Assessing the persistence, mobility and toxicity of emerging organic contaminants in Croatian karst springs used for drinking water supply.

Emerging organic contaminants (EOCs) are a vast group of often (very)persistent, (very)mobile and toxic (PMT/vPvM) substances that are continuously released worldwide, posing environmental and human health risks. Research on occurrence and behavior of EOCs in karst is in its infancy, thus policy measures and legislative control of these compounds in groundwater are still lacking. The Dinaric karst aquifers are an essential source of drinking water for almost half of Croatia's territory. Intense karstification, complex heterogeneous characteristics, and high fracture-cavernous porosity result in rapid, far-reaching groundwater flow and large karst springs, but also high intrinsic vulnerability due to low contaminant attenuation. To prioritize future monitoring and establish appropriate thresholds for EOCs detected in Croatian karst drinking water resources, in silico tools based on quantitative structure-activity relationships were used in PBT (persistence, bioaccumulation, and toxicity) and PMT/vPvM analyzes, while toxicological assessment helped identify potential threats to human health. In 33 samples collected during two sampling campaigns in 2019 at 16 karst springs and one lake used for water supply, we detected 65 compounds (EOCs and some legacy chemicals), of which 7 were classified as potentially PBT or vPvB compounds (PFOS, PFHxS, PFHpA, PFOA, PFNA, boscalid, and azoxystrobin), while only 2 compounds were assessed as not PMT/vPvM. This finding underlines that most of detected EOCs potentially endanger karst (ground)water ecosystems and important drinking water sources in Croatia. Comparison of maximum concentrations with existing or derived drinking water guideline values revealed how 2 of 65 detected compounds represent a potential risk to human health at lifelong exposure (sulfadiazine and hydrochlorothiazide), while 5 chemicals warrant additional human health impacts studies and groundwater monitoring. Although most compounds do not individually pose a significant risk to human health at current environmental levels, their potential synergistic and long-term effects remain unknown.

Emerging organic contaminants in springs of the highly karstified Dinaric region.

Emerging organic contaminants (EOCs) have become of increasing interest due to concerns about their impact on humans and the wider environment. Karst aquifers are globally widespread, providing critical water supplies and sustaining rivers and ecosystems, and are particularly susceptible to pollution. However, EOC distributions in karst remain quite poorly understood. This study looks at the occurrence of EOCs in the Croatian karst, which is an example of the "classical" karst, a highly developed type of karst that occurs throughout the Dinaric region of Europe. Samples were collected from 17 karst springs and one karst lake used for water supply in Croatia during two sampling campaigns. From a screen of 740 compounds, a total of 65 compounds were detected. EOC compounds from the pharmaceutical (n = 26) and agrochemical groups (n = 26) were the most frequently detected, while industrials and artificial sweeteners had the highest concentrations (range 8-440 ng/L). The number of detected compounds and the frequency of detection demonstrate the vulnerability of karst to EOC pollution. Concentrations of 5 compounds (acesulfame, sucralose, perfluorobutane sulfonate, emamectin B1b, and triphenyl phosphate) exceeded EU standards and occurred at concentrations that are likely to be harmful to ecosystems. Overall, most detections were at low concentrations (50 % <1 ng/L). This may be due to high dilution within the exceptionally large springs of the Classical karst, or due to relatively few pollution sources within the catchments. Nevertheless, EOC fluxes are considerable (10 to 106 ng/s) due to the high discharge of the springs. Temporal differences were observed, but without a clear pattern, reflecting the highly variable nature of karst springs that occurs over both seasonal and short-term timescales. This research is one of a handful of regional EOC investigations in karst groundwater, and the first regional study in the Dinaric karst. It demonstrates the need for more frequent and extensive sampling of EOCs in karst to protect human health and the environment.

Data on occurrence and ecotoxicological risk of emerging contaminants in Dinaric karst catchment of Jadro and Zrnovnica springs.

