Pesticide Dissipation Research Articles

Quantitative analysis of acetamiprid and imidacloprid residues in tomato fruits under greenhouse conditions

A selective liquid chromatographic analytical method was studied for determination of two neonicotinoids, acetamiprid and imidacloprid, in tomato fruits under greenhouse conditions in Egypt. The fruits were extracted and cleaned up by QuEChERS method followed by HPLC determination. The method showed a good linearity with a determination coefficient (R2) of higher than 0.99 for the 0.0125–0.15 µg/mL concentration range. The method was validated using a blank tomato spiked at 5, 25 and 50 mg/kg and the recovery percentages were 83.71, 94.52 and 97.49% for acetamiprid and 88.59, 89.63 and 90.18% for imidacloprid, respectively. The rates of dissipation of both pesticides were studied and the preharvest intervals (PHIs) were calculated. Imidacloprid dissipated faster than acetamiprid and half-life periods were 1.30 and 2.07 days, respectively. Acetamiprid and imidacloprid residues were below the already established European maximum residue limits (EU MRLs) (0.5 mg/kg) 3 and 5 days after application, respectively.

Degradation of Dicloran in Irradiated Water-Sediment Systems

Shallow water systems are uniquely susceptible to environmental processes such as photolysis and hydrolysis that can influence the dissipation of pesticides into sediments. The fungicide dicloran has previously been shown to undergo photolysis and is reported to dissipate in soils and sediments. The photodegradation and dissipation of dicloran in freshwater and seawater was monitored in a laboratory-simulated shallow water system. While no difference was observed between freshwater and seawater systems in the presence of simulated sunlight, the dissipation of dicloran in dark trial systems differed between salinities; 30% of the applied mass dissipated into the sediment in freshwater vs 22% in seawater, and the photodegradation rate and half-life were also impacted by the presence of sediment. The potential for dicloran to dissipate and photodegrade affects the overall behavior of dicloran between waters. Differences in chemical behavior with sediment presence and potential for photodegradation have the capacity to impact organisms within the ecosystem and suggest that these factors may need to be implemented into chemical exposure assessments dependent upon location.

Dissipation Behavior of Three Fungicides during the Industrial Processing of PaeoniaeRadix Alba and Associated Processing Factors.

Before being administered as medicinal products, Chinese herbal medicines (CHMs) must be processed and decocted for human consumption. While the presence of pesticide residues in CHMs is a major concern, pesticide dissipation behavior during CHM processing has rarely been reported. In this study, the dissipation of three pesticide residues in the CHM Paeoniae Radix Alba (PRA) was investigated during each step of industrial processing. The boiling process was found to significantly reduce pesticide residues (61–89%), and the peeling process also contributed to pesticide degradation (29–68%). The high temperature (60 °C) during the drying process led to further pesticide degradation. The processing factors of all three pesticides after each processing step were less than one, and the processing factors for the overall process were lower than 0.027, indicating that industrial processing clearly reduced the amount of pesticide residues (97.3–99.4%). The findings provide guidance for the safe use of fungicides in CHMs and can help establish maximum residue limits for PRA to reduce human exposure to pesticides.

Degradation of microplastic seed film-coating fragments in soil

Encapsulating fungicides and/or insecticides in film-coatings applied to agronomic seeds has become a widely accepted method for enhancing seed germination and overall seedling health by protecting against many diseases and early-season insect pests. Despite advancements in seed film-coating technologies, abrasion of the seed coating can occur during handling and mechanical planting operations, resulting in variable amounts of detached fragments entering the soil. The present study investigated the degradation in soil of these plastic-like, small-sized fragments, referred to here as microplastic coating fragments. Degradation of microplastic coating fragments in soil was found to be highly variable. The lowest degradation rate (≤48 days) was observed in fragments detached from seeds coated with a commercial polymer mixture, while fragments from a biodegradable plastic formulation degraded completely within 32 days. When spores of the plant growth-promoting bacterium, Bacillus subtilis, were incorporated into the bioplastic, degradation was even more rapid (≤24 days). The fragment degradation rate was unaffected by incorporating two commonly used neonicotinoid insecticides, imidacloprid or thiacloprid, into either coating formulations, but insecticide dissipation rates in soil were more rapid when added associated with seed coating fragments than when spiked in directly. Half-lives of these two insecticides were reduced by up to 27% in fragments from bioplastic-coated seeds. These results are consistent with variable and not easily predicted soil degradation rates for seed coating fragments, with enhanced dissipation of coating-entrapped pesticides and with a higher degradation rate for biodegradable seed coating incorporating selected microbial strains.

