Evaluation of a TiO2 photocatalysis treatment on nitrophenols and nitramines contaminated plant wastewaters by solid-phase extraction coupled with ESI HPLC-MS.

Nitration reactions of aromatic compounds are commonly involved in different industrial processes for pharmaceutical, pesticide or military uses. For many years, most of the manufacturing sites used lagooning systems to treat their process effluents. In view of a photocatalytic degradation assay, the wastewater of a lagoon was investigated by using HPLC coupled with mass spectrometry. The wastewater was highly concentrated in RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and two herbicides Dinoterb (2-tert-butyl-4,6-dinitrophenol) and Dinoseb (2-sec-butyl-4,6-dinitrophenol). First of all, an analytical method using solid-phase extraction (SPE) combined with HPLC ESI MS/MS was put in work for identification and titration of RDX, HMX and the two dinitrophenols in a complex natural matrix. Then, the UV/TiO2 treatment was investigated for pollutants removal. Dinitrophenolic compounds were significantly degraded after a 8-h-exposition of the wastewater/TiO2 suspension, whereas RDX and HMX were poorly affected.

Qualitative and quantitative evolution of polyphenolic compounds during composting of an olive-mill waste-wheat straw mixture.

Olive-mill wastes represent a significant environmental problem in Mediterranean areas due to their important production during a short period of time. Their high polyphenol, lipid and organic acid concentrations turn them into phytotoxic wastes. This work examined the evolution of polyphenolic compounds during the composting of an olive-mill waste-wheat straw mixture by using quantitative (Folin-Ciocalteu) and qualitative (High Pressure Liquid Chromatography, HPLC) analyses. The polyphenol content decreased strongly by 93% while the significant correlations obtained between polyphenol content and different humification indices and lignin losses suggested that polyphenols contribute to the synthesis of humic substances. In addition, the significant correlation found between germination index, polyphenols and humification indices must be related to the progressive substrate detoxification as humification process progressed, leading to a non-phytotoxic and partially humified end-product. Nine polyphenolic compounds were identified by HPLC, most of which had disappeared by the end of composting, when only traces of hydroxytyrosol, caffeic and syringic acids and oleuropein were detected.

Fate of polycyclic aromatic hydrocarbons during composting of activated sewage sludge with green waste.

The level and fate of 16 polycyclic aromatic hydrocarbons (PAHs), targeted by the US Environmental Protection Agency (USEPA), has been studied over 90 days of composting of activated sludge with green waste, under a semi-arid climate. The total PAH calculated from the sum of the amounts of the 16 PAHs in the initial mixture of activated sludge and green waste, was lower than accepted European Union cut-off limits by about 0.48mgkg(-1). The treatment by composting led to a decrease of all PAHs mainly in the stabilization phase, but some differences could be observed between PAHs with three or fewer aromatic rings (N< or = 3) and those with four or more (N> or = 4). The former (except phenanthrene) exhibited a continuous decrease, while the latter PAHs with N of four or more and phenanthrene showed increases in the intermediate stages (30-60 days). This indicates the high potential sorption mainly of PAH with high molecular weight (> or = N4) plus phenanthrene, their tight adsorption makes them inaccessible for microbial attack. The high molecular weight PAHs showed a greater reduction of their bioavailability than those of low molecular weight. Naphthalene, with the lowest molecular weight, showed the smallest decrease (about 67.8%) compared to other PAHs of higher molecular weight (decrease reaching 100%). This is in agreement with the fact that the adsorption is less reversible with increased numbers of fused aromatic rings or an increase of their hydrophobicity.

Microbial community dynamics during composting of sewage sludge and straw studied through phospholipid and neutral lipid analysis.

