Vibeke Ernstsen

Reduction of nitrate by Fe2+ in clay minerals

In the 12 km2 catchment area of Syv creek, Denmark, moderate to high concentrations of nitrate (NO3−) occurred in the upper part of the oxidized zone (oxic-I), but dropped within the lower suboxic part (oxic-II), to below the detection limit in the unoxidized zone. Structural Fe2+ in the clay minerals made up 10 to 12% of the Fe in the oxidized zone and increased to approximately 50% in the unoxidized zone. Concurrent with changes in the distribution of structural Fe2+ the clay mineral constituents changed. Vermiculite was typically found in the oxidized zone whereas chlorite was found in the unoxidized zone only. A conversion of illite and chlorite into vermiculite seems to take place. A significant correlation between NO3− and the amount of reduced Fe2+ in the suboxic (oxic-II) zone, indicates that primary structural Fe2+ in the clay minerals is the reductant in a NO3− reduction process.

Nitrate reduction in geologically heterogeneous catchments--a framework for assessing the scale of predictive capability of hydrological models.

In order to fulfil the requirements of the EU Water Framework Directive nitrate load from agricultural areas to surface water in Denmark needs to be reduced by about 40%. The regulations imposed until now have been uniform, i.e. the same restrictions for all areas independent of the subsurface conditions. Studies have shown that on a national basis about 2/3 of the nitrate leaching from the root zone is reduced naturally, through denitrification, in the subsurface before reaching the streams. Therefore, it is more cost-effective to identify robust areas, where nitrate leaching through the root zone is reduced in the saturated zone before reaching the streams, and vulnerable areas, where no subsurface reduction takes place, and then only impose regulations/restrictions on the vulnerable areas. Distributed hydrological models can make predictions at grid scale, i.e. at much smaller scale than the entire catchment. However, as distributed models often do not include local scale hydrogeological heterogeneities, they are typically not able to make accurate predictions at scales smaller than they are calibrated. We present a framework for assessing nitrate reduction in the subsurface and for assessing at which spatial scales modelling tools have predictive capabilities. A new instrument has been developed for airborne geophysical measurements, Mini-SkyTEM, dedicated to identifying geological structures and heterogeneities with horizontal and lateral resolutions of 30-50 m and 2m, respectively, in the upper 30 m. The geological heterogeneity and uncertainty are further analysed by use of the geostatistical software TProGS by generating stochastic geological realisations that are soft conditioned against the geophysical data. Finally, the flow paths within the catchment are simulated by use of the MIKE SHE hydrological modelling system for each of the geological models generated by TProGS and the prediction uncertainty is characterised by the variance between the predictions of the different models.

Transport modes and pathways of the strongly sorbing pesticides glyphosate and pendimethalin through structured drained soils

Leaching of the strongly sorbing pesticides glyphosate and pendimethalin was evaluated in an 8-month field study focussing on preferential flow and particle-facilitated transport, both of which may enhance the leaching of such pesticides in structured soils. Glyphosate mainly sorbs to mineral sorption sites, while pendimethalin mainly sorbs to organic sorption sites. The two pesticides were applied in equal dosage to a structured, tile-drained soil, and the concentration of the pesticides was then measured in drainage water sampled flow-proportionally. The leaching pattern of glyphosate resembled that of pendimethalin, suggesting that the leaching potential of pesticides sorbed to either the inorganic or organic soil fractions is high in structured soils. Both glyphosate and pendimethalin leached from the root zone, with the average concentration in the drainage water being 3.5 and 2.7 μg L(-1), respectively. Particle-facilitated transport (particles >0.24 μm) accounted for only a small proportion of the observed leaching (13-16% for glyphosate and 16-31% for pendimethalin). Drain-connected macropores located above or in the vicinity of the drains facilitated very rapid transport of pesticide to the drains. That the concentration of glyphosate and pendimethalin in the drainage water remained high (>0.1 μg L(-1)) for up to 7d after a precipitation event indicates that macropores between the drains connected to underlying fractures were able to transport strongly sorbing pesticides in the dissolved phase. Lateral transport of dissolved pesticide via such discontinuities implies that strongly sorbing pesticides such as glyphosate and pendimethalin could potentially be present in high concentrations (>0.1 μg L(-1)) in both water originating from the drainage system and the shallow groundwater located at the depth of the drainage system.

Numerical analysis of water and solute transport in variably-saturated fractured clayey till

This study numerically investigates the influence of initial water content and rain intensities on the preferential migration of two fluorescent tracers, Acid Yellow 7 (AY7) and Sulforhodamine B (SB), through variably-saturated fractured clayey till. The simulations are based on the numerical model HydroGeoSphere, which solves 3D variably-saturated flow and solute transport in discretely-fractured porous media. Using detailed knowledge of the matrix, fracture, and biopore properties, the numerical model is calibrated and validated against experimental high-resolution tracer images/data collected under dry and wet soil conditions and for three different rain events. The model could reproduce reasonably well the observed preferential migration of AY7 and SB through the fractured till, although it did not capture the exact depth of migration and the negligible impact of the dead-end biopores in a near-saturated matrix. A sensitivity analysis suggests fast flow mechanisms and dynamic surface coating in the biopores, and the presence of a plough pan in the till.

