Leaching of pesticides through normal-tillage and low-tillage soil--a lysimeter study. I. Isoproturon

Isoproturon is a herbicide, which was used in Denmark against grass weeds and broad-leaved weeds until 1998. Isoproturon has frequently been detected in ground water monitoring studies. Leaching of isoproturon (N,N-dimethyl-N'-(4-(1-methylethyl)-phenyl)urea) and its metabolites, N'-(4-isopropylphenyl)-N-methylurea and N'-(4-isopropylphenyl)urea was studied in four lysimetres, two of them being replicates from a low-tillage field (lysimeter 3 and 4), the other two being replicates from a normal tillage field (lysimeter 5 and 6). In both cases the soil was a sandy loam soil with 13-14% clay. The lysimetres had a surface area of 0.5 m2 and a depth of 110 cm. Lysimeter 3 and 4 were sprayed with unlabelled isoproturon while lysimeter 5 and 6 was sprayed with a mixture of 14C-labelled and unlabelled isoproturon. The total amount of isoproturon sprayed onto each lysimeter was 63 mg, corresponding to 1.25 kg active ingredient per ha. The lysimeters were sprayed with isoproturon on October 26, 1997. The lysimetres were installed in an outdoor system in Research Centre Flakkebjerg and were thus exposed to normal climatic conditions of the area. A mean of 360 l drainage water were collected from lysimeter 3 and 4 and a mean of 375 litres from lysimeter 5 and 6. Only negligible amounts of isoproturon and its primary metabolites were found in the drainage water samples, and thus no significant difference between the two lysimeter sets was shown. In a total of 82 drainage water samples, evenly distributed between the four lysimetres isoproturon was found in detectable amounts in two samples and N'-(4-isopropylphenyl)urea was found in detectable amounts in two other samples. The detection limit for all the compounds was 0.02 microg/l. 48% and 54% of the added radioactivity were recovered from the upper 10 cm soil layer in lysimeter 5 and 6, respectively, and 17 and 14% from 10-20 cm's depth. By extraction first with an aquatic CaCl2 solution 0.49% of the added radioactivity was extracted from the upper 10 cm layer in lysimeter 5. In the subsequent extraction with acetonitril, 1.19% of the added radioactivity was extracted. In lysimeter 6, upper 10 cm, 0.2% were extracted with water and 0.56% were extracted with acetonitril. Below 10 cm's depth no measurable amounts could be extracted.     

Leaching and degradation of 21 pesticides in a full-scale model biobed

Filling and cleaning of pesticide sprayers presents a potential risk of pollution of soil and water. Three different solutions for handling sprayers have been suggested: Filling and cleaning in the field, filling and cleaning on hard surfaces with collection of the waste water, and filling and cleaning on a biobed, which is an excavation lined with clay and filled with a mixture of chopped straw, sphagnum and soil with turf on top, and with increased sorption capacity and microbial activity for degradation of the pesticides. In the present study the degradation and leaching of 21 pesticides (5 g of each) was followed in an established full-scale model biobed. Percolate was collected and analysed for pesticide residues, and the biobed material was sampled at three different depths and analysed by liquid chromatography double mass spectrometry (LC-MSMS). During the total study period of 563 days, no traces of 10 out of 21 applied pesticides were detected in the percolate (detection limits between 0.02 and 0.9 μg l⁻¹) and three pesticides were only detected once and at concentrations below 2 μg l⁻¹. During the first 198 days before second application, 14% of the applied herbicide bentazone was detected in the leachate with maximum and mean concentrations of 445 and 172 μg l⁻¹, respectively. About 2% of the initial mecoprop and fluazifop dose was detected in the percolate, with mean concentrations of 23 μg l⁻¹, while MCPA and dimethoate had mean concentrations of 3.5 and 4.7 μg l⁻¹, respectively. Leachate concentrations for the remaining pesticides were generally below the detection limit (0.02–0.9 μg l⁻¹, below 1% of applied). Sorption studies of five pesticides showed that compounds with a low K_d value appeared in the leachate. After 169 days, all pesticides in the biobed profile were degraded to a level below 50% of the calculated initial dose. Pesticides with K_oc values above 100 were primarily found in the uppermost 10 cm and degraded slowest due to the low bioavailability. The 11 most degradable pesticides were all degraded such that less than 3% remained in the biobed after 169 days.

Following second pesticide application of the biobed, leachate was sampled 215 and 365 days after the treatment. This showed the same pesticides to be leached out and at concentrations comparable to those of the first treatment. The same pesticides as after the first treatment were retained in the biobed.     

