Dissolved organic matter fractions formed during composting of winery and distillery residues: evaluation of the process by fluorescence excitation-emission matrix

The aim of the present paper is to assess the maturity degree reached by different samples of several mixtures from winery and distillery residues composted using the Rutgers composting system, by means of excitation-emission matrix (EEM) fluorescence spectroscopy. The composts were sampled once a week for about 200d. EEM spectra indicate the presence of different fluorophores. The fluorescence intensities of these peaks show trends related to the maturity of the composting samples selected. The "contour density" of EEM maps is strongly modified through time. We have used the quantitative method of fluorescence regional integration (FRI). The EEMs were delineated into five excitation-emission regions. The degree of compost maturity could be correlated with the percentage of the volumetric integration under the EEM within each region. Further refinement of these techniques should provide a relatively rapid method for assessing the suitability of the compost to soil application.     

三维荧光区域积分评估城市污水中溶解性有机物去除

以三维荧光技术为手段,结合荧光区域积分和聚类分析,考察某城市污水厂污水处理过程中溶解性有机物的去除状况。研究结果表明,采用三维荧光区域积分可以表征城市污水中易降解、可降解和难降解有机物相对含量的变化趋势,能够有效识别污水中溶解性有机物的指纹特征。城市污水中类蛋白等易降解物质含量约占总荧光物质的50%,在污水厂曝气池缺氧段,易降解基质被大量去除。曝气池顺水流方向约225 m处,溶解性有机物的去除已基本完成。三维荧光光谱中区域II和III的积分标准体积与TOC的皮尔森相关指数分别为0.964和0.970。和其他荧光指数相比,这2个区域的积分标准体积与TOC的相关度更高。     

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.     

The comparison study of compost and natural organic matter samples

Sewage sludge is a serious problem facing modern wastewater treatment plants. One of the methods to safely utilize the sludge is through composting and the agricultural use of the final product.In this study the compost samples from municipal sewage sludge are compared to the natural, rich in organic matter samples. Based on physicochemical properties of the material, the maturity indices are obtained to evaluate the quality of organic matter and estimate the similarities between the samples.The study shows that one-dimensional analysis like that based on maturity indices does not provide satisfactory answers concerning the nature of such complex materials. The data set of the analysis naturally possesses a multidimensional character so that the employment of advanced chemometric techniques like cluster analysis show a number of features which were hidden within the ‘data flood’.The major conclusion of this work is that the compost from sewage sludge is similar to peat in the significance of the properties of the organic matter. Moreover, the organic matter of agricultural soil, which is most stable and has been naturally matured over a long period of time, differs substantially from the other samples.     

接种外源微生物菌剂对香蕉茎秆堆肥的影响

为了研究接种外源微生物菌剂对香蕉茎秆堆肥的影响,本实验采用高温好氧堆肥技术,设计了对照（不接菌）、接种白腐菌及棱盖多孔菌3个处理,探讨了不同处理堆肥过程中堆体温度、水分、pH值、电导率、有机碳、C/N、发芽指数及堆肥质量的变化情况。结果表明,接种微生物菌剂处理的温度均高于对照,且高温期持续时间相对较长,以接种白腐菌处理的高温持续时间最长;接种外源微生物菌剂对堆肥含水率、pH、EC、全碳、C/N变化影响不大;与对照相比,接种白腐菌可增加全氮及全钾的含量,有利于提高堆肥产品质量;接种白腐菌处理在36 d（GI〉50%）就达到腐熟,比对照提前8 d腐熟,明显缩短堆肥腐熟时间;而接种棱盖多孔菌处理比对照推迟10 d腐熟,共需54 d不利于香蕉茎秆堆肥的进行。     

Investigation of organic matter dynamics during in-vessel composting of an aged coal-tar contaminated soil using fluorescence excitation-emission spectroscopy

