Maria Vittoria Pinna

Sorption behavior of sulfamethazine on unamended and manure-amended soils and short-term impact on soil microbial community

In this study we investigated the sorption of sulfamethazine (SMZ) in two soils with different physico-chemical properties and the sulfonamide short-term influence on the microbial community structure and function. The presence of manure increased the SMZ sorption, the uppermost level being measured on soil with the lower pH and the higher manure content allowed by the Italian regulation. The sulfonamide desorption was hysteretic on both soils. SMZ addition to soil at the concentration of 53.6 μg/g had a significant short-term negative impact on readily culturable bacteria, potential metabolic activity (Biolog CLPP) and soil enzyme activity. Moreover, a shift of the culturable microbial populations towards a lower bacteria/fungi ratio was observed after SMZ addition. Despite the observed SMZ effects disappeared almost completely after 7 day, structural changes of microbial communities were still present in SMZ-treated soils. The results presented are remarkable since previous studies addressing the SMZ impact on soil microbial parameters failed to highlight any significant effect of the sulfonamide on microbial abundance and diversity.

Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems

The photodegradation of two quinolinecarboxylic herbicides, 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and 3,7-dichloroquinoline-8-carboxylic acid (QCl), was studied in aqueous solution at different irradiation wavelengths. The effect of sunlight irradiation was investigated also in the presence of titanium dioxide (TiO(2)). UV irradiation degraded rapidly QMe affording 7-chloro-3-methylquinoline (MeQ) through a decarboxylation reaction. The reaction rate was lower in the presence of dissolved organic carbon (DOC) because of the adsorption of the herbicide on the organic components. Instead, QCl was stable under both UV light and sunlight irradiation. The irradiation of QMe or QCl solutions with simulated sunlight in the presence of TiO(2) produced the complete mineralization of the two herbicides.

Gold(III) derivatives with C(4)-aurated 1-phenylpyrazole

The reaction of 1-phenylpyrazole (HL), with gold(III) chloride has been studied. Besides a 1:1 adduct [Au(HL)Cl 3 ] 1 , where the ligand is bonded through the nitrogen atom, several C(4) aurated species have been isolated. Thus treatment of [AuCl 3 ] 2 with HL in dichloromethane solution affords a complex, [Au(L)Cl 2 . HCl] n , 2 , where the gold atom is bonded to the 4-carbon atom of the pyrazole ligand. Deprotonation of complex 2 by means of the not coordinating base 1,8-bis(dimethylamino)naphthalene (proton sponge), B, affords the salt [BH][Au(L)Cl 3 ], 3 , whereas reaction of 2 with 3,5-Me 2 py and PPh 3 (molar ratio 1:2) gives the neutral species trans -[Au(L)(3,5-Me 2 py)Cl 2 ], 4 , and cis -[Au(L)(PPh 3 )Cl 2 ], 5 , respectively. The structure of compound 4 solved by X-ray diffraction, unambiguously shows the anionic ligand L bonded to the gold ion through the C4 atom. Alternatively, compounds 4 and 5 can be obtained in two steps, i.e. deprotonation of 2 with NaOH to give [Au(L)Cl 2 ] n , 6 , and reaction of 6 with 3,5-Me 2 py and PPh 3 , respectively. The new species were characterized by elemental analyses, conductivity measurements, IR, NMR and FAB-MS spectroscopy.

Effect of Undesalted Dissolved Organic Matter from Composts on Persistence, Adsorption, and Mobility of Cyhalofop Herbicide in Soils

The effect of undesalted dissolved organic matter (DOM) extracted from composts on the degradation, adsorption, and mobility of cyhalofop herbicide in soils was studied. A paddy-field sediment poor in organic matter (OM), an OM-rich forest soil, and DOM from agroindustrial or municipal waste compost were used. DOM increased the cyhalofop-acid but not the cyhalofop-butyl solubility in water. The degradation of cyhalofop-butyl in the sediment was slow, giving cyhalofop-acid as the only metabolite, whereas in forest soil, the process was faster, and three byproducts were detected. Soil pretreatment with DOM did not modify the degradation pattern but only reduced the adsorption of cyhalofop-butyl by soil, whereas it increased the adsorption of cyhalofop-acid. Among the cationic components of DOM solutions, the potassium ion seems to be related to the increased adsorption of the cyhalofop-acid in both OM-poor and OM-rich soils, yielding reversible complexes with the former and favoring hydrophobic interactions with the latter.

Soil sorption and leaching of active ingredients of Lumax ® under mineral or organic fertilization

The study describes the soil sorption of the herbicide Lumax®, composed of S-metolachlor (MTC), terbuthylazine (TBZ), and mesotrione (MST), as influenced by mineral and organic fertilizers. The investigation was performed on a sandy soil of an agricultural area designated as a Nitrate Vulnerable Zone, where mineral and organic fertilizers were applied for many years. Two organic fertilizers, cattle manure and slurry, respectively, and a mineral fertilizer with a nitrification inhibitor, Entec®, were compared. According to the experiments, performed with a batch method, the sorption conformed to Freundlich model. The extent of sorption of Lumax® ingredients was closely related to their octanol-water partition coefficient Kow. The respective desorption was hysteretic. Leaching trials were carried out by using water or solutions of DOM or Entec® as the eluants. Only the elution with the mineral fertilizer promoted the leaching of Lumax® active ingredients.