The composting process involves a succession of different communities of microorganisms that decompose the initial material, transforming it into a stable final product. In this work, the levels of phospholipid fatty acid (PLFA), neutral lipid fatty acid (NLFA) and sterol were monitored in compost versus time, as indicators of the activity of various microorganisms (Gram-positive or Gram-negative bacteria, fungi, etc.). During composting, the PLFA and NLFA from Gram-negative bacteria and eukaryotes (2-OH 10; 3-OH 12; 2-OH 14; 13:0; 16:1; 18:1 trans) as well as some sterols of plant origin (e.g. monostearin sterols) decreased until the end of composting. In contrast, the branched fatty acids with iso- and anteiso-forms (i-15:0; a-15:0; i-16; i-17) increased mainly in the thermophilic phase, but decreased right after. The PLFA 18:2 (6; 9), which is used as an index of the occurrence of some fungi, rose strongly at the beginning of composting, but fell after peak heating. In contrast, the other main sterol indicative of fungi, ergosterol, decreased at the beginning of the thermophilic phase, but increased strongly by the end of composting. Accordingly, cluster and PCA analysis separated the PLFA of Gram-negative bacteria and eukaryotic cells from those of Gram-positive bacteria and long-chain fatty acids. The fungal PLFA considered, 18:2 (9, 12), was clustered more closely to iso- and anteiso-branched PLFAs. Stigmasterol, squalene and cholesterol occurred in the lower right part of the loading plot and were clustered more closely to iso-, anteiso-branched PLFAs and 18:2 w 6,9 suggesting their relationship to microbial activities. We also observed the tendency of resistance of fatty acid PLFAs and NLFAs of long chain (19:0 (cis-9); 20:0) and some recalcitrant sterols, e.g. sitosterol, at the end of composting. The presence of high levels of the latter in the final stage indicates their contribution to the structural stability of organic matter fractions. These recalcitrant components were more clustered and occurred in the lower right part of the loading plot.

Photochemical UV/TiO2 treatment of olive mill wastewater (OMW).

Olive mill wastewater (OMW) was treated by photocatalysis using TiO2 under UV irradiation on the laboratory scale. The chemical oxygen demand, the coloration at 330nm, and the level of phenols all showed decreases which, after a 24-h treatment, reached 22%, 57% and 94%, respectively. The differences between these three values indicate the persistence of colourless, non-phenolic compounds. Application of the novel Fictitious Atomic-Group Separation method showed an increase in carbon oxidation state and confirmed that the attack primarily concerns, aromatic moieties. A fine spectroscopic study revealed the occurrence of three successive phases during the degradation process, thought to correspond to three different categories of molecules in the OMW and the presence of pectin compounds.

13C NMR study of the effect of aerobic treatment of olive mill wastewater (OMW) on its lipid-free content.

Olive mill wastewater was treated by an aerobic bio-process at different values of pH (with or without addition of lime), for 45 days on a laboratory scale, to evaluate the reduction of the organic load. The lipid content showed an appreciable change in relation to the applied treatment both for total lipids and for the different fractions (neutral lipids, monoglycerides and phospholipids). 13C NMR spectroscopy was performed on initial and final samples both raw and after lipid extraction. The main spectral differences were observed in the C-alkyl region (0-50 ppm), in the C O-alkyl/N-alkyl region (50-110 ppm), and in the C-carboxylic (160-200 ppm) region, providing information on the alterations occurring in the different biochemical entities composing this complex biomatrix (e.g. lipids and carbohydrates) according to the treatment.

Optimisation of biodegradation conditions for the treatment of olive mill wastewater.

The aim of the present paper was to optimise the conditions of aerobic treatment of olive mill wastewater. To do so, the waste was treated following the experimental optimal design methodology studying the set of factors susceptible to influence the treatment (pH, C/N ratio, aeration and temperature). The results of a first series of experiments showed a strong correlation between the reduction in the levels of polyphenols and three of the parameters studied, i.e. the C/N ratio, aeration and temperature. Optimised conditions led to a 94% drop in polyphenols. Then, for a finer study of the conditions, just two parameters were varied, the pH and the C/N ratio. The results showed that the conditions of pH modification (addition of lime or sodium hydroxide) and the C/N ratio (urea or ammonium nitrate) allowed the microbiological activity to be very significantly improved. This led to polyphenol reductions of 51% and 76%.

Structural study of the fulvic fraction during composting of activated sludge-plant matter: elemental analysis, FTIR and 13C NMR.

The starting fulvic structures isolated from an initial mixture of activated sludge and plant matter presented abundant peptide structures and hydrocarbons that absorb in FTIR spectra around (1650 and 1560 cm(-1)) and 1072 cm(-1), respectively. They also present a high resonance signal in the O- and N-alkyl areas of (13)C NMR spectra. As composting proceeded, some changes led to the formation of the molecular structures of fulvic fraction as demonstrated by a decrease of intensity of compounds absorbing around 1072 cm(-1) and an increase of those absorbing around 1140 cm(-1). The resonance of O- and N-substituted alkyl carbon also decreased from 55.7% to 33.8%, with an increase in the intensity of aromatic carbons, alkyls and carboxyls. These data indicate that the microbial community that developed during composting used polysaccharides as an energy source, structures which are supplied in abundance in the initial material. The fulvic fraction of the final compost is much richer in aromatic structures and aliphatic ethers/esters, which are most likely preserved from the original material but probably also synthesized through the microbial activities. The occurrence of alkyl ethers/esters at the end of composting is demonstrated by strong absorbance around 1140 cm(-1) in the FTIR spectra and large peaks at 32 and 174 ppm in the NMR spectra. These structures could also be produced following the creation of ether/ester bonds during the humification process.

