Laura Delgado-Moreno

Compost and vermicompost of olive cake to bioremediate triazines-contaminated soil

The use of organic amendments to bioremediate potential organic pollutants of soil and water has become an increasingly relevant issue in the last years. This strategy has been applied to four triazine herbicides in a typical calcareous agricultural soil of the Mediterranean area. The soil was amended with olive cake, compost and vermicompost of olive cake at rates four times higher than the agronomic dose in order to stimulate biodegradation of simazine, terbuthylazine, cyanazine and prometryn, added in a mixture to the soils. Degradation studies were carried out in sterile and microbially active soil to evaluate the effect of the chemical and biological degradation of triazines. The residual herbicide concentrations at the end of the degradation assay showed no significant differences between non amended and amended soil. However, the addition of compost and vermicompost enhanced the biological degradation rate of triazines during the first week of incubation, with half-lives ranging form 5 to 18 days for the amended soils, whilst negligible degradation occurred in non-amended soil during this period. In contrast, olive cake did not significantly modify the degradation of triazines in spite that the addition of this amendment to soil resulted in the highest dehidrogenase activity values. In all the substrates, degradation of cyanazine and prometryn was faster (between 1.5 and two times higher) than those of terbuthylazine and simazine, without significant relationship with sorption parameters. The first order kinetic equation satisfactorily explained the experimental data for all triazines. A biphasic model, such as that proposed by Hoerl, was better to predict the very rapid triazines decay during the first week of incubation in soil amended with compost and vermicompost.

Occurrence and toxicity of three classes of insecticides in water and sediment in two Southern California coastal watersheds.

The occurrence of chlorpyrifos, diazinon, pyrethroids, and fipronil was investigated in two watersheds along the southern California coast. Paired surface water and sediment samples were collected under dry and wet (after significant rain events) weather conditions. Insecticide concentrations in water and sediment were higher following rain events than during the dry season. Chlorpyrifos was the most frequently detected compound (>88%). Pyrethroids were detected in 74 and 100% of the water and sediment samples, respectively, with bifenthrin detected most frequently. Trans-permethrin was detected at the highest concentration followed by bifenthrin. Bifenthrin and trans-permethrin water concentrations were significantly correlated (P < 0.01) with the suspended solid level, suggesting transport facilitated by suspended particles. In 80% of the wet season samples with 100% of Ceriodaphnia dubia mortality, chlorpyrifos concentrations were >100 ng L(-1). Sediment pyrethroid levels (0.5-1100 ng g(-1)) were frequently higher than the respective Hyalella azteca LC(50) values, with bifenthrin as the primary contributor of H. azteca toxicity.

Improved Measurements of Partition Coefficients for Polybrominated Diphenyl Ethers

Polybrominated diphenyl ethers (PBDEs) are a class of widely used brominated flame retardants with strong hydrophobicity. Due to their strong affinity for organic matter, accurate measurement of adsorption coefficients for PBDEs using conventional batch methods can be confounded by biases caused by their sorption to dissolved organic carbon (DOC). In this study, sorption isotherms were constructed for BDE-47 and BDE-99 in sediments by using different methods to measure the aqueous phase concentration Cw. Upon centrifugation, Cw measured by automated solid-phase microextraction (Cw-SPME) was consistently smaller than by liquid-liquid extraction (Cw-LLE), suggesting substantial association of PBDEs with DOC. Significant underestimations (1.2-106-fold) of sediment-water partition coefficient Kd occurred when Cw was measured by LLE. The log KDOC values derived from the SPME measurements ranged from 5.10 to 8.02 for eight congeners from BDE-28 to BDE-183, suggesting a strong tendency for PBDEs to complex with DOC. This study showed that PBDE congeners have larger sorption coefficients than would be measured by the conventional method. The high affinity to DOC also means a potential for DOC-facilitated transport, thus enhancing the environmental mobility of PBDEs.

