Mineralization,metabolism and formation of non-extractable residues of 14C-labelled organic contaminants during pilot-scale composting of municipal biowaste

Use of municipal biowaste for composting instead of its disposal has become a major source of concern as regards contamination by hazardous substances. To elucidate the hazard potential of compost application, municipal biowaste was amended with 14C-labelled model substances (pyrene, simazine) and incubated in a pilot-scale composting simulation system. A mass balance incorporating the mineralization, metabolism and sorption of the two model substances was established over a period of 370 days. The results are quite different for the two chemicals, reflecting their intrinsic properties: more than 60% of the applied 14C-simazine resulted in non-extractable residues (NER). Silylation experiments indicated that the formation of NER from simazine and its metabolites was due to both physical entrapment in the matrix and chemical binding. The mineralization and formation of NER represented the major pathways of disappearance for pyrene during one year of composting, accounting for 60 and 26% of initially applied 14C-activity, respectively. Mineralization occurred delayed after the thermophilic phase. As regards remobilization, release of pyrene from NER during composting could be excluded, whereas simazine, data were inconclusive in this respect.     

Organic micropollutants’ distribution within sludge organic matter fractions explains their dynamic during sewage sludge anaerobic digestion followed by composting

The simultaneous fate of organic matter and 4 endocrine disruptors (3 polycyclic aromatic hydrocarbons (PAHs) (fluoranthene, benzo(b)fluoranthene, and benzo(a)pyrene) and nonylphenols (NP)) was studied during the anaerobic digestion followed by composting of sludge at lab-scale. Sludge organic matter was characterized, thanks to chemical fractionation and 3D fluorescence deciphering its accessibility and biodegradability. Total chemical oxygen demand (COD) removal was 41% and 56% during anaerobic digestion and composting, respectively. 3D fluorescence highlighted the quality changes of organic matter. During continuous anaerobic digestion, organic micropollutants’ removal was 22?±?14%, 6?±?5%, 18?±?9%, and 0% for fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, and nonylphenols, respectively. Discontinuous composting allowed to go further on the organic micropollutants’ removal as 34?±?8%, 31?±?20%, 38?±?10%, and 52?±?6% of fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, and nonylphenols were dissipated, respectively. Moreover, the accessibility of PAH and NP expressed by their presence in the various sludge organic matter fractions and its evolution during both treatments was linked to both the quality evolution of the organic matter and the physicochemical properties of the PAH and NP; the presence in most accessible fractions explained the amount of PAH and NP dissipated.

     

The use of elemental sulphur as organic alternative to control pH during composting of olive mill wastes

High values of pH may represent a limitation for the agricultural use of the composts, not only when used as soil-less substrate but also as soil amendment in high pH soils. The addition of elemental S during the maturation phase of the composting process was evaluated as suitable method to reduce pH of the composts under the organic agriculture regulations. A compost prepared with two phase olive mill waste (OMW) and sheep litter (SL) was used to study the effect of elemental sulphur addition on the pH of the composting mixture. Initially, different bench scale experiments were designed in order to study the influence of moisture, sulphur concentration, and incubation temperature on the sulphur oxidation rate and thus on the pH of the compost. A concentration of 0.5% in sulphur (dry weight basis) and moisture of 40% were proposed as the optimum conditions to decrease the compost pH by 1.1 units without increasing in EC to levels that may suppose a limitation for its agricultural use. Finally, these optimum experimental conditions found at bench scale were tested at full scale in a commercial composting plant treating the same organic materials by windrowing. The pH values of the composting mixture were reduced by one unit after 2 weeks following the addition of elemental S causing no negative effects on the final compost quality.     

A laboratory study of the mineralization and binding of 14C-labeled herbicide rimsulfuron in a rendzina soil.

The fate of pyrimidine-2-14C-rimsulfuron in a rendzina soil was investigated using a laboratory microcosm approach. Measurement of CO2 evolution suggested that rimsulfuron applied at 5 times the recommended dose did not affect soil respiration. Under abiotic conditions, no mineralization of 14C-rimsulfuron into 14C-CO2 occurred and under biotic ones it was very low reaching 0.75% of the applied 14C-rimsulfuron after 246 days of incubation. The analysis of data showed that a three-half order model provided the best fit for the mineralization curve. Extractable 14C-residues decreased over time to 70-80% of the applied 14C-rimsulfuron at the end of the incubation. After 246 days of incubation, non extractable residues (NER) accounted for up to 24.7% of the applied 14C-rimsulfuron and were distributed according to organic carbon in soil size fractions, suggesting a progressive incorporation process of NER to soil humus.     

