Single First-order Research Articles

Subjectivity of visual assessments in FOCUS kinetics and acceptability of first-order fits for regulatory modelling

The degradation half-life (DegT50) of a substance in soil plays an important role in the approval process of a plant protection product and is a sensitive input parameter for regulatory models. It is usually derived through least squares optimizations of mathematical models to measured degradation data according to EU FOCUS degradation kinetics guidance. A strong consensus on degradation parameters provides a solid foundation for parts of the environmental risk assessment. The DegT50 of a substance for regulatory modeling is preferably derived from a single first-order (SFO) model as this is currently the only kinetic model implemented in EU regulatory models of the environmental fate of pesticides. However, kinetic optimisation tools do not always provide a regulatory acceptable SFO fit even though a visual inspection of the data suggests it may be possible. It was therefore hypothesized that more acceptable SFO fits might be achieved by adapting the objective function that is minimized during the optimization.Eight objective functions with varying weightings were tested on 29 laboratory soil degradation datasets. A web-based app was developed to allow experts in environmental safety of plant protection products to visually assess the goodness of fits resulting from different objective functions. The visual assessments and a quantitative metric, newly introduced in the proposed update of the FOCUS guidance, show that the acceptability of SFO fits can be increased, but no single objective function exclusively improves all fits. The assessment reveals that expert judgment is very subjective. Participants tended to change their mind when judging the acceptance of a fit, assumingly caused by a learning curve or a period of calibration.It is concluded that different objective functions could be considered in the kinetic assessment as it can improve the acceptability of SFO fits and hence endpoints for regulatory modeling. This study reveals that various qualitative factors influence the visual judgment of experts when performing a kinetic modeling assessment. The proposed quantitative metric seems to be in alignment with the visual assessment of fits to derive modeling endpoints and a promising step toward less subjective kinetic modeling assessments.

Efficient dissipation of acetamiprid, metalaxyl, S-metolachlor and terbuthylazine in a full-scale free water surface constructed wetland in Bologna province, Italy: A kinetic modeling study

The study investigated the dissipation ability of a vegetated free water surface (FWS) constructed wetland (CW) in treating pesticides-contaminated agricultural runoff/drainage water in a rural area belonging to Bologna province (Italy). The experiment simulated a 0.1% pesticide agricultural water runoff/drainage event from a 12.5-ha farm by dissolving acetamiprid, metalaxyl, S-metolachlor, and terbuthylazine in 1000 L of water and pumping it into the CW. Water and sediment samples from the CW were collected for 4 months at different time intervals to determine pesticide concentrations by multiresidue extraction and chromatography-mass spectrometry analyses. In parallel, no active compounds were detected in the CW sediments during the experimental period. Pesticides dissipation in the wetland water compartment was modeled according to best data practices by fitting the data to Single First Order (SFO), First Order Multi-Compartment (FOMC) and Double First Order in Parallel (DFOP) kinetic models. SFO (except for metalaxyl), FOMC and DFOP kinetic models adequately predicted the dissipation for the four investigated molecules, with the DFOP kinetic model that better fitted the observed data. The modeled distribution of each pesticide between biomass and water in the CW highly correlated with environmental indexes as Kow and bioconcentration factor. Computed DT50 by DFOP model were 2.169, 8.019, 1.551 and 2.047 days for acetamiprid, metalaxyl, S-metolachlor, and terbuthylazine, respectively. Although the exact degradation mechanisms of each pesticide require further study, the FWS CW was found to be effective in treating pesticides-contaminated agricultural runoff/drainage water within an acceptable time. Therefore, this technology proved to be a valuable tool for mitigating pesticides runoff occurring after intense rain events.

Flash Pyrolysis Kinetics of Extracted Lignocellulosic Biomass Components

Biomass is a complex material mainly composed of the three lignocellulosic components: cellulose, hemicellulose and lignin. The different molecular structures of the individual components result in various decomposition mechanisms during the pyrolysis process. To understand the underlying reactions in more detail, the individual components can be extracted from the biomass and can then be investigated separately. In this work, the pyrolysis kinetics of extracted and purified cellulose, hemicellulose and lignin are examined experimentally in a small-scale fluidized bed reactor (FBR) under N2 pyrolysis conditions. The FBR provides high particle heating rates (approx. 104 K/s) at medium temperatures (573–973 K) with unlimited reaction time and thus complements typically used thermogravimetric analyzers (TGA, low heating rate) and drop tube reactors (high temperature and heating rate). Based on the time-dependent gas concentrations of 22 species, the release rates of these species as well as the overall rate of volatiles released are calculated. A single first-order (SFOR) reaction model and a 2-step model combined with Arrhenius kinetics are calibrated for all three components individually. Considering FBR and additional TGA experiments, different reaction regimes with different activation energies could be identified. By using dimensionless pyrolysis numbers, limits due to reaction kinetics and heat transfer could be determined. The evaluation of the overall model performance revealed model predictions within the ±2σ standard deviation band for cellulose and hemicellulose. For lignin, only the 2-step model gave satisfying results. Modifications to the SFOR model (yield restriction to primary pyrolysis peak or the assumption of distributed reactivity) were found to be promising approaches for the description of flash pyrolysis behavior, which will be further investigated in the future.