Contribution by different organic fractions to triazines sorption in Calcaric Regosol amended with raw and biotransformed olive cake

A soil, olive cake, compost and vermicompost of olive cake, were subjected to sequential laboratory extraction to progressively remove water-soluble, lipid and alkali-soluble (humic-type) fractions. Sorption experiments with triazines were carried out with non-amended and amended soil and with soil residues in the intermediate stages during the laboratory removal of the different organic fractions. Herbicide sorption in soil amended with olive cake was between two and three times higher than sorption in composted substrates. In non-amended soil, the removal of humic and fulvic acids led to a decrease of triazines sorption indicating the importance of these fractions in the sorption of these pesticides. The greater triazines sorption in soil amended with olive cake could be associated with the high concentration of water-soluble substances. In contrast, olive cake lipids did not favour the sorption of the more hydrophobic herbicides as indicated by the fact that the sorbed amount increased 30-40% when this fraction was removed. No significant (P>0.05) differences in K(oc) values were found in soils amended with compost and vermicompost in the course of the progressive removal of the different organic fractions, indicating triazine sorption was related more with the total amount of organic matter than with its chemical composition.

Enhancing pesticide degradation using indigenous microorganisms isolated under high pesticide load in bioremediation systems with vermicomposts.

In biobed bioremediation systems (BBSs) with vermicomposts exposed to a high load of pesticides, 6 bacteria and 4 fungus strains were isolated, identified, and investigated to enhance the removal of pesticides. Three different mixtures of BBSs composed of vermicomposts made from greenhouse (GM), olive-mill (OM) and winery (WM) wastes were contaminated, inoculated, and incubated for one month (GMI, OMI and WMI). The inoculums maintenance was evaluated by DGGE and Q-PCR. Pesticides were monitored by HPLC-DAD. The highest bacterial and fungal abundance was observed in WMI and OMI respectively. In WMI, the consortia improved the removal of tebuconazole, metalaxyl, and oxyfluorfen by 1.6-, 3.8-, and 7.7-fold, respectively. The dissipation of oxyfluorfen was also accelerated in OMI, with less than 30% remaining after 30d. One metabolite for metalaxyl and 4 for oxyfluorfen were identified by GC-MS. The isolates could be suitable to improve the efficiency of bioremediation systems.

Design of experiments in environmental chemistry studies: Example of the extraction of triazines from soil after olive cake amendment

The disposal of natural, composted and vermicomposted olive cake for modifying the fate of triazine herbicides with different physicochemical properties (terbuthylazine, cyanazine, simazine and prometryn) has been tested. Experimental design (surface response methodology plus desirability function) to multicriteria optimization was carried out to evaluate both dose and type of amendment to retain the cited analytes and to develop two simple and low cost analytical methods for extracting triazines from soil. From a methodological point of view, classical and D-optimal designs were employed depending on the problem. Thus, the best combination of soil amount and solvent ratio, the most important parameters affecting triazine extraction from soil, was looked for by means of Central Composite Designs. Under the optimized conditions, the range of triazines recovery was 75-85% for shaking extraction and 87-107% for ultrasonic extraction. Regarding the amendment assay, D-optimal design was selected to keep the reliability of the estimations. Natural olive cake added to the soil at a high dose (8%) reduced herbicide recovery to ca. 50-60% for terbuthylazine, prometryn and simazine, while cyanazine recovery was negligible. Design of experiment provides an efficient working strategy to explore those conditions which ensure the optimum or target value of several responses evaluated simultaneously.

Behavior of bensulfuron-methyl in an agricultural alkaline soil

A field experiment to determine the available bensulfuron-methyl (BSM) in the upper soil layer was conducted in an agricultural area in the South of Spain. To facilitate herbicide analysis, two application rates were employed, 200 g ha−1 and 5 kg ha−1. Samples of upper soil and soil solution were collected. Soil solution was sampled by means of metallic samplers, placed at a depth of 35 cm. In the plots receiving the lower dose ceramic suction, porous cups were also installed. Results from soil solution samples showed that the maximum BSM concentration was found after 8-10 days for the high irrigation supply (945 mm) and after 18-25 days for the lower irrigation regime (405 mm). The mathematical model FOCUSPELMO 1.1.1 was applied to interpret the data obtained in the field experiments. In general, there was a reasonable agreement between experimental and simulated data for soil samples, although the model did not acceptably predict herbicide concentrations in water soil samples. Ceramic cups sampled a higher soil water volume and more frequently than did the metallic samplers. However some variable results were attributed to preferential flow.

