An analytical framework on the leaching potential of veterinary pharmaceuticals: A case study for the Netherlands.

Veterinary pharmaceuticals (VPs) residues may end up on the soil via manure, and from there can be transported to groundwater due to leaching. In this study an analytical framework to estimate the leaching potential of VPs at the national scale is presented. This approach takes soil-applied VPs concentrations, soil-hydraulic and soil-chemical properties, groundwater levels, sorption and degradation of VPs into account. For six commonly soil-applied VPs in the Netherlands, we assess quantities leached to groundwater and their spatial distribution, as well as the relative importance of processes that drive leaching. Our results for VPs Oxytetracycline, Doxycycline, and Ivermectin indicate that maximum quantities that may leach to groundwater are very low, i.e. ≪1 µg/ha, hence spatial differences are not investigated. For VPs Sulfadiazine and Flubendazole we identify a few regions that are potentially prone to leaching, with leached quantities higher than 1 µg/ha. Leaching patterns of these two VPs are dominated by soil properties and groundwater levels rather than soil-applied quantities. For Dexamethasone, even though applied on the soil in much lower concentrations compared to other investigated VPs, spatially widespread leaching to groundwater is found, with leached quantities higher than 1 µg/ha. Due to the leaching affinity of Dexamethasone, variations in the soil-applied amounts have significant influence on the quantities leached to groundwater. Dexamethasone is highlighted as important for the future environmental risk assessment efforts. This study has shown that the leaching potential of VPs is not determined by one single parameter, but by a combination of parameters. This combination also depends on the compound investigated.

The impact of phosphorus on projected Sub-Saharan Africa food security futures.

Sub-Saharan Africa must urgently improve food security. Phosphorus availability is one of the major barriers to this due to low historical agricultural use. Shared socioeconomic pathways (SSPs) indicate that only a sustainable (SSP1) or a fossil fuelled future (SSP5) can improve food security (in terms of price, availability, and risk of hunger) whilst nationalistic (SSP3) and unequal (SSP4) pathways worsen food security. Furthermore, sustainable SSP1 requires limited cropland expansion and low phosphorus use whilst the nationalistic SSP3 is as environmentally damaging as the fossil fuelled pathway. The middle of the road future (SSP2) maintains today's inadequate food security levels only by using approximately 440 million tonnes of phosphate rock. Whilst this is within the current global reserve estimates the market price alone for a commonly used fertiliser (DAP) would cost US$ 130 ± 25 billion for agriculture over the period 2020 to 2050 and the farmgate price could be two to five times higher due to additional costs (e.g. transport, taxation etc.). Thus, to improve food security, economic growth within a sustainability context (SSP1) and the avoidance of nationalist ideology (SSP3) should be prioritised.

Emission estimation and prioritization of veterinary pharmaceuticals in manure slurries applied to soil.

Veterinary pharmaceuticals (VPs) are emitted into the environment and transfer to groundwater and surface water is diffuse and complex, whereas actual information on the fate is frequently limited. For 17 VPs of potential concern in the Netherlands, we assessed sources and emission due to animal slurry applications to soil. Hence, we examined the use of VPs in four livestock sectors in the Netherlands for 2015-2018, and quantified animal excretion rates and dissipation during slurry storage. For almost all VPs, administrated quantities to the animals during the period 2015-2018 decreased. VP concentrations during a storage period of six months could decrease between 10 and 98% depending on the compound. Predicted concentrations of VPs in slurries after storage compared well with measured concentrations in the literature. Based on the storage model outcomes, we developed a residue indicator, that quantifies the potential for residues in applied slurry. This indicator agrees well with the most frequently detected VPs in the Dutch slurries, and is therefore useful to prioritize measures aiming at reducing VP emissions into the environment.

Comparison of the individual salinity and water deficit stress using water use, yield, and plant parameters in maize.

Though water deficit and salinity effects on plants have similarities, they are physiologically different. This motivated us to separately explore the effects of salinity and water deficit on water consumption, yield, and some plant parameters for maize (Zea mays L., var. SC704). Greenhouse experiments were conducted during two seasons. In one experiment, maize was cultivated in wet soil (matric potential of - 10 kPa), and the irrigation water salinity was varied between treatments (osmotic potentials up to - 336 kPa). In a parallel experiment, five water deficit levels were maintained by irrigating with water to accomplish the same daily water uptake as in the salinity treatments. The experiments were conducted in pots with a randomized design and four replicates. Salinity and water deficit stress significantly affected yield and other plant parameters. However, root dry matter in autumn was not significant. We observed a profound effect of evaporative demand on most of the plant parameters and water use, such as water use efficiency (WUE). For same water use rate, the values of osmotic and matric potential were different. In spring season, the ratios of matric to osmotic potential were 0.25, 0.46, 0.44, and 0.43 in corresponding D1, D2, D3, and D4 water deficit and S1, S2, S3, and S4 salinity treatments. For autumn season, these ratios were 0.26, 0.36, 0.34, and 0.36. We concluded crop models that lump water deficit and salinity (additively or multiplicatively) to predict yields can result in inappropriate predictions.

