Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N(2), N(4)-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'(W)) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb(T)) in pure water. Experimental breakthrough volumes (Vb(E)) were first determined using purified and deionized water as the matrix for selected compounds having Vb(T) < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4-5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb(E) curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5-6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb(E) in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Spatial trends of polyfluorinated compounds in guillemot (Uria aalge) eggs from North-Western Europe

Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.     

Use of electrochemical technology to increase the quality of the effluents of bio-oxidation processes. A case studied

In this work, it has been studied the use of conductive-diamond electrochemical oxidation (CDEO) as a refining technology to assure the quality of the effluents of door manufacturing processes (DMP). To do this, the raw effluents of these factories have been treated by a combination of physicochemical, biological and CDEO treatments. CDEO was found to be a feasible alternative to the refinement of a wooden DMP waste. It can successfully decrease the organic load of the effluents of the biological oxidation with low energy requirements. In addition, in case of incidents in the biological process, CDEO can treat successfully the effluents of the coagulation process. The effluents of the biological treatment have also been treated by CDEO in order to check the possible use of electrochemical technology to increase the biodegradability of the effluents and their possible recycle to the biological treatment. Unfortunately, electrochemical technology was found to be not adequate to increase the biodegradability of the effluents of a biological treatment. The hard oxidation conditions generated during CDEO do not lead to the accumulation of intermediates but to the almost direct formation of carbon dioxide. Lowering the current density or changing the electrodes can not enhance the biodegradability of the effluents of an electrochemical cell.     

Sorption of copper, zinc and lead on soil mineral phases

Soil mineral phases play a significant role in controlling heavy metal mobility in soils. The effective study of their relation needs the integrated use of several analytical methods. In this study, analytical electron microscopy analyses were combined with sequential chemical extractions on soils spiked with Cu, Zn and Pb. Our aims were to study the metal sorption capacity of soil mineral phases and the effect of presence of iron oxide and carbonate on this property of soil minerals. Copper and Pb were found to be characterized by higher and stronger sorption on the studied samples than Zn. Only the former two metals showed significant differences in their immobilized metal amounts on the studied samples and soil mineral particles. Highest metal amounts were sorbed on the swelling clay mineral particles (smectites and vermiculites), but iron-oxide phases may also have similar lead sorption capacity. Alkaline conditions due to the carbonate content of soils resulted both in increased sorption on the mineral particles for Cu and in enhanced role of precipitation for all the studied metals. On the other hand, the intimate association of phyllosilicates and iron resulted in significant increase in metal sorption capacity of the given particle. The results of sequential extractions could be successfully completed by the analytical electron microscopy analyses for studying the sorption capacity of discrete mineral particles. Their integrated use helps us in better understanding the heavy metal-mineral interactions in soils.     

Minimization of the environmental impact in the unhairing of bovine hides

This study tests an alternative method to the traditional unhairing method used during the process of tanning the hides. The new method is based on the substitution of sodium sulfide by hydrogen peroxide as an unhairing agent in both hair recovery and recirculation of the floats employed in the process. The properties of the hides obtained using the two methods have been compared and the results indicate that those hides have similar physical, chemical, and organoleptic properties. However, the differences existing from an environmental point of view are significant. These include reductions of water consumption (approx 70%), chemical oxygen demand (approx 35%), toxicity (98%) and total kjendhal nitrogen (50%). Also, the risk associated with the production of hydrogen sulfide is eliminated, which implies a great improvement in terms of safety for the workers. Given the large amounts of water and chemical pollution discharged in the process, the reductions in absolute values represent a significant improvement. A financial assessment was carried out to demonstrate that the proposed new system is 16% more economic than the traditional one.     

