Biomedical subjects

Nicholas Jarvis

Publications and source records attributed to Nicholas Jarvis.

8 recordsLinked to original sources

PubMed2006

Controls on atrazine leaching through a soil-unsaturated fractured limestone sequence at Brévilles, France.

The objective of this study was to identify the main controls on atrazine leaching through luvisols and calcisols overlying fissured limestone using the dual-permeability model MACRO. The model parameterisation was based on a combination of direct measurements (e.g. hydraulic properties, adsorption and degradation), literature data and calibration against bromide leaching experiments in field plots. A Monte Carlo sensitivity analysis was carried out for a typical application pattern, considering two different depths of unsaturated limestone (15 and 30 m). MACRO calibrations to the field experiments demonstrated the occurrence of strong macropore flow in the luvisol, while transport in the calcisol could be described by the advection-dispersion equation. MACRO simulations of tritium and atrazine leaching qualitatively matched tritium concentration profiles measured in the limestone and atrazine concentrations measured in piezometers and in aquifer discharge via a spring. The sensitivity analysis suggested that the thickness of the limestone, as well as the transport properties and processes occurring in the unsaturated rock (e.g. matrix vs. fissure flow) will have little significant long-term effect on atrazine leaching, mainly because degradation is very slow in the limestone. No mineralization of atrazine was detected in one-year incubations and a mean half-life of 10 years was assumed in the simulations. Instead, processes occurring in the soil exerted the main control on predicted atrazine leaching, especially variations in the degradation rate and the strength of sorption and macropore flow. However, fissure flow in unsaturated rock is expected to exert a much more significant control on groundwater contamination for compounds that degrade more readily in the deep vadose zone.

Atrazine↗

PubMed2006

User subjectivity in Monte Carlo modeling of pesticide exposure.

Monte Carlo techniques are increasingly used in pesticide exposure modeling to evaluate the uncertainty in predictions arising from uncertainty in input parameters and to estimate the confidence that should be assigned to the modeling results. The approach typically involves running a deterministic model repeatedly for a large number of input values sampled from statistical distributions. In the present study, six modelers made choices regarding the type and parameterization of distributions assigned to degradation and sorption data for an example pesticide, the correlation between the parameters, the tool and method used for sampling, and the number of samples generated. A leaching assessment was carried out using a single model and scenario and all data for sorption and degradation generated by the six modelers. The distributions of sampled parameters differed between the modelers, and the agreement with the measured data was variable. Large differences were found between the upper percentiles of simulated concentrations in leachate. The probability of exceeding 0.1 microg/L ranged from 0 to 35.7%. The present study demonstrated that subjective choices made in Monte Carlo modeling introduce variability into probabilistic modeling and that the results need to be interpreted with care.

Monte Carlo Method↗

PubMed2005

Cadmium solubility and sorption in a long-term sludge-amended arable soil.

Cadmium solubility and sorption in an arable clay loam soil that had received sewage sludge for 41 years were compared to an unsludged control in batch studies. Soil pH dominated Cd sorption, explaining >92% of the variation in Kd values in both treatments. At any pH, Cd sorption was apparently slightly but significantly (p < 0.05) smaller in the sludge-amended soil compared to the control, even though the organic carbon content was 70% larger and the ammonium oxalate-extractable iron content was roughly doubled. Correction for dissolved organic carbon (DOC) complexation with the speciation model WHAM reduced the difference in sorption between treatments, but the sludged soil still had significantly smaller Kd values (p < 0.01). Batch equilibrations without addition of Cd showed that there was no significant difference in the solubility of "native" cadmium (defined as EDTA-extractable Cd) in sludged and control soils. The reason for the lack of increase in Cd sorption in the sludge-amended soil has not been established, but it may be due to competition for sorption sites on humic compounds with sludge-derived Fe and trace metals such as zinc. The fact that the pyrophosphate-extractable (i.e., organically associated) iron content was seven times larger in the sludged soil provides some supporting evidence for this hypothesis.

