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.     

垃圾渗滤液处理工艺中有机污染物的三维荧光光谱

利用荧光发射和三维荧光光谱研究了三峡库区某垃圾堆场的渗滤液及其处理工艺出水溶解性有机质(DOM)的荧光光谱特性。堆场渗滤液的DOM含有类酪氨酸、色氨酸及紫外区类富里酸,特征荧光峰中心位于E_x/E_m=275 nm/305 nm,为高激发波长类酪氨酸,与前人的研究结果并不一致,这可能与垃圾的堆放期有关。渗滤液和各处理工艺出水的荧光指数f_450/500均大于1.9,表明腐殖质主要为微生物源。渗滤液在处理前后荧光峰特征和强度均发生明显改变,类蛋白荧光强度与DOC值变化趋势基本一致。生化处理工艺中,类蛋白荧光强度降低了66.4%～95.5%,紫外区类富里酸荧光强度只降低了28.8%,显示类蛋白质具有良好的可生化性,而类富里酸相对较难生化降解。三维荧光光谱能反映渗滤液处理过程中污染物的种类、性质和数量等变化信息,能快速地进行定性分析、定量评价。     

Changes in the chemical composition of water-extractable organic matter during composting: distribution between stable and labile organic matter pools

Aerobic decomposition and stabilization of organic matter during the composting of waste materials is primarily due to the biochemical transformation of water-soluble compounds in the liquid phase by the microbial biomass. For this reason water-soluble organic matter represents the most active fraction of compost, both biologically and chemically, and thus should directly reflect the biochemical alteration of organic matter. This work aims to elucidate the microbial-mediated processes responsible for the distribution of soluble organic matter between stable and labile pools with composting time. Accordingly, chemical analysis as well as UV absorption, and ¹H and ¹³C-NMR spectroscopy of samples collected during the industrial composting of urban waste revealed microbial induced transformation of water-extractable organic matter over time. The chemical composition changed from labile, hydrophilic, plant-derived organic compounds in the beginning to predominately stable, hydrophobic moieties comprising lignin-derived phenols and microbially-derived carbohydrates at later stages of composting.     

工业园区污水厂处理过程中溶解性有机物的三维荧光特征分析

随着工业园区的不断发展,工业园区污水处理越来越引起人们关注。污水中溶解性有机物(dissolved organic matter, DOM)的组分特征对污水处理效果有显著影响。因此,通过三维荧光光谱(excitation-emission-matrix spectra, 3D-EEMs)结合平行因子(parallel factor, PARAFAC)分析,考察了江西5家工业园区污水厂的DOM组分沿程变化特征及其来源特征。结果表明：工业园区污水厂进水COD/DOC在3.74~8.05,进水中有机物芳香化程度比一般城市污水厂的进水高;各工业园区污水厂处理过程中全部水样的荧光物质均呈现类蛋白质>类腐殖质、腐殖化程度较低的特征,DOM来源主要受到生物源的影响;污水厂对类色氨酸芳香蛋白和类腐殖质有机物的削减效果相对较好(21%~43%),对类SMP有机物的削减效果较弱(0%~3%);类色氨酸芳香蛋白(Ex/Em=235 nm/335 nm;Ex/Em=235 nm/340 nm)和类SMP物质(Ex/Em=285 nm/315 nm;Ex/Em=290 nm/320 nm)为江西五家工业园区污水厂出水中持续存在的DOM。本研究结果可为进一步了解工业园区污水厂的DOM沿程变化特征提供科学参考。     

Influences of adding easily degradable organic waste on the minimization and humification of organic matter during straw composting

To find a better composting process with low greenhouse gas emission and high humus production, the effect of adding kitchen waste on reduction and humification of organic matter during straw composting was studied. Three processes were compared, consisting of different ratios of straw and kitchen waste (1:2, 1:1, and 2:1). At four time points over a 62-d incubation, the reduction and humification of compost was evaluated by measuring the total mass, carbon content, and humic material content of the compost. Treatment 1 (straw/kitchen waste ratio of 1:2) reduced the total mass of compost the most. Treatment 2 (straw/kitchen waste ratio of 1:1) reduced the total carbon content the most, reflecting the highest emission of greenhouse gas. Treatment 3 produced the most humic acid material and released the lowest amount of carbon. Hence, from the point of view of reducing greenhouse gas emissions and increasing stable organic matter such as humus and humic acid during composting, treatment #3 was optimal. The three treatments resulted in significant differences in microbial biomass and enzyme activity during composting. The highest amount of active microbial biomass was associated with the largest reduction in compost mass (treatment 1). Higher proportions of straw (treatments 2 and 3), which contains more lignin, were associated with greater β-glycosidase activity, which may generate more humus that can improve soil quality. Dehydrogenase activity seemed to be the most important microbial factor in organic carbon catabolism or humification.     

