In pastures, the application of limestone is often performed after removal of the animals for proper development and establishment of regrowth. Together with this practice, the use of picloram in high concentrations for dicotyledonous weeds is common. Therefore, the evaluation of the behavior of this herbicide in these conditions is critical. The objective of this study was to determine the leaching of the picloram, in the soil with different pH and cultivated with Urochloa brizantha (signalgrass) trimmed or not. The experiment was plotted in a subdivided plot with four repetitions, where the plots were constituted by factors pH (5.3 and 6.4) and Urochloa brizantha managements (trimmed and no trimmed). The subplots were composed by depths (0 to 50 cm). The picloram was applied to the top of the columns after 65 days after emergency. A rain of intensity of 60 mm was simulated 12 h after the herbicide application. Picloram concentration was quantified by the high-performance liquid chromatography. Besides that, a control treatment was added without the presence of the signalgrass, for each substrate. The picloram was not detected in the percolated water through the columns. Picloram leached to deeper layers in the soil with pH 6.4, independently of the signalgrass management. The signalgrass reduced the leaching of the picloram, and those no-trimmed demonstrate a higher capacity to retain the herbicide in superficial layers. The liming of the soil increases the pH and reduces the amount of organic matter in the soil, which favors the leaching of picloram to the layer of 30–35 cm. Trimming of Urochloa brizantha reduces the capacity of this forage to reduce the leaching of picloram.

Herbicides with long residual period may increase the risk of environmental contamination. Adequate management of forage can reduce the half-life of the picloram, one of the most herbicides used in weed control. This study aims to determine the half-life of picloram, using high-performance liquid chromatography in a cultivated soil with Brachiaria brizantha trimmed or not. Brachiaria brizantha was cultivated in 60 pots filled with samples of oxisol, and 30 others were kept uncultivated with this forage. This plant was cut off close to the ground, after 60 days of emergency on 30 vessels. Picloram was applied in all of the plots. Soil samples were collected at 2, 16, 30, 44, 58, 72, 86, 120, 150, and 180 days after the application of this herbicide. These samples were air-dried and stored at − 20 °C. Picloram was extracted by HPLC/UV-Vis detector. Half-life of this herbicide was calculated using kinetics models. The mere presence of roots in treatment with signalgrass cutoff did not reduce the concentrations of this herbicide, except when the emergence of new leaves occurred. The absence of B. brizantha cultivation in areas with application of picloram increases the risk of environmental contamination and successive crops due to the half-life of this herbicide. Brachiaria brizantha reduced half-life picloram and environmental risk in pastures. The validation method is suitable for determining picloram in low concentrations in soil.

We investigated the effects of four commercial formulations of herbicides (glyphosate [GLY], metsulfuron-methyl [MET], bispyribac-sodium [BIS], and picloram [PIC]) individually, and in three 50:50 mixtures (GLY–MET, GLY–BIS, GLY–PIC) on the common toad Rhinella arenarum (Anura: Bufonidae) tadpoles. Enzymatic parameters such as, glutathione S-transferase (GST), butyrylcholinesterase (BChE) and acetylcholinesterase (AChE) activities, as well as erythrocyte nuclear abnormalities (ENA) were studied. Interactions between herbicides in mixtures were evaluated and classified as additive, synergistic, or antagonistic. Toxicity results (48-h LC₅₀) showed that PIC was the most toxic herbicide, followed by BIS, GLY, and MET, while GLY–PIC was the most toxic mixture, followed by GLY–BIS, and GLY–MET. All commercial herbicide formulations and their mixtures significantly inhibited BChE activity in exposed tadpoles. The AChE activity was also inhibited by all herbicides and their mixtures, except by GLY–BIS. The inhibition of GST activity was only significant for GLY, MET, PIC, and GLY–MET. A significant increase in the frequency of ENA was found for tadpoles exposed either to commercial herbicide formulations or to mixtures, except for GLY. All the mixtures showed synergism for BChE activity while for AChE only the GLY–MET and GLY–PIC mixtures acted synergistically. GLY–MET showed synergism for GST, whereas for ENA, the mixture GLY–BIS was antagonistic. This study with R. arenarum tadpoles demonstrates that the interactions between three of the most intensively used herbicides in soybean crops results in synergistic effects on mortality and neurotoxicity and synergistic or additive effects in genotoxicity.

Valle del Mayo is an important agricultural area at the northwest of Mexico where up to 20,000 L of a mix composed of glyphosate and tordon is used in drains and canals. This study was carried out in order to evaluate the cellular damage caused by glyphosate, aminomethylphosphonic acid (AMPA), and picloram in agricultural workers. Biomonitoring was performed through the quantification of herbicides in urine using HPLC (high-performance liquid chromatography) to then evaluate the cellular damage in exposed people by means of an evaluation of micronuclei and cellular proliferation in lymphocyte cultures. The urine samples (n = 30) have shown a concentration of up to 10.25 μg/L of picloram and 2.23 μg/L of AMPA; no positive samples for glyphosate were reported. The calculation of the external dose reveals that agricultural workers ingest up to 146 mg/kg/day; however, this concentration does not surpass the limits that are allowed internationally. As for the results for the micronuclei test, 53% of the workers showed cellular damage, and the nuclear division index test reported that there was a significant difference (P < 0.05) between the exposed and the control population, which indicated that the exposure time to pesticides in the people of Valle del Mayo can induce alterations which can cause chronic damage.

