Model-based integration and analysis of biogeochemical and isotopic dynamics in a nitrate-polluted pyritic aquifer.

Leaching of nitrate from agricultural land to groundwater and the resulting nitrate pollution are a major environmental problem worldwide. Its impact is often mitigated in aquifers hosting sufficiently reactive reductants that can promote autotrophic denitrification. In the case of pyrite acting as reductant, however, denitrification is associated with the release of sulfate and often also with the mobilization of trace metals (e.g., arsenic). In this study, reactive transport modeling was used to reconstruct, quantify and analyze the dynamics of the dominant biogeochemical processes in a nitrate-polluted pyrite-containing aquifer and its evolution over the last 50 years in response to changing agricultural practices. Model simulations were constrained by measured concentration depth profiles. Measured (3)H/(3)He profiles were used to support the calibration of flow and conservative transport processes, while the comparison of simulated and measured sulfur isotope signatures acted as additional calibration constraint for the reactive processes affecting sulfur cycling. The model illustrates that denitrification largely prevented an elevated discharge of nitrate to surface waters, while sulfate discharges were significantly increased, peaking around 15 years after the maximum nitrogen inputs.

Improving load estimates for NO3 and P in surface waters by characterizing the concentration response to rainfall events.

For the evaluation of action programs to reduce surface water pollution, water authorities invest heavily in water quality monitoring. However, sampling frequencies are generally insufficient to capture the dynamical behavior of solute concentrations. For this study, we used on-site equipment that performed semicontinuous (15 min interval) NO(3) and P concentration measurements from June 2007 to July 2008. We recorded the concentration responses to rainfall events with a wide range in antecedent conditions and rainfall durations and intensities. Through sequential linear multiple regression analysis, we successfully related the NO(3) and P event responses to high-frequency records of precipitation, discharge, and groundwater levels. We applied the regression models to reconstruct concentration patterns between low-frequency water quality measurements. This new approach significantly improved load estimates from a 20% to a 1% bias for NO(3) and from a 63% to a 5% bias for P. These results demonstrate the value of commonly available precipitation, discharge, and groundwater level data for the interpretation of water quality measurements. Improving load estimates from low-frequency concentration data just requires a period of high-frequency concentration measurements and a conceptual, statistical, or physical model for relating the rainfall event response of solute concentrations to quantitative hydrological changes.

Tracing veterinary antibiotics in the subsurface - A long-term field experiment with spiked manure.

The purpose of this long-term experiment was on gaining more insights into the environmental behaviour of veterinary antibiotics in the subsurface after application with manure. Therefore, manure spiked with a bromide tracer and eight antibiotics (enrofloxacin, lincomycin, sulfadiazine, sulfamethazine, tetracycline, tiamulin, tilmicosin and tylosin) in concentrations of milligrams per litre were applied at an experimental field site. Their pathway was tracked by continuous extraction of soil pore water at different depths and systematic sampling of groundwater for a period of two years. Seven target compounds were detected in soil pore water of which four leached into groundwater. Concentrations of the detected target compounds were, with few exceptions, in the range of nanograms per litre. It was concluded that a large fraction of the investigated antibiotics sorbed or degraded already within the first meter of the soil. Further, it was inferred from the data that long and warm dry periods cause attenuation of the target compounds through increased degradation or sorption occurring in the soil. In addition, the comprehensive data-set allowed to estimate a retardation factor between 1.1 and 2.0 for sulfamethazine in a Plaggic Anthrosol soil, and to classify the individual compounds by environmental relevance based on transport behaviour and persistence. According to the distribution of resistant genes in the environment, sulfamethazine was found to be the most mobile and persistent substance.

Comparison of methods for the detection and extrapolation of trends in groundwater quality.

Land use changes and the intensification of agriculture since the 1950s have resulted in a deterioration of groundwater quality in many European countries. For the protection of groundwater quality, it is necessary to (1) assess the current groundwater quality status, (2) detect changes or trends in groundwater quality, (3) assess the threat of deterioration and (4) predict future changes in groundwater quality. A variety of approaches and tools can be used to detect and extrapolate trends in groundwater quality, ranging from simple linear statistics to distributed 3D groundwater contaminant transport models. In this paper we report on a comparison of four methods for the detection and extrapolation of trends in groundwater quality: (1) statistical methods, (2) groundwater dating, (3) transfer functions, and (4) deterministic modeling. Our work shows that the selection of the method should firstly be made on the basis of the specific goals of the study (only trend detection or also extrapolation), the system under study, and the available resources. For trend detection in groundwater quality in relation to diffuse agricultural contamination, a very important aspect is whether the nature of the monitoring network and groundwater body allows the collection of samples with a distinct age or produces samples with a mixture of young and old groundwater. We conclude that there is no single optimal method to detect trends in groundwater quality across widely differing catchments.

Degassing of 3H/3He, CFCs and SF6 by denitrification: measurements and two-phase transport simulations.

The production of N2 gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of 3H/3He, CFCs and SF6 as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R2=69%), as well as the 3H (R2=79%) and 3He (R2=76%) concentrations observed in a 3H/3He data set using simple 2D models. We found that the TDG correction of the 3H/3He age overestimated the control 3He/3He age by 2.1 years, due to the accumulation of 3He in the gas phase. The total uncertainty of degassed 3H/3He ages of 6 years (+/-2 sigma) is due to the correction of degassed 3He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak 3He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF6 is highly susceptible to degassing. We conclude that 3H/3He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.

