC-PFA > C-PFA > C-PCA.

Selected problems with boron determination in water treatment processes. Part I: comparison of the reference methods for ICP-MS and ICP-OES determinations.

The aim of the study was to compare the two reference methods for the determination of boron in water samples and further assess the impact of the method of preparation of samples for analysis on the results obtained. Samples were collected during different desalination processes, ultrafiltration and the double reverse osmosis system, connected in series. From each point, samples were prepared in four different ways: the first was filtered (through a membrane filter of 0.45 µm) and acidified (using 1 mL ultrapure nitric acid for each 100 mL of samples) (FA), the second was unfiltered and not acidified (UFNA), the third was filtered but not acidified (FNA), and finally, the fourth was unfiltered but acidified (UFA). All samples were analysed using two analytical methods: inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES). The results obtained were compared and correlated, and the differences between them were studied. The results show that there are statistically significant differences between the concentrations obtained using the ICP-MS and ICP-OES techniques regardless of the methods of sampling preparation (sample filtration and preservation). Finally, both the ICP-MS and ICP-OES methods can be used for determination of the boron concentration in water. The differences in the boron concentrations obtained using these two methods can be caused by several high-level concentrations in selected whole-water digestates and some matrix effects. Higher concentrations of iron (from 1 to 20 mg/L) than chromium (0.02-1 mg/L) in the samples analysed can influence boron determination. When iron concentrations are high, we can observe the emission spectrum as a double joined and overlapping peak.

Effect of weathering transformations of coal combustion residuals on trace elements mobility in view of the environmental safety and sustainability of their disposal and use. II. Element release.

This paper is the second one of two companion papers. It presents results of a study aimed at assessing the effect of real time weathering transformations of Coal Combustion Residuals (CCRs) on trace element binding/release and its environmental implications. The study is based on the chemical composition of pore solutions extracted from primary alkaline Class F CCRs, 0 to >40 years old, sampled from the surface layer and vertical profiles at four selected typical CCRs impoundments. The long-term weathering transformations were found to lead to gradual acidification to pH < 4 of this primary alkaline material, due to internal processes of mineral formation/dissolution. Direct analysis of the pore solutions and a statistical analysis have shown different susceptibility of many trace elements to release during internal acidification processes occurring at consecutive Wash-out I (pH > 8), Dissolution II (8 ≥ pH ≥ 7) and Delayed Release III (pH < 7) stages of weathering compared to that at external sources of pH. The elements occurring in the CCRs are represented by three major groups showing the highest release to pore water: (a) within the acidic pH range (Na, K, Zn, Fe, Cd, Mo, Cr, B, Mn, Be and Ni; (b) within the near-neutral pH range (Al, V, Ba, Cu and Ag) and also Sb, Hg and Co not analyzed at pH < 7; (c) within the alkaline pH range (Ca, Mg, Pb, As, Se, Tl). Elements whose concentrations exceeded the threshold values for good chemical status of groundwater (TVs) at all weathering stages over the entire pH range studied were K, Al, B, Cr, Mo, V, As, Se, Sb and Hg, while Na, Zn, Fe and Cd showed particularly high delayed release at pH < 7, thus confirming the need of a precautionary approach to CCRs uncontrolled disposal and bulk reuse as common fill in view of long term environmental safety and sustainability.