Wastes from the olive oil production in sustainable bioremediation systems to prevent pesticides water contamination

Installation of biobed biopurification systems at farm level, traditionally composed of soil, peat and straw, to reduce point source contamination is difficult in some countries where peat is not environmentally or economically feasible. This study evaluates the use of local organic wastes from olive oil production such as wet olive cake and its vermicompost as substitutes of peat and olive tree pruning as substitute of straw to perform robust biobeds capable of removing mixtures of pesticides at high concentrations. Adsorption capacity of the novel biomixtures was comparable to or higher than traditional one. The biomixture with soil and olive tree pruning showed the highest pesticides adsorption, except for imidacloprid. The biomixture with soil, vermicompost and olive tree pruning showed dissipation efficiency of dimethoate, imidacloprid and oxyfluorfen (>73%) higher than traditional biobed. Meanwhile, the biomixture with soil and vermicompost was the alternative biomixture with the highest dissipation of diuron (54%) and tebuconazole (35%) but it was lower than traditional biomixture (59 and 47% for diuron and tebuconazole, respectively). The low dissipation of these compounds (<60%) is probably due to competitive and/or inhibitory phenomena between the pesticides in the mixture. Labile organic compounds from biomixture components such as water-soluble carbon constitute a more available carbon source for microorganisms that may counteracted the negative impact of high pesticide load on biomixture microbial populations, but they may have limited the pesticides dissipation. Novel biomixtures composed of olive oil mill waste may be a sustainable and less expensive alternative to traditional biomixture.

Biodegradation of high doses of commercial pesticide products in pilot-scale biobeds using olive-oil agroindustry wastes

Biobeds systems containing soil, peat and straw (SPS) are used worldwide to eliminate pesticide point-source contamination, but implantation is difficult when peat and/or straw are not available. Novel biobeds composed of soil, olive pruning and wet olive mill cake (SCPr) or its vermicompost (SVPr) were assayed at pilot scale for its use in olive grove areas. Their removal efficiency for five pesticides applied at high concentration was compared with the biobed with SPS. The effect of a grass layer on the efficiency of these biobeds was also evaluated. Pesticides were retained mainly in the upper layer. In non-planted biobeds with SCPr and SVPr, pesticides dissipation was higher than in SPS, except for diuron. In the biobed with SVPr, with the highest pesticide dissipation capacity, the removed amount of dimethoate, imidacloprid, tebuconazole, diuron and oxyfluorfen was 100, 80, 73, 75 and 50%, respectively. The grass layer enhanced dehydrogenase and diphenol-oxidase activities, modified the pesticides dissipation kinetics and favored the pesticide downward movement. One metabolite of imidacloprid, 3 of oxyfluorfen and 4 of diuron were identified by GC-MS. These novel biobeds represent an alternative to the traditional one and a contribution to promote a circular economy for the olive-oil production.

Innovative application of biobed bioremediation systems to remove emerging contaminants: Adsorption, degradation and bioaccesibility

Biobed bioremediation systems (BBSs) are widely used to prevent point-source pesticide contamination of water. However, these systems have never been investigated for possible elimination of emerging contaminants (ECs). In this study, two biobed systems, involving biomixtures elaborated with soil and raw olive mill cake (SCP) or its vermicompost (SVP), were assayed to determine their effectiveness in removing the ECs diclofenac, ibuprofen and triclosan from effluent wastewater. Adsorption, incubation and bioaccesibility experiments were carried out. The SCP and SVP biomixtures showed greater adsorption capacity than the soil (S), used as reference. In SVP and S, the degradation rates of the ECs applied were similar and over 94% of these compounds was removed after 84 days of incubation. However, SCP biomixture had a lower removal rate and the percentage of ECs removed ranged from 32 to 68%. In SVP, the bioaccesible fraction (E) reveals that approximately 82% of triclosan and diclofenac adsorption occurred in bioaccesible sites, thus explaining the more efficient decontamination observed in this biomixture. The relationship established between the bioaccesible and biodegradable fractions suggests that E values are a useful tool for predicting the endpoints of ECs biodegradation in bioremediation systems. UPLC/Q-TOF-MS analysis of samples showed different metabolite products.