Nuria Vela

Photocatalytic degradation of eight pesticides in leaching water by use of ZnO under natural sunlight.

Photodegradation of eight pesticides in leaching water at pilot plant scale using the tandem ZnO/Na(2)S(2)O(8) as photosensitizer/oxidant and compound parabolic collectors under natural sunlight is reported. The pesticides, habitually used on pepper culture and belonging to different chemical groups were azoxyxtrobin, kresoxim-methyl, hexaconazole, tebuconazole, triadimenol, and pyrimethanil (fungicides), primicarb (insecticide), and propyzamide (herbicide). As expected, the influence of the semiconductor used at 150 mg L(-1) on the degradation of pesticides was very significant in all cases. Photocatalytic experiments show that the addition of photosensitizer strongly improves the elimination of pesticides in comparison with photolytic tests; significantly increasing the reaction rates. The use of Na(2)S(2)O(8) implies a significant reduction in treatment time showing a quicker reaction time than ZnO alone. On the contrary, the addition of H(2)O(2) into illuminated ZnO suspensions does not improve the rate of photooxidation. The disappearance of the pesticides followed first-order kinetics according to Langmuir-Hinshelwood model and complete degradation occurs from 60 to 120 min. The disappearance time (DT(75)), referred to the normalized illumination time (t(30 W)) was lower than 3 min in all cases.

Assessment of agro-industrial and composted organic wastes for reducing the potential leaching of triazine herbicide residues through the soil

In this study, we examined the effect of four different organic wastes--composted sheep manure (CSM), spent coffee grounds (SCG), composted pine bark (CPB) and coir (CR)--on the sorption, persistence and mobility of eight symmetrical and two asymmetrical-triazine herbicides: atrazine, propazine, simazine, terbuthylazine (chlorotriazines), prometon (methoxytriazine), prometryn, simetryn, terbutryn (methylthiotriazines), metamitron and metribuzin (triazinones). The downward movement of herbicides was monitored using disturbed soil columns packed with a clay loam soil (Hipercalcic calcisol) under laboratory conditions. For unamended and amended soils, the groundwater ubiquity score (GUS) was calculated for each herbicide on the basis of its persistence (as t½) and mobility (as KOC). All herbicides showed medium/high leachability through the unamended soils. The addition of agro-industrial and composted organic wastes at a rate of 10% (w:w) strongly decreased the mobility of herbicides. Sorption coefficients normalized to the total soil organic carbon (KOC) increased in the amended soils. These results suggest that used organic wastes could be used to enhance the retention and reduce the mobility of the studied herbicides in soil.

Use of farming and agro-industrial wastes as versatile barriers in reducing pesticide leaching through soil columns.

Increased interest has been recently focused on assessing the influence of the addition of organic wastes related to movement of pesticides in soils of low organic matter (OM) content. This study reports the effect of two different amendments, animal manure (composted sheep manure) and agro-industrial waste (spent coffee grounds) on the mobility of 10 pesticides commonly used for pepper protection on a clay-loam soil (OM = 0.22%). The tested compounds were azoxystrobin, cyprodinil, fludioxonil, hexaconazole, kresoxim-methyl, pyrimethanil, tebuconazole, and triadimenol (fungicides), pirimicarb (insecticide), and propyzamide (herbicide). Breakthrough curves were obtained from disturbed soil columns. Cumulative curves obtained from unamended soil show a leaching of all pesticides although in different proportions (12-65% of the total mass of compound applied), showing triadimenol and pirimicarb the higher leachability. Significant correlation (r = 0.93, p<0.01) was found between the observed and bibliographical values of GUS index. The addition of the amendments used drastically reduced the movement of the studied pesticides. Only two pesticides were found in leachates from amended soils, pyrimethanil (<1%) for both, and pirimicarb (44%) in the soil amended with spent coffee grounds. A decrease in pesticide leaching was observed with the increase in dissolved organic matter (DOM) of leachates. The results obtained point to the interest in the use of organic wastes in reducing the pollution of groundwater by pesticide drainage.