Formation, characterization and release of non-extractable residues of [14C] -labeled organic xenobiotics in soils

The amount of non-extractable residues (NER) of organic xenobiotics in the soil can considerably exceed the amount of extractable residues which are accessible to normal residue analysis. The NER therefore present a burden to the soil, the toxicological and ecotoxicological potential of which is largely unknown. For the characterization of bound residues and their binding type, special solubilization methods such as supercritical fluid extraction are applied and experiments with radiolabeled model polymers are performed. Mineralization experiments with [¹⁴C] labeled xenobiotics in natural soil show that a total degradation is still also possible in the environment when in a bound form. Ecotoxicological effects of non-extractable residues may be recorded when their concentration is high, when the parent compound exhibits a high ecotoxicity and the applied detection method is sufficiently sensitive.     

Distribution,fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, ¹⁴C- and ¹³C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied ¹⁴C was mineralized. The bioavailable, water extractable portion was low (9 % of applied ¹⁴C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied ¹⁴C was incorporated into organo-clay complexes as NER, whereas 9 % of applied ¹⁴C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Degradation of organic pollutants in Mediterranean forest soils amended with sewage sludge

The degradation of two groups of organic pollutants in three different Mediterranean forest soils amended with sewage sludge was studied for nine months. The sewage sludge produced by a domestic water treatment plant was applied to soils developed from limestone, marl and sandstone, showing contrasting alkalinity and texture. The compounds analysed were: linear alkylbenzene sulphonates (LAS) with a 10–13 carbon alkylic chain, and nonylphenolic compounds, including nonylphenol (NP) and nonylphenol ethoxylates with one and two ethoxy groups (NP1EO + NP2EO). These compounds were studied because they frequently exceed the limits proposed for sludge application to land in Europe. After nine months, LAS decomposition was 86–96%, and NP + NP1EO + NP2EO decomposition was 61–84%, which can be considered high. Temporal trends in LAS and NP + NP1EO + NP2EO decomposition were similar, and the concentrations of both types of compounds were highly correlated. The decomposition rates were higher in the period of 6–9 months (summer period) than in the period 0–6 months (winter + spring period) for total LAS and NP + NP1EO + NP2EO. Differences in decay rates with regard to soil type were not significant. The average values of decay rates found are similar to those observed in agricultural soils.     

Formation of non-extractable pesticide residues: observations on compound differences, measurement and regulatory issues

Six major use pesticides (Atrazine, Dicamba, Isoproturon, Lindane, Paraquat and Trifluralin) with differing physico-chemical properties were evaluated for the significance of 'bound' or non extractable residue formation. Investigations were carried out in purpose-built microcosms where mineralization, volatilisation, 'soil water' extractable and organic solvent extractable residues could be quantified. Extractable residues were defined as those accessible by sequential extraction where the solvent used became increasingly non-polar. Dichloromethane was the 'harshest' solvent used at the end of the sequential extraction procedure. (14)C-labelled volatilised and (14)CO(2) fractions were trapped on exit from the microcosm. The pesticides were categorised into 3 classes based on their behaviour. (i) Type A (Atrazine, Lindane and Trifluralin) in which ring degradation was limited as was the formation of non-extractable residues; the remainder of the (14)C-activity was found in the extractable fraction. (ii) Type B (Dicamba and Isoproturon) in which approximately 25% of the (14)C-activity was mineralised and a large portion was found in the non-extractable fraction after 91 days. Finally, Type C (Paraquat) in which almost all of the (14)C-activity was quickly incorporated into the non-extractable fraction. The implications of the data are discussed, with respect to the variability and significance of regulatory aspects of non-extractable residues.     

Distribution, fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, (14)C- and (13)C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied (14)C was mineralized. The bioavailable, water extractable portion was low (9 % of applied (14)C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied (14)C was incorporated into organo-clay complexes as NER, whereas 9 % of applied (14)C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Treatment system for solid matrix contaminated with fluoranthene. I--Modified extraction technique.