Leaching and degradation of corn and soybean pesticides in an Oxisol of the Brazilian Cerrados

Pesticide pollution of ground and surface water is of growing concern in tropical countries. The objective of this pilot study was to evaluate the leaching potential of eight pesticides in a Brazilian Oxisol. In a field experiment near Cuiabá, Mato Grosso, atrazine, chlorpyrifos, lambda-cyhalothrin, endosulfane alpha, metolachlor, monocrotofos, simazine, and trifluraline were applied onto a Typic Haplustox. Dissipation in the topsoil, mobility within the soil profile and leaching of pesticides were studied for a period of 28 days after application. The dissipation half-life of pesticides in the topsoil ranged from 0.9 to 14 d for trifluraline and metolachlor, respectively. Dissipation curves were described by exponential functions for polar pesticides (atrazine, metolachlor, monocrotofos, simazine) and bi-exponential ones for apolar substances (chlorpyrifos, lambda-cyhalothrin, endosulfane alpha, trifluraline). Atrazine, simazine and metolachlor were moderately leached beyond 15 cm soil depth, whereas all other compounds remained within the top 15 cm of the soil. In lysimeter percolates (at 35 cm soil depth), 0.8-2.0% of the applied amounts of atrazine, simazine, and metolachlor were measured within 28 days after application. Of the other compounds less than 0.03% of the applied amounts was detected in the soil water percolates. The relative contamination potentials of pesticides, according to the lysimeter study, were ranked as follows: metolachlor > atrazine = simazine > monocrotofos > endsulfane alpha > chlorpyrifos > trifluraline > lambda-cyhalothrin. This order of the pesticides was also achieved by ranking them according to their effective sorption coefficient Ke, which is the ratio of Koc to field-dissipation half-life.     

Grid lysimeter study of steady state chloride transport in two Spodosol types using TDR and wick samplers.

Solute transport in soils is affected by soil layering and soil-specific morphological properties. We studied solute transport in two sandy Spodosols: a dry Spodosol developed under oxidizing conditions of relatively deep groundwater and a wet Spodosol under periodically reducing conditions above a shallow groundwater table. The wet Spodosol is characterized by a diffuse and heterogeneous humus-B-horizon (i.e., Spodic horizon), whereas the dry Spodosol has a sharp Spodic horizon. Drainage fluxes were moderately variable with a coefficient of variation (CV) of 25% in the wet Spodosol and 17% in the dry Spodosol. Solute transport in 1-m-long and 0.8-m-diameter soil columns was investigated using spatial averages of solute concentrations measured by a network of 36 Time Domain Reflectometry (TDR) probes. In the dry Spodosol, solute transport evolves from stochastic-convective to convective-dispersive at a depth of 0.25 m, coinciding with the depth of the Spodic horizon. Chloride breakthrough at the bottom of the soil columns was adequately well predicted by a convection-dispersion model. In the wet Spodosol, solute transport was heterogeneous over the entire depth of the column. Chloride breakthrough at 1 m depth was predicted best using a stochastic-convective transport model. The TDR sampling volume of 36 probes was too small to capture the heterogeneous flow and concomitant transport in the wet Spodosol.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State-Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, alpha and beta endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino-Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6% leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (alpha-endosulfan), 1.47E-162 (beta-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

A monitoring study of workers handling pesticides in warehouses and godowns.

Monitoring observations made on 60 operators involved in pesticide application work in godowns and warehouses and 60 matched control workers are reported. Occupational exposure history and medical history are noted. Biochemical investigations, plasma and RBC cholinesterase estimations are included along with medical examination of the workers. Workers were found to be mostly exposed to Celphos, DDVP, Malathion, Pyrethrum, etc, and the use of protective devices were very limited. Cases of significant reduction in plasma and RBC cholinesterase activity were found. Frequency of symptoms like dizziness, headache, lachrymation, burning sensation in eyes, nausea and anorexia, etc, were much more in the exposed workers. No cases of clinical poisoning attributable to occupational exposure to pesticides were reported by the workers.     

