Improved Lumped-Parameter and Numerical Modeling of Unsaturated Water Flow and Stable Water Isotopes.

Characterizing unsaturated water flow in the subsurface is a requirement for understanding effects of droughts on agricultural production or impacts of climate change on groundwater recharge. By employing an improved lumped-parameter model (LPM) approach that mimics variable flow we have interpreted stable water isotope data (δ18 O and δ2 H), taken over 3 years at a lysimeter site located in Germany. Lysimeter soil cores were characterized by sandy gravel (Ly1) and clayey sandy silt (Ly2), and both lysimeters were vegetated with maize. Results were compared with numerical simulation of unsaturated flow and stable water isotope transport using HYDRUS-1D. In addition, both approaches were extended by the consideration of preferential flow paths. Application of the extended LPM, and thus varying flow and transport parameters, substantially improved the description of stable water isotope observations in lysimeter seepage water. In general, findings obtained from the extended LPM were in good agreement to numerical modeling results. However, observations were more difficult to describe mathematically for Ly2, where the periodicity of seasonal stable water isotope fluctuation in seepage water was not fully met by numerical modeling. Furthermore, an extra isotopic upshift improved simulations for Ly2, probably controlled by stable water isotope exchange processes between mobile soil water and quasi-immobile water within stagnant zones. Finally, although LPM requires less input data compared with numerical models, both approaches achieve comparable decision-support integrity. The extended LPM approach can thus be a powerful tool for soil and groundwater management approaches.

Development and application of a numerical dynamic model for pesticide residues in apple orchards.

BACKGROUND: Limited understanding of the fate of pesticides in apple orchards may lead to recurring pests or pose risks to food safety. In this study, through a field experiment conducted in an apple orchard, a dynamic plant uptake model, coupled with a soil water model, was developed to simulate measured pesticide concentrations in soil and different plant compartments. RESULTS: Results showed that the overall model could adequately describe the data set of four pesticides in the apple orchard. An estimated 15%-24.7% of applied pesticides were deposited on leaves and 0.37%-0.58% on fruits. Decreasing pesticide concentrations in fruits were observed after pesticide application, with 9.6%-64.8% of this decrease explained by biodegradation, 29.8%-75.8% by fruit growth dilution and 11.3%-47.6% by wash-off. Furthermore, a first estimation of dietary risks indicated that ingestion of the apples may not represent an acute or chronic risk to human health. CONCLUSION: The dynamic plant uptake model, coupled with the tipping buckets soil water model, could successfully be fitted to describe to the data set for the fate of four pesticides applied in an apple orchard. The contribution of different pathways to pesticide concentration was highly influenced by precipitation, fruit growth dilution and the characteristics of different pesticides. This model can improve our understanding of pesticide fate in apple orchards and has great potential for supporting food safety assessment and decision-making to minimize impacts arising from pesticide applications. © 2022 Society of Chemical Industry.

A review on risk assessment in managed aquifer recharge.

Managed aquifer recharge (MAR) refers to a suite of methods that is increasingly being applied worldwide for sustainable groundwater management to tackle drinking or irrigation water shortage or to restore and maintain groundwater ecosystems. The potential for MAR is far from being exhausted, not only due to geological and hydrogeological conditions or technical and economic feasibility but also due to its lack of acceptance by the public and policymakers. One approach to enable the safe and accepted use of MAR could be to provide comprehensive risk management, including the identification, analysis, and evaluation of potential risks related to MAR. This article reviews current MAR risk assessment methodologies and guidelines and summarizes possible hazards and related processes. It may help planners and operators select the appropriate MAR risk assessment approaches and support the risk identification process. In addition to risk assessment (and subsequent risk treatment) related to the MAR implementation phase, this review also addresses risk assessment for MAR operation. We also highlight the limitations and lessons learned from the application and development of risk assessment methodologies. Moreover, developments are recommended in the area of MAR-related risk assessment methodologies and regulation. Depending on data availability, collected methodologies may be applicable for MAR sites worldwide. Integr Environ Assess Manag 2022;18:1513-1529. © 2022 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Monte Carlo Simulations as a Decision Support to Interpret δ15 N Values of Nitrate in Groundwater.