A laboratory-scale ultrasonication technique was developed for fluoranthene extraction from soils and sediments where the utilized organic solvent would be recovered after the extraction process. Therefore, the remedied soils and sediments would be free from toxicant and trace of added chemicals. The developed ultrasonication technique outlined here is an integrated part of a complete remediation system consisting of extraction and solar detoxification reactors. This paper investigates extraction efficiencies under different conditions, outlines solvent recovery technique and compares extraction efficiency of the developed ultrasonication technique with a commercially available laboratory-scale sonication bath. The spiked soil sample with fluoranthene (19.4 microg g(-1)) and organic solvent was ultrasonicated at 40 degrees C for 20 min. The sonicated mixture was allowed to settle for 10 min before the extract gravitated into the modified solar reactor for fluoranthene detoxification. The added solvents were removed from the remedied soil before it was released to site. The mixture of cyclohexane and ethanol (CH:ETOH) (3:1) was the favorable solvent from among 10 organic solvents because of its high extraction efficiency, safety and low cost. Preliminary results indicated that the developed extraction technique recovered more than 93% of fluoranthene from soil samples.     

Insight into the dynamic microbial community and core bacteria in composting from different sources by advanced bioinformatics methods

Microbial communities are important for high composting efficiency and good quality composts. This study was conducted to compare the changes of physicochemical and bacterial characteristics in composting from different raw materials, including chicken manure (CM), duck manure (DM), sheep manure (SM), food waste (FW), and vegetable waste (VW). The role and interactions of core bacteria and their contribution to maturity in diverse composts were analyzed by advanced bioinformatics methods combined sequencing with co-occurrence network and structural equation modeling (SEM). Results indicated that there were obviously different bacterial composition and diversity in composting from diverse sources. FW had a low pH and different physiochemical characteristics compared to other composts but they all achieved similar maturity products. Redundancy analysis suggested total organic carbon, phosphorus, and temperature governed the composition of microbial species but key factors were different in diverse composts. Network analysis showed completely different interactions of core bacterial community from diverse composts but Thermobifida was the ubiquitous core bacteria in composting bacterial network. Sphaerobacter and Lactobacillus as core genus were presented in the starting mesophilic and thermophilic phases of composting from manure (CM, DM, SM) and municipal solid waste (FW, VW), respectively. SEM indicated core bacteria had the positive, direct, and the biggest (>?80%) effects on composting maturity. Therefore, this study presents theoretical basis to identify and enhance the core bacteria for improving full-scale composting efficiency facing more and more organic wastes.

     

Environmental fate of amitrole: influence of dissolved organic matter

In this study the environmental fate of amitrole in terrestrial and aquatic model ecosystems was investigated. Under aerobic conditions mineralization of amitrole is the main degradation pathway. The experiments revealed that the leaching behaviour is low in the presence or the absence of dissolved organic matter (DOM) despite the high water solubility due to a strong binding of amitrole to soil constituents. Under anaerobic conditions the addition of DOM increases the transport of amitrole in soil columns. The tests with water/sediment model ecosystems showed that the mineralization of amitrole is lower in comparison to aerobic soil experiments. Up to 80.6% of the applied 14C-labelled amitrole transfer into the sediment and about 1/3 of this amount formed bound residues, which are not extractable.     

Laboratory studies on volatilization and mineralization of 14c‐p,p'‐DDT in soil,release of bound residues and dissipation from solid surfaces

Abstract

In support of field data, laboratory studies were conducted on volatilization, mineralization and binding of ¹⁴C‐p,p'‐DDT in soils at Sao Paulo. Incubation of soil for 6 weeks did not result in volatilized organics or mineralization; with >95% extractable radiocarbon in the form of p,p'‐DDT. Small amounts of bound residues (1.8%) were detected in soil. These data confirm the very slow dissipation of DDT in the field which presumably relates to the acidic pH of soil (4.5–4.8).

Bound ¹⁴C‐residues in soils treated with ¹⁴C‐p,p'‐DDT at Praia Grande and Sao Paulo could be released (5–21%) by sulphuric acid treatment. The released residue had the composition: 69–90% DDT, 7–32% DDD and 0–3% DDE. Incubation of soil bound ¹⁴C‐residues with fresh inoculum for 3 months did not result in release of ¹⁴C.

