José Antonio Rodríguez-Liébana

Persistence of two neonicotinoid insecticides in wastewater, and in aqueous solutions of surfactants and dissolved organic matter.

Wastewater treatment plants receive organic contaminants, such as pesticides, which reach the sewage system from domestic, industrial or agricultural activities. In wastewater, which is a complex mixture of organic and inorganic compounds, biotic or abiotic degradation of contaminants can be affected by the presence of co-solutes. The photodecomposition in natural sunlight of two neonicotinoid insecticides, thiamethoxam and thiacloprid, was investigated in wastewater, aqueous extracts of sewage sludge and in aqueous surfactant solutions, which are abundant in wastewater. Dissipation in the dark was also studied in wastewater, due to reduction of transmitted sunlight in wastewater ponds. With regard to photolysis, thiamethoxam degraded rapidly in all the aqueous solutions. Among them sewage sludge extracts slightly modified (average half-life 17.6h), wastewater increased (13.7h) and non-ionic surfactants led, as a family, to the highest dissipation rates (average 6.2h), with respect to control water (18.7h). Additionally this pesticide also underwent a slower biodegradation process in wastewater in the dark under anaerobic conditions (around 25d). A metabolite of thiamethoxam from the biological decomposition in wastewater was identified by HPLC/MS. On the other hand thiacloprid was found to be resistant to photo- and biodecomposition and remained almost unchanged during the experimental periods in all the tested media.

Sorption of hydrophobic pesticides on a Mediterranean soil affected by wastewater, dissolved organic matter and salts.

Irrigation with treated wastewaters as an alternative in countries with severe water shortage may influence the sorption of pesticides and their environmental effects, as wastewater contains higher concentrations of suspended and dissolved organic matter and inorganic compounds than freshwater. We have examined the sorption behaviour of three highly hydrophobic pesticides (the herbicide pendimethalin and the insecticides α-cypermethrin and deltamethrin) on a Mediterranean agricultural soil using the batch equilibration method. We considered wastewater, extracts from urban sewage sludge with different dissolved organic carbon contents, and inorganic salt solutions, using Milli Q water as a control. All pesticides were strongly retained by soil although some sorption occurred on the walls of the laboratory containers, especially when wastewater and inorganic salt solutions were used. The calculation of distribution constants by measuring pesticide concentrations in soil and solution indicated that pendimethalin sorption was not affected whereas α-cypermethrin and deltamethrin retention were significantly enhanced (ca. 5 and 2 times, respectively) when wastewater or salt solutions were employed. We therefore conclude that the increased sorption of the two pesticides caused by wastewater cannot be only the result of its dissolved organic carbon content, but also of the simultaneous presence of inorganic salts in the solution.

Pesticide mobility and leachate toxicity in two abandoned mine soils. Effect of organic amendments.

Abandoned mine areas, used in the past for the extraction of minerals, constitute a degraded landscape which needs to be reintegrated to productive or leisure activities. However these soils, mainly composed by silt or sand and with low organic matter content, are vulnerable to organic and inorganic pollutants posing a risk to the surrounding ecosystems and groundwater. Soils from two mining areas from Andalusia were evaluated: one from Nerva (NCL) in the Iberian Pyrite Belt (SW Andalusia) and another one from the iron Alquife mine (ALQ) (SE Andalusia). To improve soil properties and fertility two amendments, stabilised sewage sludge (SSL) and composted sewage sludge (CSL), were selected. The effect of amendment addition on the mobility of two model pesticides, thiacloprid and fenarimol, was assessed using soil columns under non-equilibrium conditions. Fenarimol, more hydrophobic than thiacloprid, only leached from native ALQ, a soil with lower organic carbon (OC) content than NCL (0.21 and 1.4%, respectively). Addition of amendments affected differently pesticide mobility: thiacloprid in the leachates was reduced by 14% in NCL-SSL and by 4% in ALQ-CSL. Soil OC and dissolved OC were the parameters which explained pesticide residues in soil. Chemical analysis revealed that leachates from the different soil columns did not contain toxic element levels, except As in NCL soil. Finally ecotoxicological data showed moderate toxicity in the initial leachates, with an increase coinciding with pesticide maximum concentration. The addition of SSL slightly reduced the toxicity towards Vibrio fischeri, likely due to enhanced retention of pesticides by amended soils.