Performance evaluation of lysimeter experiments for simulating pesticide dissipation in paddy fields. Part 2: Nursery-box application and foliar application.

Comparative experiments investigating the dissipation of four nursery-box-applied pesticides and three foliar-applied pesticides were conducted using lysimeters and in actual paddy fields. In the lysimeter experiments, there were test plots for submerged application for both application types. Analytical concentrations of the pesticides in paddy water were evaluated using appropriate kinetic models. The detection levels of pesticides in the paddy water for the nursery-box and foliar applications were 10-77% and 42-79% of the submerged application, respectively. The times required for 50% dissipation (DT 50s) in case of the nursery-box and foliar applications were 0.8-10.4 days and 0.5-2.7 days, respectively. Although overall dissipations were affected by the physicochemical properties of the pesticide and the experimental design in the test plots, the initial detection levels in the lysimeters, governed by the runoff at transplanting and the deposition at spraying, were comparable with those in the actual paddy fields.

Performance evaluation of lysimeter experiments for simulating pesticide dissipation in paddy fields. Part 1: Submerged application of granular pesticides.

Three-year comprehensive experiments were conducted to compare the dissipation patterns of a total of 16 pesticides, including 3 metabolites, as granular formulations applied in lysimeters and paddy fields with two soil types. Analytical concentrations of the target pesticides in paddy water were analyzed using a granular kinetic model consisting of the following parameters: release rate, decrease rate, and dissolved concentration. Results of parameter grouping analyses of the kinetic models showed that 56% of data reproducibility (entire grouping) was obtained between replicates for the lysimeters. In comparisons between the lysimeters and paddy fields, 48% of decrease rates and 34% of release rates were grouped, although significant differences were observed with a nearly 90% difference for dissolved concentrations. These differences might be attributed to the hydrological components such as water management and meteorological covariates in paddy fields, the daily percolation in lysimeters and the adsorption-desorption kinetics between paddy water and soil.

Pesticide Dissipation and Enzyme Activities in Ungrassed and Grassed Biomixtures, Composed of Winery Wastes, Used in Biobed Bioremediation Systems

The biomixture composition and the presence of a grass layer in a biobed bioremediation system can improve the performance of these systems to minimize pesticide point-source contamination. In this study, a novel biomixture composed with organic wastes from vineyards and wine industries (vermicompost of winery wastes and vine shoots) and top soil (W) was elaborated. The impact of three pesticides, commonly used in vineyards, on its microbial activity and on the development of turfgrass was determined in a short-term experiment. Moreover, the dissipation of the assayed pesticides was evaluated to stablish their distribution patterns between the turfgrass and the biomixture. For comparison, the original biomixture composed with top soil, peat, and straw (P) was also studied. After 15 days of pesticide application, the development of the turfgrass in both biomixtures was similar. However, the oxidoreductases (dehydrogenase and ortho-diphenol oxidase) and the hydrolytic (FDA and β-glucosidase) enzyme activities were greater in W-biomixture than in P-biomixture. The dissipation of metalaxyl and imidacloprid recorded in the W-biomixtures was significantly greater than in the P-biomixtures. The pesticide dissipation in W-biomixtures followed the same order of their octanol water partition coefficients. Except for tebuconazole, the lower biological activity in the P-biomixture would explain the limited pesticide dissipation. In the grassed biomixtures, most (> 83%) of the non-dissipated imidacloprid and tebuconazole remained in the biomixtures, while metalaxyl was rapidly translocated to the aerial part of the turfgrass. Our results show the potential capability of the novel biomixture as an alternative to the original one in a biobed.