High chrome exhaustion in a non-float tanning process using a sulphonic aromatic acid

Tanning processes performed in drums consume large amounts of water and chemicals, most of which end up in the wastewater. This study explores an alternative approach at an industrial scale to the traditional pickle-chrome tanning method. The new method replaces formic and sulphuric acids with sulphonic aromatic acid. Because it is done without float, there is a sizeable reduction in the amount of added salt and chrome salt as well as an increase in temperatures at the end of the tanning process. From an environmental perspective, the new method offers important advantages. For instance, there is no float addition in the tannage. Also, there are reductions of 94% and 99%, respectively, in the discharge of chlorides and chrome, as well as a 75% reduction in the residual float. Our financial assessment demonstrated that the new method is 42% cheaper than a traditional approach.     

Fungal bioremediation of the creosote-contaminated soil: influence of Pleurotus ostreatus and Irpex lacteus on polycyclic aromatic hydrocarbons removal and soil microbial community composition in the laboratory-scale study

The aim of this study was to determine the efficacy of selected basidiomycetes in the removing of polycyclic aromatic hydrocarbons (PAH) from the creosote-contaminated soil. Fungi Pleurotus ostreatus and Irpex lacteus were supplemented with creosote-contaminated (50-200 mg kg(-1) PAH) soil originating from a wood-preserving plant and incubated at 15 °C for 120 d. Either fungus degraded PAH with 4-6 aromatic rings more efficiently than the microbial community present initially in the soil. PAH removal was higher in P. ostreatus treatments (55-67%) than in I. lacteus treatments (27-36%) in general. P. ostreatus (respectively, I. lacteus) removed 86-96% (47-59%) of 2-rings PAH, 63-72% (33-45%) of 3-rings PAH, 32-49% (9-14%) of 4-rings PAH and 31-38% (11-13%) of 5-6-rings PAH. MIS (Microbial Identification System) Sherlock analysis of the bacterial community determined the presence of dominant Gram-negative bacteria (G-) Pseudomonas in the inoculated soil before the application of fungi. Complex soil microbial community was characterized by phospholipid fatty acids analysis followed by GC-MS/MS. Either fungus induced the decrease of bacterial biomass (G- bacteria in particular), but the soil microbial community was influenced by P. ostreatus in a different way than by I. lacteus. The bacterial community was stressed more by the presence of I. lacteus than P. ostreatus (as proved by the ratio of the fungal/bacterial markers and by the ratio of trans/cis mono-unsaturated fatty acids). Moreover, P. ostreatus stimulated the growth of Gram-positive bacteria (G+), especially actinobacteria and these results indicate the potential of the positive synergistic interaction of this fungus and actinobacteria in creosote biodegradation.     

Increased thyroid volume, prevalence of thyroid antibodies and impaired fasting glucose in young adults from organochlorine cocktail polluted area: outcome of transgenerational transmission?

In 137 females (F) and 94 males (M) aged 21-35 years from organochlorines (OCs) polluted area (POLL) increased thyroid volume (ThV), prevalence of antibodies to thyroperoxidase (TPOab), thyrotropin receptor (TRab) and of impaired fasting glucose (IFG) was found compared to 116 F and 107 M from background pollution area (BCGR). In F and M from POLL also strikingly increased level of PCBs, DDE and HCB was found. Such findings were compared to the generation of their parents aged 41-55 years consisting of 320F/213M from POLL and 406F/231M from BCGR. However, in spite of strikingly lower level of those OCs in young adults from POLL, they showed about the same prevalence of adverse health signs as the old generation. From such reason 44 young F and 40 young M with lowest PCBs level from POLL were selected to obtain nearly the same PCB level as found in all young F and M from BCGR. In such PCB adjusted groups the prevalence of TPOab, TRab, IFG and increased ThV was still significantly higher than that in all young subjects from BCGR. At the same time, also the level of DDE and HCB in such PCBs adjusted groups was considerably lower. It was concluded that such adverse effects in young adults from POLL possibly did not result from their actual OCs levels, but very likely from their exposure to high OCs levels of their mothers during their prenatal and perinatal life. Thus, the data may be compatible with present views on transgenerational transmission of endocrine disruptors action.