Effect of positional isomerism on the abiotic degradation of pesticides: Case of m- and p-imazamethabenz-methyl

The effect of positional isomerism on chemical and photochemical degradations of the Imazamethabenz-methyl (IMBM), a pesticide of the imidazolinone family, has been studied. IMBM is proposed in the form of a mixture of the two positional isomers: meta and para. The development of an effective HPLC method (resolution factor R=1.3) allows us to follow either the abiotic disappearance of the meta and para IMBM and the formation of their breakdown products. The abiotic degradation studies include the chemical hydrolysis, as well as the direct and the indirect photodecomposition. We used TiO(2), a well-known initiator of hydroxyl radicals, to highlight the role of *OH in the indirect photodegradation. This work confirms the different behaviours of positional isomers in the environment. Indeed the chemical or direct photochemical degradation is faster for the meta isomer than for the para. Whereas, concerning IMBM, there is not any prevalent influence of this type of isomerism on the indirect photochemical degradation. The degradation products were tentatively identified by LC-MS, NMR and IR and a degradation pathway was proposed.     

Leachable 226Ra in Philippine phosphogypsum and its implication in groundwater contamination in Isabel, Leyte, Philippines

Phosphogypsum (PG), the major waste material in phosphate fertilizer processing, has been known to contain enhanced levels of naturally-occurring radionuclides especially (226)Ra.The lack of radioactivity data regarding Philippine phosphogypsum and its environmental behavior in the Philippine setting has brought concern on possible contamination of groundwater beneath the phosphogypsum ponds in Isabel, Leyte, Philippines. The radioactivity of Philippine phosphogypsum was determined and the leaching of (226)Ra from phosphogypsum and through local soil was quantified. Level of (226)Ra in groundwater samples in Isabel, Leyte, Philippines was also quantified to address the primary concern. It was found that the (226)Ra activity in Philippine phosphogypsum is distributed in a wide range from 91.5 to 935 Bq/kg. As much as 5% of (226)Ra can be leached from Philippine PG with deionized water. In vitro soil leach experiments suggest that the soil in the phosphate fertilizer plant area would be able to deter the intrusion of (226)Ra into the water table. Compared to reported values of natural groundwater levels of (226)Ra, the concentration of this radionuclide in Isabel, Leyte groundwater suggest that there is no (226)Ra intrusion brought about by the presence of phosphogypsum ponds in the area.     

Spatial distribution and enteroparasite contamination in peridomiciliar soil and water in the Apucaraninha Indigenous Land,southern Brazil

The prevalence and distribution of soil and water samples contaminated with enteroparasites of humans and animals with zoonotic potential (EHAZP) in Apucaraninha Indigenous Land (AIL), southern Brazil, was evaluated. An environmental survey was conducted to evaluate the presence of parasitic forms in peridomiciliary soil and associated variables. Soil samples were collected from 40/293 domiciles (10 domiciles per season), from November 2010 to June 2011, and evaluated by modified methods of Faust et al. and Lutz. Analyses of water from seven consumption sites were also performed. The overall prevalence of soil samples contaminated by EHAZP was 23.8 %. The most prevalent parasitic forms were cyst of Entamoeba spp. and eggs of Ascaris spp. The highest prevalence of contaminated soil samples was observed in winter (31 %). The probability map obtained with geostatistical analyses showed an average of 47 % soil contamination at a distance of approximately 140 m. The parasitological analysis of water did not detect Giardia spp. or Cryptosporidium spp. and showed that all collection points were within the standards of the Brazilian law. However, the microbiological analysis showed the presence of Escherichia coli in 6/7 sampled points. Despite the low level of contamination by EHAZP in peridomiciliar soil and the absence of pathogenic protozoa in water, the AIL soil and water (due to the presence of fecal coliforms) are potential sources of infection for the population, indicating the need for improvements in sanitation and water treatment, in addition periodic treatment of the population with antiparasitic.     

Mineralization and Transfer Processes of <Superscript>14</Superscript>C-labeled Pesticides in Outdoor Lysimeters

A recently designed two-chamber-lysimeter-test-system allows the detailed investigation of degradation, transport and transfer processes of ¹⁴C-labeled substances in soil–plant–atmosphere-systems under outdoor conditions. With this test system it is feasible to distinguish between ¹⁴C-emissions from soil surfaces and ¹⁴C-emissions from plant surfaces in soil monoliths under real environmental conditions. Special soil humidity sensors allow the measurement of soil water content near to the soil surface, in 1 and 5 cm depth. The behavior of organic chemicals can be followed for a whole vegetation period and a mass balance for the applied chemical can be established. Some selected results of the herbicides isoproturon and glyphosate – using the two-chamber-lysimeter-test-system – are presented to demonstrate its applicability for the identification and quantification of the processes that govern pesticide behavior in soil–plant-systems. Mineralization of ¹⁴C-isoproturon was very different in four different soils; the mineralization capacity of the soils ranged from 2 to 60%. Leaching of isoproturon in general was very low, but depending on the soil type and environmental conditions isoproturon and its metabolites could be leached via preferential flow, especially shortly after application. For the herbicide ¹⁴C-glyphosate no accumulation of residues in the soil and no leaching of the residues to deeper soil layers could be observed after three applications. Glyphosate was rapidly degraded to AMPA in the soil. Glyphosate and AMPA were accumulated in soy bean nodules.     