Adsorption↗

PubMed2005

Sorption, degradation and leaching of the fungicide iprodione in a golf green under Scandinavian conditions: measurements, modelling and risk assessment.

In cold climates, fungicides are used on golf greens to prevent snow mould causing serious damage to the turf. However, fungicide residues have been detected in runoff from golf courses, which may lead to restrictions on use. There is therefore an urgent need to improve understanding of the processes affecting leaching of fungicides from turfgrass systems to allow identification of green construction and management practices that minimize environmental impacts. In this study we monitored the leaching of the fungicide iprodione in a putting green. Sorption and degradation of iprodione was measured in batch and incubation experiments, and the simulation model MACRO was used as a risk assessment tool. Degradation of iprodione was bi-phasic, with a rapid initial phase (half-life 17 h) caused by enhanced biodegradation. Degradation rates slowed considerably after 5 days, with half-lives of up to 38 days. Sorption of iprodione was linear, with a K(oc) value of ca 400 cm(3) g(-1). MACRO reasonably accurately matched measured drainflows and concentrations of iprodione in soil and drainflow. However, peak concentrations in drainage were underestimated, which was attributed to preferential finger flow due to water repellency. The results also showed the importance of the organic matter content in the green root zone in reducing leaching. It was concluded that, with 'reasonable worst-case' use, losses of iprodione from greens can occur at concentrations exceeding water quality limits for aquatic ecosystems. Snow mould problems should be tackled by adopting green root zone mixes that minimize leaching and 'best management practices' that would avoid the need for intensive prophylactic use of fungicides.

Adsorption↗

PubMed2005

Linking a one-dimensional pesticide fate model to a three-dimensional groundwater model to simulate pollution risks of shallow and deep groundwater underlying fractured till.

The one-dimensional pesticide fate model MACRO was loose-linked to the three-dimensional discrete fracture/matrix diffusion model FRAC3DVS to describe transport of the pesticide mecoprop in a fractured moraine till and local sand aquifer (5-5.5 m depth) overlying a regional limestone aquifer (16 m depth) at Havdrup, Denmark. Alternative approaches to describe the upper boundary in the groundwater model were examined. Field-scale simulations were run to compare a uniform upper boundary condition with a spatially variable upper boundary derived from Monte-Carlo simulations with MACRO. Plot-scale simulations were run to investigate the influence of the temporal resolution of the upper boundary conditions for fluxes in the groundwater model and the effects of different assumptions concerning the macropore/fracture connectivity between the two models. The influence of within-field variability of leaching on simulated mecoprop concentrations in the local aquifer was relatively small. A fully transient simulation with FRAC3DVS gave 20 times larger leaching to the regional aquifer compared to the case with steady-state water flow, assuming full connectivity with respect to macropores/fractures across the boundary between the two models. For fully transient simulations 'disconnecting' the macropores/fractures at the interface between the two models reduced leaching by a factor 24. A fully connected, transient simulation with FRAC3DVS, with spatially uniform upper boundary fluxes derived from a MACRO simulation with 'effective' parameters is therefore recommended for assessing leaching risks to the regional aquifer, at this, and similar sites.

Agriculture↗

PubMedDate not supplied

Modeling macropore flow effects on pesticide leaching: inverse parameter estimation using microlysimeters.