In-vessel composting of an aged coal-tar contaminated soil from a manufactured gas plant site was investigated over 98days using laboratory-scale in-vessel composting reactors. The composting reactors were operated at 18 different operational conditions using a logistic three-factor factorial design with three temperatures (T=38, 55 and 70 degrees C), four soil to green waste ratios (S:GW; 0.6:1, 0.7:1, 0.8:1 and 0.9:1 on a dry weight basis) and three moisture contents (MC; 40%, 60% and 80%). Excitation-emission matrix (EEM) fluorescence spectroscopy was used to investigate organic matter dynamics in the composting mixture. The results of this investigation indicated that formation of humic substances can be monitored by fluorescence excitation-emission matrix, and provided evidence of progressive mineralization or humification of the composting mixture. Peak excitation wavelength shifts and peak fluorescence intensity can both be used as indicators to monitor the humification or maturation of compost. Finally, the fluorescence index can be applied to investigate the origin of humic substances and fulvic acids, and the humification or maturation of compost.     

Use of 15N-depleted artificial compost in bound residue studies

Association of bound residues to soil humic matter may be accomplished by different binding mechanisms such as sequestration in hydrophobic interiors of the organic material or covalent linkage to the organic matter. The structures and chemical environments of compounds can be observed by NMR spectroscopy. We applied 15N-NMR spectroscopy to study the soil-bound residues of 15N-labeled simazine. As the 15N-isotope has a low sensitivity and natural abundance 15N-NMR experiments require long measurement times and often result in low signal-to-noise (S/N) ratios. Therefore, in addition to the use of 15N-labeled simazine, 15N-depleted compost was used to reduce the amount of background signal and enhance the sensitivity. The compost was produced from maize and wheat plants grown on sand with 15N-depleted NH4NO3 as sole nitrogen source. The plants were freeze-dried, ground and mixed with sand for composting. After a composting period of 224 days analysis of the compost revealed a 15N-content of 267 ppm as opposed to a natural abundance of 3650 ppm. Characterization of this artificial compost produced parameter values similar to those of a natural compost. The 13C-NMR-spectra of the humic and fulvic acids during different stages of maturity showed that there was a shift from single-bond functional groups to more complex double-bond and aromatic structures. Experiments with this compost showed an increased signal intensity. The improved sensitivity made it possible to obtain interpretable NMR signals in contrast to experiments with 15N-simazine on native soil where no signals were detectable. The data indicated that the bound residues of simazine are composed of metabolites resulting from N-dealkylation and triazine ring destruction. Silylation of the bound residues showed a very strong binding of the residues to the matrix as only a small fraction could be solubilized.     

Investigating the effect of landfill leachates on the characteristics of dissolved organic matter in groundwater using excitation–emission matrix fluorescence spectra coupled with fluorescence regional integration and self-organizing map

For the purpose of investigating the effect of landfill leachate on the characteristics of organic matter in groundwater, groundwater samples were collected near and in a landfill site, and dissolved organic matter (DOM) was extracted from the groundwater samples and characterized by excitation–emission matrix (EEM) fluorescence spectra combined with fluorescence regional integration (FRI) and self-organizing map (SOM). The results showed that the groundwater DOM comprised humic-, fulvic-, and protein-like substances. The concentration of humic-like matter showed no obvious variation for all groundwater except the sample collected in the landfill site. Fulvic-like substance content decreased when the groundwater was polluted by landfill leachates. There were two kinds of protein-like matter in the groundwater. One kind was bound to humic-like substances, and its content did not change along with groundwater pollution. However, the other kind was present as “free” molecules or else bound in proteins, and its concentration increased significantly when the groundwater was polluted by landfill leachates. The FRI and SOM methods both can characterize the composition and evolution of DOM in the groundwater. However, the SOM analysis can identify whether protein-like moieties was bound to humic-like matter.     