Thiacloprid adsorption and leaching in soil: Effect of the composition of irrigation solutions

Pressure on groundwater resources has increased during the last decades due to the growing demand, especially in arid and semiarid regions, such as the Mediterranean basin, with frequent drought periods. In order to partially remediate this environmental problem of world concern, irrigation of agricultural lands with adequately treated wastewaters (TWW) is becoming a common management practice. The complex composition of these low-quality waters may influence the behavior of organic contaminants in soils. A calcareous soil with low organic carbon content was selected for the assessment of the adsorption and leaching of the neonicotinoid insecticide thiacloprid (THC). Different solutions were evaluated: TWW after a secondary treatment, a saline solution and solutions with a range of dissolved organic carbon concentration (DOC, 3-300mgL-1). The addition of an organic fertilizer (fertiormont) to the soil was also assessed, in an attempt to reduce THC mobility. Sorption of thiacloprid, a relatively polar pesticide, was similar under all the conditions considered, though an adsorption decrease was observed when DOC concentration increased. The transport of THC through soil columns was retarded with all the treatments, with the lower effects corresponding to TWW and the saline solution. Addition of fertiormont and irrigation with DOC at 3mgL-1 resulted in a reduction of pesticide leached (34% and 38%, respectively) in comparison with the control (66%), but surprisingly not for DOC at high concentration (55%), possibly due to co-elution of the pesticide with DOC. Therefore the transport of polar compounds, like THC, could be affected by the composition of the irrigation solutions, altering their impact to environmental water resources.

Adsorption-desorption of dimethenamid and fenarimol onto three agricultural soils as affected by treated wastewater and fresh sewage sludge-derived dissolved organic carbon

The use of treated wastewaters (TWW) in agriculture is widening in areas suffering drought, such as southern Europe, to preserve freshwater supply for human consumption. The composition of TWW, especially concerning their organic carbon (OC) content, has been demonstrated to influence the processes governing the behavior of non-ionic pesticides in soils. Three OC-poor agricultural soils (SV, RM1 and RM3) from the province of Granada (Spain) were chosen for the assessment of the adsorption and desorption of the herbicide dimethenamid (DIM) and the fungicide fenarimol (FEN). TWW and sewage sludge extracts at different dissolved OC (DOC) concentrations (30, 90 and 300 mg L-1) were considered to evaluate their effect on pesticide adsorption-desorption. As expected by their properties, DIM and FEN were weakly and moderately adsorbed to the soils, respectively. Soil OC seemed to be the major factor controlling FEN adsorption, whereas the mineral fraction played a key role in DIM adsorption, especially in RM1 with high clay:OC ratio. Although TWW did not significantly modify the adsorption of pesticides, it enhanced DIM desorption from the three soils. Adsorption of FEN to SV and RM3 was directly related to the concentration of DOC, possibly due to co-sorption phenomena. Hysteretic desorption was found in all cases, indicating partially reversible adsorption. While FEN desorption was not altered by the solutions, the use of sludge extracts at the highest DOC concentration (300 mg L-1) enhanced DIM desorption as occurred with TWW. Interactions with DOC in solution seemed to predominate for this less hydrophobic compound, thus increasing the risk of natural waters contamination if TWW will be used.

Adsorption of nutrients on natural Spanish clays for enriching seed coatings

Coating seeds with nutrients remains an effective way of supplying fertilizers for the establishment and development of seedlings. Clays have been proposed, among other coating materials, because of their low price and favorable properties. Nine natural clays (R1-R9), collected in the eastern Andalusian region (south of Spain), were evaluated for the retention of P, Mn and Zn, with the ultimate goal of designing enriched seed coatings. The clays were similar in composition, with high Ca content. Various equations were used for the fitting of kinetic and adsorption data. Adsorption rates of Mn were higher with R2, R6 was the clay in which Zn exhibited the most rapid kinetics, while P was adsorbed on R7 at the highest rate. Slower adsorption rates corresponded in all cases to Zn. The pseudo-second order model adequately explained the experimental kinetic data of Mn, Zn and P on the different sorbents. Adsorption isotherms indicated that the maximum adsorption capacity on the analyzed clays was ranged as Zn > Mn > > P. Clays were able to retain nutrients for long periods of time (up to 96 days) and desorption was inversely related with adsorption. Simultaneous addition on selected clays of Zn and Mn led to significantly higher nutrient desorption. The co-presence in clays of various compounds (nutrients and/or pesticides) affected their release, so this aspect deserves special attention in coating design. Results obtained suggest the feasibility of using these clay materials enriched with nutrients for seed coating.