Chemical identification and quantification of volatile organic compounds emitted by sewage sludge.

The recycling of organic waste products (e.g. sewage sludge, SS) is currently being promoted as a substitute for mineral fertilizers for agricultural lands. The spreading of SS allows the recycling of the nutrients and organic matter it contains. SS contains various pollutants such as volatile organic compounds (VOCs) that adversely affect the ecosystem and human health through ozone production and serve as critical precursors of atmospheric secondary organic aerosols. There are very few studies quantifying the gaseous compounds emitted from SS, and those studies primarily address their odorant properties for identifying suitable odour abatement techniques. There is an urgent need for more comprehensive quantitative information on VOCs emitted from SS as aerosol precursors. In this context, an experimental study was performed on SS samples taken from a wastewater treatment plant located in France. Undigested SS (UDSS), digested SS (DSS) and SS with 30% and 60% dryness were collected from different stages of treatment sequence and analyzed using atmospheric simulation chambers coupled to proton-transfer-reaction quadrupole ion-guide time-of-flight mass spectrometer. Our study revealed that SS samples emitted a large spectrum of VOCs. 380 compounds were detected, quantified and classified into different chemical groups. The VOC emissions increased with the increase in the dryness of the sample; the highest being in SS 60%, followed by SS 30%, UDSS and DSS. OVOCs were dominant in SS 60%. The statistical analysis showed that the anaerobic digestion and the dewatering to 60% of dryness decreased the emissions of sulphuric compounds. Aromatic compounds and indoles (e.g. skatole) were emitted significantly from the UDSS. Some of these VOCs can serve as precursor gases for atmospheric aerosol formation. The experimental dataset obtained in this study provides an accurate inventory reference for the VOC emissions from SS samples and shows the impacts of the treatment on emission characteristics of VOCs.

Superior residual fertiliser value in soil with phosphorus recycled from urine in layered double hydroxides.

Layered double hydroxides (LDHs) of magnesium (Mg) and aluminium (Al) are ion exchangers that can be used as slow release phosphorus (P) fertilisers. These LDHs can be used successfully to concentrate P from waste streams such as urine. This study was set up to test the fertiliser potential of P derived from urine and concentrated on LDHs. Ryegrass was grown in a pot trial using a P- and N-deficient soil where different urine derived fertilisers, i.e. LDH-P, stored urine and urine mixed with sludge as a source of P were compared to different mineral N and P doses in a full factorial design. Plants were grown for 75 days with four cuttings and did not exhibit salinity stress in stored urine treatments. Plant growth and P uptake responded to N, P doses in mineral fertilizer treatments with significant N-P interaction. The fertiliser use efficiency of urine fertilisers was lower than that of mineral fertilisers at equivalent total nutrient input for stored urine, due to lower N availability, and for urine mixed with sludge due to lower P availability. In contrast, the yield and P uptake of ryegrass grown on LDH loaded with P from urine (LDH-P) showed equal fertiliser P use as mineral fertiliser. Interestingly, the residual soil P after harvest, scored by the sum of isotopically exchangeable P in soil and the P uptake, was higher for LDH-P than for mineral P, confirming slow release properties of LDH that limit loss of P by fixation in soil.

Process type is the key driver of the fate of organic micropollutants during industrial scale treatment of organic wastes.

Organic micropollutants (OMPs) such as polycyclic aromatic hydrocarbons, nonylphenols and pharmaceutical products are ubiquitous in organic wastes generated by most human activities. Those wastes are mainly recycled by land spreading, most often after treatments, such as liming, dewatering, composting or anaerobic digestion. It has been shown essentially at lab scales that biological treatments have an effect on the removal of some OMPs. However, less is known on the role of each step of industrial treatment lines combining physico-chemical and biological treatments on the OMP fate and removal. The present study focuses on the impact of waste treatment on the fate of 53 OMPs along 10 industrial treatment lines treating urban, agricultural wastes or mixtures. The combination of studying a diversity of organic wastes and of OMPs with different characteristics (solubility, ionic charges, hydrophobicity etc.), sampling in situ industrial sites, quantifying native OMP concentrations and looking at each step of complete treatment lines allows for a global and representative view of the OMP fate in the French organic waste treatment sector. Less studied wastes, i.e. territorial mixtures, revealed intermediate OMP contents and compositions, between urban and agricultural wastes. Dewatering and liming, usually dismissed, had a noticeable effect on concentrations. Anaerobic digestion and composting had significant effects on the removal of all pollutant families. Combination of processes enhanced most OMP dissipation. Here we showed for the first time that the process type rather than the waste origin affects dissipation of organic micropollutants. Such data could be used to build and validate dynamic models for the fate of OMPs on solid waste treatment plants.