Reactivity of the plant growth regulator paclobutrazol (cultar) with two tropical soils of the northeast semiarid region of Brazil

The reactivity of paclobutrazol (PBZ, a plant growth retardant) with a Yellow Ultisol and a Vertisol from the semiarid northeast region of Brazil was evaluated through batch sorption experiments and modeling. Although not instantaneous, the sorption kinetic of PBZ (pure and formulated) was fast (a few hours) in both soils. The sorption kinetics were well described by a second-order (dS(t)/dt=k(2)(S(e2)-S(t))(2)) but not by a first-order model. The sorption isotherms were found to be linear and the calculated K(D) values were 8.8 +/- 0.11 and 7.4 +/- 0.2 L kg(-1) for pure PBZ in the Ultisol and the Vertisol, respectively. The corresponding K(OC) values were 1275 +/- 34 (logK(OC) = 3.11) and 1156 +/- 49 (logK(OC) = 3.06) L kg(-1), respectively. Considering the very different texture of the two soils and the similar K(OC) values determined, these results showed that in both soils, the sorption of PBZ is dominantly controlled by organic matter, although some interactions of PBZ with iron oxides (goethite) were observed in the Ultisol. Based on these sorption parameters a low leachability potential of PBZ in soils is anticipated, as they correspond to a groundwater ubiquity score (GUS) ranging from 2.0 to 2.7, i.e., moderately to not mobile, in contradiction with the actual groundwater situation in Brazil. This work stresses the need to evaluate and predict the risk associated with aquifer contamination by this widely used plant growth regulator.     

Geochemistry of high arsenic groundwater in Chia-Nan plain, Southwestern Taiwan: possible sources and reactive transport of arsenic

Major ion, trace element, and stable isotope analyses were performed on groundwater samples collected during November 2005 and 2006 in Chia-Nan plain of southwestern Taiwan to examine As mobilization in aquifers. The high concentrations of As, Fe and Mn in the groundwater is consistent with low Eh values (under moderately reduced state). Moreover, the observed Na/Cl and SO(4)/Cl molar ratios in groundwater demonstrate the influence of seawater intrusion. Seawater intrusion could provide required electron acceptors (i.e., SO(4)) for bacterial sulfate reduction and promote reducing conditions that are favorable for As mobilization. The concurrent increases in the concentrations of Fe and Mn from 2005 to 2006 may be caused by bacterial Fe(III) and Mn(IV) reduction. Geochemical modeling demonstrate that As(III) is the dominant As species and the presence of Fe-bearing carbonates, sulfides, and oxide phases may locally act as potential sinks for As. Mud volcano fluids were also collected and analyzed to assess the possible source of As in the Chia-Nan plain groundwater. The oxygen and hydrogen isotopic signatures indicate that the As-rich mud volcano fluids may have been modified by chemical exchange with (18)O-rich crustal rocks and possibly originated from mixing of deep brines with circulating meteoric water. Thus As in the Chia-Nan plain groundwater may have been evolved from deep crustal fluids or rock sources. The hydrogeochemistry and widespread As enrichment in groundwater of Chia-Nan plain result from multiple processes, e.g., de-watering of deep crustal fluids, seawater intrusion, and biogeochemical cycling of Fe, As, and S in alluvial sediments.     

Hydrogeochemical behavior of arsenic-enriched groundwater in the deltaic environment: comparison between two study sites in West Bengal, India

Groundwaters have been collected from deltaic areas of West Bengal (Chakdaha and Baruipur blocks) to record their hydrogeochemical characteristics, and to verify the mechanism of arsenic (As) release. The data reveals that shallow (<70 m) groundwaters in both areas are of Ca-Mg-HCO(3) type; however deeper (>70 m) groundwaters in Baruipur areas are slightly enriched with Na, Cl and SO(4), indicating possible saline water intrusion. The groundwater is anoxic (mean Eh: -124 and -131 mV) with high levels of As (mean: 116 and 293 mug/L), Fe (mean: 4.74 and 3.83 mg/L), PO(4) (mean: 3.73 and 3.21 mg/L) and Mn (mean: 0.37 and 0.49 mg/L), respectively for Chakdaha and Baruipur areas. The observed values of As and bicarbonate (mean: 409 and 499 mg/L) in the shallow aquifer are indicative of redox processes (e.g., oxidation of organic matter) favouring the release of As. Moreover, the presence of DOC in the shallow aquifer suggests that organic matter is young and reactive, and may actively engage in redox driven processes. Our study further confirms that both Fe- and Mn-reduction processes are the dominant mechanisms for As release in these groundwaters.