Co-composting of distillery wastes with animal manures: carbon and nitrogen transformations in the evaluation of compost stability

The aim of this work was to study the viability of recycling the solid wastes generated by the winery and distillery industry by means of co-composting with animal manures, as well as to evaluate the quality of the composts obtained. Two piles, using exhausted grape marc and cattle manure or poultry manure, respectively (at ratios, on a fresh weight basis, of 70:30), were composted by the Rutgers static pile composting system. Throughout the composting process, a number of parameters were monitored, such as pH, electrical conductivity, organic matter, water-soluble carbon, water-soluble polyphenols, different forms of nitrogen (organic nitrogen, ammonium and nitrate) and humification indices (humification ratio, humification index, percentage of humic acid-like C, polymerisation ratio and cation exchange capacity), as well as the germination index. Organic matter losses followed first-order kinetics equation in both piles, the highest organic matter mineralisation rate being observed with exhausted grape marc and cow manure. On the other hand, the mixture with the lowest C/N ratio, using exhausted grape marc and poultry manure, showed the highest initial ammonium contents, probably due to the higher and more labile N content of poultry manure. The increase in the cation exchange capacity revealed the organic matter humification during composting. In contrast, other humification parameters, such as the humification ratio and the humification index, did not show the expected evolution and, thus, could not be used to assess compost maturity. Composting produced a degradation of the phytotoxic compounds, such as polyphenols, to give composts without a phytotoxic character. Therefore, composting can be considered as an efficient treatment to recycle this type of wastes, due to composts presented a stable and humified organic matter and without phytotoxic effects, which makes them suitable for their agronomic use.     

Direct and indirect impact of sewage sludge compost spreading on Quercus coccifera monoterpene emissions in a Mediterranean shrubland

Monoterpene emissions of Quercus coccifera L. were repeatedly measured during the two years following the spreading of a sewage sludge compost at rates of 50 Mg ha⁻¹ and 100 Mg ha⁻¹, in a twelve-year-old post-fire Mediterranean shrubland. We also monitored the patterns of change in soil and leaf nutrient content, plant water potential, chlorophyll fluorescence, and plant growth. Compost spreading resulted in weak changes in leaf nutrient content and plant water status, and therefore no significant effect on monoterpene emissions at leaf scale, except during one summer sampling, probably related to advanced leaf maturity with the highest compost rate. However, compost increased plant growth, particularly the leaf biomass. The results suggest that compost spreading in Mediterranean shrublands has no strong short-term effect on Q. coccifera monoterpene emissions at leaf level, but may indirectly increase volatile organic compound fluxes at the stand scale, which may contribute to regional ozone pollution.     

Effect of inoculating microbes in municipal solid waste composting on characteristics of humic acid

Municipal solid waste (MSW) compost contains a significant amount of humic substances. In this study, the compost consisted of residual MSW with the metal, plastic and glass removed. In order to enhance degradation processes and the degree of composting humification, complex microorganisms (Bacillus casei, Lactobacillus buchneri and Candida rugopelliculosa) and ligno-cellulolytic (Trichoderma and White-rot fungi) microorganisms were respectively inoculated in the composting process. During the MSW composting, humic acid (HA) was extracted and purified. Elements (C, N, H, O) and spectroscopic characteristics of the HA were determined using elementary analyzer, UV, Fourier transform infrared (FTIR), and fluorescence spectroscopy. The elements analysis, UV, FTIR and fluorescence spectra all led to the same conclusion, that is inoculations with microbes led to a greater degree of aromatization of HA than in the control process (CK) with no inoculation microbes. This indicated that inoculation with microbes in composting would improve the degree humification and maturation processes, in the following order: lingo-cellulolytic>complex microorganisms>CK. And mixed inoculation of MSW with complex microorganisms and lingo-cellulolytic during composting gave a greater degree of HA aromatization than inoculation with complex microorganisms or lingo-cellulolytic alone. But comparing with the HA of soil, the HA of MSW compost revealed a lower degree of aromatization.     

二丁与连翘药渣联合堆肥腐熟度评价

为了对不同比例的二丁与连翘药渣堆肥腐熟度进行评价,采用条垛式好氧堆肥方式,将二丁和连翘两种药渣按照5种不同的比例进行堆肥处理,通过分析堆肥过程中温度、pH、C/N和发芽指数等指标的变化规律,对堆肥腐熟度进行评价。结果表明:在试验处理条件下及堆肥周期内,单一药渣堆肥的两组处理未能完全腐熟,混合药渣堆肥的3组处理均已达到完全腐熟的标准,说明两种药渣混合后进行堆肥,可以有效促进堆肥的顺利进行,且二丁与连翘比例为2∶1(质量比)时发酵效果最好。3组混合药渣的发酵产物可以作为有机肥或土壤改良剂施用,也可以与化肥配合,制备成有机/无机配方肥。     