Photocatalytic degradation of substituted phenylurea herbicides in aqueous semiconductor suspensions exposed to solar energy

The photocatalyzed degradation of the biocides chlorotoluron, diuron, fluometuron, isoproturon and linuron (substituted phenylurea herbicides) was investigated in aqueous suspensions of ZnO, TiO2, WO3, SnO2 and ZnS at pilot plant scale under natural sunlight. Comparison of the five catalysts showed that ZnO is the most effective for catalyzing the removal of all the compounds studied. The primary degradation of the herbicides followed a pseudo-first order kinetics. In our conditions, the time required for 90% degradation ranged from 23 to 47min for isoproturon and linuron, respectively, when using the tandem ZnO/Na2S2O8. Eight transformation products were identified by HPLC-MS(2) during the experiments, although at the end of the photoperiod (240min), their concentrations were below detection limits. Based on derivative identification, the proposed metabolic pathways would involve N-demethylation and N-demethoxylation of the N-methoxy-N-methyl substituted ureas and N-demethylation of the N,N-dimethylurea-substituted compounds.

Behavior of Triazole Fungicide Residues from Barley to Beer

Triazole fungicides (TZFs) are sterol biosynthesis inhibitors (SBIs). The mechanism of action of the azole (triazole and imidazole) fungicides lies in their ability to interfere with the biosynthesis of fungal biosteroids and inhibit ergosterol biosynthesis. They are classified as demethylation inhibitors (DMIs), the most important SBIs. Based on the current information, an overview on the behavior and fate of TZF residues during malting and brewing stages (mashing, boiling, and fermentation) is reviewed. In the first phase, TZF residues may remain into the malt. Later, TZF residues can be transferred from the malt to sweet wort and beer inducing in some cases of stuck/sluggish fermentation for both lager and ale beer. As a consequence, some organoleptic properties of the beer may be altered. Therefore, studies to examine the behavior of TZFs during beer brewing are necessary to assess the beer quality and perform a dietary risk assessment.

Use of different organic wastes in reducing the potential leaching of propanil, isoxaben, cadusafos and pencycuron through the soil

In this study, we examined the effect of four different organic wastes (OW)—composted sheep manure (CSM), spent coffee grounds (SCG), composted pine bark (CPB) and coir (CR)—on the potential groundwater pollution of propanil and isoxaben (herbicides), cadusafos (insecticide) and pencycuron (fungicide) under laboratory conditions. For this purpose, leaching studies were conducted using disturbed soil columns filled with a clay loam soil (Hipercalcic calcisol). The addition of organic matter (OM) drastically reduced the movement of the studied pesticides. The results obtained point to the interest in the use of agro-industrial and composted OW in reducing the groundwater pollution by pesticide drainage.

Valorization of Organic Wastes to Reduce the Movement of Priority Substances Through a Semiarid Soil

In this work, we examined the effect of two different organic wastes, composted sheep manure and coir, on the sorption, persistence, and mobility of three pesticides (alachlor, chlorfenvinphos, and chlorpyrifos) included as priority substances in European Directive 2013/39/EU. With this aim, leaching studies were conducted using disturbed soil columns filled with a typical agricultural soil (hipercalcic calcisol) from a semiarid area (southeastern Spain) to determine their potential for groundwater pollution. The three compounds were found in leachates of unamended soil although in different proportions: 53% (alachlor), 9% (chlorfenvinphos), and 6% (chlorpiryfos). The addition of organic wastes significantly increased the sorption of the studied pesticides. As a consequence, the half-lives of the studied pesticides were higher in amended than in unamended soils. A marked reduction of the amount recovered in leachates was observed in the amended soils, except for chlorpiryfos, whose recoveries barely changed. According to their potential groundwater pollution calculated as the groundwater ubiquity score (GUS) index, alachlor and chlorfenvinphos show medium leachability while chlorpiryfos is unlikely to leach.