Phospholipid fatty acid analysis to monitor the co-composting process of olive oil mill wastes and organic household refuse.

The co-composting of olive oil mill wastes and household refuse was followed for 5 months. During the thermophilic phase of composting, the aerobic heterotrophic bacteria (AHB) count, showed a significant rise with a slight regression of fungal biomass. In the same way, phospholipid fatty acids PLFAs common in bacteria, showed a significant increase of hydroxyl and branched PLFAs. The evaluation of the ratio of octadecenoic PLFAs to stearic acid (C18:1omega/C18:0) revealed a significant reduction while a significant rise in the length of aliphatic chains evaluated by the stearic acid to palmitic acid ratio (C18:0/C16:0) was noted during the stabilization phase. The follow-up of PLFAs, indicates the degree of biodegradation that occurs during composting, it can be regarded an indicator of the stability and maturity of the end product.

Chemical and spectroscopic analysis of olive mill waste water during a biological treatment.

The treatment of olive mill waste water was studied on the laboratory scale. Physico-chemical analyses showed the final products had a mean pH of 5.4 without neutralisation and 5.7 when lime was added to the process. Raising the pH by adding lime had a positive outcome on the degradation of phenols, whose levels were reduced by over 76%. The lime also changed the structure of the organic matter, as seen in the infra-red spectra. Combining the FT-IR and 13C NMR data showed that with addition of lime, the density of aliphatic groups decreased to the benefit of aromatic groups, indicating that polymerisation of the organic matter occurred during the bioprocess. Under our experimental conditions, the biotransformation of olive mill waste water appears to favour the stabilisation of the organic matter through mechanisms analogous to those that lead to the formation of humus in the soil.

Assessment of the genotoxicity of olive mill waste water (OMWW) with the Vicia faba micronucleus test.

The present study concerns the genotoxicity of olive mill waste water (OMWW) generated in mills producing olive oil in Morocco. The Vicia faba micronucleus test was used to evaluate the genotoxicity of OMWW and the six major phenolic compounds identified by HPLC in this effluent. Five dilutions of OMWW were tested: 0.1, 1, 5, 10 and 20%. Maleic hydrazide was used as a positive control. The results showed that OMWW was genotoxic at 10% dilution. In order to investigate the components involved in this genotoxicity, the six major phenols present in this effluent, oleuropein, gallic acid, 4-hydroxyphenyl acetic acid, caffeic acid, paracoumaric acid and veratric acid, were studied at concentrations corresponding to the genotoxic concentration of the OMWW itself. Two phenols, gallic acid and oleuropein induced a significant increase in micronucleus frequency in Vicia faba; the four other phenols had no significant genotoxic effect. These results suggest that under the experimental conditions of our assay, OMWW genotoxicity was associated with gallic acid and oleuropein.

Treatment of olive mill waste-water by aerobic biodegradation: an analytical study using gel permeation chromatography, ultraviolet-visible and Fourier transform infrared spectroscopy.

Liquid waste from olive oil mills was digested following inoculation with soil microorganisms and fractionated through various grades of gel. The fractionation showed the range of sizes of the molecules in the waste. In addition, the disappearance of the low molecular weight fraction, which is retained by the gel, and the increase of the high molecular weight fraction, which is excluded by the gel, during the last stages of the microbial treatment, indicates polymerisation of the low-molecular-weight subunits. Characterization of the fractions by UV-visible and FTIR spectroscopy confirmed the increase in their degree of polymerisation during the treatment. This is paralleled by a reduction in the amount of aliphatic components and a concomitant increase in aromatic structures.

Eliminating toxic compounds by composting olive mill wastewater-straw mixtures.