二丁与连翘药渣联合堆肥腐熟度评价

为了对不同比例的二丁与连翘药渣堆肥腐熟度进行评价,采用条垛式好氧堆肥方式,将二丁和连翘两种药渣按照5种不同的比例进行堆肥处理,通过分析堆肥过程中温度、pH、C/N和发芽指数等指标的变化规律,对堆肥腐熟度进行评价。结果表明:在试验处理条件下及堆肥周期内,单一药渣堆肥的两组处理未能完全腐熟,混合药渣堆肥的3组处理均已达到完全腐熟的标准,说明两种药渣混合后进行堆肥,可以有效促进堆肥的顺利进行,且二丁与连翘比例为2∶1(质量比)时发酵效果最好。3组混合药渣的发酵产物可以作为有机肥或土壤改良剂施用,也可以与化肥配合,制备成有机/无机配方肥。     

Evaluating spectroscopic and chromatographic techniques to resolve dissolved organic matter via end member mixing analysis

Real-time or near real-time in-situ monitoring of dissolved organic matter (DOM) composition in natural waters and engineered treatment systems provides critical information to water quality scientists and engineers, particularly when the monitoring techniques can provide some information about the chemical nature of DOM. The efficacy of various indices derived from rapid, low-cost spectroscopic and chromatographic techniques to discriminate DOM composition was tested for samples prepared from well-defined mixtures of purified Aldrich humic acid (PAHA) and Suwannee River fulvic acid (SRFA). Sensitivities of the discrimination indices were examined by comparing (1) the differences between measured values and those predicted based from mass balance and the end member characteristics, and (2) the linear correlations between index values and mass ratios of the DOM mixtures. Size exclusion chromatography (SEC) results revealed that the weight-average molecular weight (MW(w)) may be a useful approach for tracking DOM mixing processes, although the number-average molecular weight (MW(n)) may be better for distinguishing different DOM compositions. Specific ultraviolet absorbance measured at 254 nm (SUVA(254)) performed better as a discrimination index than did two previously recommended absorbance ratios, both in terms of making better predictions of intermediate compositions and in exhibiting a more linear correlation with PAHA mass ratio. Several well-defined peaks in the derivative absorption spectra (301 and 314 nm for the first derivative, 217 nm for the third derivative, and 211 and 224 nm for the fourth derivative) also were found to be promising potential DOM discrimination indices. Finally, a fluorescence ratio based on humic- versus fulvic-like fluorescence proved to be a superior DOM discrimination index for the two DOM end members studied here. In general, this study illustrates the evaluation process that should be followed to develop rapid, low-cost discrimination indices to monitor DOM compositions based on end member mixing analyses.     

Evaluation of ozone exposure indices in exposure-response modeling

In exposure-response modeling, a major concern is the numerical definition of exposure in relating crop loss to O3, yet few indices have been considered. This paper addresses research in which plant growth was regressed for soybean, wheat, cotton, corn, and sorghum against 613 numerical exposure indices using the Box-Tidwell model. When the minimum sum of squared errors criterion was used, optimum performance was not attained for any single index; however, near optimum performances were achieved by two censored cumulative indices and from a class of indices called the generalized, phenologically weighted, cumulative impact indices (GPWCIs). The top-performing GPWCIs accumulated concentrations, used sigmoid weighting schemes emphasizing O3 concentrations of 0.06 ppm (118 microg m(-3)) or higher, and had phenological weighting schemes with greatest weight occurring 20 to 40 days prior to crop maturity. These findings indicate that (1) peak concentrations are important, but lower concentrations should be included in the calculations, (2) increased plant sensitivity occurs between flowering and maturity, and (3) plants respond to cumulative exposure impact.     