Urban hydrogeology: Transport routes and mixing of water and solutes in a groundwater influenced urban lowland catchment.

Urban areas in coastal lowlands host a significant part of the world's population. In these areas, cities have often expanded to unfavorable locations that have to be drained or where excess rain water and groundwater need to be pumped away in order to maintain dry feet for its citizens. As a result, groundwater seepage influences surface water quality in many of such urban lowland catchments. This study aims at identifying the flow routes and mixing processes that control surface water quality in the groundwater-influenced urban catchment Polder Geuzenveld, which is part of the city of Amsterdam. Geuzenveld is a highly paved urban area with a subsurface rain water collection system, a groundwater drainage system, and a main surface water system that receive runoff from pavement and roofs, shallow groundwater and direct groundwater seepage, respectively. We conducted a field survey and systematic monitoring to identify the spatial and temporal variations in water quality in runoff, ditch water, drain water, and shallow and deep groundwater. We found that Geuzenveld receives a substantial inflow of deep, O2-depleted groundwater, which is enriched in ammonium and phosphorus due to the subsurface mineralization of organic matter under sulfate-reducing conditions. This groundwater is mixed in the ditches during wet periods with O2-rich runoff, and iron- and phosphate-rich drain water. Unlike natural catchments, the newly created, separated urban flow routes lead to mixing of water in the main surface water itself, shortcutting much of the soil and shallow subsurface. This leads to low O2 and high ammonia concentrations in dry periods, which might be mitigated by water level management or artificially increasing O2 levels by water inlet or artificially aeration of the main water canals. Further research is necessary how to optimize artificial urban systems to deliver a better ecological and chemical status of the surface water.

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.

Monitoring strategies at phreatic wellfields: a 3D travel time approach.

Ground water quality networks for monitoring phreatic drinking water wellfields are generally established for two main purposes: (1) the short-term safeguarding of public water supply and (2) signaling and predicting future quality changes in the extracted ground water. Six monitoring configurations with different well locations and different screen depths and lengths were evaluated using a numerical model of the 3D ground water flow toward a partially penetrating pumping well in a phreatic aquifer. Travel times and breakthrough curves for observation and pumping wells were used to judge the effectiveness of different design configurations for three monitoring objectives: (1) early warning; (2) prediction of future quality changes; and (3) evaluation of protection measures inside a protection zone. Effectiveness was tested for scenarios with advective transport, first-order degradation, and linear sorption. It is shown that the location and especially the depth of the observation wells should be carefully chosen, taking into account the residence time from the surface to the observation well, the residual transit times to the extraction well, and the transformation and retardation rates. Shallow monitoring was most functional for a variety of objectives and conditions. The larger the degradation rates or retardation, the shallower should the monitoring be for effective early warning and prediction of future ground water quality. The general approach followed in the current study is applicable for many geohydrological situations, tuning specific monitoring objectives with residence times and residual transit times obtained from a site-specific ground water flow model.

Climate change impacts on the leaching of a heavy metal contamination in a small lowland catchment.

The Keersop catchment (43km(2)) in the south of The Netherlands has been contaminated by the emissions of four zinc ore smelters. The objective of this study was to assess the effects of future projected climate change on the hydrology and the leaching of heavy metals (i.e. Cd and Zn) in the catchment. The numerical, quasi-2D, unsaturated zone Soil Water Atmosphere Plant model was used with 100-year simulated daily time series of precipitation and potential evapotranspiration. The time series are representative of stationary climates for the periods 1961-1990 ("baseline") and 2071-2100 ("future"). The time series of future climate were obtained by downscaling the results of eight regional climate model (RCM) experiments, driven by the SRES A2 emissions scenario, using change factors for a series of climate statistics and applying them to stochastic weather generator models. The time series are characterized by increased precipitation in winter, less precipitation in summer, and higher air temperatures (between 2°C and 5°C) throughout the year. Future climate scenarios project higher evapotranspiration rates, more irrigation, less drainage, lower discharge rates and lower groundwater levels, due to increased evapotranspiration and a slowing down of the groundwater system. As a result, lower concentrations of Cd and Zn in surface water are projected. The reduced leaching of heavy metals, due to drying of the catchment, showed a positive impact on a limited aspect of surface water quality.

Application and evaluation of a new passive sampler for measuring average solute concentrations in a catchment scale water quality monitoring study.

We present a field based testing, optimization, and evaluation study of the SorbiCell sampler (SC-sampler); a new passive sampling technique that measures average concentrations over longer periods of time (days to months) for various substances. We tested the SC-sampler within a catchment-scale monitoring study of NO(3) and P concentrations in surface water and tile drain effluent. Based on our field experiences, we optimized the flow velocity control and the sample volume capacity of the SC-samplers. The SC-samplers were capable of reproducing the NO(3) concentration levels and the seasonal patterns that were observed with weekly conventional grab sampling and continuous water quality measurements. Furthermore, we demonstrated that average measurements produce more consistent load estimates than "snapshot" concentrations from grab sampling. Therefore, when the purpose of a monitoring program is to estimate reliable (trends in) average concentrations or loads, the SC-samplers are a cost-effective alternative for grab sampling.