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.

Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1mug/l in all tested profiles while metribuzine always exceeded the 0.1mug/l threshold value.

Fluorescence imaging applied to tracer distributions in variably saturated fractured clayey till.

The study of mechanisms controlling preferential flow and transport in variably saturated fractured clayey till is often hindered by insufficient spatial resolution or unknown measuring volume. With the objective to study these mechanisms while circumventing the obstacles, tracer experiments with two fluorescent tracers Acid Yellow 7 (AY7) and Sulforhodamine B (SB) were performed at three different rain events for a fall and a summer season. Irrigated areas were excavated down to depths of 2.8 m and the movement of both tracers in the exposed profiles was delineated simultaneously by high spatial resolution apparent concentration maps (pixel approximately 1 mm(2)) obtained with an imaging device. The device consists of a light source and a CCD camera, both equipped with tracer-specific-filters for fluorescent light. The fluorescence images were corrected for nonuniform lighting, changing surface roughness, and varying optical properties of the soil profile. The resulting two-dimensional apparent concentration distribution profiles of the tracers showed that: (i) relative low water content in the upper 10 cm of the irrigated till in summer had a pronounced retardation effect on the AY7-migration and no effect on the SB-migration; (ii) the dead-end biopores were not activated in the fall season; (iii) only 3D fracture-plans connected to hydraulically active 1D-biopores contributed to the leaching; (iv) the tracer migration primary followed macropores during both seasons, though AY7 also followed a topsoil piston transport in summer; (v) the highest tracer pixel apparent concentrations were often found in macropores and most pronounced in the summer season; and (vi) 3D-dilution in fractures seems to play a dominating role in AY7-migration in the fall season.

Reduction of nitrate in clayey subsoils controlled by geochemical and microbial barriers

Vertical distribution of redox zones, concentrations of redox‐sensitive constituents, numbers of aerobic heterotrophic bacteria, and potential denitrification activity were studied in 1‐m cores taken at the transition between the oxidized and reduced layers in two Danish clayey subsoils. Based on the matrix soil colors, a redox sequence of oxidized, suboxic, and reduced zones was identified at both sites. The geochemical composition of the oxidized brown colored zone (to depths of 2.6 and 3.2 m) was characterized by high concentrations of NO3 − and low amounts of total organic carbon, exchangeable forms of NH4 +, Fe2+, and Mn2+, and structural Fe(II) in the clay minerals. In the underlying 20‐ to 30‐cm‐deep suboxic zone, decreasing NO3 − concentrations were observed together with increasing amount of exchangeable forms of Fe2+ and Mn2+, and structural Fe(II). Finally, in the reduced grey zone, NO3 − was no longer present and maximum concentrations of other redox sensitive constituents occurred. Throughout...

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 Morans 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 populations 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.

Impact of Basic Soil Parameters on Pesticide Disappearance Investigated by Multivariate Partial Least Square Regression and Statistics

Dissipation time is a key parameter when studying and modeling the environmental fate of pesticides. This study was conducted to characterize the variability of pesticide disappearance in soil and to identify possible controlling parameters related to intrinsic soil properties and microbiology. Multivariate data analysis was used to study spatial variability in three horizons from 24 sandy soil profiles. The time for 50% disappearance (DT(50)) was characterized for two herbicides, metribuzin (MBZ) and MCPA, and methyltriazine amine (MTA; transformation product of metsulfuron-methyl, tribenuron-methyl, thifensulfuron-methyl, and chlorsulfuron). Normal and log-normal distributions were compared for DT(50) and soil properties and descriptive statistics were calculated. Conformity with log-transformed distributions was observed and assuming normality of the DT(50) data would cause 5 to 35% overestimation. Mean DT(50) were: MCPA 9.5, MBZ 168, and MTA 127. Significant effect of soil depth on DT(50) was shown for MCPA and MBZ, with low values in deeper horizons. Simple linear correlation for combinations of MCPA, MTA, pH, and total organic carbon (TOC) was observed. Using partial least squares regression (PLS) 71 to 85% of the total DT(50) variance was explained. A specific predictor variable could not be identified as the controlling components differed within horizons and compounds. For MCPA the overall important predictor variables were microbiology and TOC, whereas for MTA and MBZ it was inorganic variables (Al, Fe, cation exchange capacity, base saturation percent, and pH) and microbiology. The study indicates that PLS generated input data can improve pesticide fate modeling and reduce the uncertainty in dissipation estimation.