Karst catchments are valuable drinking water sources and fragile habitats to many endemic species. This dataset presents initial insights into the occurrence and ecotoxicological risk of 21 emerging contaminants (ECs) (including 11 pharmaceuticals, 4 lifestyle products, 2 personal care products, 3 agricultural and 1 industrial compound) detected in Dinaric karst catchment of Jadro and Zrnovnica springs in Croatia. Contaminants concentrations were determined with UHD Q-TOF LC/MS and UHP LC/MS in samples from two springs (Jadro and Zrnovnica), one river (Cetina), and a deep borehole (Gizdavac). Persistence (P), bioaccumulation (B), mobility (M) and toxicity (T) of detected ECs were assessed based on in silico strategy for PBT assessment and recently developed REACH PMT/vPvM guidelines. Risk quotients were calculated from PNEC values and measured contaminants' concentrations. In addition, physicochemical properties (estimated and existing experimental values of solubility in water, log KOW, log KOC, and pKa) of detected substances and water (measured values of temperature and electrolytic conductivity) are provided. This dataset could be useful for setting up the regular monitoring and improvement of existing water-related legislative, water safety plans, for modelling contaminant transport and identification of potential sources, and lastly for comparison with other studies conducted in karst aquifers. The present dataset was interpreted and discussed in the article entitled "Ecotoxicological aspects related to the occurrence of emerging contaminants in the Dinaric karst aquifer of Jadro and Zrnovnica springs" by Selak et al. (2022).

Ecotoxicological aspects related to the occurrence of emerging contaminants in the Dinaric karst aquifer of Jadro and Zrnovnica springs.

Karst aquifers are globally important source of drinking water and harbor specific ecosystems that are vulnerable to anthropogenic contamination. This paper provides insights into the occurrence and ecotoxicological characterization of 21 emerging contaminants (ECs) detected in the karst catchment of Jadro and Zrnovnica springs (Dinarides, Croatia). Karst springs used for water supply, surface water, and groundwater were sampled during seven campaigns. The ECs concentration levels ranged from 0.3 ng/L (tramadol in Jadro spring) to 372 ng/L (1H-benzotriazole in Cetina River). DEET was the most frequently detected ECs with an average concentration of around 50 ng/L in both surface water and groundwater. To prioritise detected ECs, their persistence (P), bioaccumulation (B), mobility (M) and toxicity (T) were assessed based on in silico strategy for PBT assessment and recently developed REACH PMT guidelines. PBT scores ranging below the threshold of 0.5, indicated non-PBT compounds of expected low concern. However, only 4 out of 21 detected ECs were not assessed as PMT/vPvM. Concerningly, 20 ECs were categorised as very mobile. Karst springs exhibited larger proportions of ECs meeting PMT/vPvM criteria than surface water. To characterise the contamination extent and estimate the incidence of adverse effects of detected ECs, a preliminary environmental risk assessment (ERA) was conducted. Most ECs posed no environmental risk with RQ values predominantly below 0.01. The total risk quotient RQsite accentuated Cetina River as having the highest risk compared to other sampling sites. This is the first study on ECs in Croatian karst, contributing to a growing need to understand the impacts of emerging contaminants in karst aquifers, which are still largely unexplored.

Groundwater level and electrical conductivity datasets acquired within pumping tests on Ilovik Island in Croatia.

The small karst island of Ilovik is the most southern of inhabited islands in the Croatian part of the Adriatic Sea. During summer tourist season the number of inhabitants increases significantly, and securing the additional freshwater quantities was needed. Given the hydrogeological and geomorphological setting of the island, possibility of brackish groundwater exploitation was considered. Hence, borehole drilling accompanied with pumping tests at three specified locations was carried out. During the pumping tests in two campaigns, groundwater level was measured manually every 2 hours in boreholes, while groundwater electric conductivity and temperature were periodically measured in situ. The sea level was observed at the reference point located near port. Given dataset consists of electrical conductivity, temperature, groundwater and seawater levels. The research article connected with these data (Terzic et al., 2020) provides hydrogeological interpretation of brackish groundwater lens on small karst island.