COP-compost: a software to study the degradation of organic pollutants in composts.

Composting has been demonstrated to be effective in degrading organic pollutants (OP) whose behaviour depends on the composting conditions, the microbial populations activated and interactions with organic matters. The fate of OP during composting involves complex mechanisms and models can be helpful tools for educational and scientific purposes, as well as for industrialists who want to optimise the composting process for OP elimination. A COP-Compost model, which couples an organic carbon (OC) module and an organic pollutant (OP) module and which simulates the changes of organic matter, organic pollutants and the microbial activities during the composting process, has been proposed and calibrated for a first set of OP in a previous study. The objectives of the present work were (1) to introduce the COP-Compost model from its convenient interface to a potential panel of users, (2) to show the variety of OP that could be simulated, including the possibility of choosing between degradation through co-metabolism or specific metabolism and (3) to show the effect of the initial characteristics of organic matter quality and its microbial biomass on the simulated results of the OP dynamic. In the model, we assumed that the pollutants can be adsorbed on organic matter according to the biochemical quality of the OC and that the microorganisms can degrade the pollutants at the same time as they degrade OC (by co-metabolism). A composting experiment describing two different (14)C-labelled organic pollutants, simazine and pyrene, were chosen from the literature because the four OP fractions simulated in the model were measured during the study (the mineralised, soluble, sorbed and non-extractable fractions). Except for the mineralised fraction of simazine, a good agreement was achieved between the simulated and experimental results describing the evolution of the different organic fractions. For simazine, a specific biomass had to be added. To assess the relative importance of organic matter dynamics on the organic pollutants' behaviour, a sensitivity analysis was conducted. The sensitivity analysis demonstrated that the parameters associated with organic matter dynamics and its initial microbial biomass greatly influenced the evolution of all the OP fractions, although the initial biochemical quality of the OC did not have a significant impact on the OP evolution.

Simulation of Organic Matter and Pollutant Evolution during Composting: The COP-Compost Model.

Organic pollutants (OPs) are potentially present in composts and the assessment of their content and bioaccessibility in these composts is of paramount importance. In this work, we proposed a model to simulate the behavior of OPs and the dynamic of organic C during composting. This model, named COP-Compost, includes two modules. An existing organic C module is based on the biochemical composition of the initial waste mixture and simulates the organic matter transformation during composting. An additional OP module simulates OP mineralization and the evolution of its bioaccessibility. Coupling hypotheses were proposed to describe the interactions between organic C and OP modules. The organic C module, evaluated using experimental data obtained from 4-L composting pilots, was independently tested. The COP-Compost model was evaluated during composting experiments containing four OPs representative of the major pollutants detected in compost and targeted by current and future regulations. These OPs included a polycyclic aromatic hydrocarbon (fluoranthene), two surfactants (4--nonylphenol and a linear alkylbenzene sulfonate), and an herbicide (glyphosate). Residues of C-labeled OP with different bioaccessibility were characterized by sequential extraction and quantified as soluble, sorbed, and nonextractable fractions. The model was calibrated and coupling the organic C and OP modules improved the simulation of the OP behavior and bioaccessibility during composting.

Composting in small laboratory pilots: performance and reproducibility.