Dissipation of selected insecticides and fungicides applied during pre-harvest on mandarin and orange trees in Uruguay

The dissipation of 4 commercial pre-harvest pesticides used in two Citrus species under field conditions is presented. The influence of agroecological region, the Citrus species and weather conditions on abamectin, spinosad, imidacloprid and difenoconazole dissipation rate on fruits were evaluated. A validated ethyl acetate method coupled to liquid chromatography-tandem mass spectrometry allowed the determination of pesticide residues having recoveries of 72–115%, relative standard deviations ≤16% and quantification limits below the international Maximum Residue Levels (MRLs). After 35–40 days from pesticides spraying, all residues were below the international required MRL. For each citrus species, the influence of the agroecological region on the pesticide dissipation was assessed. Film-protected fruits against direct radiation and rain showed higher residue levels of imidacloprid and spinosad than the non-protected ones. Either for orange or mandarin, abamectin residues were detectable only at the first day after application. These findings provide useful information to state safer pre harvest intervals and to ensure food safety and compliance with good agricultural practices.

Modelling the behavior of pesticide residues in tomatoes and their associated long-term exposure risks

This study is focused on the dissipation behavior of 7 fungicides and 5 insecticides applied in tomatoes after a third spraying at recommended and double doses by considering 6 kinetic models which allow estimating the pesticides half-lives (t1/2). Except studying the pesticides dissipation, another scope of our manuscript was investigating the risk to human health after application of different pesticide treatments in tomatoes. The pesticides analysis in tomatoes at harvest showed that the residues were below the maximum residue level (MRL), with the exception of chlorotalonil (included in Group 2B - “Possibly carcinogenic to humans”) and bifenthrin for recommended dose treatments, while for double dose treatments, the MRLs was exceeded for 7 pesticides, once again including chlorotalonil. For recommended dose treatments, the 1st order kinetic model is confirmed only for metalaxyl-M. The values of pesticides t1/2 ranged from 0.006 days (for chlorothalonil) to 48.59 days (for myclobutanil). For double dose treatments, the 1st order kinetic model is confirmed for deltamethrin and triadimenol. In this case, the values of pesticides t1/2 ranged from 0.32 to 10.67 days. Further, consumers' exposure was estimated by calculating the long-term risk based on hazard quotient (HQ). The results indicated that the risks generated by pesticide residues in tomatoes applied in recommended or double doses are in an acceptable limit, except for chlorothalonil which may pose a threat for children health. However, if we consider the cumulative hazard index (HI) values which were higher than 1, consumption of tomatoes containing pesticides residues may cause harmful non-carcinogenic health effects.

Dissipation of Pre-Harvest Pesticides on ‘Clementine’ Mandarins after Open Field Application, and Their Persistence When Stored under Conventional Postharvest Conditions

The dissipation of field-applied difenoconazole, imidacloprid, pyraclostrobin and spinosad on Clementine mandarins (Citrus clementina Hort. ex Tan.) under controlled conditions throughout the citrus production chain was assessed. At harvest, 42 days after application, the dissipation of these pesticides were 80, 92, and 48% for difenoconazole, imidacloprid, pyraclostrobin, respectively, and spinosad was below the level of detectability. At day 28 after application, spinosad was no longer detected. The model equations that best describe the dissipation curves of these pesticides on Clementine mandarins showed different patterns. Their half-life on Clementine, calculated by the best-fitted experimental data, were 19.2 day (1st-order model) for difenoconazole, 4.1 day (Root Factor (RF) 1st-order model) for imidacloprid, 39.8 day (2nd-order model) for pyraclostrobin and 5.8 day (1st-order model) for spinosad. These results are the first record of pyraclostrobin persistence on mandarins, showing a longer half-life in this matrix than those reported for any other fruit. The treated fruit were harvested and submitted to the usual postharvest treatments: first, a hypochlorite drenching was performed; as a second step, imazalil and wax were applied, and then the mandarins were stored at 4 °C. After 32 days, cold storage caused no significant effects on the residue levels of the four pesticides compared with those determined on freshly harvested mandarins. All residues were below their Codex and European Union (EU) maximum residue limit (MRL) for mandarin since the spray application day.

