National Assessment of Long-Term Groundwater Response to Pesticide Regulation.

Quantitative assessments of long-term, national-scale responses of groundwater quality to pesticide applications are essential to evaluate the effectiveness of pesticide regulations. Retardation time in the unsaturated zone (Ru) was estimated for selected herbicides (atrazine, simazine, and bentazon) and degradation products (desethylatrazine (DEA), desisopropylatrazine (DIA), desethyldesisopropylatrazine (DEIA), and BAM) using a multidecadal time series of groundwater solute chemistry (∼30 years) and herbicide sales (∼60 years). The sampling year was converted to recharge year using groundwater age. Then, Ru was estimated using a cross-correlation analysis of the sales and the frequencies of detection and exceedance of the drinking water standard (0.1 µg/L) of each selected compound. The results showed no retardation of the highly polar, thus mobile, parent compounds (i.e., bentazon), while Ru of the moderately polar compounds (i.e., simazine) was about a decade, and their degradation products showed even longer Ru. The temporal trends of the degradation products did not mirror those of the sale data, which were attributed to the various sale periods of the parent compounds, sorption of the parent compounds, and complex degradation pathways. The longer Ru in clayey/organic sediments than in sandy sediments further confirmed the role of soil-specific retardation as an important factor to consider in groundwater protection.

Analysis of the geological control on the spatial distribution of potentially toxic concentrations of As and F- in groundwater on a Pan-European scale.

The distribution of the high concentrations of arsenic (As) and fluoride (F-) in groundwater on a Pan-European scale could be explained by the geological European context (lithology and structural faults). To test this hypothesis, seventeen countries and eighteen geological survey organizations (GSOs) have participated in the dataset. The methodology has used the HydroGeoToxicity (HGT) and the Baseline Concentration (BLC) index. The results prove that most of the waters considered in this study are in good conditions for drinking water consumption, in terms of As and/or F- content. A low proportion of the analysed samples present HGT≥ 1 levels (4% and 7% for As and F-, respectively). The spatial distribution of the highest As and/or F- concentrations (via BLC values) has been analysed using GIS tools. The highest values are identified associated with fissured hard rock outcrops (crystalline rocks) or Cenozoic sedimentary zones, where basement fractures seems to have an obvious control on the distribution of maximum concentrations of these elements in groundwaters.

Drinking Water Criteria for Arsenic in High-Income, Low-Dose Countries: The Effect of Legislation on Public Health.

Due to the potential health risks at very low concentrations, the criterion for arsenic in drinking water has been debated. High-income, low-dose countries are uniquely positioned to follow WHO's recommendation of keeping concentrations "as low as reasonably possible." In this policy analysis, 47646 arsenic analyses from Denmark are used to follow the effect of lowering the national criterion from 50 to 5 µg/L. The first 3 years (2002-2004) following the criterion change, 106 waterworks were identified as noncompliant. An additional 64 waterworks were identified as noncompliant in the next 12 years (2005-2016). Of the 106 waterworks initially (2002-2004) aware of the violation, an average concentration drop from 6 to 3 µg/L was observed during a 6 year period following a lag time of 1 year. After this point, no further improvements were observed. Thirteen years after regulation was imposed, 25 of 170 waterworks were still in violation. The results suggest that legislation alone is insufficient to ensure better drinking water quality at some waterworks and that stakeholders' drivers and barriers to change also play an important role. In an exploration of five legislation scenarios, this study showed that a criterion of 1 µg/L would require action by more than 500 Danish waterworks, with treatment costs from 0.06 to 0.70 €/m3. These scenarios illustrate that it can be technically feasible and affordable to lower the arsenic criterion below 5 µg/L in low-dose, high-income countries. However, more information is needed to apply a cost-benefit model, and comparative studies from other counties are warranted.

A high-resolution nitrate vulnerability assessment of sandy aquifers (DRASTIC-N).