Fate of metolachlor under subirrigation in a sandy soil: a lysimeter study

A three-year field lysimeter study was conducted to investigate the role of subirrigation systems in reducing the risk of water pollution from metolachlor (2-chloro-N-(2-ethyl-6-methlphenyl)-N-(2-methoxy-1-methylethyl)ace tamide). Nine large PVC lysimeters, 1 m long x 0.45 m diameter, were packed with a sandy soil. Three water table management treatments, i.e. two subirrigation treatments with constant water table depths of 0.4 and 0.8 m, respectively, and a free drainage treatment in a completely randomized design with three replicates were used. Corn (Zea mays L.) was grown in each lysimeter, and at the beginning of summer of each year metolachlor was applied, at the locally recommended rate of 2.75 kg a.i./ha. Soil and water samples were collected at different time intervals after each natural or simulated rainfall event. Metolachlor was extracted from these samples and analyzed using Gas Chromatography. Results obtained in this three year study, (1993-1995), lead to the conclusion that metolachlor is quite mobile since it leached to a depth of 0.85 m below the soil surface quite early in the growing season. Metolachlor concentrations decreased with depth as well as with time. The shallower water table in the 0.4 m subirrigation treatment showed less residues in the soil solution than that of other treatments. However, a mass balance study, supported by an independent laboratory investigation, shows that water table management, statistically, has no significant effect on the reduction of metolachlor residues in sandy soils.     

Fate of metolachlor under subirrigation in a sandy soil: A lysimeter study

Abstract

A three‐year field lysimeter study was conducted to investigate the role of subirrigation systems in reducing the risk of water pollution from metolachlor (2‐chloro‐N‐(2‐ethyl‐6‐methlphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide). Nine large PVC lysimeters, 1 m long x 0.45 m diameter, were packed with a sandy soil. Three water table management treatments, i.e. two subirrigation treatments with constant water table depths of 0.4 and 0.8 m, respectively, and a free drainage treatment in a completely randomized design with three replicates were used. Corn (Zea mays L.) was grown in each lysimeter, and at the beginning of summer of each year metolachlor was applied, at the locally recommended rate of 2.75 kg a.i./ha. Soil and water samples were collected at different time intervals after each natural or simulated rainfall event. Metolachlor was extracted from these samples and analyzed using Gas Chromatography.

Results obtained in this three year study, (1993–1995), lead to the conclusion that metolachlor is quite mobile since it leached to a depth of 0.85 m below the soil surface quite early in the growing season. Metolachlor concentrations decreased with depth as well as with time. The shallower water table in the 0.4 m subirrigation treatment showed less residues in the soil solution than that of other treatments. However, a mass balance study, supported by an independent laboratory investigation, shows that water table management, statistically, has no significant effect on the reduction of metolachlor residues in sandy soils.     

Transport and degradation of pesticides in a biopurification system under variable flux Part II: A macrocosm study

Transport of bentazone, isoproturon, linuron, metamitron and metalaxyl were studied under three different flows in macrocosms. The aim was to verify the observations from Part I of the accompanying paper, with an increase in column volume and decrease in chemical and hydraulic load. Very limited breakthrough occurred in the macrocosms for all pesticides, except bentazone, at all flows.From batch degradation experiments, it was observed that the lag time of metamitron and linuron decreased drastically in time for all flows, indicating a growth in the pesticide degrading population. This in contrast to isoproturon and metalaxyl, where an increase in lag time could be observed in time for all flows. From the batch degradation experiments, it could be concluded that the influence of flow on the lag time was minimal and that the inoculation of the pesticide-primed soil had a little surplus value on degradation.     

Leaching potential of some phenylureas and their main metabolites through laboratory studies

BACKGROUND, AIMS AND SCOPE: Laboratory studies were conducted with the aim of defining the leaching potential of some phenylureas and their metabolites. A first study was performed for calculating their leaching index (as GUS) on the base of intrinsic properties: persistence (as DT50) and mobility (as Koc) in soil. Another study consisted of aged column leaching experiments whose meaning was to semi-quantify the occurrence of the tested compounds in the leachates, so simulating in field conditions. METHODS: The tested compounds were: diuron, linuron and monolinuron (parents); 3,4-dichloroaniline (DCA), 4-chloroaniline (CLA), 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl)urea (DCPU), 1-(4-chlorophenyl)urea (CPU) and monuron, this latter considered both as a metabolite and parent compound. The Koc values of the examined substances were determined by the HPLC screening methods, according to the OECD TG 121. DT50 determinations and aged column leaching experiments were carried out according to SETAC procedures. RESULTS AND DISCUSSION: The examined compounds showed a rather wide range of persistence in soil, with DT50 values less than 2 days for DCA and CLA, close to 8 days for DCPU and CPU and from 16 (diuron) up to 24.8 (DCPMU) days for the others. Their mobility was generally high, based on their Koc values, which ranged from 33 (CPU) to 406 (linuron). The GUS indices indicated that monuron has a clear potential to contaminate groundwater (> 2.8); DCPMU, monolinuron, CPU and diuron are intermediate contaminants (1.8-2.8). Linuron, DCPU, CLA and DCA exhibited a non-leaching behaviour (< 1.8). The aged leaching column experiments showed that parents were found in the leachates at very high percentages respect to the doses applied. The metabolites reached much less percentages, the highest values were observed for monuron from diuron (5.7), CPU (7.2) and DCPMU (8.2%). CONCLUSION: Diuron, Monuron, CPU and DCPMU on the basis of their intrinsic properties, formation from their parents and occurrence in leachates from aged column leaching studies, seem to possess the characteristics of groundwater contaminants. The methodological approach of this study is relatively easy and rapid, hence it can represent a tool for a first screening of compounds such as pesticide metabolites (generally available only in small quantities and for which a field study is not conceivable) or other compounds for which not adequate environmental data are available.     