The Dissipative Potential of Gamma Irradiation in Residues of Imidacloprid and Thiamethoxam in the Postharvest of Common Beans.

Pesticide residues remaining from bean cultivation, sensitive to optimal doses of gamma irradiation, can be transformed into other less harmful or nonharmful substances, increasing the quality of the beans before the food arrives at the consumer's table. Irradiation of the grains after harvest also eliminates the need for application of other pesticides to preserve the grains during storage, as the technique is capable of eradicating deteriorating agents, such as microorganisms and insects.

Behavior of pesticides and their metabolites in traditional Chinese medicine Paeoniae Radix Alba during processing and associated health risk

In Traditional Chinese Medicine (TCM), crude herbs are processed to obtain the medicinal parts of the plant, from which extracts are prepared for people to take as medicine. However, there is no report on the pesticide residual behavior in Chinese medicines during processing at present, and thus, a systematic study of the effects of different processing factors (PF) on pesticide removal in Chinese medicines and the associated risk of dietary exposure is urgently needed. This study main investigated the dissipation and metabolism of pesticides in Chinese medicine Paeoniae Radix Alba during processing, and the calculated pesticide PFs were also used to assess the risk of dietary exposure. For analyze samples, a simple and high-throughput multiresidue pesticide analysis method was developed and validated for pesticides and their metabolites in P. Radix. based on QuEChERS procedure combined with HPLC-MS/MS. Recoveries at three concentration levels were within 61.37%–117.82% with an associated precision RSD < 15% indicating satisfactory accuracy. TCM processing could be useful for the partial removal of several pesticide residues, with removal rate reaching 98%. The polarity is the dominant variable, which with a high contribution was the effectiveness of the treatment and the concentration factors for pesticides. The hazard quotients of all pesticides were much lower than the safety level, indicating low risk of dietary exposure. Results are of great theoretical and practical value for the scientific evaluation of the safety of Chinese medicines, improvement of the quality and safety level of Chinese medicine.

Assessment of occupational and dietary exposure to pesticide residues.

Plant protection products (PPPs) are pesticides containing at least one active substance that drives specific actions against pests (diseases). PPPs are regulated in the EU and cannot be placed on the market or used without prior authorisation. EFSA assesses the possible risks of the use of active substances to humans and environment. Member States decide whether or not to approve their use at EU level. Furthermore, Member States decide at national level on the authorisation of PPPs containing approved substances. In agriculture, exposure to PPPs and their residues during occupational tasks is estimated prior to product authorisation, using models fed with study‐specific (e.g. absorption, dissipation) and default values. Exposure of workers to pesticide residues reduces with the pesticide's dissipation time during crop‐related tasks. However, the current risk assessment gap is that no methodology is available to calculate the re‐entry interval (REI) for workers, which specifies how long they should wear personal protective clothing during their first entry into pesticide‐sprayed crops. Protective clothing (such as gloves) can reduce pesticide residue exposure to an acceptable level of worker safety. Within the European Food Risk Assessment Fellowship Programme (EU‐FORA) assignment, a methodology was developed to calculate agricultural‐use‐specific and pesticide‐specific REIs for which period workers should wear gloves. This was an assignment of the Dutch Ministry of Social Affairs and Employment. Another important aspect of risk assessment to ensure consumer safety is dietary risk assessment. A critical evaluation of residue studies and metabolism of the pesticide in question in crops results in a residue definition for dietary risk assessment and for enforcement and monitoring to define maximum residue limits allowed legally on or in raw agricultural commodities when applying pesticides according to good agricultural practices. This work was assigned by the Dutch Ministry of Health, Welfare and Sport and contributes to the work of the Joint FAO/WHO Meeting on Pesticide Residues.