Groundwater protection against agricultural diffuse nitrate pollution is of paramount importance for safeguarding groundwater-dependent aquatic ecosystems and protecting human health by securing clean groundwater for drinking water production. Nitrate vulnerability assessment of aquifers is the core of a scientifically sound strategy for management and protection of groundwater by authorities. A multitude of methods exists for assessing intrinsic aquifer vulnerability. The objective of this paper is to develop a nitrate-specific groundwater vulnerability assessment method based on the globally recognized DRASTIC method, which was developed by the US Environmental Protection Agency in the 1980s. We propose a new method "DRASTIC-N″ for assessing aquifer nitrate vulnerability, which for the first time expands the seven original geological and hydrogeological parameters with a geochemical parameter for redox condition. The development of DRASTIC-N is based on the longstanding Danish practice of performing detailed groundwater mapping based on dense sampling of geophysical, geological, and geochemical data. DRASTIC-N is compared to the widely used and documented Danish nitrate vulnerability assessment method SCANVA in a study area where the primary aquifer used for drinking water production is composed of heterogeneous sandy glacial deposits. Both SCANVA and DRASTIC-N result in vulnerability maps, which show similar patterns of nitrate vulnerability with a fair overall agreement of 71%. DRASTIC-N provides a framework for systematic and transparent application, which can facilitate stakeholder involvement and help authorities in groundwater protection and decision-making with regards to nitrate pollution. DRASTIC-N is suitable for nitrate vulnerability assessments of glacially deposited sandy aquifers, an abundant and important water resource worldwide, potentially threatened by nitrate pollution from anthropogenic activities.

Lithium in drinking water and the incidence of bipolar disorder: A nation-wide population-based study.

OBJECTIVE: Animal data suggest that subtherapeutic doses, including micro doses, of lithium may influence mood, and lithium levels in drinking water have been found to correlate with the rate of suicide. It has never been investigated whether consumption of lithium may prevent the development of bipolar disorder (primary prophylaxis). In a nation-wide population-based study, we investigated whether long-term exposure to micro levels of lithium in drinking water correlates with the incidence of bipolar disorder in the general population, hypothesizing an inverse association in which higher long-term lithium exposure is associated with lower incidences of bipolar disorder. METHODS: We included longitudinal individual geographical data on municipality of residence, data from drinking water lithium measurements and time-specific data from all cases with a hospital contact with a diagnosis of mania/bipolar disorder from 1995 to 2013 (N=14 820) and 10 age- and gender-matched controls from the Danish population (N= 140 311). Average drinking water lithium exposure was estimated for all study individuals. RESULTS: The median of the average lithium exposure did not differ between cases with a diagnosis of mania/bipolar disorder (12.7 µg/L; interquartile range [IQR]: 7.9-15.5 µg/L) and controls (12.5 µg/L; IQR: 7.6-15.7 µg/L; P=.2). Further, the incidence rate ratio of mania/bipolar disorder did not decrease with higher long-term lithium exposure, overall, or within age categories (0-40, 41-60 and 61-100 years of age). CONCLUSION: Higher long-term lithium exposure from drinking water was not associated with a lower incidence of bipolar disorder. The association should be investigated in areas with higher lithium levels than in Denmark.

Iodine concentrations in Danish groundwater: historical data assessment 1933-2011.

In areas where water is a major source of dietary iodine (I), the I concentration in drinking water is an important factor for public health and epidemiological understandings. In Denmark, almost all of the drinking water is originating from groundwater. Therefore, understanding the I variation in groundwater and governing factors and processes are crucial. In this study, we perform uni- and multivariate analyses of all available historical Danish I groundwater data from 1933 to 2011 (n = 2,562) to give an overview on the I variability for first time and to discover possible geochemical associations between I and twenty other elements and parameters. Special attention is paid on the description and the quality assurance of this complex compilation of historical data. The high variability of I in Danish groundwater (

Modeling groundwater redox conditions at national scale through integration of sediment color and water chemistry in a machine learning framework.

Redox conditions play a crucial role in determining the fate of many contaminants in groundwater, impacting ecosystem services vital for both the aquatic environment and human water supply. Geospatial machine learning has previously successfully modelled large-scale redox conditions. This study is the first to consolidate the complementary information provided by sediment color and water chemistry to enhance our understanding of redox conditions in Denmark. In the first step, the depth to the first redox interface is modelled using sediment color from 27,042 boreholes. In the second step, the depth of the first redox interface is compared against water chemistry data at 22,198 wells to classify redox complexity. The absence of nitrate containing water below the first redox interface is referred to as continuous redox conditions. In contrast, discontinuous redox conditions are identified by the presence of nitrate below the first redox interface. Both models are built using 20 covariate maps, encompassing diverse hydrologically relevant information. The first redox interface is modelled with a mean error of 0.0 m and a root-mean-squared error of 8.0 m. The redox complexity model attains an accuracy of 69.8 %. Results indicate a mean depth to the first redox interface of 8.6 m and a standard deviation of 6.5 m. 60 % of Denmark is classified as discontinuous, indicating complex redox conditions, predominantly collocated in clay rich glacial landscapes. Both maps, i.e., first redox interface and redox complexity are largely driven by the water table and hydrogeology. The developed maps contribute to our understanding of subsurface redox processes, supporting national-scale land-use and water management.