A lysimeter experiment to investigate the leaching of veterinary antibiotics through a clay soil and comparison with field data

Pharmaceuticals used in livestock production may be present in manure and slurry as the parent compound and/or metabolites. The environment may therefore be exposed to these substances due to the application of organic fertilisers to agricultural land or deposition by grazing livestock. For other groups of substances that are applied to land (e.g. pesticides), preferential flow in clay soils has been identified as an extremely important mechanism by which surface water pollution can occur. This lysimeter study was therefore performed to investigate the fate of three antibiotics from the sulphonamide, tetracycline and macrolide groups in a clay soil. Only sulphachloropyridazine was detected in leachate and soil analysis at the end of the experiment showed that almost no antibiotic residues remained. These data were analysed alongside field data for the same compounds to show that soil tillage which breaks the connectivity of macropores formed over the summer months, prior to slurry application, significantly reduces chemical mobility.     

Comparative study of accessibility of distinctive pesticides

Interactions of micro-contaminants with soil may play a crucial role in their environmental fate and possible harmful effects. Major goals of our investigations were to model the availability of widely used pesticides and characterize adsorption capabilities of distinctive soil types by the accomplishment of extensive comparative studies and application of several extraction methods. Environmental and biological relevance of these examinations is enhanced by the fact that intrinsic features and specific details of pesticide accessibility have not been revealed so far by a comparative approach. Five different experimental methods were assessed for modelling accessibility of five selected pesticides. The applied models for regaining the pesticides showed diverse efficiency in extraction capability in cases of the different soil types (sandy, brown forest and alluvial soils). The amounts of the obtained pesticides were determined by using gas-chromatography coupled to mass spectrometry (GC-MS) and high pressure liquid chromatography coupled to mass spectrometry (HPLC-MS). Accessibility of pesticides was also compared in cases of sterilized and real soil samples in order to estimate the extent of the influence of microflora. Aqueous extraction solvents proved to be suitable for accurate assessment of the accessible amounts of pesticides, as their effectivity was at least as high as that of the applied organic solvents. In our studies pesticide-soil interactions have comprehensively been characterized, and possible influences of environmental factors on the accessibility have also been revealed. Our study might be regarded as a tentative approach to model some significant circumstances playing key roles in pesticides' possible bioavailability.     

Heavy metals in urban soils of East St. Louis, IL. Part II: Leaching characteristics and modeling

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.     

Leaching of oryzalin and diuron through undisturbed vineyard soil columns under outdoor conditions

Field studies monitoring herbicide pollution in the vineyards of Burgundy (France) have revealed that drinking water reservoirs are contaminated with several pre-emergence herbicides. An assessment of the leaching of two such herbicides, diuron and oryzalin, was therefore performed using lysimeters, under outdoor conditions, from May 2001 to May 2002. Four vineyard soils from Vosne-Romanée (Burgundy) were chosen along a topolithosequence: a rendosol and three calcosols. After 673 mm of rainfall, greater amounts of diuron than oryzalin were measured in percolates: respectively 0.10-0.84% and 0.02-0.43% of applied herbicide, depending on soils. Measurements for diuron metabolites detected greater amounts of DCPMU than DCPU in the percolates: respectively 0.05-0.13% and 0-0.04% of the applied diuron. At the end of the monitoring period, more residues of diuron than oryzalin were recovered in the soil profiles: respectively 4.6-9% and 1.4-4.4%. The oryzalin residues were found mainly in the upper 10 cm of soil columns, whereas diuron residues were present in the whole core. The mobility of both oryzalin and diuron seems fairly well-related to soil organic carbon content; the mobility of diuron is also related to soil texture (sand and coarse material contents). Under such experimental conditions, this study confirms that diuron leaching, and therefore potential groundwater contamination, is greater than that of oryzalin.     

Heavy Metals in Urban Soils of East St. Louis,IL Part II: Leaching Characteristics and Modeling

ABSTRACT

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.     