Mulch of plant residues at the soil surface impact the leaching and persistence of pesticides: A modelling study from soil columns

Crop residues left on the soil surface as mulch greatly influence the fate of pesticides in conservation agricultural practices because most of the applied pesticide is intercepted by mulch before passing to the soil. Modelling of pesticide losses from wash-off and leaching will greatly improve our understanding of the environmental consequences of pesticides in these systems. The PASTIS model, which simulates water transfer, mulch decomposition, and pesticide dynamics, was adapted in this new version to model the interactions between pesticides and mulch in order to simulate the impact of mulch on pesticide dynamic. Parameters of mulch dynamics and pesticide degradation and retention processes were estimated using independent incubation experiments. The PASTIS model was tested with experimental laboratory data that were obtained from two pesticides (Glyphosate and s-metolachlor) applied to soil columns where mulch composed of maize and dolichos was placed at the soil surface impacted by two rain intensities (a high and infrequent intensity and a light and frequent intensity). Simulations indicated good agreement between simulated and experimental values. After 1 day, 45–46% of the pesticides leached from the mulch and 54–55% remained in the mulch for both pesticides and both rain intensities. During the experiment, pesticide wash-off was greater for the high and infrequent rain (56–57%) compare to light and frequent rain (39–45%) for both pesticides. A smaller amount of S-metolachlor washed off with the light and frequent rain intensity (39%) than glyphosate (45%) because of its lower desorption rate from mulch residues. Glyphosate was more degraded (37–45%) than s-metolachlor (17–37%), which agrees with preliminary incubation experiments that were used for parameter estimation. A sensitivity analysis indicated that the saturation index of mulch at which pesticides started their diffusion in the rainwater and the time of the first rainfall were the two parameters that influenced the most output variables of our model. This study suggests that the PASTIS model developed for pesticide dissipation in mulch is a useful tool to evaluate the potential risk of pesticide leaching to the groundwater in conservation agriculture systems.

Pesticide degradation and export losses at the catchment scale: Insights from compound-specific isotope analysis (CSIA)

Although pesticides undergo degradation tests prior to use, determining their export, degradation and persistence under field conditions remains a challenge for water resource management. Compound specific isotope analysis (CSIA) can provide evidence of contaminant degradation extent, as it is generally independent of non-destructive dissipation (e.g., dilution, sorption, volatilization) regulating environmental concentrations. While this approach has been successfully implemented in subsurface environments, its application to pesticides in near-surface hydrological contexts at catchment scale is lacking. This study demonstrates the applicability of CSIA to track pesticide degradation and export at catchment scale and identify pesticide source areas contributing to changes in stable isotope signature in stream discharge under dynamic hydrological contexts. Based on maximum shifts in carbon stable isotope signatures (Δδ13C = 4.6 ± 0.5‰) of S-metolachlor (S-met), a widely used herbicide, we estimate maximum degradation to have reached 96 ± 3% two months after first application. Maximum shifts in nitrogen isotope signatures were small and inverse (Δδ15N=−1.3±0.6‰) indicating potential secondary isotope effects during degradation. In combination with a mass balance approach including S-met main degradation products, total catchment non-destructive dissipation was estimated to have reached 8 ± 7% of the applied product. Our results show that CSIA can be applied to evaluate natural attenuation of pesticides at catchment scale. By providing a more detailed account of pesticide dissipation and persistence under field conditions we anticipate the contribution of pesticide CSIA to the improvement of regulatory and monitoring strategies.

