Mobility and persistence of pesticides and emerging contaminants in age-dated and redox-classified groundwater under a range of land use types.

Understanding groundwater contamination patterns is hampered by the heterogeneous groundwater age and redox status over the depth range typically sampled for identifying pesticides and emerging contaminants threats. This study explores depth patterns of groundwater age and redox status across various land use types, unraveling spatial and temporal trends of pesticides and emerging contaminants using data from groundwater quality monitoring in the south of the Netherlands. The Netherlands is an ideal testing ground due to its high population density and widespread groundwater contamination from multiple sources. 146 multi-level observation wells were age-dated using 3H/3He, and contaminant concentrations were analyzed based on recharge year, land use type, and redox conditions, mitigating uncertainties from spatial and depth-dependent variations in both groundwater age and redox status. Redox-recharge year diagrams were developed to visually evaluate contaminant patterns in relation to these factors and to assess concentration patterns in relation to contamination history. Most detections of pesticides, metabolites, and emerging contaminants occurred in the youngest recharge periods (2000-2010 and 2010-2020) and in agricultural areas. However, certain contaminants, including BAM, desphenyl-chloridazon, short-chain PFCAs, PFOA, and EDTA, were consistently found in older water and Fe- or SO4-reduced conditions, indicating their mobility and persistence in the regional groundwater system. Comparing the presence of contaminants in specific redox classes and recharge periods with known application or leaching history provides insights into retardation (e.g., PFOS) and degradation (e.g., 2-hydroxy-atrazine, benzotriazole), explaining lower detection frequencies in earlier recharge periods. Identifying recharge years from age-dated groundwater helps relate contaminants to farmland application or river water recharge periods, revealing leaching history and contamination origins. The presented framework has the potential to enhance the interpretation of large groundwater datasets from dedicated, short-screened observation wells, such as those from the Danish GRUMO network, the Dutch monitoring networks, and parts of the US National Water Quality Program.

Nitrate trend reversal in Dutch dual-permeability chalk springs, evaluated by tritium-based groundwater travel time distributions.

Historical use of fertilizer and manure on farmlands is known to have a lasting impact on ecosystems and water resources, but few studies assess the legacy of nitrate pollution on groundwater and surface water after farming applications were reduced. We studied the response of nitrate in spring water to a reduction of nitrogen fertilizer applications in agriculture realized since the mid-1980s. We assessed the travel time distribution of groundwater based on a time series of tritium measurements for 90 springs and small brooks that drain a dual porosity chalk aquifer. The travel time distributions were constrained using the tritium data in combination with time series of nitrate concentrations, applying a shape-free travel time distribution model. A clear trend reversal of nitrate concentrations was observed and simulated for springs with a large fraction of young water (< 30 years old) whereas the nitrate response in springs with relatively older water was attenuated and delayed. We conclude that obtaining a time series of tritium data helps to constrain age distributions of water that is discharged from dual permeability aquifers. The fraction of water aged <30 years was a meaningful parameter to distinguish between different types of springs. Nitrate trends in springs that drain large fractions of young water (> 0.6) show higher peak concentrations, shorter lag-time between leaching and outflow peaks and steeper declines after trend reversal, relative to trends in springs which are dominantly fed by older groundwater. The study thus shows that the nitrate legacy of groundwater systems is strongly determined by the range of their travel time distributions, and trend reversal in receiving springs and surface waters may appear within 10 to 15 years after measures to reduce nitrate losses from farming.

Presence and fate of veterinary antibiotics in age-dated groundwater in areas with intensive livestock farming.

The combination of emerging antibiotic resistance and lack of discovery of new antibiotic classes poses a threat to future human welfare. Antibiotics are administered to livestock at a large scale and these may enter the environment by the spreading of manure on agricultural fields. They may leach to groundwater, especially in the Netherlands which has some of the most intensive livestock farming and corresponding excessive manure spreading in the world. This study investigates the presence of antibiotics in groundwater in two regions with the most intensive livestock farming in the Netherlands. If so, the hydrochemical conditions were further elaborated. Ten multi-level wells with in total 46 filters were sampled, focusing on relatively young, previously age-dated groundwater below agricultural fields. Twenty-two antibiotics were analyzed belonging to the following antibiotic groups: tetracyclines, sulfonamides, trimethoprims, ß-lactams, macrolides, lincosamides, quinolones, nitrofurans and chloramphenicol. The samples were analyzed for these antibiotics by LC-MS/MS ESI-POS/NEG (MRM) preceded by solid phase extraction which resulted in importantly low detection limits. Six antibiotics were found above detection limits in 31 filters in seven wells: sulfamethazine, sulfamethoxazole, lincomycin, chloramphenicol, ciprofloxacin, and sulfadiazine. The concentrations range from 0.3 to 18 ng L-1. Sulfonamides were detected at all measured depths down to 23 meters below surface level with apparent groundwater ages up to 40 years old. No antibiotics were detected below the nitrate/iron redox cline, which suggests that the antibiotics might undergo degradation or attenuation under nitrate-reducing redox conditions. This study provides proof that antibiotics are present in groundwater below agricultural areas in the Netherlands due to the spreading of animal manure.