Intense farming is often associated with the excessive use of manure or fertilizers and the subsequent deterioration of the groundwater quality in many aquifers worldwide. Stable isotopes of dissolved nitrate (δ15 N and δ18 O) are widely used to determine sources of nitrate contamination and denitrification processes in groundwater but are often difficult to interpret. Thus, Monte Carlo simulations were carried out for a site in lower Bavaria, Germany, in order to explain δ15 N observations in a porous groundwater system with two aquifers, the main aquifer (MA) and several smaller perched aquifers (PA). For evaluating potential contributions, frequency distributions of δ15 N were simulated deriving from (I) the mixing of different nitrate sources, related to land use, as input to groundwater, combined with (II) transport of nitrate in groundwater and (III) microbial denitrification. Simulation results indicate a source-driven isotopic shift to heavier δ15 N values of nitrate in groundwater, which may be explained by land use changes toward a more intensified agriculture releasing high amounts of manure. Microbial denitrification may play a role in the PA, with simulated δ15 N distributions close to the observations. Denitrification processes are however unlikely for the MA, as reasonable simulation curve fits for such a scenario were obtained predominantly for unrealistic portions of nitrate sources and related land use. The applied approach can be used to qualitatively and quantitatively evaluate the influence of different potential contributions, which might mask each other due to overlapping δ15 N ranges, and it can support the estimation of nitrate input related to land use.

Characterizing Water Flow in Vegetated Lysimeters with Stable Water Isotopes and Modeling.

We have used stable water isotopes (δ18 O, δ2 H) in combination with lumped-parameter modeling for characterizing unsaturated flow in two lysimeters vegetated with maize. The lysimeters contained undisturbed soil cores dominated by sandy gravel (Ly1) and clayey sandy silt (Ly2). Stable water isotopes were analyzed in precipitation and lysimeter outflow water over about 3 years. The mean transit time of water T and dispersion parameter PD , obtained from modeling, were higher for the silt soil in Ly2 than for the gravel soil in Ly1 (T of 362 vs. 129 d, PD of 0.7 vs. 0.12). The consideration of preferential flow (PF) paths could substantially improve the model curve fits, with 13 and 11% contribution of PF for Ly1 and Ly2 as best estimates. Different assumptions were compared to estimate the input function, that is, stable water isotope content in the recharging water. Using the isotopic composition of precipitation as input (no modification) resulted in reasonable model estimations. Best model fits for the entire observation were obtained by weighting the recharging isotopes according to average precipitation within periods of 3 and 6 months, in correspondence to changing vegetation phases and seasonal influences. Input functions that consider actual evapotranspiration could significantly improve modeling at some periods, however, this led to deviations between modeled and observed δ18 O at other periods. This may indicate the influence of variable flow, so that dividing the whole observation period into hydraulically characteristic sub-periods for lumped-parameter modeling (which implements steady-state flow) is recommended for possible further improvement.

Microbial Turnover of Glyphosate to Biomass: Utilization as Nutrient Source and Formation of AMPA and Biogenic NER in an OECD 308 Test.

Environmental fate assessment of chemicals involves standardized simulation tests with isotope-labeled molecules to balance transformation, mineralization, and formation of nonextractable residues (NER). Methods to predict microbial turnover and biogenic NER have been developed, having limited use when metabolites accumulate, the chemicals are not the only C source, or provide for other macroelements. To improve predictive capability, we extended a recently developed method for microbial growth yield estimation to account for incomplete degradation and multiple-element assimilation and combined it with a dynamic model for fate description in soils and sediments. We evaluated the results against the unique experimental data of 13C3-15N co-labeled glyphosate turnover with AMPA formation in water-sediment systems (OECD 308). Balancing 13C- and 15N- fluxes to biomass showed a pronounced shift of glyphosate transformation from full mineralization to AMPA formation. This may be explained by various hypotheses, for example, the limited substrate turnover inherent to the batch conditions of the test system causing microbial starvation or inhibition by P release. Modeling results indicate initial N overload due to the lower C/N ratio in glyphosate compared to average cell composition leading to subsequent C demand and accumulation of AMPA.

Impact of bacterial activity on turnover of insoluble hydrophobic substrates (phenanthrene and pyrene)-Model simulations for prediction of bioremediation success.