Macropore flow is a key factor determining pesticide fate, but models accounting for this process need parameters that cannot be easily measured. This study was conducted to investigate the use of inverse techniques to estimate parameters controlling macropore flow and pesticide fate in the dual-permeability model MACRO. Undisturbed columns were sampled at three landscape positions (hilltop, slope, hollow) with contrasting texture and organic carbon content. Transient leaching experiments were performed for an anionic tracer and the herbicide MCPA (4-chloro-2methylphenoxy acetic acid) during a 4-mo period, first under natural rainfall, and then under controlled irrigation in the laboratory. The tracer breakthrough for the liner-textured soil from the hilltop showed strong evidence of macropore flow, resulting in a rapid leaching of MCPA, while leaching was minimal from the organic-rich hollow soil, since macropore flow was weaker and adsorption stronger. The MACRO model was linked to the inverse modeling program SUFI (Sequential Uncertainty Fitting) to enable calibration of nine key model parameters. Based on calculated model efficiencies, MACRO-SUFI gave generally good predictions of water movement and tracer and pesticide transport, although some errors were attributed to difficulties in simulating the effects of soil moisture on degradation and the timing of water outflows. Even after calibration, significant uncertainties remained for some key parameters controlling macropore flow. Nevertheless, the parameter estimates were significantly different between landscape positions and could also be related to basic soil properties. The posterior uncertainty ranges could probably be reduced with a more exhaustive sampling of the parameter space and improved experimental designs.

2-Methyl-4-chlorophenoxyacetic Acid↗

PubMedDate not supplied

Modeling organic carbon dynamics and cadmium fate in long-term sludge-amended soil.

A model is described that may help to resolve uncertainty and controversy over the long-term consequences of sludge applications to arable land, especially with regard to the effects of sludge adsorption characteristics on trace metal solubility and bioavailability (e.g., the sludge "time bomb" or sludge "protection" hypotheses). Mass balances of organic and inorganic material derived from sludge and crop residues are simulated. Each pool has a potentially different adsorption affinity for trace metals, and this leads to changes in the adsorption capacity of sludge-amended soil that influence leaching and crop uptake. Model simulations were compared with measured changes in organic carbon and ethylenediaminetetraacetic acid (EDTA)-extractable cadmium contents in a clay loam soil following 41 years of sludge applications. The model adequately reproduced the data, although discrepancies in the vertical distribution of Cd were attributed to the effects of macropore transport and root-uptake driven recirculation. A Monte Carlo sensitivity analysis demonstrated that the most important parameters affecting leaching and crop uptake were the Cd loading and parameters controlling adsorption, especially the partition coefficient for sludge-derived inorganic material and the exponent regulating the effect of pH on sorption. Scenario simulations show that no general conclusions can be drawn with respect to the validity of the sludge "time bomb" and sludge "protection" hypotheses. Either may occur, or neither, depending on three key system parameters: the ratio of sludge adsorption capacity to the initial adsorption capacity of the soil, the proportion of the sludge adsorption capacity contributed by the inorganic fraction, and the sludge Cd loading.

Cadmium↗

PubMedDate not supplied

Simulating solute transport in a structured field soil: uncertainty in parameter identification and predictions.

Dual-permeability models have been developed to account for the significant effects of macropore flow on contaminant transport, but their use is hampered by difficulties in estimating the additional parameters required. Therefore, our objective was to evaluate data requirements for parameter identification for predictive modeling with the dual-permeability model MACRO. Two different approaches were compared: sequential uncertainty fitting (SUFI) and generalized likelihood uncertainty estimation (GLUE). We investigated six parameters controlling macropore flow and pesticide sorption and degradation, applying MACRO to a comprehensive field data set of bromide andbentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2dioxide] transport in a structured soil. The GLUE analyses of parameter conditioning for different combinations of observations showed that both resident and flux concentrations were needed to obtain highly conditioned and unbiased parameters and that observations of tracer transport generally improved the conditioning of macropore flow parameters. The GLUE "behavioral" parameter sets covered wider parameter ranges than the SUFI posterior uncertainty domains. Nevertheless, estimation uncertainty ranges defined by the 5th and 95th percentiles were similar and many simulations randomly sampled from the SUFI posterior uncertainty domains had negative model efficiencies (minimum of -3.2). This is because parameter correlations are neglected in SUFI and the posterior uncertainty domains were not always determined correctly. For the same reasons, uncertainty ranges for predictions of bentazone losses through drainflow for good agricultural practice in southern Sweden were 27% larger for SUFI compared with GLUE. Although SUFI proved to be an efficient parameter estimation tool, GLUE seems better suited as a method of uncertainty estimation for predictions.

Benzothiadiazines↗