基于三维荧光及平行因子分析的南昌市某河可溶性有机物溯源及治理策略

地表河流污染物溯源对污染物防治及河流生态环境改善具有重要意义。三维荧光光谱(3D-EEM)的图谱形状、荧光峰位置、荧光峰强度、荧光峰个数信息和荧光参数可作为水体中可溶性有机物(DOM)的荧光特征。结合平行因子分析(PARAFAC)对南昌市某河的3D-EEMs进行分析并进行DOM溯源研究,结果表明,该河DOM主要包含3个荧光组分,分别为类腐殖质荧光组分C1(λ_Ex/λ_Em=245 nm/430 nm)、类氨基酸和类腐殖质组分的混合物C2(λ_Ex/λ_Em=240,300 nm/365 nm)和类色氨酸荧光组分C3(λ_Ex/λ_Em=225,275 nm/335 nm),分别占总荧光组分的35.93%,26.62%和37.45%。该河基本满足地表水环境质量标准(GB 3838-2002)III类水标准,浮游植物主要为蓝绿藻,河流中磷的来源复杂。污染物溯源结果表明,该河DOM腐殖化程度较低,生物活性较强,主要来源于浮游植物和微生物代谢降解和沉积物在冲击和水力作用下产生的内源污染。建议该河采用生态修复技术并辅助水体曝气系统治理DOM污染,并持续防止河流引入外源污染。     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Comparison of molecular transformation of dissolved organic matter in vermicomposting and thermophilic composting by ESI-FT-ICR-MS

Environmental Science and Pollution Research - The aim of this study was to investigate the effects of vermicomposting (VC) and thermophilic composting (TC) on the molecular transformation of...     

荧光光谱技术在堆肥腐熟度评价中的应用

高温好氧堆肥是世界各国资源化利用固体有机废弃物最重要的途径之一,堆肥腐熟度是评价堆肥过程及堆肥产品质量的重要尺度.荧光光谱(FS)技术具有诸多优点,目前已广泛应用于不同来源有机质结构特征的研究,其在堆肥腐熟度评价中具有广阔的应用前景.在分析了FS技术的原理及特点的基础上,从发射光谱、激发光谱、同步FS和三维FS方面详实综述了FS技术在有机固体废弃物堆肥物质转化及腐熟度评价中的应用原理及其国内外进展,并对FS技术在堆肥腐熟度评价中存在的问题及发展前景进行了评述.     

Thermal and spectroscopic analysis of organic matter degradation and humification during composting of pig slurry in different scenarios

Environmental Science and Pollution Research - In this work, different analytical techniques (thermal analysis, 13C cross-polarization magic angle spinning (CPMAS) NMR and Fourier transform...     

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.     

Spectroscopic characterization of the structural and functional properties of natural organic matter fractions

Natural organic matter (NOM) is known to be complex in nature with varying structural and functional characteristics. In this study, an aquatic NOM was fractionated into the polyphenolic-rich (NOM-PP) and the carbohydrate-rich (NOM-CH) fractions in an attempt to better characterize their chemical and structural properties along with a reference soil humic acid (SHA). Various spectroscopic techniques were employed for the study, including ultraviolet-visible (UV/Vis). 13C-nuclear magnetic resonance, Fourier-transform infrared, fluorescence, and electron paramagnetic resonance spectroscopies. Results indicate that the relative abundance of aromatic C=C and methoxyl (-OCH3) functional groups are in the order of SHA > NOM-PP > NOM-CH. However, the aquatic NOM-PP and NOM-CH fractions are characterized by high contents of carboxylic and alcoholic functional groups relative to the SHA. In particular, the NOM-PP fraction appears to contain more phenolic and ketonic functional groups than the NOM-CH and SHA fractions, and it gives a strong fluorescence and high paramagnetic spin count. On the other hand, the NOM-CH fraction possesses a relatively low amount of carbon but a high amount of oxygen or oxygen-containing structural features, such as carbohydrate-OH and carboxylic groups, and shows the least fluorescence intensity and paramagnetic spin counts. Results of these spectroscopic studies confirm the heterogeneous nature of NOM, and point out the importance of isolation and improved characterization of various NOM subcomponents in order to better understand the behavior and roles of NOM in the natural environment.     

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient (K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.     

The effects of particle size, organic matter content, crop residues and dissolved organic matter on the sorption kinetics of atrazine and isoproturon by clay soil

Reliable predictions of the fate and behaviour of pesticides in soils is dependent on the use of accurate ‘equilibrium’ sorption constants and/or rate coefficients. However, the sensitivity of these parameters to changes in the physicochemical characteristics of soil solids and interstitial solutions remains poorly understood. Here, we investigate the effects of soil organic matter content, particle size distribution, dissolved organic matter and the presence of crop residues (wheat straw and ash) on the sorption of the herbicides atrazine and isoproturon by a clay soil. Sorption K_d's derived from batch ‘equilibrium’ studies for both atrazine and isoproturon by <2 mm clay soil were approximately 3.5 L/kg. The similarity of K_oc's for isoproturon sorption by the <2 mm clay soil and <2 mm clay soil oxidised with hydrogen peroxide suggested that the sorption of this herbicide was strongly influenced by soil organic matter. By contrast, K_oc's for atrazine sorption by oxidised soil were three times greater than those for <2 mm soil, indicating that the soil mineral components might have affected sorption of this herbicide. No significant differences between the sorption of either herbicide by <2 mm clay soil and (i) <250 μm clay soil, (ii) clay soil mixed with wheat straw or ash at ratios similar to those observed under field conditions, (iii) <2 mm clay soil in the presence of dissolved organic matter as opposed to organic free water, were observed.     