Influence of solar heating on herbicide dissipation in polluted soils

ABSTRACT Solar heating techniques were tested to enhance the dissipation of eight herbicides belonging to four different chemical families (phenylurea, triazine, dinitroaniline and diphenylether derivatives). Guano, vermicompost, green manure, and goat manure were used as biofumigants for biosolarization. In all experiments, the soil was covered with high-density polyethylene (HDPE) film along 60 d after treatment and the results were compared with control plots. A significant increase in the soil temperature from 2 to 6 °C was detected in solarized soils as compared to control plots being probably the direct hydrothermal effect the most important factor on herbicide degradation. The behaviour of herbicides in mulched soils presents a faster phase of disappearance (15 d) followed by a slower phase (15–60 d). The mean half-lives ranged from 98 d in control plots to 17 d in the solarized soil amended with goat excrements manure being isoproturon and trifluralin the more and the less persistent herbicides, respectively. In all cases, significant differences (p < 0.05) in the persistence were observed between control soil and solarized soils for all herbicides. Therefore, the use of solar heating techniques, especially biosolarization can be considered as an environmentally friendly tool to enhance herbicide disappearance from the soil. Abbreviations: Aclonifen (AF); Biosolarized soil (BS); Chlorotoluron (CL); Control soil (CS); Goat manure (GTM); Green manure (GRM); Guano (GAN); Half-life time (t½); High-density polyethylene (HDPE); Isoproturon (IR); Metribuzin (MZ); Organic amendment (OA); Organic matter (OM); Organisation for Economic Co-operation and Development (OECD); Oxyfluorfen (OF); Pendimethalin (PL); Relative humidity (RH); Single first-order (SFO); Solarized soil (SS); Terbuthylazine (TZ); Trifluralin (TL); Vermicompost (VRC).

Determination of Zero Dimensional, Apparent Devolatilization Kinetics for Biomass Particles at Suspension Firing Conditions

As part of the strive for a carbon neutral energy production, biomass combustion has been widely implemented in retrofitted coal burners. Modeling aids substantially in prediction of biomass flame behavior and thus in boiler chamber conditions. In this work, a simple model for devolatilization of biomass at conditions relevant for suspension firing is presented. It employs Arrhenius parameters in a single first order (SFOR) devolatilization reaction, where the effects of kinetics and heat transfer limitations are lumped together. In this way, a biomass particle can be modeled as a zero dimensional, isothermal particle, facilitating computational fluid dynamic calculations of boiler chambers. The zero dimensional model includes the effects of particle aspect ratio, particle density, maximum gas temperature, and particle radius. It is developed using the multivariate data analysis method, partial least squares regression, and is validated against a more rigorous semi-2D devolatilization model. The model has the capability to predict devolatilization time for conditions in the parameter ranges; radius (39–1569 μμm), density (700–1300 kg/m3), gas temperature (1300–1900 K), aspect ratio (1.01–8). Results show that the particle radius and gas phase temperature have a large influence on the devolatilization rate, and the aspect ratio has a comparatively smaller effect, which, however, cannot be neglected. The impact of aspect ratio levels off as it increases. The model is suitable for use as stand alone or as a submodel for biomass particle devolatilization in CFD models.

Evaluating plant residue decline data with KinGUII and TREC: results from case studies involving also non-SFO kinetic models

BackgroundFoliage residue decline data are used to refine the risk assessment for herbivorous birds and mammals foraging in fields treated with plant protection products. For evaluation, current EFSA guidance has a clear focus on single-first order (SFO) kinetic models. However, other kinetic models are well established in other areas of environmental risk evaluations (e.g., soil residue assessment), and easy-to-use calculation tools have become available now. We provide case studies with 6 fungicides how such evaluations can be conducted with two of these tools (KinGUII and TREC) that have been developed by Bayer.ResultsSFO kinetics provided the best fits only for 13 of 36 residue decline studies conducted in a standardized design under field conditions. Biphasic models (double first order in parallel, hockey stick) were often superior and sometimes more conservative for risk assessment. The additional effort is manageable when using software such as KinGUII and TREC, and appears justified by the more reliable outcome of the evaluations.ConclusionsFurther research would be useful to better assess the extent to which non-SFO better fits foliage residue decline, but our study suggests that it may be a significant proportion. Therefore, we encourage the use of biphasic models in the regulatory risk assessment for herbivorous birds and mammals, in the ongoing revision of the European Food Safety Authority (EFSA) guidance document from 2009.