Effects of different ratios of pig manure to fungus residue on physicochemical parameters during composting

This study examined physicochemical parameters to assess their effectiveness as stability and maturity indicators during the process of composting pig manure and fungus residue at different ratios. The results showed that composting mixtures with all ratios of pig manure to fungus residue maintained a temperature exceeding 50 °C for more than 10 days during composting and met the requirement for pathogen destruction. The treatment containing mainly pig manure showed higher nitrogen loss and a shorter thermophilic phase and maturity time than the treatment containing mainly fungus residue. The germination index (GI) values indicated that compost maturity was achieved in the final compost with initial ratios of pig manure to fungus residue of 9:1–7:3 (GIs of 101.4%, 91.2%, and 81.3%); the ratio of 6:4 did not reach compost maturity (GI of 63.8%) and had an inhibitory effect on seed germination. The results of this study suggest that a ratio of pig manure to fungus residue of approximately 8:2 can be considered suitable for the efficient and quality composting of pig manure and fungus residue.

Implications: Co-composting of pig manure and edible fungi residue with appropriate proportion can effectively reduce the risk of environmental pollution caused by agricultural wastes, as well as achieve a safer and high-quality organic fertilizer, which can be used to improve physical and chemical properties of the soil, increase crop yields, and promote agricultural sustainable development. Therefore, technique of co-composting of pig manure and edible fungi residue has a wide prospect of application in practical production all over the world.     

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.     

Assessment of nematode community structure as a bioindicator in river monitoring

Nematode communities from river water and sediments were assessed for the abundance, feeding types, maturity indices and nematode channel ratio (NCR). The sampling sites studied included different levels of pollution and contamination from agricultural, industrial and sewage sources. The nematode abundance found in the sediment samples was more than that in the water samples. The lowest nematode abundance in sediment samples and the lowest NCR in water samples were both found at the industrial pollution site. Water samples showed positive correlation between the NCR and river pollution index (RPI). Mean maturity indices in sediment samples were inversely correlated with RPI. The pollutant source determined the relationship between NCR and pollution level, while maturity index always showed negative correlation with pollutant level regardless of the pollutant sources. The nematode abundance and its community structure were both reliable bioindicators for monitoring long-term river pollution in both qualitative and quantitative aspects.     

Synchronous-scan fluorescence spectra of Chlorella vulgaris solution

The characterization of the Chlorella vulgaris solution was carried out using synchronous-scan spectroscopy. The range of concentration of algae and Fe(III) in aqueous solutions were 5 × 10⁸–8 × 10⁹ cells l⁻¹ and 10–60 μM, respectively. Effective characterization method used was synchronous-scan fluorescence spectroscopy. The wavelength difference (Δλ) of 90 nm was maintained between excitation and emission wavelengths; 90 nm was found to be the best Δλ for effective characterization of Chlorella vulgaris solution with or without quencher species (e.g., Fe(III), humic acid (HA)) for the first time. The peak was observed at about EX 236.6 nm/EM 326.6 nm for synchronous-scan fluorescence spectra. The fluorescence quenching of algae in system of algae–Fe(III)–HA was studied using synchronous-scan spectroscopy for the first time. Fe(III) was clearly the effective quencher. The relationship between I₀/I (quenching efficiency) and c (concentration of Fe(III) added) was a linear correlation for the algae solution with Fe(III). Also, Aldrich humic acid was found to be an effective quencher. pH effect on synchronous-scan fluorescence intensity of algal solution with Fe(III) and/or HA was evident.     

Fluorescence behaviour of Zn and Ni complexes of humic acids from different sources

Conventional fluorescence spectroscopy in the excitation, emission and synchronous scan modes and three-dimensional fluorescence spectroscopy in the form of an excitation-emission matrix (EEM) of fluorescence intensity as a function of excitation and emission wavelengths have been applied to the study of three humic acids (HAs) extracted from soil (SHA), peat (PHA) and compost (CHA) and their interaction products with Zn(II) and Ni(II) ions. Fluorescence spectra of HAs appear to be related to the nature and origin of the sample. A strong reduction of intensity of all peaks is observed in the spectra of HAs-metal complexes as compared to those of untreated HAs. Ni(II) exhibits greater quenching ability than Zn(II). Fluorescence quenching measured for complexes of HAs at increasing Ni(II) concentrations was linearly correlated with metal ion concentration. The different capacity to interact with metal ions showed by various HAs is attributed to their different molecular complexity.