Assessing groundwater denitrification spatially is the key to targeted agricultural nitrogen regulation.

Globally, food production for an ever-growing population is a well-known threat to the environment due to losses of excess reactive nitrogen (N) from agriculture. Since the 1980s, many countries of the Global North, such as Denmark, have successfully combatted N pollution in the aquatic environment by regulation and introduction of national agricultural one-size-fits-all mitigation measures. Despite this success, further reduction of the N load is required to meet the EU water directives demands, and implementation of additional targeted N regulation of agriculture has scientifically and politically been found to be a way forward. In this paper, we present a comprehensive concept to make future targeted N regulation successful environmentally and economically. The concept focus is on how and where to establish detailed maps of the groundwater denitrification potential (N retention) in areas, such as Denmark, covered by Quaternary deposits. Quaternary deposits are abundant in many parts of the world, and often feature very complex geological and geochemical architectures. We show that this subsurface complexity results in large local differences in groundwater N retention. Prioritization of the most complex areas for implementation of the new concept can be a cost-efficient way to achieve lower N impact on the aquatic environment.

Association Between Estimated Geocoded Residential Maternal Exposure to Lithium in Drinking Water and Risk for Autism Spectrum Disorder in Offspring in Denmark.

Importance: Lithium is a naturally occurring and trace element that has mood-stabilizing effects. Maternal therapeutic use of lithium has been associated with adverse birth outcomes. In animal models, lithium modulates Wnt/ß-catenin signaling that is important for neurodevelopment. It is unknown whether exposure to lithium in drinking water affects brain health in early life. Objective: To evaluate whether autism spectrum disorder (ASD) in offspring is associated with maternal exposure to lithium in drinking water during pregnancy. Design, Setting, and Participants: This nationwide population-based case-control study in Denmark identified 8842 children diagnosed with ASD born from 2000 through 2013 and 43 864 control participants matched by birth year and sex from the Danish Medical Birth Registry. These data were analyzed from March 2021 through November 2022. Exposures: Geocoded maternal residential addresses during pregnancy were linked to lithium level (range, 0.6 to 30.7 µg/L) in drinking water estimated using kriging interpolation based on 151 waterworks measurements of lithium across all regions in Denmark. Main Outcomes and Measures: ASD diagnoses were ascertained using International Statistical Classification of Diseases and Related Health Problems, Tenth Revision codes recorded in the Danish Psychiatric Central Register. The study team estimated odds ratios (ORs) and 95% CIs for ASD according to estimated geocoded maternal exposure to natural source of lithium in drinking water as a continuous (per IQR) or a categorical (quartile) variable, adjusting for sociodemographic factors and ambient air pollutants levels. The study team also conducted stratified analyses by birth years, child's sex, and urbanicity. Results: A total of 8842 participants with ASD (male, 7009 [79.3%]) and 43 864 control participants (male, 34 749 [79.2%]) were studied. Every IQR increase in estimated geocoded maternal exposure to natural source of lithium in drinking water was associated with higher odds for ASD in offspring (OR, 1.23; 95% CI, 1.17-1.29). Elevated odds among offspring for ASD were estimated starting from the second quartile (7.36 to 12.67 µg/L) of estimated maternal exposure to drinking water with lithium and the OR for the highest quartile (more than 16.78 µg/L) compared with the reference group (less than 7.39 µg/L) was 1.46 (95% CI, 1.35-1.59). The associations were unchanged when adjusting for air pollution exposures and no differences were apparent in stratified analyses. Conclusions and Relevance: Estimated maternal prenatal exposure to lithium from naturally occurring drinking water sources in Denmark was associated with an increased ASD risk in the offspring. This study suggests that naturally occurring lithium in drinking water may be a novel environmental risk factor for ASD development that requires further scrutiny.

Geographical Distribution and Pattern of Pesticides in Danish Drinking Water 2002-2018: Reducing Data Complexity.