Small-scale reactors (<10 l) have been employed in composting research, but few attempts have assessed the performance of composting considering the transformations of organic matter. Moreover, composting at small scales is often performed by imposing a fixed temperature, thus creating artificial conditions, and the reproducibility of composting has rarely been reported. The objectives of this study are to design an innovative small-scale composting device safeguarding self-heating to drive the composting process and to assess the performance and reproducibility of composting in small-scale pilots. The experimental setup included six 4-l reactors used for composting a mixture of sewage sludge and green wastes. The performance of the process was assessed by monitoring the temperature, O(2) consumption and CO(2) emissions, and characterising the biochemical evolution of organic matter. A good reproducibility was found for the six replicates with coefficients of variation for all parameters generally lower than 19%. An intense self-heating ensured the existence of a spontaneous thermophilic phase in all reactors. The average loss of total organic matter (TOM) was 46% of the initial content. Compared to the initial mixture, the hot water soluble fraction decreased by 62%, the hemicellulose-like fraction by 68%, the cellulose-like fraction by 50% and the lignin-like fractions by 12% in the final compost. The TOM losses, compost stabilisation and evolution of the biochemical fractions were similar to observed in large reactors or on-site experiments, excluding the lignin degradation, which was less important than in full-scale systems. The reproducibility of the process and the quality of the final compost make it possible to propose the use of this experimental device for research requiring a mass reduction of the initial composted waste mixtures.

Modelling of organic matter dynamics during the composting process.

Composting urban organic wastes enables the recycling of their organic fraction in agriculture. The objective of this new composting model was to gain a clearer understanding of the dynamics of organic fractions during composting and to predict the final quality of composts. Organic matter was split into different compartments according to its degradability. The nature and size of these compartments were studied using a biochemical fractionation method. The evolution of each compartment and the microbial biomass were simulated, as was the total organic carbon loss corresponding to organic carbon mineralisation into CO(2). Twelve composting experiments from different feedstocks were used to calibrate and validate our model. We obtained a unique set of estimated parameters. Good agreement was achieved between the simulated and experimental results that described the evolution of different organic fractions, with the exception of some compost because of a poor simulation of the cellulosic and soluble pools. The degradation rate of the cellulosic fraction appeared to be highly variable and dependent on the origin of the feedstocks. The initial soluble fraction could contain some degradable and recalcitrant elements that are not easily accessible experimentally.

Usefulness of TAO model to predict and manage the transformation in soil of carbon and nitrogen forms from West-Africa urban solid wastes.

The TAO model of Transformation of Added Organic materials (AOM) calibrated on AOMs and substrates of temperate areas was used to assess the transformations in soil of carbon and nitrogen forms of AOMs: raw materials, selected mixtures and composts from Ouagadougou urban wastes. AOMs were studied in terms of chemical and biochemical contents and for their C and N mineralization during incubations in a typical Ferric Lixisol of the sub-urban agriculture of Ouagadougou. The TAO model was used to predict the transformations of C (very labile, resistant and stable organic C) and N (very labile, resistant and stable organic N, produced and immobilized inorganic N) forms driven by AOM biochemical data. Without any change in calibration formulae, TAO predicted accurately the C transformations and inorganic N production of most of the tested AOMs, with a tendency to slightly overestimate C mineralization of previously well-composted materials and re-mineralization of immobilized N. Complementary adjustments using more complete data from laboratory experiments are suggested, but the model agrees with other data collected in the field and appears as a promising tool to optimise the management of urban wastes in the tropical area as well as for agro industrial organic fertilizers of the temperate zone. This application suggests ways to improve the management of urban wastes aiming to optimize agricultural yields, system sustainability and C sequestration in soil.

Influence of bulking agents on organic matter evolution during sewage sludge composting; consequences on compost organic matter stability and N availability.