Hydrolysis and adsorption of cyhalofop-butyl and cyhalofop-acid on soil colloids.

A study was undertaken to investigate the stability of cyhalofop-butyl (2 R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), an aryloxyphenoxy-propionic herbicide, at different pH values. The hydrolysis of CyB was faster in nonsterile than in sterile water. In sterile medium, CyB degraded only to (2 R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA), whereas in nonsterile water, also the metabolites (2 R)-2-[4-(4-carbamoyl-2-fluorophenoxy)phenoxy]propanoic acid (CyAA) and (2 R)-2-[4-(4-carboxyl-2-fluorophenoxy)phenoxy]propanoic acid (CyD) were detected. The adsorption of CyB onto clays, iron oxide, and dissolved organic matter (DOM), using a batch equilibrium method, was also studied. A lipophilic bond is responsible for CyB adsorption on DOM. CyB was adsorbed on Fe(III)- and Ca-clays through hydrogen bonding between the carbonyl oxygen and water surrounding the exchangeable cations. In the interlayer of K-clay, CyB was hydrolyzed to CyA, which remained adsorbed therein as a monomer. The acid CyA was adsorbed only by the Fe-oxide through complexation. The CyA-Fe-oxide complex was stable and did not undergo degradation.

The first gold(III) dinuclear cyclometallated derivatives with a single oxo bridge

The reaction of the gold(III) cyclometallated complexes [Au(L)Cl][BF4] [L = N2C10H7(CHMeC6H4)-6 1 or N2C10H7(CMe2C6H4)-6 2, where N2C10H8 = 2,2′-bipy] with AgBF4 in acetone solution affords the acetonyl derivatives [Au(L){CH2C(O)Me}][BF4], 3 and 4, and the dinuclear oxo-bridged complexes [Au2(L)2(µ-O)][BF4]2, 5 and 6; the crystal structure of complex 6 gives evidence for an unprecedented unsupported Au–O–Au bridge.

Direct and indirect photolysis of cyhalofop in aqueous systems

The photodegradation of the aryloxyphenoxy propionic herbicide cyhalofop-butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), and of its primary metabolite (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA) was studied in water at different irradiation wavelengths. The sunlight irradiation was investigated also in the presence of humic acid (HA), Fe oxide, titanium dioxide (TiO2) and zinc oxide (ZnO) as photocatalysts. CyB and CyA were rapidly degraded by UV irradiation. CyB afforded the butyl ester of 2-[3-(4-cyano-2-fluorophenyl)-4-hydroxy-phenoxy]propanoic acid (CyI), a metabolite arising from a photo-Fries rearrangement. Instead, CyA yielded (R)-2-4-(4-carboxyl-2-fluorophenoxy)phenoxypropanoic acid (CyD), a dicarboxylic acid arising from the photo-hydrolysis of cyano group via amide. CyB was stable in simulated sunlight also in the presence of the catalysts tested. The irradiation of a CyA solution, in the presence of HA or Fe oxide, with simulated sunlight did not produce any significant degradation. In the same experimental conditions, CyA was totally mineralized in the presence of TiO2 and ZnO.

Effects of a municipal sewage sludge amendment on triasulfuron soil sorption and wheat growth

The influence of municipal sewage sludge (SL) as a soil amendment on the sorption and activity of the herbicide triasulfuron (TRS, [2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide]) was studied. Weed control was checked in a greenhouse on a wheat (Triticum turgidum L. subsp. durum) crop. At the highest SL amount allowed by Italian regulation, TRS sorption onto soil increased by 7 times and weed control was unaffected. A vegetative bloom and an early heading phase were noted. To compare inorganic fertilization (N, P, and K) and SL amendment, a greenhouse fertilization experiment was carried out. The SL-amended crop developed larger leaf surfaces, higher biomass, and a forward heading compared to that fertilized with N, P, and K. The SL hormone-like activity was evaluated by measuring auxin- and gibberellin-like activity of sewage sludge.

Fenhexamid Adsorption Behavior on Soil Amended with Wine Lees

The adsorption of fenhexamid (FEN) [N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide] on vineyard soil amended with wine lees (WL) produced by vinery was studied. The adsorption extent depends on WL fraction. The addition of the centrifuged solid lees (SWL) increases the FEN adsorption on soil. Most likely, the organic insoluble fraction formed mainly by dead fermentation yeasts is responsible for the observed increase. The adsorption measured on some deactivated yeasts of wine fermentation shows that Saccharomyces cerevisiae are the most active in FEN retention. On the other hand, the soil amendment with whole WL decreases considerably the fungicide adsorption. This opposite effect may be the result of FEN hydrophobic bonds with the dissolved organic matter of lees that keeps fungicide in solution. This hypothesis is substantiated by the increased FEN solubility in the supernatant of centrifuged wine lees (LWL). The results of soil column mobility confirm that the elution with LWL increases the mobility of FEN in soil.