Pesticides are a large and heterogenous group of chemicals with a complex geographic distribution in the environment. The purpose of this study was to explore the geographic distribution of pesticides in Danish drinking water and identify potential patterns in the grouping of pesticides. Our data included 899,169 analyses of 167 pesticides and metabolites, of which 55 were identified above the detection limit. Pesticide patterns were defined by (1) pesticide groups based on chemical structure and pesticide-metabolite relations and (2) an exploratory factor analysis identifying underlying patterns of related pesticides within waterworks. The geographic distribution was evaluated by mapping the pesticide categories for groups and factor components, namely those detected, quantified, above quality standards, and not analysed. We identified five and seven factor components for the periods 2002-2011 and 2012-2018, respectively. In total, 16 pesticide groups were identified, of which six were representative in space and time with regards to the number of waterworks and analyses, namely benzothiazinone, benzonitriles, organophosphates, phenoxy herbicides, triazines, and triazinones. Pesticide mapping identified areas where multiple pesticides were detected, indicating areas with a higher pesticide burden. The results contribute to a better understanding of the pesticide pattern in Danish drinking water and may contribute to exposure assessments for future epidemiological studies.

Trace elements in drinking water and the incidence of attention-deficit hyperactivity disorder.

BACKGROUND: Trace elements have been suggested to have neurotoxic effects and increase the risk of neurodevelopmental disorders, but studies of a potential role of trace elements in relation to Attention-Deficit/Hyperactivity Disorder (ADHD) are very limited. The objective of this study was to conduct an exploratory analysis investigating the associations between 17 geogenic trace elements (Ba, Co, Eu, I, Li, Mo, Rb, Re, Rh, Sb, Sc, Se, Si, Sr, Ti, U and Y) found in Danish drinking water and the risk of developing ADHD. METHODS: In this cohort study, 284,309 individuals, born 1994-2007, were followed for incidence of ADHD from the age of five until the end of study, December 31, 2016. We conducted survival analyses, using Poisson regression to estimate incidence rate ratios (IRRs) with 95 % confidence intervals (CI) in three different confounder adjustment scenarios. RESULTS: In a model including adjustments for age, sex, calendar year, parental socio-economic status, neighborhood level socio-economic status and parental psychiatric illness, we found that six of the 17 trace elements (Sr, Rb, Rh, Ti, Sb and Re) were associated with an increased risk of ADHD, whereas two (Ba and I) were inversely associated with ADHD. However, when including region as a covariate in the model, most trace elements were no longer associated with ADHD or the association changed direction. Four trace elements (I, Li, Rb, and Y) remained significantly associated with ADHD but in an inverse direction and for three of these (I, Li and Y), we found significant interactions with region in their association with ADHD. CONCLUSION: The trace elements under investigation, at levels found in Danish drinking water, do not seem to contribute to the development of ADHD and our findings highlight the importance of examining consistency of associations across geographic areas.

Nationwide Drinking Water Sampling Campaign for Exposure Assessments in Denmark.

Nationwide sampling campaign of treated drinking water of groundwater origin was designed and implemented in Denmark in 2013. The main purpose of the sampling was to obtain data on the spatial variation of iodine concentration and speciation in treated drinking water, which was supplied to the majority of the Danish population. This data was to be used in future exposure and epidemiologic studies. The water supply sector (83 companies, owning 144 waterworks throughout Denmark) was involved actively in the planning and implementation process, which reduced significantly the cost and duration of data collection. The dataset resulting from this collaboration covers not only iodine species (I-, IO3-, TI), but also major elements and parameters (pH, electrical conductivity, DOC, TC, TN, F-, Cl-, NO3-, SO42-, Ca²âº, Mg²âº, K⁺, Na⁺) and a long list of trace elements (n = 66). The water samples represent 144 waterworks abstracting about 45% of the annual Danish groundwater abstraction for drinking water purposes, which supply about 2.5 million Danes (45% of all Danish residents). This technical note presents the design, implementation, and limitations of such a sampling design in detail in order (1) to facilitate the future use of this dataset, (2) to inform future replication studies, or (3) to provide an example for other researchers.

Association of Lithium in Drinking Water With the Incidence of Dementia.