Picloram (4-amino-3,5,6-trichloropicolinic acid) is a liquid auxinic herbicide used to control broad-leaved weeds. Picloram is representing a possible hazard to ecosystems and human health. Therefore, in this study, DNA methylation changes and DNA damage levels in Phaseolus vulgaris exposed to picloram, as well as whether humic acid (HA) has preventive effects on these changes were investigated. Random amplified polymorphic DNA (RAPD) techniques were used for identification of DNA damage and coupled restriction enzyme digestion-random amplification (CRED-RA) techniques were used to detect the changed pattern of DNA methylation. According to the obtained results, picloram (5, 10, 20, and 40 mg/l) caused DNA damage profile changes (RAPDs) increasing, DNA hypomethylation and genomic template stability (GTS) decreasing. On the other hand, different concentrations of applied HA (2, 4, 6, 8, and 10%) reduced hazardous effects of picloram. The results of the experiment have explicitly indicated that HAs could be an alternative for reducing genetic damage in plants. In addition to the alleviate effects of humic acid on genetic damage, its epigenetic effect is hypomethylation.

Tordon is a widely used herbicide formulation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-amino-3,5,6-trichloropicolinic acid (picloram), and it is considered a toxic herbicide. The purposes of this work were to assess the feasibility of a microbial consortium inoculated in a lab-scale compartmentalized biobarrier, to remove these herbicides, and isolate, identify, and evaluate their predominant microbial constituents. Volumetric loading rates of herbicides ranging from 31.2 to 143.9 g m⁻³ day⁻¹, for 2,4-D, and 12.8 to 59.3 g m⁻³ day⁻¹for picloram were probed; however, the top operational limit of the biobarrier, detected by a decay in the removal efficiency, was not reached. At the highest loading rates probed, high average removal efficiencies of 2,4-D, 99.56 ± 0.44; picloram, 94.58 ± 2.62; and chemical oxygen demand (COD), 89.42 ± 3.68, were obtained. It was found that the lab-scale biofilm reactor efficiently removed both herbicides at dilution rates ranging from 0.92 to 4.23 day⁻¹, corresponding to hydraulic retention times from 1.087 to 0.236 days. On the other hand, few microbial strains able to degrade picloram are reported in the literature. In this work, three of the nine bacterial strains isolated cometabolically degrade picloram. They were identified as Hydrocarboniphaga sp., Tsukamurella sp., and Cupriavidus sp.

Slow-release formulations of the herbicide picloram (PCM, 4-amino-3,5,6-trichloropyridine-2-carboxylic acid) were designed based on its adsorption on pillared clays (pillared clays (PILCs)) for reducing the water-polluting risk derived from its use in conventional formulations. Fe–Al PILCs were synthesized by the reaction of Na⁺-montmorillonite (SWy-2) with base-hydrolyzed solutions of Fe and Al. The Fe/(Fe + Al) ratios used were 0.15 and 0.50. The PCM adsorption isotherms on Fe–Al PILCs were well fitted to Langmuir and Freundlich models. The PCM adsorption capacity depended on the Fe content in the PILCs. Slow-release formulations were prepared by enhanced adsorption of the herbicide from PCM-cyclodextrin (CD) complexes in solution. CDs were able to enhance up to 2.5-fold the solubility of PCM by the formation of inclusion complexes where the ring moiety of the herbicide was partially trapped within the CD cavity. Competitive adsorption of anions such as sulfate, phosphate, and chloride as well as the FTIR analysis of PCM-PILC complexes provided evidence of formation of inner sphere complexes of PCM-CD on Fe–Al PILCs. Release of the herbicide in a sandy soil was lower from Fe–Al PILC formulations relative to a PCM commercial formulation.

An analytical methodology using automatic thermal desorption (ATD) and GC/MS was developed for the determination of 28 pesticides of different chemical classes (dichlobenil, carbofuran, trifluralin, clopyralid, carbaryl, flazasulfuron, mecoprop-P, dicamba, 2,4-MCPA, dichlorprop, 2,4-D, triclopyr, cyprodinil, bromoxynil, fluroxypyr, oxadiazon, myclobutanil, buprofezin, picloram, trinexapac-p-ethyl, ioxynil, diflufenican, tebuconazole, bifenthrin, isoxaben, alphacypermethrin, fenoxaprop and tau-fluvalinate) commonly used in nonagricultural areas in atmospheric samples. This methodology was developed to evaluate the indoor and outdoor atmospheric contamination by nonagricultural pesticides. Pesticides were sampled passive sampling tubes containing Tenax® adsorbent. Since most of these pesticides are polar (clopyralid, mecoprop-P, dicamba, 2,4-MCPA, dichlorprop, 2,4-D, triclopyr, bromoxynil, fluroxypyr, picloram, trinexapac-p-ethyl and ioxynil), a derivatisation step is required. For this purpose, a silylation step using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MtBSTFA) was added before thermal desorption. This agent was chosen since it delivers very specific ions on electronic impact (m/z = M-57). This method was established with special consideration for optimal thermal desorption conditions (desorption temperature, desorb flow and duration; trap heating duration and flow; outlet split), linear ranges, limits of quantification and detection which varied from 0.005 to 10 ng and from 0.001 to 2.5 ng, respectively, for an uncertainty varied from 8 to 30 %. The method was applied in situ to the analysis of passive tubes exposed during herbicide application to an industrial site in east of France.