Many attempts for bioremediation of polycyclic aromatic hydrocarbon (PAH) contaminated sites failed in the past, but the reasons for this failure are not well understood. Here we apply and improve a model for integrated assessment of mass transfer, biodegradation and residual concentrations for predicting the success of remediation actions. First, we provide growth parameters for Mycobacterium rutilum and Mycobacterium pallens growing on phenanthrene (PHE) or pyrene (PYR) degraded the PAH completely at all investigated concentrations. Maximum metabolic rates vmax and growth rates µ were similar for the substrates PHE and PYR and for both strains. The investigated Mycobacterium species were not superior in PHE degradation to strains investigated earlier with this method. Real-world degradation scenario simulations including diffusive flux to the microbial cells indicate: that (i) bioaugmentation only has a small, short-lived effect; (ii) Increasing sorption shifts the remaining PAH to the adsorbed/sequestered PAH pool; (iii) mobilizing by solvents or surfactants resulted in a significant decrease of the sequestered PAH, and (iv) co-metabolization e.g. by compost addition can contribute significantly to the reduction of PAH, because active biomass is maintained at a high level by the compost. The model therefore is a valuable contribution to the assessment of potential remediation action at PAH-polluted sites.

Experimental results and integrated modeling of bacterial growth on an insoluble hydrophobic substrate (phenanthrene).

Metabolism of a low-solubility substrate is limited by dissolution and availability and can hardly be determined. We developed a numerical model for simultaneously calculating dissolution kinetics of such substrates and their metabolism and microbial growth (Monod kinetics with decay) and tested it with three aerobic phenanthrene (PHE) degraders: Novosphingobium pentaromativorans US6-1, Sphingomonas sp. EPA505, and Sphingobium yanoikuyae B1. PHE was present as microcrystals, providing non-limiting conditions for growth. Total PHE and protein concentration were tracked over 6-12 days. The model was fitted to the test results for the rates of dissolution, metabolism, and growth. The strains showed similar efficiency, with vmax values of 12-18 g dw g(-1) d(-1), yields of 0.21 g g(-1), maximum growth rates of 2.5-3.8 d(-1), and decay rates of 0.04-0.05 d(-1). Sensitivity analysis with the model shows that (i) retention in crystals or NAPLs or by sequestration competes with biodegradation, (ii) bacterial growth conditions (dissolution flux and resulting chemical activity of substrate) are more relevant for the final state of the system than the initial biomass, and (iii) the desorption flux regulates the turnover in the presence of solid-state, sequestered (aged), or NAPL substrate sources.

Phytoscreening and phytoextraction of heavy metals at Danish polluted sites using willow and poplar trees.

The main purpose of this study was to determine typical concentrations of heavy metals (HM) in wood from willows and poplars, in order to test the feasibility of phytoscreening and phytoextraction of HM. Samples were taken from one strongly, one moderately, and one slightly polluted site and from three reference sites. Wood from both tree species had similar background concentrations at 0.5 mg kg(-1) for cadmium (Cd), 1.6 mg kg(-1) for copper (Cu), 0.3 mg kg(-1) for nickel (Ni), and 25 mg kg(-1) for zinc (Zn). Concentrations of chromium (Cr) and lead (Pb) were below or close to detection limit. Concentrations in wood from the highly polluted site were significantly elevated, compared to references, in particular for willow. The conclusion from these results is that tree coring could be used successfully to identify strongly heavy metal-polluted soil for Cd, Cu, Ni, Zn, and that willow trees were superior to poplars, except when screening for Ni. Phytoextraction of HMs was quantified from measured concentration in wood at the most polluted site. Extraction efficiencies were best for willows and Cd, but below 0.5% over 10 years, and below 1‰ in 10 years for all other HMs.

Impact of activated carbon, biochar and compost on the desorption and mineralization of phenanthrene in soil.

