Table3_Occurrence and path pollution of emerging organic contaminants in mineral water of Hranice hypogenic Karst.XLSX

The Hranice hypogenic karst region includes urban, spa and agricultural areas and industry complexes that affect water quality in the region. Emerging organic contaminants (EOCs), especially pesticides and pharmaceuticals, are released into the complex aquatic system. These substances and their metabolites can affect aquatic and human life, as well as the regional development of the wider area traditionally associated with the spa. In this study, we conducted preliminary screening for pesticides and pharmaceuticals at 33 sampling sites and across different location types, including surface water, drainage water, a shallow well, groundwater and thermal karst water. Sampling occurred between February 2022 and June 2023. The results generally confirm that current land use is causing pollution in the karst system. The monitored substances were present in all water types, and in most cases the concentrations of pesticides were lower than those of their metabolites. Chloridazon desphenyl (DESPH) is the most widespread pesticide in surface, ground and hypogenic waters. Its concentrations in surface waters were 5.7 ng·L−1–2,230 ng·L−1, in groundwaters were 11.3 ng·L−1–1,490 ng·L−1 and in karst hypogenic waters 5.4 ng·L−1–378 ng·L−1. Diclofenac was the most widespread substance from the pharmaceutical group. Its concentrations ranged from 5.6 ng·L−1–549 ng·L−1 in surface waters, 8.4 ng·L−1–112 ng·L−1 in groundwaters and 5.1 ng·L−1–47.4 ng·L−1 in karst hypogenic waters. Directly in the karst hypogenic waters, the following EOCs were repeatedly detected: atrazine and its metabolites, simazin, metazachlor ethane sulfonic acid (ESA), metolachlor ESA, alachlor ESA, chloridazon DESPH, diclofenac, ibuprofen, azithromycin, bisphenol A and diethyltoluamide (DEET). The initial research hypothesis is that hydrothermal karst waters are of sub-recent age and deep circulation and, unlike surface and groundwaters, are not contaminated by recent pollutants. A certain component of these waters is therefore a shallow and shorter circulation.

赫拉尼采深成喀斯特（hypogenic karst）地区涵盖城镇、温泉疗养、农业区域及工业综合体，此类人类活动均会对区域内的水质造成不良影响。新兴有机污染物（Emerging Organic Contaminants, EOCs），尤其是农药与药物类污染物，被排放进入该复杂水生系统。此类物质及其代谢产物不仅会威胁水生生物与人类健康，还会对这片以温泉疗养为传统特色的更广区域的发展造成负面影响。
本研究于2022年2月至2023年6月期间，在33个采样点位针对农药与药物类污染物开展初步筛查工作，采样覆盖地表水、排水、浅井水、地下水及热喀斯特水等多种水体类型。研究结果总体证实，当前的土地利用方式正在对喀斯特系统造成污染。所有水体类型中均检出目标监测物质，且多数情况下农药类物质的浓度低于其代谢产物的浓度。
去苯基氯草通（Chloridazon Desphenyl, DESPH）是地表水、地下水及深成喀斯特水中分布最广泛的农药类污染物，其在地表水中的浓度范围为5.7 ng·L⁻¹至2230 ng·L⁻¹，地下水中为11.3 ng·L⁻¹至1490 ng·L⁻¹，深成喀斯特水中则为5.4 ng·L⁻¹至378 ng·L⁻¹。双氯芬酸（Diclofenac）是药物类污染物中分布最广泛的物质，其在地表水中的浓度范围为5.6 ng·L⁻¹至549 ng·L⁻¹，地下水中为8.4 ng·L⁻¹至112 ng·L⁻¹，深成喀斯特水中为5.1 ng·L⁻¹至47.4 ng·L⁻¹。
在深成喀斯特水中，还多次检出以下新兴有机污染物：阿特拉津及其代谢产物、西玛津、吡唑草胺乙磺酸（Metazachlor Ethane Sulfonic Acid, ESA）、异丙甲草胺ESA、乙草胺ESA、去苯基氯草通（DESPH）、双氯芬酸、布洛芬、阿奇霉素、双酚A以及避蚊胺（Diethyltoluamide, DEET）。
本研究初始假设为：热喀斯特水属于亚近代水体，且循环路径较深；与地表水和地下水不同，其未受到近期污染物的污染。因此，该类水体中存在一部分循环路径较浅、周期更短的水体组分。