Effects of temperature on the dissipation of total- and water-extractable pesticides in Japanese soils.

We investigated the dissipation of 27 pesticides in five Japanese soils at three temperatures and the variability of activation energies (Ea). The dissipation of total pesticides extracted sequentially using water and acetone was fitted to a single first-order (SFO) model. The Ea values calculated from the dissipation rate constants of the SFO model showed a normal distribution with a median of 61.1 kJ mol−1. The dissipation of water-extractable pesticides (i.e., phytoavailable pesticides) was fitted to a double first-order in parallel model with two dissipation rate constants: k1 and k2. The Ea values calculated from k1 and k2 showed normal or lognormal distribution, and the medians of the normal distribution calculated from k1 and k2 were 62.8 and 45.2 kJ mol−1, respectively. Furthermore, the method for estimating the biphasic dissipation of phytoavailable pesticides at different temperatures by using the median Ea values of the laboratory experiment was demonstrated in a field experiment.

Field measurement and modelling of chlorotoluron and flufenacet persistence in unamended and amended soils

The dissipation and persistence of two cereals herbicides, chlorotoluron and flufenacet, were studied in a field experiment including three replicated plots of unamended soil (S), soil amended with spent mushroom substrate (S + SMS), and soil amended with green compost (S + GC), during the winter wheat cultivation campaign. The SMS and GC organic residues were applied to the soil at rates of 140 or 85 t residue ha−1, and herbicides were sprayed as Erturon® and Herold® formulations for chlorotoluron and flufenacet, respectively. Concentrations of both herbicides and of their metabolites were regularly measured in the three soil treatments (0–10 cm) from 0 to 339 days. The dissipation kinetics fitted well the single first order (SFO) model, except that of chlorotoluron that fitted the first order multi-compartment (FOMC) model better in the unamended soil. The dissipation rates of herbicides were lower in amended than in unamended soils. The results also showed that the DT50 of chlorotoluron (66.2–88.0 days) and flufenacet (117–145 days) under field conditions were higher than those previously obtained at laboratory scale highlighting the importance of the changing environmental conditions on the dissipation process. Similarly, the formation of chlorotoluron and flufenacet metabolites under field conditions was different from that previously observed in the laboratory. The performance of the MACRO pesticide fate model, parameterized with laboratory data, was then tested against field data. There was a very good agreement between measured and simulated chlorotoluron residue levels in the three soil treatments, while the ability of the model to reproduce the dissipation of flufenacet was good in the unamended soil and very good in S + SMS and S + GC soils. MACRO might be used to estimate the remaining amounts of herbicides in amended soils from degradation data previously obtained at laboratory scale. This would help to manage herbicide doses in different environmental conditions to preserve the sustainability of agricultural systems.

Degradation Kinetics and Transformation Products of Levonorgestrel and Quinestrol in Soils.

Levonorgestrel (LNG) and quinestrol (QUN) are typical endocrine disruptors that enter the soil via sewage irrigation and sludge return. However, the fates of both compounds in soil are not well-understood. Laboratory microcosm studies were conducted to fill the gap of understanding of LNG and QUN behavior in soils. High values of goodness-of-fit indices (GFIs) were obtained using the double-first-order in parallel (DFOP) model and the single-first-order (SFO) model to fit the degradation kinetics of LNG and QUN in soils, respectively. The end-points (DT50 and DT90) of LNG and QUN were positively correlated with soil total organic carbon (TOC). Soil water content and temperature were observed to be critical factors in degradation of LNG and QUN. The degradation rates of LNG and QUN were very slow under sterile and flooded conditions, indicating that the aerobic microbial degradation was dominant in the degradation of LNG and QUN. Moreover, major transformation products were identified, and biodegradation pathways of LNG and QUN were proposed. The present study is expected to provide basic information for ecological risk assessment of LNG and QUN in the soil compartment.