Concentration/time-dependent dissipation, partitioning and plant accumulation of hazardous current-used pesticides and 2-hydroxyatrazine in sand and soil

The dissipation, partitioning dynamics and biouptake was measured for selected hazardous current-used pesticides (conazole fungicides: epoxiconazole, flusilazole, tebuconazole; prochloraz, chlorpyrifos, pendimethalin) and for a transformation product (2-hydroxyatrazine) in agricultural soil and quartz sand as representatives of a real and a worst-case scenario. Dissipation, uptake to Lactuca sativa and the freely dissolved concentration along with the organic carbon-normalized sorption coefficients (Koc) were determined on days 12, 40, and 90 following the application of compounds at three fortification levels (0.1–1.0–10 mg/kg). Conazole fungicides showed similar dissipation patterns and were more persistent in soil than prochloraz, chlorpyrifos and pendimethalin. 2-Hydroxyatrazine showed a concentration-depended decrease in persistency in soil. Lettuce roots were shown to accumulate higher amounts than shoots where the extent of root uptake was driven by compound partitioning. This was evidenced by the ability of freely dissolved concentration (Cfree) to reliably (r2 = 0.94) predict root uptake. Concentration in leaves did not exceed the maximum residue levels (MRLs) for lettuce, which was likely given by the low root-to-shoot translocation factors (TFs) of the tested compounds varying between 0.007 and 0.14. Koc values were in the range of literature values. Sorption to soil was higher than to sand for all compounds, yet following the Koc dynamics compounds did not appear to be sequestered in soil with increasing residence time. From these results, it follows that the tested compounds may persist in soil but since they did not accumulate in lettuce above MRLs, contamination of the food web is unlikely.

Predicting Pesticide Volatility Through Coupled Above- and Belowground Multiphysics Modeling

Pesticides are applied to agricultural fields to control unwanted pests but can volatilize and be transported downwind by wind currents to create the potential for non-target organism exposure. Volatilization rates change through the growing season due to pesticide application timing, meteorological differences, and the differential flux rates from soil and vegetation matrices. Field studies quantifying pesticide volatility are expensive and cannot capture the semi-infinite parameter combinations of soil, crop, management, and meteorological conditions encountered under regional agronomic practices. A numerical approach was used to simulate pesticide dissipation above- and belowground to augment field and laboratory experimental observations. Above- and belowground physics are coupled into a single numerical tool using the COMSOL Multiphysics® software package with the current emphasis on pesticide volatility into air from soil and vegetation and resulting near field neighboring air concentrations. Comparison of simulation results against experimental observations for an insecticide (chlorpyrifos) applied to potato and alfalfa fields shows good agreement (R2 0.68–0.98). Chlorpyrifos volatility from plant surfaces drives the overall volatility within the first several days post application. The maximum volatility flux rate simulated and observed were 0.79 and 0.66 μg m−2 s−1 for the alfalfa trial and 2.72 and 2.17 μg m−2 s−1 for the potato field, respectively. This coupled multiphysics tool [computational fluid dynamics (CFD), mass transfer coefficients, and variably saturated flow in soil] can be used to estimate volatility flux rates of pesticides when little or no prior knowledge is available and for extrapolating field study observations to different and diverse scenarios.

Identification of microbial species present in a pesticide dissipation process in biobed systems using typical substrates from southeastern Mexico as a biomixture at a laboratory scale

