Simón Navarro

University of Murcia, Murcia, Murcia, Spain

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Publications (66)121.49 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: In this study, the leaching of 14 substituted phenylurea herbicides (PUHs) through disturbed soil columns packed with three different soils was investigated in order to determine their potential for groundwater pollution. Simultaneously, a series of experiments were conducted to demonstrate the effect of four different organic wastes (composted sheep manure (CSM), composted pine bark (CPB), spent coffee grounds (SCG) and coir (CR)) on their mobility. All herbicides, except difenoxuron, showed medium/high leachability through the unamended soils. In general, addition of agro-industrial and composted organic wastes at a rate of 10 % (w/w) increased the adsorption of PUHs and decreased their mobility in the soil, reducing their leaching. In all cases, the groundwater ubiquity score (GUS) index was calculated for each herbicide on the basis of its persistence (as t ½) and mobility (as K OC). The results obtained point to the interest in the use of agro-industrial and composted organic wastes in reducing the risk of groundwater pollution by pesticide drainage.
    Environmental science and pollution research international. 10/2014;
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    ABSTRACT: 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.
    Journal of Environmental Science and Health Part B Pesticides Food Contaminants and Agricultural Wastes 08/2014; 49(8):601-608. · 1.10 Impact Factor
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    ABSTRACT: 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.
    Science of The Total Environment 06/2014; 493C:124-132. · 3.16 Impact Factor
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    ABSTRACT: Strategies for remediation of polluted soils are needed to accelerate the degradation and natural attenuation of pesticides. This study was conducted to assess the effect of solarization (S) and biosolarization (BS) during the summer season using organic wastes (composted sheep manure and sugar beet vinasse) for the bioremediation of soil containing residues of terbuthylazine and linuron. The results showed that both S and BS enhanced herbicide dissipation rates compared with the non-disinfected control, an effect which was attributed to the increased soil temperature and organic matter. Linuron showed similar behavior under S and BS conditions. However, terbuthylazine was degraded to a greater extent in the biosolarization experiment using sugar beet vinasse than in the both the solarization and biosolarization experiments using composted sheep manure treatments. The main organic intermediates detected during the degradation of terbuthylazine and linuron were identified, enabling the main steps of degradation to be proposed. The results confirm that both S and BS techniques can be considered as a remediation tools for polluted soils containing these herbicides.
    Journal of environmental management. 06/2014; 143C:106-112.
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    ABSTRACT: The photodegradation of indoxacarb, a broad spectrum foliar insecticide and spinosad, a natural insecticide containing two active ingredients, spinosyn A (major component) and spinosyn D (minor component), was studied in aqueous suspensions of binary (ZnO and TiO2) and ternary (Zn2TiO4 and ZnTiO3) oxides under artificial light (300-460 nm) irradiation. As expected, the influence of the semiconductor materials on the degradation of both was very significant in all cases. Photocatalytic experiments showed that the addition of semiconductors in tandem with Na2S2O8 as electron acceptor strongly improved the removal of indoxacarb and spinosad in water compared with the photolytic tests. The reaction rates significantly increased, especially for the ZnO/Na2S2O8 and TiO2/Na2S2O8 systems. The first-order equation (monophasic model) satisfactorily explained the disappearance process, although it offered no explanation for the small concentrations remaining in the process.
    Environmental Science and Pollution Research 05/2014; · 2.76 Impact Factor
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    ABSTRACT: The photocatalytic degradation of fipronil in drinking water was studied using zinc oxide (ZnO) and titanium dioxide (TiO2) as photocatalyst under irradiation by solar and artificial light. Photocatalytic experiments showed that the addition of semiconductors in tandem with the oxidant (Na2S2O8) strongly enhances the degradation rate of fipronil in comparisons carried out with photolytic experiments under artificial light. However, under solar irradiation, the photocatalytic decomposition of fipronil occurs very slowly. The residual levels of fipronil for ZnO/Na2S2O8 and TiO2/Na2S2O8 after 60 min of illumination at a constant volumetric rate of photon absorption in the photoreactor were 0.8 and 1.5 μg/L, respectively. The main intermediates (fipronil-sulfone, fipronil-sulfide, fipronil-desulfinyl and fipronil-carboxamide) detected during the degradation of fipronil in water were identified.