The influence of bulking agents on organic matter (OM) stability and nitrogen (N) availability in sludge composts was investigated. Seven mixtures were composted over a 12-week period in 170 L-reactors using the same sludge with different bulking agent mixtures. The OM evolution was characterised by carbon (C) and N mass balances in biochemical fractions. The evolution of OM stability and N potential availability were measured during soil incubations. The type of bulking agent had little influence on the intensity of OM stabilisation and the N availability in final composts. However, they influenced the time to reach similar OM stability and the biochemical evolution of OM. Depending on their ligno-cellulosic characteristics and a careful control of aeration, initial mixtures with high C:N ratio and rather biodegradable carbonaceous materials could favour the organisation of initially present mineral N or easily mineralisable sludge N and therefore limit NH3 volatilisation responsible for the low compost N availability measured.

Change of the chemical composition and biodegradability of the Van Soest soluble fraction during composting: a study using a novel extraction method.

Van Soest fractionation is widely employed to characterize exogenous organic matter. The soluble fraction of Van Soest fractionation (SOL, extracted using hot water and then neutral detergent) often increases in line with compost maturity, although it is generally considered as labile. We have developed an alternative extraction method that comprises four successive steps (extraction using hot water, sodium tetraborate, dichloromethane/methanol and chelating resin) in order to clarify the chemical nature of the SOL fraction and explain its biodegradability. This method was tested on municipal solid waste compost sampled during the thermophilic phase (MSWi) and after 8 months of composting (MSWm). Both methods extracted similar proportions of organic matter. The composition of the residues was similar in MSWm although differences were noted for the extraction of polysaccharides and lipids in the case of MSWi. The hot water extractable fraction decreased during composting. Its high biodegradability in MSWi was linked to the high polysaccharide content revealed by pyrolysis-GC/MS and FTIR spectroscopy. The increase in the sodium tetraborate extractable fraction mainly explained the increase in the SOL fraction during composting. This was made up of N-containing compounds, polysaccharides and lipids in the immature compost, and a majority of N-containing compounds in the mature compost. During composting, the stabilization of organic matter in the SOL fraction extractable by sodium tetraborate and EDTA might principally involve N-containing structures through the formation of complexes of organic matter with metal ions, especially Ca(2+), which may be broken down during extraction of the Van Soest soluble fraction. These mechanisms still need to be investigated.

Sorption and mineralization of organic pollutants during different stages of composting.

The organic pollutant (OP) content is a key factor when determining compost quality. The OPs present in feedstock materials may either be degraded during composting or stabilized in the compost by sorption interactions with organic matter (OM), which may reduce the availability of OP to microorganism degradation. It is particularly important to identify the key stages during composting that are involved in OP mineralization so as to be able to optimize the composting process and determine whether OP sorption on OM is a limiting factor to OP mineralization. Four (14)C-labeled OPs were used during the study: a polycyclic aromatic hydrocarbon (fluoranthene), two surfactants (4-n-nonylphenol - NP and sodium linear dodecylbenzene sulfonate - LAS) and a herbicide (glyphosate). The potential for compost microflora to degrade OP, and compost sorption properties, were characterized at different stages of composting. The highest levels of LAS and glyphosate mineralization were found during the thermophilic stage, at the beginning of maturation for NP and at the end of maturation for fluoranthene. A specific microflora was probably involved in the biodegradation of fluoranthene while NP, LAS and glyphosate mineralization were linked to total microbial activity. OP sorption on compost was linked to their hydrophobicity, decreasing in the order: fluoranthene>NP>LAS>glyphosate. Moreover, sorption decreased as compost maturity increased, except for glyphosate. The sorption coefficients were positively correlated to mineralization kinetics parameters for NP, LAS and glyphosate, suggesting a positive effect of sorption on increasing mineralization rates.

Typology of exogenous organic matters based on chemical and biochemical composition to predict potential nitrogen mineralization.

Our aim was to develop a typology predicting potential N availability of exogenous organic matters (EOMs) in soil based on their chemical characteristics. A database of 273 EOMs was constructed including analytical data of biochemical fractionation, organic C and N, and results of N mineralization during incubation of soil-EOM mixtures in controlled conditions. Multiple factor analysis and hierarchical classification were performed to gather EOMs with similar composition and N mineralization behavior. A typology was then defined using composition criteria to predict potential N mineralization. Six classes of EOM potential N mineralization in soil were defined, from high potential N mineralization to risk of inducing N immobilization in soil after application. These classes were defined on the basis of EOM organic N content and soluble, cellulose-, and lignin-like fractions. A decision tree based on these variables was constructed in order to easily attribute any EOM to 1 of the 6 classes.