Biobed systems are an important option to control point pollution in agricultural areas. Substrates used and microbial diversity present in a biomixture perform an essential function in pesticide dissipation. In this study, the effects of soil (50% of volume/volume [V/V] proportion for all biomixtures) and four soil-based biomixtures (miniaturized biobeds; addition of novel substrates from southeastern Mexico) on dissipation of high concentrations of 2,4-dichlorophenoxyacetic acid (2,4-D), atrazine, carbofuran, diazinon, and glyphosate and on microbial diversity in biomixtures were evaluated. Small residual amounts of all pesticides at 20 (<2%) and 41 (<1%) days were observed; however, the lowest efficiency rates were observed in soil. Glyphosate was the only pesticide that completely dissipated in soil and biomixtures. Archaea, bacteria, and fungi were identified in biobeds, with bacteria being the most diverse microorganisms according to the identified species. The presence of white-rot fungi (normally related to pesticide degradation in biomixtures) was observed. Effects of the pesticide type and of biomixtures on pesticide dissipation were significant (P<0.05); however, only the effect of biomixtures on microbial diversity was significant (P<0.05); microbial diversity and richness had a significant effect on the residual amount of pesticides (P<0.05). Microbial diversity in terms of phyla was directly related to physicochemical parameters such as organic matter, lignin, water-holding capacity, and pH of soil and biomixtures.

Bacterial Community Composition and Genes for Herbicide Degradation in a Stormwater Wetland Collecting Herbicide Runoff

Stormwater wetlands collect and attenuate runoff-related herbicides, limiting their transport into aquatic ecosystems. Knowledge on wetland bacterial communities with respect to herbicide dissipation is scarce. Previous studies showed that hydrological and hydrochemical conditions, including pesticide removal capacity, may change from spring to summer in stormwater wetlands. We hypothesized that these changes alter bacterial communities, which, in turn, influence pesticide degradation capacities in stormwater wetland. Here, we report on bacterial community changes in a stormwater wetland exposed to pesticide runoff, and the occurrence of trz, atz, puh, and phn genes potentially involved in the biodegradation of simazine, diuron, and glyphosate. Based on T-RFLP analysis of amplified 16S rRNA genes, a response of bacterial communities to pesticide exposure was not detected. Changes in stormwater wetland bacterial community mainly followed seasonal variations in the wetland. Hydrological and hydrochemical fluctuations and vegetation development in the wetland presumably contributed to prevent detection of effects of pesticide exposure on overall bacterial community. End point PCR assays for trz, atz, phn, and puh genes associated with herbicide degradation were positive for several environmental samples, which suggest that microbial degradation contributes to pesticide dissipation. However, a correlation of corresponding genes with herbicide concentrations could not be detected. Overall, this study represents a first step to identify changes in bacterial community associated with the presence of pesticides and their degradation in stormwater wetland.

Fluorescent tracers to evaluate pesticide dissipation and transformation in agricultural soils

This study evaluates the mobility and dissipation of two organic fluorescent tracers (uranine, UR and sulforhodamine-B, SRB) in soil from an agricultural field. Two plot experiments were conducted for 2.5months in 2012 and 2016 to compare the behavior of reactive fluorescent tracers (UR and SRB) to the chloroacetanilide herbicide S-metolachlor (S-MET) and bromide (BR), used as a traditional conservative tracer. SRB in top soil closely mimicked the gradual recession of S-MET, while BR overrated both top soil mobility and slow leaching of S-MET in the soil column. In contrast, UR quickly receded in the soil and was entirely dissipated at the end of the study periods. Instead, a strong fluorescent signal that was stable against acidification, and non-traceable in background samples, gradually developed at an excitation wavelength of 510nm in samples from the uppermost soil layer starting 40 (2012) and 22 (2016) days after tracer application. We hypothesize that (bio-)chemical transformation of UR accelerated tracer loss with concomitant formation of the specific transformation product TP510. By LC-MS/MS analysis we propose a probable molecular structure of TP510 and sulfonation as one likely transformation process. Overall, we anticipate our results to be a starting point to use fluorescent tracers in longer term (>2months) agricultural soil studies as a proxy for S-MET and possibly also other organic pesticides, as they are non-conservative in unsaturated soil and may follow similar dissipation and transformation patterns. At the same time their analysis is less costly and they pose smaller environmental risks.