    Journal of the Taiwan Institute of Chemical Engineers 05/2014; 45(3):981–988. · 2.64 Impact Factor
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    ABSTRACT: In the present work, potential groundwater pollution by methabenzthiazuron (MTBU) and the effect of three different amendments (composted sheep manure, composted pine bark and spent coffee grounds) on its mobility were investigated under laboratory conditions. The efficiency of ZnO and TiO2 suspensions in the photocatalytic degradation of MTBU in leaching water was also investigated. The relative and cumulative breakthrough curves were obtained from disturbed soil columns. The presence and/or addition of organic matter drastically reduced the movement of the herbicide. On other hand, photocatalytic experiments showed that the addition of ZnO and TiO2 strongly enhances the degradation rate of this herbicide compared with the results of photolytic experiments under artificial light. ZnO appeared to be more effective in MTBU oxidation than TiO2. The results obtained point to the interest of using organic wastes and heterogeneous photocatalysis for reducing the pollution of groundwater by pesticide drainage.
    Journal of environmental sciences (China). 04/2014; 26(4):757-764.
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    Journal of Environmental Management. 01/2014; 143:106–112.
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    ABSTRACT: Sulfonylurea herbicides (SUHs) are a family of environmentally compatible herbicides but their high water solubility, moderate to high mobility through the soil profile, and slow degradation rate make them potential contaminants of groundwater as demonstrated in this paper. The photodegradation of a mixture of 30 SUHs in aqueous suspensions of semiconductor materials (ZnO and TiO2 in tandem with Na2S2O8 as electron acceptor) under artificial light (300-460 nm) irradiation was investigated. As expected, the influence of both semiconductors on the degradation of SUHs was very significant in all cases. Photocatalytic experiments show that the addition of photocatalyst, especially for the ZnO/Na2S2O8 system, greatly improves the removal of SUHs compared with photolytic tests, significantly increasing the reaction rates. The first-order equation (monophasic model) satisfactorily explained the disappearance process although it overlooked small residues remaining late in the process. These residues are important from an environmental point of view and the Hoerl function (biphasic model), was a better predicter of the results obtained. In our conditions, the average time required for 90% degradation was about 3 and 30 min for ZnO/Na2S2O8 and TiO2/Na2S2O8 systems, respectively.
    Journal of Environmental Management 10/2013; 130C:361-368. · 3.06 Impact Factor
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    ABSTRACT: The photocatalyzed degradation of the biocides chlorotoluron, diuron, fluometuron, isoproturon and linuron (substituted phenylurea herbicides) was investigated in aqueous suspensions of ZnO, TiO(2), WO(3), SnO(2) 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/Na(2)S(2)O(8). 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.
    Chemosphere 01/2013; · 3.14 Impact Factor
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    ABSTRACT: The photocatalytic degradation of sixteen substituted phenylurea herbicides (PUHs) in pure water has been studied using zinc oxide (ZnO) and titanium dioxide (TiO(2)) as photocatalyst under artificial light irradiation. Photocatalytic experiments showed that the addition of these chalcogenide oxides in tandem with the oxidant (Na(2)S(2)O(8)) strongly enhances the degradation rate of these compounds in comparison with those carried out with ZnO and TiO(2) alone and photolytic tests. Comparison of catalysts showed that ZnO is the most efficient for the removal of such herbicides in optimal conditions and at constant volumetric rate of photon absorption in the photoreactor. Thus, the complete disappearance of all the studied compounds was achieved after 20min of illumination in the ZnO/Na(2)S(2)O(8) system. The main photocatalytic intermediates detected during the degradation of PUHs were identified. The probable photodegradation pathways were proposed and discussed. The main steps involved: N-demethylation of the N,N-dimethylurea-substituted compounds followed of N-demethylation and N-demethoxylation of the N-methoxy-N-methyl-substituted ureas and hydroxylation of aromatic rings and their aliphatic side-chains of both, parent compounds and intermediates.
