To clarify the effects of O3 on crop plants cultivated in Bangladesh, two Bangladeshi wheat cultivars (Sufi and Bijoy) were grown in plastic boxes filled with Andisol and exposed daily to charcoal-filtered air or O3 at 60 and 100 nl l-1 (10:00-17:00) from 13 March to 4 June 2008. The whole-plant dry mass and grain yield per plant of the two cultivars at the final harvest were significantly reduced by the exposure to O3. Although there was no significant effect of O3 on stomatal diffusive conductance to H2O of flag leaf, net photosynthetic rate of the leaf was significantly reduced by the exposure to O3. The sensitivity of growth, yield, yield components and leaf gas exchange rates to O3 was not significantly different between the two cultivars. The results obtained in the present study suggest that ambient levels of O3 may detrimentally affect wheat production in Bangladesh.

Bensulfuron-methyl sorption was studied in Andisol and Ultisol soils in view of their characteristic physical and chemical properties, presenting acidic pH and variable charge. Humic and fulvic acids (HA and FA) and humin (HUM) contributions were established. Sorption was studied by using two synthetic sorbents, an aluminum-silicate with iron oxide coverage and the same sorbent coated with humic acid. Freundlich model described Bensulfuron-methyl behavior in all sorbents (R2 0.969–0.998). Kf for soils (8.3–20.7 μg1−1/n mL1/n g−1) were higher than those reported in the literature. Organic matter, halloysite or kaolinite, and specific surface area contributed to the global process. The highest Kf for HA, FA and HUM were 539.5, 82.9, and 98.7 μg1−1/n mL1/n g−1. Model sorbents described the participation of variable charge materials with high adsorption capacity. The constant capacitance model was used to assess effects of Bensulfuron-methyl adsorption on the distribution of SOH, SOH2+ and SO− sites of sorbents. Organic matter, phyllosilicates, variable charge minerals and organo-mineral complexes contribute to bensulfuron-methyl sorption on volcanic ash-derived soils.

Extractions with mixtures of oxalic acid, ammonium oxalate, and ascorbic acid have been used to analyze trace metals that are occluded in Fe and Mn oxides in soil samples. In our experiments, the amount of Fe extracted from two Andisols decreased with increased extraction time using a mixture of 0.1 mol L⁻¹oxalic acid, 0.175 mol L⁻¹ammonium oxalate, and 0.19 mol L⁻¹ascorbic acid (OxAsc). Differential X-ray diffraction analysis showed the presence of Fe(II)C₂O₄ · 2H₂O in the residue after the extraction, and the amount of this precipitate increased with extraction time. These results indicate that the decrease in Fe extraction with time was caused by precipitation of Fe(II)C₂O₄ · 2H₂O. The amounts of some trace metals (Cd, Co, Mn, Ni, and Zn) extracted with OxAsc showed trends similar to that of Fe, whereas As, Cu, and Pb did not show this trend. A coprecipitation experiment showed that the concentrations of Cd, Co, Mn, Ni, and Zn markedly decreased after the precipitation of Fe(II)C₂O₄ · 2H₂O, whereas those of As, Cu, and Pb did not noticeably change. These results indicate that some trace metals coprecipitated with Fe(II)C₂O₄ · 2H₂O during extraction with OxAsc. This coprecipitation results in underestimation of oxide-occluded trace metals in soils; therefore, using mixtures of oxalic acid, ammonium oxalate, and ascorbic acid to extract some trace metals occluded in Fe and Mn oxides may yield erroneous data.

The behavior and possible contamination risk due to the presence of potentially harmful metals (PHM) were studied based on 2250 soil samples that were collected in a 5-year period (2013–2017) from the plain of Thessaly (prefectures of Karditsa, Trikala, and Larissa). The vertical distribution of metals was also investigated from sample profiles at three depths 0–30, 30–60, and 60–90cm. The soils of the sampling belong to four taxonomy soil orders that are dominant in the studied area (Alfisols, Inceptisols, Endisols, and Vertisols). In a novel approach, robust quadratic regression analysis on multiple variables was used to define prediction models of the concentrations of two metals: Fe which is an essential metal and the toxic Cd. Linear and quadratic regression formulae were estimated based on the iteratively reweighted least squares robust regression approach in an effort to eliminate the impact of the outliers. These formulae define how several soil properties affect the distribution of the considered metals in each soil order. The evaluation of the estimated regression equations based on the R² metric indicates that they constitute a useful, reliable, and valuable tool for managing, describing, and predicting the pollution in the studied area.