Dynamics of glyphosate and AMPA in the soil surface layer of glyphosate-resistant crop cultivations in the loess Pampas of Argentina

This study investigates the dynamics of glyphosate and AMPA in the soil surface layer of two fields growing glyphosate-resistant crops in the loess Pampas of Córdoba Province, Argentina. Glyphosate decay and AMPA formation/decay were studied after a single application, using decay kinetic models. Furthermore, glyphosate and AMPA concentrations were investigated in runoff to evaluate their off-site risk. During a 2.5-month study, cultivations of glyphosate-resistant soybean and maize received an application of 1.0 and 0.81 kg a.e. ha−1, respectively, of Roundup UltraMax©. Topsoil samples (0–1, 1–2 cm) were collected weekly (including before application) and analysed for glyphosate, AMPA and soil moisture (SM) contents. Runoff was collected from runoff plots (3 m2) and weirs after 2 erosive rainfall events, and analysed for glyphosate and AMPA contents (water, eroded-sediment). Under both cultivations, background residues in soil before application were 0.27–0.42 mg kg−1 for glyphosate and 1.3–1.7 mg kg−1 for AMPA. In the soybean area, the single-first-order (SFO) model performed best for glyphosate decay. In the maize area, the bi-phasic Hockey-Stick (HS) model performed best for glyphosate decay, due to an abrupt change in SM regimes after high rainfall. Glyphosate half-life and DT90 were 6.0 and 19.8 days, respectively, in the soybean area, and 11.1 and 15.4 days, respectively, in the maize area. In the soybean area, 24% of the glyphosate was degraded to AMPA. In the maize area, it was only 5%. AMPA half-life and DT90 were 54.7 and 182 days, respectively, in the soybean area, and 71.0 and 236 days, respectively, in the maize area. Glyphosate and AMPA contents were 1.1–17.5 times higher in water-eroded sediment than in soil. We conclude that AMPA persists and may accumulate in soil, whereas both glyphosate and AMPA are prone to off-site transport with water erosion, representing a contamination risk for surface waters and adjacent fields.

Persistence of glyphosate and aminomethylphosphonic acid in loess soil under different combinations of temperature, soil moisture and light/darkness

The dissipation kinetics of glyphosate and its metabolite aminomethylphosphonic acid (AMPA) were studied in loess soil, under biotic and abiotic conditions, as affected by temperature, soil moisture (SM) and light/darkness. Nonsterile and sterile soil samples were spiked with 16mgkg−1 of glyphosate, subjected to three SM contents (20% WHC, 60% WHC, saturation), and incubated for 30days at 5°C and 30°C, under dark and light regimes. Glyphosate and AMPA dissipation kinetics were fit to single-first-order (SFO) or first-order-multicompartment (FOMC) models, per treatment combination. AMPA kinetic model included both the formation and decline phases. Glyphosate dissipation kinetics followed SFO at 5°C, but FOMC at 30°C. AMPA followed SFO dissipation kinetics for all treatments. Glyphosate and AMPA dissipation occurred mostly by microbial activity. Abiotic processes played a negligible role for both compounds. Under biotic conditions, glyphosate dissipation and AMPA formation/dissipation were primarily affected by temperature, but also by SM. Light regimes didn't play a significant role. Glyphosate DT50 varied between 1.5 and 53.5days, while its DT90 varied between 8.0 and 280days, depending on the treatment. AMPA persisted longer in soil than glyphosate, with its DT50 at 30°C ranging between 26.4 and 44.5days, and its DT90 between 87.8 and 148days. The shortest DT50/DT90 values for both compounds occurred at 30°C and under optimal/saturated moisture conditions, while the largest occurred at 5°C and reaching drought stress conditions. Based on these results, we conclude that glyphosate and AMPA dissipate rapidly under warm and rainy climate conditions. However, repeated glyphosate applications in fallows or winter crops in countries where cold and dry winters normally occur could lead to on-site soil pollution, with consequent potential risks to the environment and human health.To our knowledge, this study is the first evaluating the combined effect of temperature, soil moisture and light/dark conditions on AMPA formation/dissipation kinetics and behaviour.