Reduction of the movement and persistence of pesticides in soil through common agronomic practices

Laboratory and field studies were conducted in order to determine the leaching potential of eight pesticides commonly used during pepper cultivation by use of disturbed soil columns and field lysimeters, respectively. Two soils with different organic matter content (soils A and B) were used. Additionally, soil B was amended with compost (sheep manure). The tested compounds were cypermethrin, chlorpyrifos-methyl, bifenthrin, chlorpyrifos, cyfluthrin, endosulfan, malathion and tolclofos-methyl. In soil B (lower organic matter content), only endosulfan sulphate, malathion and tolclofos-methyl were found in leachates. For the soil A (higher organic matter content) and amended soil B, pesticide residues were not found in the leachates. In addition, this paper reports on the use of common agronomic practices (solarization and biosolarization) to enhance degradation of these pesticides from polluted soil A. The results showed that both solarization and biosolarization enhanced the degradation rates of endosulfan, bifenthrin and tolclofos-methyl compared with the control. Most of the studied pesticides showed similar behavior under solarization and biosolarization conditions. However, chlorpyrifos was degraded to a greater extent in the solarization than in biosolarization treatment. The results obtained point to the interest in the use of organic amendment in reducing the pollution of groundwater by pesticide drainage and in the use of solarization and biosolarization in reducing the persistence of pesticides in soil.     

Photocatalytic ozonation of pesticides in a fixed bed flow through UVA-LED photoreactor

In this study, a fixed bed flow through UVA-LED photoreactor was used to compare the efficiency of ozone, photocatalysis and photocatalysis-ozone degradation, and mineralization of two pure pesticides, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA), and a commercial one, Killex®. For the degradation of the parent compounds, ozone-based processes were more effective. While for mineralization, photocatalytic processes were more effective. Photocatalytic ozonation was the most efficient process for both the degradation and mineralization of the parent compounds. The degradation rates and mineralization by photocatalytic ozonation were higher than the summation of the corresponding rates by ozonation and photocatalysis, indicating a symbiotic relationship.Overall, the photocatalytic ozonation process with the fixed bed TiO₂ reduces the time needed for the degradation and mineralization of the pesticides, reduces the costs of powder catalyst separation and overcomes the reduced efficiency of immobilized catalysts, which makes the process quite attractive for practical applications.     

A monitoring study of workers handling pesticides in warehouses and godowns

Abstract

Monitoring observations made on 60 operators involved in pesticide application work in godowns and warehouses and 60 matched control workers are reported. Occupational exposure history and medical history are noted. Biochemical investigations, plasma and RBC cholinesterase estimations are included along with medical examination of the workers. Workers were found to be mostly exposed to Celphos, DDVP, Malathion, Pyrethrum, etc, and the use of protective devices were very limited. Cases of significant reduction in plasma and RBC cholinesterase activity were found. Frequency of symptoms like dizziness, headache, lachrymation, burning sensation in eyes, nausea and anorexia, etc, were much more in the exposed workers. No cases of clinical poisoning attributable to occupational exposure to pesticides were reported by the workers.     

Formation and long-term fate of non-extractable residues in outdoor lysimeter studies

Long-term outdoor lysimeter studies using (14)C-labelled compounds allow the quantification of the 'non-extractable residue fraction'. More than 20 lysimeter studies under realistic environmental conditions showed that more than 80% of residual carbon of the molecule is retained in the topsoil layer even after several years. Generally, 50-90% of this residual radiocarbon is regarded as 'soil bound residue'. Microbial biomass is present in large quantities in topsoil and continuously influences chemical and biochemical alteration of pesticide molecules that may interact directly with the total soil organic matter. Labelling techniques using radioactive isotopes like (14)C have been used to characterize these residues in the humus matrix. Our studies have been directed to the investigation of extractability and/or bioavailability of these residues in long-term investigations.     

Glyphosate adsorption on soils of different characteristics. Influence of copper addition

Results of glyphosate (GPS) adsorption on three soils of different characteristics show that the interaction of this pesticide with the soils was not related to their CEC and clay minerals content, but to the content of iron and aluminum amorphous oxides and organic matter. The presence of Cu in treatment solutions enhanced GPS adsorption, due to several reasons: GPS coordinates strongly to Cu, and Cu GPS complexes formed seem to have higher ability to be adsorbed on the soil than free GPS; GPS adsorption can take place on sites where Cu was previously adsorbed, acting as a bridge between the soil and GPS; when Cu was present the solution pH decreased, and GPS adsorption increased, since lower pHs lead to the formation of GPS species with lower negative charge, which are adsorbed more easily on the negatively charged soil surfaces.