The evaluation of stability and maturity during the composting of cattle manure

We examined chemical, microbiological and biochemical parameters in order to assess their effectiveness as stability and maturity indicators during the composting process of cattle manure. The composting material obtained after 15 d in trenches and at different times during the maturation phase (i.e. 80, 180 and 270 d) were analyzed. We found that the material collected at the end of the active phase was inadequate to be applied to soil as organic amendment due to its high content of NH4+, its high level of phytotoxicity and the low degree of organic matter stability. After a maturation period of 80 d, the stability of the sample increased. This was shown by a reduction in the dissolved organic carbon (DOC) content and NH4+ concentration and also by a reduction in the microbial activity and biomass; however, 180 d of composting were not sufficient to reduce the phytotoxicity to levels consistent for a safe soil application. Among the various parameters studied, the change in DOC with composting time gave a good indication of stability.     

切削液废水处理过程中溶解性有机物分子质量分布和光谱特征的转化规律

以隔油-混凝沉淀-水解酸化-好氧共代谢为组合工艺处理切削液废水,探究各处理单元对不同种类有机物的转化规律和去除能力;对各处理单元出水中的溶解性有机物(DOM),采用超滤膜法进行分子质量分级,应用紫外-可见吸收光谱、三维荧光光谱等方法对各单元出水及其滤后液进行了分析。结果表明,隔油池出水DOM分子质量主要分布在<1 kDa小分子质量区间和>100 kDa的大分子质量区间,分子质量占比分别为46.04%、42.79%,混凝沉淀对大分子质量的DOM有较好的去除效果,混凝沉淀出水、水解酸化池出水、好氧池出水的DOM主要分布在<1 kDa区间。切削液废水处理过程中出现5个荧光峰,其中峰A和峰B可能为多环芳香烃和杂环化合物的混合物;峰C为石油类;峰D可能是废切削液中滋生的微生物和细菌的细胞物质及其分泌物或单环芳香烃;峰E可能为杂环化合物或多环芳烃类腐殖酸。经一级处理(隔油和混凝沉淀)后峰A和峰B的去除率分别为60%和35%;峰C和峰D去除率均大于99%。经二级处理(水解酸化和好氧共代谢),峰A和峰B的去除率分别为23%和48%。该工艺流程对切削液废水中的有机物有较好的去除效果,石油类、COD、TOC、BOD₅的总去除率可达99.99%、98.81%、98.74%、99.78%,达到了《污水排入城镇下水道水质标准》中的B级标准。     

Temporal change in the distribution patterns of hexachlorobenzene and dichlorodiphenyltrichloroethane among various soil organic matter fractions

Residence time-dependent distribution patterns of hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane (DDT) among different soil organic matter fractions of three Chinese soils were investigated. Soil organic matter (SOM) was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions using methyl isobutyl ketone (MIBK) method. Results revealed that as the residence time prolonged, the amounts of HCB and DDT in the FA, HA and BHA fractions decreased, while those in the lipid and IR fractions increased. One- and two-compartment first order, and one- and two-parameter pore-diffusion kinetic models were used to describe the mobility of HCB and DDT from the FA, HA and BHA fractions. The results suggest that excellent agreements were achieved between the experimental data and fits to the two-compartment first order kinetic model (R2>0.97). The transfer rates of HCB and DDT followed the order FA>HA>BHA.     

Comprehensive evaluation of spent mushroom substrate-chicken manure co-composting by garden waste improvement: physicochemical properties,humification process,and the spectral characteristics of dissolved organic matter

Environmental Science and Pollution Research - The performance of garden waste on spent mushroom substrate (SMS) and chicken manure (CM) co-composting efficiency and humification is unclear....     

酸碱联合调节剩余污泥过程中氮、磷和有机质的释放

实现城市污泥的减量化和资源化是污水厂面临的难题之一。通过采用(1)先酸性(pH=3)后碱性(pH=10)、(2)先碱性(pH=10)后酸性(pH=3)的两段控制方式(每段反应8 d),同时做pH不调的对比实验,研究剩余污泥水解酸化过程中氨氮、磷酸盐和溶解性COD(SCOD)、碳水化合物、蛋白质和挥发性脂肪酸(VFAs)等有机质组分的释放。结果表明,酸碱联合调节有利于各组分的释放;氮和磷在酸性条件下的释放量大于碱性,有机质在碱性条件下的释放量大于酸性;采用(2)方式,调为酸性后反应1 d,氨氮的释放量即达到最大(17.28 mg/g TS);采用(1)的调节方式反应7 d,磷酸盐能达到最佳释放量(14.16 mg/g TS);总VFAs的产生受反应时间的影响较大,其余有机质组分在(2)的调节方式下,6 d左右即可达到较大释放量。