Distribution of C and N mineralization of a sludge compost within particle-size fractions.

The contribution of particle-size fractions to carbon (C) and nitrogen (N) mineralization of sludge compost was investigated. Particle-size fractionation was performed using "dry" (sieving of total dry compost) and "wet" (dispersion of compost in water, followed by sieving) fractionation methods, then C and N mineralization of the separated fractions were measured during incubation in soil. The "dry" fractionation did not allow the actual particle-size distribution of compost to be estimated accurately. Out of all the "wet" fractions, the [0-50 microm] fraction was the most significant fraction in compost mass and contributed the most to the N mineralization of sludge compost in soil. Its low degradability, positive N mineralization and similarities with sludge OM suggest that the most humified sludge organic matter was located in this fraction, which would probably contribute to C storage and N availability after compost application in soil. Other fractions (>200 microm) were more readily biodegradable and induced N immobilization.

Effect of urban waste compost application on soil near-saturated hydraulic conductivity.

Compost application tends to increase soil fertility and is likely to modify soil hydrodynamic properties by acting on soil structural porosity. Two composts, a municipal solid waste compost (MSW) and a co-compost of green wastes and sewage sludge (SGW), have been applied every other year for 6 yr to cultivated plots located on a silt loam soil in the Parisian Basin, France. Four soil zones were defined in the topsoil after plowing: the plowpan located at the base of the plowed layer, compacted (Delta) or noncompacted (Gamma) zones located within the plowed layer, and interfurrows created by plowing and containing a large quantity of crop residues together with the recently-applied compost. To assess the effect of compost application on the near-saturated soil hydraulic conductivity, infiltration rates were measured using a tension disc infiltrometer at three water pressure potentials -0.6, -0.2, and -0.05 kPa in the various zones of the soil profile. Compost addition decreased K((sat)) in the interfurrows after plowing by almost one order of magnitude with average values of 5.6 x 10(-5) m.s(-1) in the MSW plot and 4.1 x 10(-5) m.s(-1) in the SGW plot, against 2.2 x 10(-4) m.s(-1) in the control plot. This effect had disappeared 6 mo after plowing when the average K((sat)) in the control plot had decreased to 1.9 x 10(-5) m.s(-1) while that in the compost-amended plots remained stable.

Lignin incorporation combined with electron-beam irradiation improves the surface water resistance of starch films.

We investigated the potential of an electron-beam post-treatment to tailor the properties of 70/30 and 80/20 wt. extruded starch-lignin films. The effect of a 400 kGy radiation on films differing essentially by the kind of lignins incorporated (lignosulfonates/alkali lignins) was assessed both at the macroscopic and the molecular levels. Changes in the polymer molecular structure were studied by IR spectroscopy, by thioacidolysis as well as by model compound experiments. Electron beam-irradiation at 400 kGy, a rather high dose for processing natural polymers, alters to some extent the mechanical resistance of the starch-based materials. However this treatment substantially reduces the hydrophilic surface properties of the films, while not harming their biodegradability. Involved in radical cross-coupling reactions, lignin phenolic compounds are likely to play a primary role in the formation of a hydrophobic condensed network. This study suggests that lower irradiation doses might yield biomaterials with improved usage properties.

Behavior of 14C-atrazine in Argentinean topsoils under different cropping managements.