The present work studies the changes occurring in organic matter, phenols and biotoxicity on composting olive mill wastewater with barley straw. The total organic matter decreased, a drop of 25% was reached after the stabilization phase and 52% at the end of the maturation phase. Degradation of the phenols reached 54% and 95%, respectively, after these periods. The toxicity of the water extract, evaluated by the Photobacterium phosphoreum fluorescence, decreased to disappear after only 2 months of composting. This trend was confirmed by the tight correlation between the physico-chemical and toxicity parameters, indicating that the degradation of organic matter leads to a strong reduction of the C/N ratio and of toxicity. The results obtained indicate a normal process of humification occurring during the composting of the formerly highly toxic olive mill wastewater-straw mixture and resulting in a product, which has good agricultural properties as organic fertilizer.

Agronomic and environmental impacts of a single application of heat-dried sludge on an Alfisol.

A field experiment was conducted on Alfisols in South-West France to assess the agronomic and environmental impacts of a single application of heat-dried sludge pellets at 11.1 Mg dry matter ha-1. The sludge pellets, with a moisture level of 9.5%, were spread on an irrigated crop of maize (Zea mays L.). This treatment was compared with inorganic fertilization (urea and diammonium phosphate mixed with KCl). Soil properties, yield and the composition of maize and the quality of drained water were monitored over 1 year to detect any changes resulting from sludge application. Amongst several determined soil properties, only two were significantly modified by the sludge application: The nitric nitrogen stock of the soil was higher in the inorganic fertilized plot, whereas Olsen-P soil content was higher in the sludge-amended plot. Agronomic recovery rates of N and P added by sludge were high: For the first crop following application, total amounts of N and P supplied by the sludge had the same efficiency as approximately 45% of the N and P amounts supplied by inorganic fertilizer. This ratio was 7% for the N uptake by the second maize crop. The quality and quantity of maize were equally good with both types of fertilization. During the 2 years following sludge spreading, N leaching remained as low in the sludged plot as in the inorganically fertilized one. The Cu, Zn, Cr, Cd, Pb and Ni composition of the drainage water was affected by neither of the types of amendment. From the heavy-metal contents of the soil, water and maize monitored over 1 year in the field experiment and from literature data for cow manure and atmospheric emissions, a theoretical balance between crop soil heavy-metal input and output over one century was drawn up. The long-term impact of cow manure on Zn, Ni and Cr in soil is higher than that of the studied heat-dried sludge. Obviously, sludge tended to cause a strong increase in soil Cu storage, valued for these soils, which are otherwise very Cu deficient.

Fate of polycyclic aromatic hydrocarbons during composting of lagooning sewage sludge.

The fate of 16 polycyclic aromatic hydrocarbons (PAHs), targeted by the USEPA agency, has been investigated during composting of lagooning sludge. Composting shows efficient decrease of the content and the bioavailability of each PAH. Biodegradation and sorption are suggested as the main mechanisms contributing to this decrease. During the stabilization phase of composting, extensive microbial degradation of PAHs, mainly those with a low number of aromatic rings, was achieved following development of intense thermophilic communities. However, partial sorption of PAH to non-accessible sites temporarily limits the mobility mainly of PAHs with a high number of aromatic rings plus acenaphthene and acenaphthylene, and allows them to escape microbial attack. During the maturation phase, the development of a mesophilic population could play an important role in the degradation of the remaining PAH. During this phase of composting, PAH sequestration and binding of their oxidative metabolites within new-formed humic substances might also explain PAH decrease at the end of composting. The tendency of change of content or bioavailability of various PAH compounds during composting is found to be strongly related to the number of their aromatic rings, their molecular weight and structure.

The influence of biosolids treatment files on the mobility of metal trace elements.

The production of sludge in France is estimated to be about 900,000 metric tons dry matter per year and 60% of this is recycled onto agricultural land. At present, the long term future of this procedure is open to question and among the different arguments being put forward are the levels of metallic trace elements and the risk of accumulation in soils. This study presents the behaviour of metallic trace elements in sludges from three different treatment procedures: thickened liquid sludges, dewatered sludges and dried sludges. These biosolids are mixed with a clay soil and then placed in a temperature and humidity controlled glasshouse. Several containers are seeded with ryegrass and compared with controls. For the three harvests, covering all the amendments studied (including non-amended soil), the differences are not really representative. Absorption by the ryegrass is low in all cases. For the cadmium, the chromium, the nickel and the lead, the roots are 5 to 10 times more concentrated than the leaves. The majority of these elements stay absorbed in the roots, regardless of the amendment used. The addition of the sludges has considerably reduced the uptake of water in ryegrass throughout its growth cycle. Quite apart from their fertilizing qualities, wastewater treatment plant sludges could offer important implications for irrigation.