Cyclodextrins (CDs) can improve the apparent solubility and bioavailability of a variety of organic compounds through the formation of inclusion complexes; accordingly, they are suitable for application in innovative remediation technologies of contaminated soils. However, the different interactions in the tertiary system CD/contaminant/soil matrix can affect the bioavailability of the inclusion complex through the possible sorption of CD and CD complex in the soil matrix, as well as with the potential of the sorbed CD to form the complex, concurrent with the desorption processes. This work focuses in changes produced by three different CDs in soil sorption-desorption processes of chlorpyrifos (CPF), diazinon (DZN), and chlorothalonil (CTL), and their major degradation products, 3,5,6-trichloro-2-pyridinol (TCP), 2-isopropyl-6-methyl-4-pyrimidinol, and hydroxy-chlorothalonil (OH-CTL). Cyclodextrins used were β-cyclodextrin (β-CD), methyl-β-cyclodextrin (Mβ-CD), and 2-hydroxypropyl-β-cyclodextrin (HPβ-CD). The studied soils belong to the orders Andisol, Ultisol, and Mollisol with different organic matter contents, mineral composition, and pH. The apparent sorption constants were significantly lower for the three pesticides in the presence of all CDs. The highest displacement of sorption equilibria was produced by the influence of Mβ-CD, with the most pronounced effect for CPF, a pesticide strongly sorbed on soils. The same was obtained for TCP and OH-CTL, highlighting the need to assess the risk of generating higher levels of groundwater contamination with polar metabolites if degradation rates are not controlled. The highest desorption efficiency was obtained for the systems CPF-β-CD, DZN-Mβ-CD, and CTL-Mβ-CD. Since the degree of adsorption of the complex is relevant to obtain an increase in the bioavailability of the contaminant, a distribution coefficient for the complexed pesticide in all CD–soil–pesticide system was estimated by using the apparent sorption coefficients, the stability constant for each CD–pesticide complex, and the distribution coefficients of free pesticide.

The intensive use of insecticides such as chlorpyrifos (CPF) and diazinon (DZN) in the agricultural activities worldwide has produced contamination of soils and/or transport to non-target areas including their distribution to surface and groundwaters. Cyclodextrins (CDs) have been proposed as an alternative in remediation technologies based on the separation of contaminants from soils because they could allow a higher bioavailability for their degradation with a low environmental impact. In this work, the degradation pattern of CPF and DZN and the formation and dissipation of the major degradation products 3,5,6-trichloro-2-pyridinol (TCP) and 2-isopropyl-6-methyl-4-pyrimidinol (IMPH) was established in four agricultural volcanic and non-volcanic soils belonging to Andisol, Ultisol, and Mollisol orders. Both pesticides were highly adsorbed in these soils, consequently, with a greater probability of contaminating them. In contrast, the adsorption of their two main metabolites was low or null; therefore, they are potential groundwater contaminants. The degradation processes were studied in the natural and amended soils with β-cyclodextrin (β-CD) and methyl-β-cyclodextrin (Mβ-CD) for CPF and DZN, respectively. A slow degradation of CPF and DZN was obtained for volcanic soils with observable residues until the end of the incubation time (150–180 days). In Mollisols, the higher degradation rate of CPF was favored by the neutral to basic pH, and for DZN it was related to the lower adsorption and higher bioavailability. The amendment of soils with CDs produced slower degradation rates which led to a greater concentration of the compounds at the end of the incubation time. This effect was more pronounced for DZN. The exception was the Andisol, with no significant changes for both compounds regarding the unamended soil. No residues of TCP were observed for this soil in both conditions during the whole incubation time; nevertheless, the accumulation of TCP was significant in the Ultisol and Mollisols, but the concentrations were lower for the amended soils. The accumulation of IMPH was important in Mollisol amended soils; however, their residues were observed in the volcanic soils during the whole incubation period in the natural and amended soils. An important enhancement of the microbial activity occurred in the system β-CD/CPF in Mollisols, without a more effective degradation of the insecticide. The opposite effect was observed in the system Mβ-CD/DZN mainly in the oxidative activity in all soils. The higher degradation of DZN and IMPH in natural Mollisols was related to the higher hydrolytic and oxidative activities. The stability of the inclusion complexes formed could play an important role for explaining the results obtained with the amendments.

Sorption-desorption behavior of six pesticides and some degradation products was assessed on seven agricultural volcanic and nonvolcanic soils belonging to Andisol, Ultisol, Mollisol, and Alfisol orders. The global interpretation of sorption data was performed by principal component analysis. Results showed exceptionally high sorption of glyphosate and aminomethylphosphonic acid (AMPA) (the breakdown product) on volcanic soils (K f > 1500 μg¹ ⁻ ¹ / ⁿ mL¹ / ⁿ g⁻¹) related mainly to contents of amorphous aluminum oxides (Andisols) and crystalline minerals (Ultisols). The lower sorption on nonvolcanic soils was associated to low organic matter contents and lack of significant minerals. Metsulfuron-methyl and 3,5,6-trichloro-2-pyridinol (metabolite of chlorpyrifos) were weakly to substantially sorbed on Andisols and Ultisols, but the first one was not sorbed at pH > 6.4, including nonvolcanic soils. The metabolite of diazinon, 2-isopropyl-4-methyl-6-hydroxypyrimidine, was weakly sorbed on all soils (K f = 0.4 to 3.6 μg¹ ⁻ ¹ / ⁿ mL¹ / ⁿ g⁻¹). Acidic compounds would be lixiviated in Mollisols and Alfisols, but they could leach also in Andisols and Ultisols if they reach greater depths. Atrazine and deethylatrazine sorption was related to organic carbon content; therefore, they were weakly retained on nonvolcanic soils (K f = 0.7 to 2.2 μg¹ ⁻ ¹ / ⁿ mL¹ / ⁿ g⁻¹). Chlorpyrifos was highly sorbed on all soils reaching K OC values of >8000. Finally, the significant retention of chlorothalonil and diazinon on Mollisols and Alfisols in spite of their low OC contents showed the contribution of clay minerals in the sorption process.