Sorption of PAHs to carbonaceous soil amendments reduces their dissolved concentrations, limiting toxicity but also potentially biodegradation. Therefore, the maximum abiotic desorption of freshly sorbed phenanthrene (≤5 mg kg(-1)) was measured in three soils amended with activated carbon (AC), biochar or compost. Total amounts of phenanthrene desorbed were similar between the different soils, but the amendment type had a large influence. Complete desorption was observed in the unamended and compost amended soils, but this reduced for biochar (41% desorbed) and AC (8% desorbed). Cumulative amounts mineralized were 28% for the unamended control, 19% for compost, 13% for biochar and 4% for AC. Therefore, the effects of the amendments in soil in reducing desorption were also reflected in the extents of mineralization. Modeling was used to analyze key processes, indicating that for the AC and charcoal treatments bacterial activity did not limit mineralization, but rather desorption into the dissolved phase.

Comparing the desorption and biodegradation of low concentrations of phenanthrene sorbed to activated carbon, biochar and compost.

Carbonaceous soil amendments are applied to contaminated soils and sediments to strongly sorb hydrophobic organic contaminants (HOCs) and reduce their freely dissolved concentrations. This limits biouptake and toxicity, but also biodegradation. To investigate whether HOCs sorbed to such amendments can be degraded at all, the desorption and biodegradation of low concentrations of (14)C-labelled phenanthrene (≤5 µg L(-1)) freshly sorbed to suspensions of the pure soil amendments activated carbon (AC), biochar (charcoal) and compost were compared. Firstly, the maximum abiotic desorption of phenanthrene from soil amendment suspensions in water, minimal salts medium (MSM) or tryptic soy broth (TSB) into a dominating silicone sink were measured. Highest fractions remained sorbed to AC (84±2.3%, 87±4.1%, and 53±1.2% for water, MSM and TSB, respectively), followed by charcoal (35±2.2%, 32±1.7%, and 12±0.3%, respectively) and compost (1.3±0.21%, similar for all media). Secondly, the mineralization of phenanthrene sorbed to AC, charcoal and compost by Sphingomonas sp. 10-1 (DSM 12247) was determined. In contrast to the amounts desorbed, phenanthrene mineralization was similar for all the soil amendments at about 56±11% of the initially applied radioactivity. Furthermore, HPLC analyses showed only minor amounts (<5%) of residual phenanthrene remaining in the suspensions, indicating almost complete biodegradation. Fitting the data to a coupled desorption and biodegradation model revealed that desorption did not limit biodegradation for any of the amendments, and that degradation could proceed due to the high numbers of bacteria and/or the production of biosurfactants or biofilms. Therefore, reduced desorption of phenanthrene from AC or charcoal did not inhibit its biodegradation, which implies that under the experimental conditions these amendments can reduce freely dissolved concentration without hindering biodegradation. In contrast, phenanthrene sorbed to compost was fully desorbed and biodegraded.

Simultaneous simulations of uptake in plants and leaching to groundwater of cadmium and lead for arable land amended with compost or farmyard manure.

The water budget of soil, the uptake in plants and the leaching to groundwater of cadmium (Cd) and lead (Pb) were simulated simultaneously using a physiological plant uptake model and a tipping buckets water and solute transport model for soil. Simulations were compared to results from a ten-year experimental field study, where four organic amendments were applied every second year. Predicted concentrations slightly decreased (Cd) or stagnated (Pb) in control soils, but increased in amended soils by about 10% (Cd) and 6% to 18% (Pb). Estimated plant uptake was lower in amended plots, due to an increase of K(d) (dry soil to water partition coefficient). Predicted concentrations in plants were close to measured levels in plant residues (straw), but higher than measured concentrations in grains. Initially, Pb was mainly predicted to deposit from air into plants (82% in 1998); the next years, uptake from soil became dominating (30% from air in 2006), because of decreasing levels in air. For Cd, predicted uptake from air into plants was negligible (1-5%).

Test of tree core sampling for screening of toxic elements in soils from a Norwegian site.

Tree core samples have been used to delineate organic subsurface plumes. In 2009 and 2010, samples were taken at trees growing on a former dump site in Norway and analyzed for arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), and zinc (Zn). Concentrations in wood were in averages (dw) 30 mg/kg for Zn, 2 mg/kg for Cu, and < 1 mg/kg for Cd, Cr, As and Ni. The concentrations in wood samples from the polluted test site were compared to those derived from a reference site. For all except one case, mean concentrations from the test site were higher than those from the reference site, but the difference was small and not always significant. Differences between tree species were usually higher than differences between reference and test site. Furthermore, all these elements occur naturally, and Cu, Ni, and Zn are essential minerals. Thus, all trees will have a natural background of these elements, and the occurrence alone does not indicate soil pollution. For the interpretation of the results, a comparison to wood samples from an unpolluted reference site with same species and similar soil conditions is required. This makes the tree core screening method less reliable for heavy metals than, e.g., for chlorinated solvents.