Dissipation from wooden surfaces was fairly slow. After 20 weeks, 74% of the applied radioactivity could be recovered; 44% hexane‐non‐extractable.     

Dynamics of copper and tetracyclines during composting of water hyacinth biomass amended with peat or pig manure

Composting is one of the post-treatment methods for phytoremediation plants. Due to a high potential of water hyacinth to accumulate pollutants, the physicochemical parameters, microbial activity as well as fates of copper (Cu) and tetracyclines (TCs) were investigated for the different amended water hyacinth biomass harvested from intensive livestock and poultry wastewater, including unamended water hyacinth (W), water hyacinth amended with peat (WP), and water hyacinth amended with pig manure (WPM) during the composting process. Pig manure application accelerated the composting process as evidenced by an increase of temperature, electrical conductivity (EC), NH₄-N, as well as functional diversity of microbial communities compared to W and WP treatments. Composting process was slowed down by high Cu, but not by TCs. The addition of peat significantly increased the residual fraction of Cu, while pig manure addition increased available Cu concentration in the final compost. Cu could be effectively transformed into low available (oxidizable) and residual fractions after fermentation. In contrast, less than 0.5% of initial concentrations of TCs were determined at the end of 60-day composting for all treatments in the final composts. The dissipation of TCs was accelerated by the high Cu concentration during composting. Therefore, composting is an effective method for the post-treatment and resource utilization of phytoremediation plants containing Cu and/or TCs.     

Comparison of biodegradation of surfactants in soils and sludge-soil mixtures by use of 14C-labelled compounds and automated respirometry

The biodegradability of dodecyl benzene sulphonate (LAS), nonylphenol-di-ethoxylate (NP2EO) and tridecyl-tetra-ethoxylate (LAE) in soil was examined by use of 14C experiments at two concentrations (10 and 400 mg/kg). Increasing the concentration of test chemical from 10 to 400 mg/kg resulted in a decrease in the relative maximum mineralization rate and an increase in the estimated lag times of a factor of approximately 3.5. In sludge-amended soil, the highest expected environmental concentration (just after sludge application) will be around 10 mg/kg for linear alkylbenzene sulphonate (LAS), while the concentration of NP2EO and linear alcohol ethoxylates (LAE) will be much lower. However, when using a respirometric method it is necessary to use a higher concentration of test substance in order to detect biodegradation. In our experiment, amendment with anaerobically digested sludge resulted in a decrease in the mineralization of LAS, NP2EO and LAE for all soils. Respirometric experiments were carried out at 400 mg/kg and could be used for estimation of biodegradation potential of LAS, NP2EO and LAE in soil and sludge-amended soil. For LAS, the results obtained from the respirometric experiments were similar to the results obtained in the 14C experiments, whereas NP2EO and LAE showed a faster degradation in the respirometric experiments.     

Formation of chloromethoxybenzaldehyde during composting of organic household waste

Standardized household waste was mixed with different litter amendments, straw, leaves, hardwood shavings, softwood shavings, paper, and sphagnum peat, resulting in six compost mixtures. In addition non-amended household waste was composted. Composting was done in small rotatable bins and compost samples were taken on a regular basis until day 590. Extraction and analysis of wet compost samples showed no evidence for the presence of chloroorganic compounds. Drying and re-wetting of compost samples, however, revealed that chloromethoxybenzaldehyde (CMBA) was formed in all composts at concentrations varying between 5.6 and 73.4 microg kg(-1) dry matter. CMBA was not present in the original materials. During composting, there was a clear positive relation between formation of CMBA and microbial activity, as indicated by C losses and temperature. Formation took place during the most intensive phase of composting when C losses were highest. Under anaerobic conditions, however, which prevailed initially in the non-amended compost, no CMBA was formed. Calculation of total amounts of CMBA in composts revealed that there was a small decrease during storage in the hardwood, peat, and softwood composts. However, all composts contained CMBA after 590 days. The mean concentration was 33.4 microg kg(-1) dry matter (s.d. = 21.9). Possible biocidal effects of composts when used in cultivation may be explainable by the presence of natural toxic compounds formed during composting.     