Fractionation and leaching of heavy metals in soils amended with a new biochar nanocomposite.

In this study, surface soils of the Bama Pb-Zn mine-impacted area were sampled for an area surrounding the mineral processing plant. After collecting 65 samples and analyzing them for initial Cu, Pb, Zn, and Cd metal contents, the area was zonated based on the concentration distribution using ordinary kriging in R. A single homogenous sample was prepared by mixing equal weights of each sample as being representative of the whole impacted area (ST). Next, a synthetic model soil (SM) was prepared according to the mean ST texture (SM), divided into two portions, where one portion was amended with a biochar composite (10% w/w) (SMA), both portions were artificially contaminated with Cu, Pb, Zn, and Cd (SMAC and SMC). The mixed soil ST, and the model soils SMC and SMAC, were subjected to soil sequential extraction procedure to determine the variations in fractionation of heavy metals. Results showed that the fractionation in the unamended model soil (SMC) was very close to the original real soil (ST). Moreover, in both amended and unamended soils, Cd and Pb had the highest and the lowest mobility, respectively. Zn and Cu showed intermediate mobilities. The performance of the amendment was evaluated using a 150-day column leaching test taking leachate samples at designated time intervals, and Cu, Pb, Zn, and Cd concentrations were analyzed. Results of column leaching were in good agreement with the soil fractionation as Cd and Pb showed the highest and the lowest mobilities, respectively. Leaching through the soil column was also simulated by HP1 model. Results of simulation found in acceptable proximity to the experimental data despite remarkable differences due to limitations in defining soil to the simulation system.

A modification of the constant-head permeameter to measure saturated hydraulic conductivity of highly permeable media.

The saturated hydraulic conductivity (Ks ) is a key characteristic of porous media, describing the rate of water flow through saturated porous media. It is an indispensable parameter in a broad range of simulation models that quantify saturated and/or unsaturated water flow. The constant-head permeameter test is a common laboratory method to determine Ks on undisturbed soil samples collected from the field. In this paper we show that the application of this conventional method may result in a biased Ks in the case of highly permeable media, such as the top layer of Sphagnum peat and gravel. Tubes in the conventional permeameter, that collect water under the sample, introduce a hydraulic head-dependent resistance for highly permeable media and result in an underestimation of Ks . We present a simple and low-budget alternative of the constant-head permeameter test that overcomes the disadvantages of conventional permeameters. The new method was successfully tested on intact highly permeable peatmoss collected from a northern peatland. •Conventional constant-head permeameters underestimate Ks of highly permeable media due to flow resistance in tubing systems•We developed the low-resistance permeameter to overcome this disadvantage.•Testing of the low-resistance permeameter demonstrated no systematic bias and successful application for highly permeable media.

Including hydrological self-regulating processes in peatland models: Effects on peatmoss drought projections.

The water content of the topsoil is one of the key factors controlling biogeochemical processes, greenhouse gas emissions and biosphere - atmosphere interactions in many ecosystems, particularly in northern peatlands. In these wetland ecosystems, the water content of the photosynthetic active peatmoss layer is crucial for ecosystem functioning and carbon sequestration, and is sensitive to future shifts in rainfall and drought characteristics. Current peatland models differ in the degree in which hydrological feedbacks are included, but how this affects peatmoss drought projections is unknown. The aim of this paper was to systematically test whether the level of hydrological detail in models could bias projections of water content and drought stress for peatmoss in northern peatlands using downscaled projections for rainfall and potential evapotranspiration in the current (1991-2020) and future climate (2061-2090). We considered four model variants that either include or exclude moss (rain)water storage and peat volume change, as these are two central processes in the hydrological self-regulation of peatmoss carpets. Model performance was validated using field data of a peatland in northern Sweden. Including moss water storage as well as peat volume change resulted in a significant improvement of model performance, despite the extra parameters added. The best performance was achieved if both processes were included. Including moss water storage and peat volume change consistently reduced projected peatmoss drought frequency with >50%, relative to the model excluding both processes. Projected peatmoss drought frequency in the growing season was 17% smaller under future climate than current climate, but was unaffected by including the hydrological self-regulating processes. Our results suggest that ignoring these two fine-scale processes important in hydrological self-regulation of northern peatlands will have large consequences for projected climate change impact on ecosystem processes related to topsoil water content, such as greenhouse gas emissions.