Importance: Results from animal and human studies suggest that lithium in therapeutic doses may improve learning and memory and modify the risk of developing dementia. Additional preliminary studies suggest that subtherapeutic levels, including microlevels of lithium, may influence human cognition. Objective: To investigate whether the incidence of dementia in the general population covaries with long-term exposure to microlevels of lithium in drinking water. Design, Setting, and Participants: This Danish nationwide, population-based, nested case-control study examined longitudinal, individual geographic data on municipality of residence and data from drinking water measurements combined with time-specific data from all patients aged 50 to 90 years with a hospital contact with a diagnosis of dementia from January 1, 1970, through December 31, 2013, and 10 age- and sex-matched control individuals from the Danish population. The mean lithium exposure in drinking water since 1986 was estimated for all study individuals. Data analysis was performed from January 1, 1995, through December 31, 2013. Main Outcomes and Measures: A diagnosis of dementia in a hospital inpatient or outpatient contact. Diagnoses of Alzheimer disease and vascular dementia were secondary outcome measures. In primary analyses, distribution of lithium exposure was compared between patients with dementia and controls. Results: A total of 73 731 patients with dementia and 733 653 controls (median age, 80.3 years; interquartile range, 74.9-84.6 years; 44 760 female [60.7%] and 28 971 male [39.3%]) were included in the study. Lithium exposure was statistically significantly different between patients with a diagnosis of dementia (median, 11.5 µg/L; interquartile range, 6.5-14.9 µg/L) and controls (median, 12.2 µg/L; interquartile range, 7.3-16.0 µg/L; P < .001). A nonlinear association was observed. Compared with individuals exposed to 2.0 to 5.0 µg/L, the incidence rate ratio (IRR) of dementia was decreased in those exposed to more than 15.0 µg/L (IRR, 0.83; 95% CI, 0.81-0.85; P < .001) and 10.1 to 15.0 µg/L (IRR, 0.98; 95% CI, 0.96-1.01; P = .17) and increased with 5.1 to 10.0 µg/L (IRR, 1.22; 95% CI, 1.19-1.25; P < .001). Similar patterns were found with Alzheimer disease and vascular dementia as outcomes. Conclusions and Relevance: Long-term increased lithium exposure in drinking water may be associated with a lower incidence of dementia in a nonlinear way; however, confounding from other factors associated with municipality of residence cannot be excluded.

Lithium in Drinking Water and Incidence of Suicide: A Nationwide Individual-Level Cohort Study with 22 Years of Follow-Up.

Suicide is a major public health concern. High-dose lithium is used to stabilize mood and prevent suicide in patients with affective disorders. Lithium occurs naturally in drinking water worldwide in much lower doses, but with large geographical variation. Several studies conducted at an aggregate level have suggested an association between lithium in drinking water and a reduced risk of suicide; however, a causal relation is uncertain. Individual-level register-based data on the entire Danish adult population (3.7 million individuals) from 1991 to 2012 were linked with a moving five-year time-weighted average (TWA) lithium exposure level from drinking water hypothesizing an inverse relationship. The mean lithium level was 11.6 µg/L ranging from 0.6 to 30.7 µg/L. The suicide rate decreased from 29.7 per 100,000 person-years at risk in 1991 to 18.4 per 100,000 person-years in 2012. We found no significant indication of an association between increasing five-year TWA lithium exposure level and decreasing suicide rate. The comprehensiveness of using individual-level data and spatial analyses with 22 years of follow-up makes a pronounced contribution to previous findings. Our findings demonstrate that there does not seem to be a protective effect of exposure to lithium on the incidence of suicide with levels below 31 µg/L in drinking water.

Assessment of spatial variation in drinking water iodine and its implications for dietary intake: a new conceptual model for Denmark.

Iodine is essential for human health. Many countries have therefore introduced universal salt iodising (USI) programmes to ensure adequate intake for the populations. However, little attention has been paid to subnational differences in iodine intake from drinking water caused by naturally occurring spatial variations. To address this issue, we here present the results of a Danish nationwide study of spatial trends of iodine in drinking water and the relevance of these trends for human dietary iodine intake. The data consist of treated drinking water samples from 144 waterworks, representing approx. 45% of the groundwater abstraction for drinking water supply in Denmark. The samples were analysed for iodide, iodate, total iodine (TI) and other major and trace elements. The spatial patterns were investigated with Local Moran's I. TI ranges from <0.2 to 126 µg L(-1) (mean 14.4 µg L(-1), median 11.9 µg L(-1)). Six speciation combinations were found. Half of the samples (n = 71) contain organic iodine; all species were detected in approx. 27% of all samples. The complex spatial variation is attributed both to the geology and the groundwater treatment. TI >40 µg L(-1) originates from postglacial marine and glacial meltwater sand and from Campanian-Maastrichtian chalk aquifers. The estimated drinking water contribution to human intake varies from 0% to >100% of the WHO recommended daily iodine intake for adults and from 0% to approx. 50% for adolescents. The paper presents a new conceptual model based on the observed clustering of high or low drinking-water iodine concentrations, delimiting zones with potentially deficient, excessive or optimal iodine status. Our findings suggest that the present coarse-scale nationwide programme for monitoring the population's iodine status may not offer a sufficiently accurate picture. Local variations in drinking-water iodine should be mapped and incorporated into future adjustment of the monitoring and/or the USI programmes.