Dynamic passive dosing for studying the biotransformation of hydrophobic organic chemicals: microbial degradation as an example.

Biotransformation plays a key role in hydrophobic organic compound (HOC) fate, and understanding kinetics as a function of (bio)availability is critical for elucidating persistence, accumulation, and toxicity. Biotransformation mainly occurs in an aqueous environment, posing technical challenges for producing kinetic data because of low HOC solubilities and sorptive losses. To overcome these, a new experimental approach based on passive dosing is presented. This avoids using cosolvent for introducing the HOC substrate, buffers substrate depletion so biotransformation is measured within a narrow and defined dissolved concentration range, and enables high compound turnover even at low concentrations to simplify end point measurement. As a case study, the biodegradation kinetics of two model HOCs by the bacterium Sphingomonas paucimobilis EPA505 were measured at defined dissolved concentrations ranging over 4 orders of magnitude, from 0.017 to 658 µg L(-1) for phenanthrene and from 0.006 to 90.0 µg L(-1) for fluoranthene. Both compounds had similar mineralization fluxes, and these increased by 2 orders of magnitude with increasing dissolved concentrations. First-order mineralization rate constants were also similar for both PAHs, but decreased by around 2 orders of magnitude with increasing dissolved concentrations. Dynamic passive dosing is a useful tool for measuring biotransformation kinetics at realistically low and defined dissolved HOC concentrations.

Dynamic plant uptake model applied for drip irrigation of an insecticide to pepper fruit plants.

BACKGROUND: Drip application of insecticides is an effective way to deliver the chemical to the plant that avoids off-site movement via spray drift and minimizes applicator exposure. The aim of this paper is to present a cascade model for the uptake of pesticide into plants following drip irrigation, its application for a soil-applied insecticide and a sensitivity analysis of the model parameters. RESULTS: The model predicted the measured increase and decline of residues following two soil applications of an insecticide to peppers, with an absolute error between model and measurement ranging from 0.002 to 0.034 mg kg fw(-1). Maximum measured concentrations in pepper fruit were approximately 0.22 mg kg fw(-1). Temperature was the most sensitive component for predicting the peak and final concentration in pepper fruit, through its influence on soil and plant degradation rates. CONCLUSION: Repeated simulations of pulse inputs with the cascade model adequately describe soil pesticide applications to an actual cropped system and reasonably mimic it. The model has the potential to be used for the optimization of practical features, such as application rates and waiting times between applications and before harvest, through the integrated accounting of soil, plant and environmental influences.

Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations.

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. "Measurements" are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.

Degradation of PCB congeners by bacterial strains.

Biological in situ methods are options for the remediation of contaminated sites. An approach to quantify biodegradation by soil bacteria was developed, combining experiment with mathematical modelling. We performed in vitro assays to investigate the potential and kinetics of the wild-type degrader, Burkholderia sp. strain LB400 (expressing bph) and the genetically modified Pseudomonas fluorescens strains F113pcb and F113L::1180 (expressing bph under different promoters) to metabolise individual congeners of polychlorinated biphenyls (PCBs). Kinetics of metabolism was analysed using the Monod model. Results revealed similar patterns of degradable PCB congeners for LB400 and F113L::1180. The degree of PCB degradation was comparable for LB400 and F113L::1180 but was much lower for F113rifpcb. In additional mesocosm experiments with PCB-contaminated soil, the F113 derivatives demonstrated a good survival ability in willow (Salix sp.) rhizosphere. Strain F113L::1180 in combination with willow plants is expected to degrade a large spectrum of PCB congeners in soil. The data from the experiments were used to calculate the time scale of the degradation process in a PCB-contaminated soil. The uncertainty of the model predictions due to the uncertainties of experimental removal velocities and bacterial cell density in soil was quantified.