Integration of transport concepts for risk assessment of pesticide erosion.

Environmental contamination by agrochemicals has been a large problem for decades. Pesticides are transported in runoff and remain attached to eroded soil particles, posing a risk to water and soil quality and human health. We have developed a parsimonious integrative model of pesticide displacement by runoff and erosion that explicitly accounts for water infiltration, erosion, runoff, and pesticide transport and degradation in soil. The conceptual framework was based on broadly accepted assumptions such as the convection-dispersion equation and lognormal distributions of soil properties associated with transport, sorption, degradation, and erosion. To illustrate the concept, a few assumptions are made with regard to runoff in relatively flat agricultural fields: dispersion is ignored and erosion is modelled by a functional relationship. A sensitivity analysis indicated that the total mass of pesticide associated with soil eroded by water scouring increased with slope, rain intensity, and water field capacity of the soil. The mass of transported pesticide decreased as the micro-topography of the soil surface became more distinct. The timing of pesticide spraying and rate of degradation before erosion negatively affected the total amount of transported pesticide. The mechanisms involved in pesticide displacement, such as runoff, infiltration, soil erosion, and pesticide transport and decay in the topsoil, were all explicitly accounted for, so the mathematical complexity of their description can be high, depending on the situation.

Saltwater Upconing Due to Cyclic Pumping by Horizontal Wells in Freshwater Lenses.

This article deals with the quantification of saltwater upconing below horizontal wells in freshwater lenses using analytical solutions as a computationally fast alternative to numerical simulations. Comparisons between analytical calculations and numerical simulations are presented regarding three aspects: (1) cyclic pumping; (2) dispersion; and (3) finite horizontal wells in a finite domain (a freshwater lens). Various hydrogeological conditions and pumping regimes within a dry half year are considered. The results show that the influence of elastic and phreatic storage (which are not taken into account in the analytical solutions) on the upconing of the interface is minimal. Furthermore, the analytical calculations based on the interface approach compare well with numerical simulations as long as the dimensionless interface upconing is below 1/3, which is in line with previous studies on steady pumping. Superimposing an analytical solution for mixing by dispersion below the well over an analytical solution based on the interface approach is appropriate in case the vertical flow velocity around the interface is nearly constant but should not be used for estimating the salinity of the pumped groundwater. The analytical calculations of interface upconing below a finite horizontal well compare well with the numerical simulations in case the distance between the horizontal well and the initial interface does not vary significantly along the well and in case the natural fluctuation of the freshwater lens is small. In order to maintain a low level of salinity in the well during a dry half year, the dimensionless analytically calculated interface upconing should stay below 0.25.

Rain events decrease boreal peatland net CO2 uptake through reduced light availability.

Boreal peatlands store large amounts of carbon, reflecting their important role in the global carbon cycle. The short-term exchange and the long-term storage of atmospheric carbon dioxide (CO2 ) in these ecosystems are closely associated with the permanently wet surface conditions and are susceptible to drought. Especially, the single most important peat forming plant genus, Sphagnum, depends heavily on surface wetness for its primary production. Changes in rainfall patterns are expected to affect surface wetness, but how this transient rewetting affects net ecosystem exchange of CO2 (NEE) remains unknown. This study explores how the timing and characteristics of rain events during photosynthetic active periods, that is daytime, affect peatland NEE and whether rain event associated changes in environmental conditions modify this response (e.g. water table, radiation, vapour pressure deficit, temperature). We analysed an 11-year time series of half-hourly eddy covariance and meteorological measurements from Degerö Stormyr, a boreal peatland in northern Sweden. Our results show that daytime rain events systematically decreased the sink strength of peatlands for atmospheric CO2 . The decrease was best explained by rain associated reduction in light, rather than by rain characteristics or drought length. An average daytime growing season rain event reduced net ecosystem CO2 uptake by 0.23-0.54 gC m(-2) . On an annual basis, this reduction of net CO2 uptake corresponds to 24% of the annual net CO2 uptake (NEE) of the study site, equivalent to a 4.4% reduction of gross primary production (GPP) during the growing season. We conclude that reduced light availability associated with rain events is more important in explaining the NEE response to rain events than rain characteristics and changes in water availability. This suggests that peatland CO2 uptake is highly sensitive to changes in cloud cover formation and to altered rainfall regimes, a process hitherto largely ignored.