Development of functional composts using spent coffee grounds,poultry manure and biochar through microbial bioaugmentation

Spent coffee grounds (SCG), poultry manure, and agricultural waste-derived biochar were used to manufacture functional composts through microbial bioaugmentation. The highest yield of tomato stalk-based biochar (40.7%) was obtained at 450°C with a surface area of 2.35 m² g^?1. Four pilot-scale composting reactors were established to perform composting for 45 days. The ratios of NH₄⁺–N/NO₃^?–N, which served as an indicator of compost maturity, indicate rapid, and successful composting via microbial bioaugmentation and biochar amendment. Moreover, germination indices for radish also increased by 14–34% through augmentation and biochar amendment. Microbial diversity was also enhanced in the augmented and biochar-amended composts by 7.1–8.9%, where two species of Sphingobacteriaceae were dominant (29–43%). The scavenging activities of 2,2-diphenyl-1-picrylhydrazyl (DPPH) were enhanced by 14.1% and 8.6% in the fruits of pepper plants grown in the presence of the TR-2 (augmentation applied only) and TR-3 (both augmentation and biochar amendment applied) composts, respectively. Total phenolic content was also enhanced by 68% in the fruits of the crops grown in TR-3. Moreover, the other compost, TR-L (augmentation applied only), boosted DPPH scavenging activity by 111% in leeks compared with commercial organic fertilizer, while TR-3 increased the phenolic content by 44.8%. Composting facilitated by microbial augmentation and biochar amendment shortened the composting time and enhanced the quality of the functional compost. These results indicate that functional compost has great potential to compete with commercially available organic fertilizers and that the novel composting technology could significantly contribute to the eco-friendly recycling of organic wastes such as spent coffee grounds, poultry manure, and agricultural wastes.     

Spectroscopic characterization of water extractable organic matter during composting of municipal solid waste

This paper aims to characterize the evolution of water extractable organic matter (WEOM) during the composting of municipal solid waste (MSW), and investigate the correlation between maturity and WEOM characteristics. WEOM was extracted at different stages of MSW composting (0, 7, 14, 21, and 51 d) and characterized by FTIR, UV-Vis, and fluorescence spectroscopy. The results obtained show that the composting process decreased aliphatics, alcohols, polysaccharides, as well as protein-like materials, and increased aromatic polycondensation, humification, oxygen-containing functional groups, molecular weight, and humic-like materials. The maturity of MSW during composting was characterized by the presence of the peak with an excitation/emission wavelength pair of 289/421 nm in excitation-emission matrix spectra.     

Impact of composting strategies on the treatment of soils contaminated with organic pollutants

Chemical pollution of the environment has become a major source of concern. Studies on degradation of organic compounds have shown that some microorganisms are extremely versatile at catabolizing recalcitrant molecules. By harnessing this catabolic potential, it is possible to bioremediate some chemically contaminated environmental systems. Composting matrices and composts are rich sources of xenobiotic-degrading microorganisms including bacteria, actinomycetes and lignolytic fungi, which can degrade pollutants to innocuous compounds such as carbon dioxide and water. These microorganisms can also biotransform pollutants into less toxic substances and/or lock up pollutants within the organic matrix, thereby reducing pollutant bioavailability. The success or failure of a composting/compost remediation strategy depends however on a number of factors, the most important of which are pollutant bioavailability and biodegradability. This review discusses the interactions of pollutants with soils; look critically at the clean up of soils contaminated with a variety of pollutants using various composting strategies and assess the feasibility of using composting technologies to bioremediate contaminated soil.     

Generalized models for prediction of pentachlorophenol dissipation dynamics in soils

Dissipation of pentachlorophenol (PCP) in soil was investigated and the chemical relationships with soil properties were addressed. The results indicate that the dissipation of extractable PCP residues can be described using first-order kinetics equations, with a half-dissipation time (T(1/2)) ranging from 6.5 to 173.3d. The sharply different patterns of PCP dissipation in different soils were closely related to soil properties. Correlations of stepwise regression equations obtained were significant at 0.01 probability level between soil parameters and extractable PCP residues (R(2)=0.974**) as well as T(1/2) values (R(2)=0.882**). Using pH together with organic carbon content (OC) and soil particle size distribution, the dissipation dynamics of PCP in soil could be accurately predicted.