Dissipation and transport of quizalofop-p-ethyl herbicide in sunflower cultivation under field conditions

In the present study, the field dissipation and transport of quizalofop-p-ethyl by water and sediment runoff were investigated in sunflower experimental cultivation under Mediterranean conditions. The cultivation was carried out in silty clay soil plots with two different slopes of 1 and 5%. The soil dissipation rate of quizalofop-p-ethyl was fast and can be described by both single first-order (SFO) and Gustafson and Holden (first-order multi compartment (FOMC)) kinetics. The half-life of quizalofop-p-ethyl ranged from 0.55 to 0.68 days and from 0.45 to 0.71 days when SFO and FOMC kinetics were applied, respectively. No herbicide residues were detected below the 10-cm soil layer. A single detection of quizalofop-p-ethyl was observed in runoff water (3 days after application (DAA)) at relatively low concentrations (from 1.70 to 2.04 μg L(-1)). In sediment, it was detected in the samplings of 3 and 25 DAA at concentrations that never exceeded 0.126 μg g(-1). The estimated total losses of quizalofop-p-ethyl as percentage of the initial applied active ingredient were low both in water and sediment (less than of 0.021 and 0.005%, respectively). Quizalofop-p-ethyl residues were detectable for 18 DAA in the stems and leaves of the plants and 6 DAA in the root system. No herbicide residues were detected in inflorescences and seeds of sunflower plants. Experimental data showed minimal risk for the contamination of soil and adjacent water bodies.

Deriving sulfamethoxazole dissipation endpoints in pasture soils using first order and biphasic kinetic models

Single first-order (SFO) kinetic model is often used to derive the dissipation endpoints of an organic chemical in soil. This model is used due to its simplicity and requirement by regulatory agencies. However, using the SFO model for all types of decay pattern could lead to under- or overestimation of dissipation endpoints when the deviation from first-order is significant. In this study the performance of three biphasic kinetic models — bi-exponential decay (BEXP), first-order double exponential decay (FODED), and first-order two-compartment (FOTC) models was evaluated using dissipation datasets of sulfamethoxazole (SMO) antibiotic in three different soils under varying concentration, depth, temperature, and sterile conditions. Corresponding 50% (DT50) and 90% (DT90) dissipation times for the antibiotics were numerically obtained and compared against those obtained using the SFO model. The fit of each model to the measured values was evaluated based on an array of statistical measures such as coefficient of determination (R2adj), root mean square error (RMSE), chi-square (χ2) test at 1% significance, Bayesian Information Criteria (BIC) and % model error. Box–whisker residual plots were also used to compare the performance of each model to the measured datasets. The antibiotic dissipation was successfully predicted by all four models. However, the nonlinear biphasic models improved the goodness-of-fit parameters for all datasets. Deviations from datasets were also often less evident with the biphasic models. The fits of FOTC and FODED models for SMO dissipation datasets were identical in most cases, and were found to be superior to the BEXP model. Among the biphasic models, the FOTC model was found to be the most suitable for obtaining the endpoints and could provide a mechanistic explanation for SMO dissipation in the soils.

Transformation kinetics of 6-methoxybenzoxazolin-2-one in soil

Wheat (Triticum aestivum L.) and other cereals produce allelochemicals as natural defense compounds against weeds, fungi, insects and soil-borne diseases. The main benzoxazinoid allelochemical of wheat is 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA), bound as β-glucoside and released upon plant injury. When leached from wheat to soil, DIMBOA is microbially transformed to 6-methoxy-benzoxazolin-2-one (MBOA). Exploiting benzoxazinoids and their degradation products as substitutes for synthetic pesticides depends on knowledge of transformation pathways and kinetics. In an MBOA degradation experiment at a concentration of 2400 nmol g–1 soil, the previously identified transformation products 2-amino-7-methoxy-phenoxazin-3-one (AMPO) and 2-acetylamino-7-methoxy-phenoxazin-3-one (AAMPO) were quantified. Three different kinetic models were applied to MBOA transformation kinetics; single first-order (SFO), first-order multi-compartment, and double first-order in parallel. SFO proved to be adequate and was subsequently applied to the transformations of MBOA, AMPO and AAMPO. Degradation endpoints, expressed as degradation time (DT), were calculated for MBOA, AMPO and AAMPO to test whether the maximum values for synthetic pesticides set by the European Commission and the Danish Environmental Protection Agency were exceeded. DT50 values for MBOA and AMPO were 5.4 d and 321.5 d, respectively, and DT90 values were 18.1 d and 1068 d, respectively. The DT50 value for AMPO exceeded the maximum value. The persistence, concentrations and toxicity of metabolites such as AMPO should be considered when breeding cereal crops with increased levels of benzoxazinoids.

A Minimum-Maximum Problem for Differential Expressions

In the study of approximate methods for solving ordinary differential equations, an interesting question arises. To state it roughly for a single first order expression, let y0(t) be the solution of the equation(1.1)which satisfies the initial condition y(a) = na. Let nb be an approximation to the value of y0 at a later time, t = b.