    Journal of hazardous materials 12/2012; 244-245C:370-379. · 4.14 Impact Factor
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    ABSTRACT: A sensitive method for the simultaneous determination of 30 sulfonylurea herbicides in tap and leaching waters has been developed. Liquid chromatography tandem-mass spectrometry (LC-MS(2)) in electrospray ionization positive mode was used for the separation, identification and quantification of these compounds. The procedure involves a preconcentration step based on solid-phase extraction with a silica-based bonded C(18) cartridge (Sep-Pak Plus) and a N-vinyl-pyrrolidone polymer cartridge (Oasis HLB). The best results were obtained with Oasis HLB using methanol as elution solvent. Average recoveries of 30 analytes from water samples were in the range of 79-115% with a relative standard deviation of <6.1%. The limits of quantification (LOQs) obtained in tap and leaching water samples were in the range of 0.1-5.9 and 0.4-5.8ngL(-1), respectively. The proposed method was used to determine sulfonylurea herbicide levels in leaching water samples taken from three lysimeters located in an experimental greenhouse.
    Talanta 11/2012; 101:273-82. · 3.50 Impact Factor
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    ABSTRACT: A sensitive multiresidue method for the simultaneous determination of sixteen phenylurea herbicides and their main metabolites in amended soils has been developed. Liquid chromatography tandem-mass spectrometry (LC-MS²) in electrospray ionization positive mode was used for the separation, identification and quantification of these compounds. The procedure involves initial single phase extraction of soil sample with acetonitrile by sonication, followed by liquid-liquid partitioning formed by addition of NaCl. The average recovery by the LC-MS² method obtained for these compounds varied from 76.2 to 107.9% with a relative standard deviation ranging from 2.1 to 5.8%. The method presents good linearity (R²>0.99) over the range assayed 10-1000 μg L⁻¹ (except N-phenylurea 50-1000 μg L⁻¹). The detection limits for the compounds studied varied from 0.1 to 9.0 ng g⁻¹.
    Journal of Chromatography A 08/2012; 1257:81-8. · 4.61 Impact Factor
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    ABSTRACT: In this study, the potential groundwater pollution of 12 substituted phenylurea herbicides (chlorbromuron, chlorotoluron, diuron, fenuron, fluometuron, isoproturon, linuron, metobromuron, metoxuron, monolinuron, Monuron, and neburon) was investigated under laboratory conditions. For this purpose, leaching studies were conducted using disturbed soil columns filled with two different agricultural soils, one hypercalcic calcisol (HC) and the other endoleptic phaeozem (EP). In the case of the HC, all of the studied herbicides were found in leachates, while for the EP only, chlorbromuron, chlorotoluron, isoproturon, monolinuron, and, especially, fenuron were recovered. For both soils, the groundwater ubiquity score (GUS) index was calculated for each herbicide on the basis of its persistence (as t(1/2)) and mobility (as K(OC)). The half-lives obtained were markedly higher in the EP (217-518 days) than in the HC (71-178 days). As a consequence, higher values of GUS indexes were observed for EP. The ratio of the GUS between the EP and the HC was about 1.3.
    Journal of Agricultural and Food Chemistry 05/2012; 60(21):5279-86. · 3.11 Impact Factor
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    ABSTRACT: In the present study, the photocatalytic degradation of five sulfonylurea herbicides (chlorsulfuron, flazasulfuron, nicosulfuron, sulfosulfuron and triasulfuron) has been investigated in aqueous suspensions of zinc oxide (ZnO), tungsten (VI) oxide (WO(3)), tin (IV) oxide (SnO(2)) and zinc sulfide (ZnS) at pilot plant scale under natural sunlight. Photocatalytic experiments, especially those involving ZnO photocatalysis, showed that the addition of semiconductors in tandem with the oxidant (Na(2)S(2)O(8)) strongly enhances the degradation rate of the herbicides in comparisons carried out with photolytic tests. The degradation of the herbicides follows a first order kinetics according to the Langmuir-Hinshelwood model. In our conditions, the amount of time required for 50% of the initial pesticide concentration to dissipate (t(½)) ranged from 8 to 27 min (t(30W)=0.3-1.2 min) for sulfosulfuron and chlorsulfuron, respectively in the ZnO/Na(2)S(2)O(8) system. None of the studied herbicides was found after 120 min of illumination (except chlorsulfuron, 0.2 μg L(-1)).