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) behavior was studied in four surface soils during incubations in laboratory conditions. Soils were chosen in relation to their cropping management (tillage and no tillage) and crop rotation system (continuous soybean [Glycine mar (L.) Merr.] and maize (Zea mays L.)-soybean rotation). A natural soil under brushwood was sampled as a reference. Atrazine use in field conditions was associated with maize cropping, thus only one soil received atrazine every other year. Atrazine behavior was characterized through the balance of 14C-U-ring atrazine radioactivity among the mineralized fraction, the extractable fraction, and the nonextractable bound residues. Soil organic matter capacity to form bound residues was characterized using soil size fractionation. Accelerated atrazine mineralization was only observed in the soil receiving atrazine in field conditions. Atrazine application every other year was enough to develop a microflora adapted to triazine ring mineralization. Bound residue formation was rapid and increased with soil organic matter content. The coarsest soil size fractions (2000-200 and 200-50 microm) containing the nonhumified organic matter presented the highest capacity to form bound residues. No effect of tillage system was observed, probably because of the uniform sampling depth at 20 cm, hiding the stratification pattern of soil organic matter in non-tilled soils.

Characterization of an atrazine-degrading Pseudaminobacter sp. isolated from Canadian and French agricultural soils.

Atrazine, a herbicide widely used in corn production, is a frequently detected groundwater contaminant. Fourteen bacterial strains able to use this herbicide as a sole source of nitrogen were isolated from soils obtained from two farms in Canada and two farms in France. These strains were indistinguishable from each other based on repetitive extragenic palindromic PCR genomic fingerprinting performed with primers ERIC1R, ERIC2, and BOXA1R. Based on 16S rRNA sequence analysis of one representative isolate, strain C147, the isolates belong to the genus Pseudaminobacter in the family Rhizobiaceae. Strain C147 did not form nodules on the legumes alfalfa (Medicago sativa L.), birdsfoot trefoil (Lotus corniculatus L.), red clover (Trifolium pratense L.), chickpea (Cicer arietinum L.), and soybean (Glycine max L.). A number of chloro-substituted s-triazine herbicides were degraded, but methylthio-substituted s-triazine herbicides were not degraded. Based on metabolite identification data, the fact that oxygen was not required, and hybridization of genomic DNA to the atzABC genes, atrazine degradation occurred via a series of hydrolytic reactions initiated by dechlorination and followed by dealkylation. Most strains could mineralize [ring-U-(14)C]atrazine, and those that could not mineralize atrazine lacked atzB or atzBC. The atzABC genes, which were plasmid borne in every atrazine-degrading isolate examined, were unstable and were not always clustered together on the same plasmid. Loss of atzB was accompanied by loss of a copy of IS1071. Our results indicate that an atrazine-degrading Pseudaminobacter sp. with remarkably little diversity is widely distributed in agricultural soils and that genes of the atrazine degradation pathway carried by independent isolates of this organism are not clustered, can be independently lost, and may be associated with a catabolic transposon. We propose that the widespread distribution of the atrazine-degrading Pseudaminobacter sp. in agricultural soils exposed to atrazine is due to the characteristic ability of this organism to utilize alkylamines, and therefore atrazine, as sole sources of carbon when the atzABC genes are acquired.

Characterisation of DNA gyrase and measurement of drug accumulation in clinical isolates of Acinetobacter baumannii resistant to fluoroquinolones.

Twelve clinical isolates of Acinetobacter baumannii highly resistant to pefloxacin (MIC > or = 32 mg/L) and to ciprofloxacin (MIC > or = 16 mg/L), were studied. A susceptible isolate used as a reference (MIC of 0.032 and 0.25 mg/L for ciprofloxacin and pefloxacin, respectively) accumulated 85 mg of pefloxacin per litre of cell volume within 10 min, from a solution containing 10 mg/L of antibiotic. One resistant isolate accumulated the same amount of pefloxacin, while the 11 others accumulated between 40 and 70 mg/L of cell volume. The differences between reference and resistant isolates with respect to ciprofloxacin and sparfloxacin accumulation were less pronounced. There were no apparent differences in the outer membrane protein profiles of susceptible and resistant isolates. DNA gyrase was isolated from four A. baumannii and the minimum concentration of fluoroquinolones, required to inhibit gyrase-catalysed supercoiling of plasmid DNA was 5- to 80-fold higher for the resistant isolates than for the reference strain. Although most isolates showed some degree of reduced fluoroquinolone accumulation, a DNA gyrase mutation was more likely to be the main mechanism of the high level resistance encountered.