Can frequent precipitation moderate the impact of drought on peatmoss carbon uptake in northern peatlands?

Northern peatlands represent a large global carbon store that can potentially be destabilized by summer water table drawdown. Precipitation can moderate the negative impacts of water table drawdown by rewetting peatmoss (Sphagnum spp.), the ecosystem's key species. Yet, the frequency of such rewetting required for it to be effective remains unknown. We experimentally assessed the importance of precipitation frequency for Sphagnum water supply and carbon uptake during a stepwise decrease in water tables in a growth chamber. CO2 exchange and the water balance were measured for intact cores of three peatmoss species (Sphagnum majus, Sphagnum balticum and Sphagnum fuscum) representative of three hydrologically distinct peatland microhabitats (hollow, lawn and hummock) and expected to differ in their water table-precipitation relationships. Precipitation contributed significantly to peatmoss water supply when the water table was deep, demonstrating the importance of precipitation during drought. The ability to exploit transient resources was species-specific; S. fuscum carbon uptake increased linearly with precipitation frequency for deep water tables, whereas carbon uptake by S. balticum and S. majus was depressed at intermediate precipitation frequencies. Our results highlight an important role for precipitation in carbon uptake by peatmosses. Yet, the potential to moderate the impact of drought is species-specific and dependent on the temporal distribution of precipitation.

Multi-surface modeling to predict free zinc ion concentrations in low-zinc soils.

Multi-surface models are widely used to assess the potential ecotoxicological risk in metal-contaminated soils. Their accuracy in predicting metal speciation in soils with low metal levels was not yet tested. Now highly sensitive analytical techniques are available to experimentally validate such models at low concentration levels. The objective of this study was to test the accuracy of a multi-surface model to predict the Zn(2+) concentration and to improve our understanding of Zn bioavailability in low-Zn soils. High-Zn soils were included as controls. Model parameters were determined independently on the basis of earlier peer-reviewed publications. Model output was validated against free Zn(2+) concentrations determined with the soil column Donnan membrane technique in a range of soils varying in potentially available Zn, organic matter, clay silicate, and iron (hydr)oxide contents and pH. Deviations between predicted Zn(2+) concentrations and experimentally determined values over the whole Zn concentration range were less or equal to the experimental standard error, except for one low-Zn soil. The Zn(2+) concentration was mainly controlled by adsorption, where organic matter was predicted to be the dominant soil sorbent. The predicted Zn(2+) concentration depends more sensitively upon changes of the reactive Zn pool (application of 0.6, 1.2, 2.4, and 3.6 mg of Zn kg(-1) of soil) and organic matter content (± 0.2 and 0.4%) than pH changes (± 0.5 and 1 pH unit).

How does tree density affect water loss of peatlands? A mesocosm experiment.

Raised bogs have accumulated more atmospheric carbon than any other terrestrial ecosystem on Earth. Climate-induced expansion of trees and shrubs may turn these ecosystems from net carbon sinks into sources when associated with reduced water tables. Increasing water loss through tree evapotranspiration could potentially deepen water tables, thus stimulating peat decomposition and carbon release. Bridging the gap between modelling and field studies, we conducted a three-year mesocosm experiment subjecting natural bog vegetation to three birch tree densities, and studied the changes in subsurface temperature, water balance components, leaf area index and vegetation composition. We found the deepest water table in mesocosms with low tree density. Mesocosms with high tree density remained wettest (i.e. highest water tables) whereas the control treatment without trees had intermediate water tables. These differences are attributed mostly to differences in evapotranspiration. Although our mesocosm results cannot be directly scaled up to ecosystem level, the systematic effect of tree density suggests that as bogs become colonized by trees, the effect of trees on ecosystem water loss changes with time, with tree transpiration effects of drying becoming increasingly offset by shading effects during the later phases of tree encroachment. These density-dependent effects of trees on water loss have important implications for the structure and functioning of peatbogs.

Improved management of winter operations to limit subsurface contamination with degradable deicing chemicals in cold regions.