    Chemosphere 02/2012; 87(8):954-61. · 3.14 Impact Factor
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    ABSTRACT: 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.
    Chemosphere 08/2011; 85(8):1375-82. · 3.14 Impact Factor
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    ABSTRACT: In this work, a rapid and sensitive analytical multiresidue method has been developed for the simultaneous determination of 48 pesticides and 19 metabolites in waters (tap, leaching and sewage), using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with triple quadrupole in selected reaction monitoring (SRM) mode. The procedure involves initial single phase extraction of samples with acetonitrile by sonication, followed by liquid-liquid partition aided by "salting out" process using NaCl. Matrix influence on recoveries was evaluated for the three waters. More than 50% of the compound presented very low signal suppression. The method presents good linearity over the range assayed 10-500 μg L(-1) and the most frequent detection limits was 0.05 ng mL(-1). The average recovery by the LC-MS/MS method obtained for these compounds varied from 74.6 to 111.2% with a relative standard deviation between 2.5 and 8.9%. The proposed method was used to determine pesticides levels in leaching water samples from 5 lysimeters from an experimental greenhouse located in Murcia.
    Talanta 08/2011; 85(2):975-82. · 3.50 Impact Factor
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    ABSTRACT: The efficiency of ZnO and TiO(2) suspensions in the photocatalytic degradation of two fungicides (cyprodinil and fludioxonil) in leaching water was investigated. The experiments were carried out at pilot plant scale using compound parabolic collectors under natural sunlight. The blank experiments for both irradiated compounds solutions showed that both oxides strongly enhanced the removal of the fungicides. The addition of an oxidant (Na(2)S(2)O(8)) to the ZnO or TiO(2) increased the rate of photooxidation. The degradation of cyprodinil and fludioxonil followed first order kinetics according to the Langmuir-Hinshelwood model. Complete degradation of both fungicides was achieved within 4 h (t(30W)=18 min) when treated with illuminated ZnO. The disappearance time (DT(75)), when referred to the normalized illumination time (t(30W)), was lower than 40 and 550 min (t(30W)=2 and 40 min) for both fungicides using ZnO or TiO(2), respectively. ZnO appeared to be more effective in cyprodinil and fludioxonil oxidation than TiO(2) probably due to its nonstoichiometry.
    Chemosphere 08/2011; 85(8):1262-8. · 3.14 Impact Factor
  • Simón Navarro, Nuria Vela, Ginés Navarro
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    ABSTRACT: The fate and behaviour of five sterol biosynthesis-inhibiting (SBI) fungicides (cyproconazole, diniconazole, epoxiconazole, flutriafol, and tebuconazole) during different stages of beermaking (malting, mashing and boiling) on laboratory scale was assessed. A significant correlation (r > 0.93, P < 0.05) was observed between amounts removed after steeping and the octanol/water partition coefficient (as log KOW) of the fungicides. Although in smaller proportion than steeping, germination and kilning were significant stages on the fungicide dissipation. The carryover after malting ranged from 30% to 40% of the initial residues on barley. After mashing, a substantial fraction was removed with the spent grains in all cases (36–49%) whereas a weak fall after boiling was observed for the fungicide residues (⩽2.5%). The calculated transfer factors (TFs) do not indicate a concentration effect after processing in any case (TFs < 1). Finally, after the storage of malt and spent grains (3 months) a slow fall in the residual content was observed.
    Food Chemistry. 01/2011; 124(1):278-284.
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    ABSTRACT: 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.
    Journal of hazardous materials 01/2011; 187(1-3):206-12. · 4.14 Impact Factor

Publication Stats

370 Citations
121.49 Total Impact Points

Institutions

  • 1980–2014
    • University of Murcia
      • • Department of Agricultural Chemistry, Geology and Pedology
      • • Facultad de Química
      Murcia, Murcia, Spain
  • 2011–2013
    • Instituto Murciano de Investigación y Desarrollo Agrario y Alimentario
      Murcia, Murcia, Spain