This paper gives an overview of management considerations required for better control of deicing chemicals in the unsaturated zone at sites with winter maintenance operations in cold regions. Degradable organic deicing chemicals are the main focus. The importance of the heterogeneity of both the infiltration process, due to frozen ground and snow melt including the contact between the melting snow cover and the soil, and unsaturated flow is emphasised. In this paper, the applicability of geophysical methods for characterising soil heterogeneity is considered, aimed at modelling and monitoring changes in contamination. To deal with heterogeneity, a stochastic modelling framework may be appropriate, emphasizing the more robust spatial and temporal moments. Examples of a combination of different field techniques for measuring subsoil properties and monitoring contaminants and integration through transport modelling are provided by the SoilCAM project and previous work. Commonly, the results of flow and contaminant fate modelling are quite detailed and complex and require post-processing before communication and advising stakeholders. The managers' perspectives with respect to monitoring strategies and challenges still unresolved have been analysed with basis in experience with research collaboration with one of the case study sites, Oslo airport, Gardermoen, Norway. Both scientific challenges of monitoring subsoil contaminants in cold regions and the effective interaction between investigators and management are illustrated.

Modeling of the solid-solution partitioning of heavy metals and arsenic in embanked flood plain soils of the rivers Rhine and Meuse.

The aim of this study is to predict the solid-solution partitioning of heavy metals in river flood plain soils. We compared mechanistic geochemical modeling with a statistical approach. To characterize the heavy metal contamination of embanked river flood plain soils in The Netherlands, we collected 194 soil samples at 133 sites distributed in the Dutch part of the Rhine and Meuse river systems. We measured the total amounts of As, Cd, Cr, Cu, Ni, Pb, and Zn in the soil samples and the metal fraction extractable by 2.5 mM CaCl2. We found a strong correlation between heavy metal contamination and organic matter content, which was almost identical for both river systems. Speciation calculations by a fully parametrized model showed the strengths and weaknesses of the mechanistic approach. Cu and Cd concentrations were predicted within one log scale, whereas modeling of Zn and Pb needs adjustment of some model parameters. The statistical fitting approach produced better results but is limited with regard to the understanding it provides. The log RMSE for this approach varied between 0.2 and 0.32 for the different metals. The careful modeling of speciation and adsorption processes is a useful tool for the investigation and understanding of metal availability in river flood plain soils.

Competition effects for copper between soil, soil solution, and yeast in a bioassay for Folsomia candida Willem.

We investigated the accumulation of copper (Cu) by the springtail Folsomia candida Willem, if exposed to Cu-contaminated sandy soil with yeast as a food source. Commonly, the dissolved and the easily desorbed Cu fractions are assumed to be available for uptake, and as both fractions depend on pH, a pH dependency of copper uptake and accumulation is expected. In recent studies with springtails this dependency was not observed. To explain this, we show that both the adsorption of copper by yeast and by soil is indeed pH dependent; however, these dependencies differ. Addition of yeast as a food source to copper-contaminated soil leads to competition for copper by yeast and soil that suppresses the pH dependency of copper adsorption by yeast. This may cause a pH dependency not to be observed in copper accumulation by springtails if they predominantly feed on yeast in bioassays. We conclude that the addition of artificial food sources in bioassays may affect the cause-effect relationships that are investigated. A combination of (soil) chemical experimentation and modeling and ecotoxicological studies may help in identifying such bias and, therefore, with interpreting bioassays.

Preferential flow of bromide, bentazon, and imidacloprid in a Dutch clay soil.

Leaching to ground water and tile drains are important parts of the environmental assessment of pesticides. The aims of the present study were to (i) assess the significance of preferential flow for pesticide leaching under realistic worst-case conditions for Dutch agriculture (soil profile with thick clay layer and high rainfall) and (ii) collect a high-quality data set that is suitable for testing pesticide leaching models. The movement of water, bromide, and the pesticides bentazon [3-isopropyl-1H-2, 1,3-benzothiadiazine-4(3H)-one-2,2-dioxide] and imidacloprid [1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine] was monitored in a clay soil for about 1 yr. The 1.2-ha field was located in the central part of the Netherlands (51 degrees 53' N, 5 degrees 43' E). The soil was a Eutric Fluvisol cropped with winter wheat (Triticum aestivum L.). Tile drains were present at a 0.8- to 0.9-m depth and the ground water level fluctuated between a 0.5- and 2-m depth. All chemicals were applied in spring. None of the soil concentration profiles showed bimodal concentration distributions. However, for each substance the highest concentration in drain water was found in the first drainage event after its application, which indicates preferential flow. This preferential flow is probably caused by permanent macropores that were present in the 0.3- to 1.0-m layer. At the time of the first drainage event, the drain water concentration of each substance was about an order of magnitude higher than its ground water concentration. Thus, the flux concentrations in drain water proved to be a more sensitive detector of preferential flow than the resident concentrations in the soil profile and the ground water.