Effect of humification processes on polyaromatic hydrocarbons concentration during wastewater treatment.

The aim of the present work was to compare the concentration changes of polyaromatic hydrocarbons (PAH) and the course of humification processes during wastewater treatment. Studies of samples from a biological-mechanical wastewater treatment plant in Sosnowiec-Zagórze (Poland) were carried out. Determination of PAH was performed both for wastewater sludge and sludge water. Observations of the course of humification processes for humic acid fractions isolated from sludges were conducted. Analysis of PAH extracted from wastewaters and from sludge was performed by means of high-performance liquid chromatography. Investigations of humification processes were conducted by electron paramagnetic resonance and nuclear magnetic resonance methods. The elementary composition changes in the structure of the extracted humic acids were determined. It was found that polyaromatic hydrocarbons appear during the processes of humification. Their content in water decreased only after the process of sludge aeration; however, sludge water leaving the settlers was PAH-enriched.     

Investigation of the solvent extracts of humic organic matter (HOM) isolated from the Ravenna Lagoon to study environmental pollution and microbial communities

Solvent extracts of HOM isolated from highly polluted sediments from the Ravenna Lagoon were studied. Diagnostic indicators included polycyclic aromatic hydrocarbons (PAHs) and nonylphenols as hazardous organic pollutants to characterize anthropogenic pollution, as well as fatty acids (FA, analysed as methyl esters, FAME) to characterize microbial communities responsible for natural attenuation processes. The distribution of PAHs including cyclopentafused surrogates pointed to a significant pyrogenic origin, characteristic for methane combustion. The PAH distribution was characterized by high concentrations of highly carcinogenic analytes with molecular weights of 276Da (benzo[ghi]perylene prevailing) and 300Da (coronene prevailing). The PAH pattern as obtained by solvent extraction was very different from that obtained from pyrolysis/thermochemolysis of the HOM polymeric matrix. The FA pattern indicated strong bacterial input, with a significant contribution from methanotrophic bacteria as revealed by monounsaturated members with n:1omega8 and n:1omega5 double bonds in the alkyl chain. Terrestrial inputs as revealed by FAME analysis beyond C(20) with pronounced even-over-odd discrimination were of minor significance. This was confirmed by the pattern of nC(24)-nC(30) alcohols in strong even-over-odd prevalence occurring in relatively low concentrations. The hopane hydrocarbon distribution reflected a distinctive impact from industrial processes utilizing heavy fractions of petroleum as feedstock. Hopanols along with the 17beta(H),21beta(H)-bishomohopanoic acid pointed to hopane producers, including methanotrophic and sulfate-reducing bacteria. Nonylphenols, which could not be detected in the pyrograms of solvent-extracted HOM matrix, had a total concentration of about 70microg g(-1) referred to the HOM in the solvent extract. In addition to common phytosterols including beta-sitosterol, coprostanol could be detected in the solvent extracts pointing to human fecal matter contamination. Concentration of resin acids turned out to be very low, thus no harmful environmental effects are to be expected from these compounds.     

Influence of soil organic matter on the leaching of polycyclic aromatic hydrocarbons in soil

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl2 solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The nonoxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r2=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.     

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.     

Pyrolysis of humic acids from digested and composted sewage sludge

Humic acids (HAs) were extracted from four digested sewage sludge samples composted for four months, one, two and four years. HAs were pyrolyzed at three different temperatures applying both conventional and in situ methylation (ISM) pyrolysis. The pyrolysates were analyzed using gas chromatography-mass spectrometry (GC/MS). Derivatization (ISM) and pyrolysis temperature had dramatic effects on the composition and relative amounts of the pyrolysates. Among the derivatized HA fragments aliphatic compounds prevailed under all the pyrolysis conditions tested. Aromatic substances consisting mainly of guaiacyl-type compounds were detected in higher abundances only at elevated temperatures. Without ISM the contribution of aromatic structures to the total pyrogram was considerably greater than that of the aliphatics. Increase of the pyrolysis temperature from 450 degrees C to 600 degrees C had smaller effect on the proportions and composition of the compounds studied than increase from 350 degrees C to 450 degrees C.     

INFLUENCE OF SOIL ORGANIC MATTER ON THE LEACHING OF POLYCYCLIC AROMATIC HYDROCARBONS IN SOIL

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl₂ solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The non-oxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour, by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r²=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.     

Formation characteristics of aerosol particles from pulverized coal pyrolysis in high-temperature environments

The formation characteristics of aerosol particles from pulverized coal pyrolysis in high temperatures are studied experimentally. By conducting a drop-tube furnace, fuel pyrolysis processes in industrial furnaces are simulated in which three different reaction temperatures of 1000, 1200, and 1400 degrees C are considered. Experimental observations indicate that when the reaction temperature is 1000 degrees C, submicron particles are produced, whereas the particle size is dominated by nanoscale for the temperature of 1400 degrees C. Thermogravimetric analysis of the aerosol particles stemming from the pyrolysis temperature of 1000 degrees C reveals that the thermal behavior of the aerosol is characterized by a three-stage reaction with increasing heating temperature: (1) a volatile-reaction stage, (2) a weak-reaction stage, and (3) a soot-reaction stage. However, with the pyrolysis temperature of 1400 degrees C, the volatile- and weak-reaction stages almost merge together and evolve into a chemical-frozen stage. The submicron particles (i.e., 1000 degrees C) are mainly composed of volatiles, tar, and soot, with the main component of the nanoscale particles (i.e., 1400 degrees C) being soot. The polycyclic aromatic hydrocarbons (PAHs) contained in the aerosols are also analyzed. It is found that the PAH content in generated aerosols decreases dramatically as the pyrolysis temperature increases.     

Isolation of the stable fraction (the core) of the humic acid

Humic acid consists of a recalcitrant (unhydrolysed fraction) (the core) and labile (hydrolysable fraction) fraction. Core-humic acid (core-HA) isolation was performed by treating source material with apolar and polar solvents (organic solvents+acid hydrolysis) before alkaline extraction. Leonardite, soil Ah horizont and dry blood were chosen for this study because of their different origin and degree of humification. Chemical analysis (elemental analysis, total acidity, E(4):E(6)), spectroscopic analysis (DRIFT and (1)H NMR), and complete mass balance were used to investigate the effect of purifying humic acids. The results obtained showed that purification produced a slight modification of Leonardite humic acids as was expected for these highly humified organic matrices. On the other hand, about 500 g kg(-1) of soil humic acids were lost by purification. The fractions lost mainly consisted of carbohydrates. Dry blood showed the presence of humic acids that contrasted with its origin, thus indicating the limitations of the common analytical methods used for HA extraction. Nevertheless, in practice, purification caused the complete disappearance (914 g kg(-1) of HA was lost) of these HAs. The results obtained in this work suggest that the HA fraction isolated (named core-HA) effectively represents the HA structure proposed by the existing literature, since the purification proposed was able to eliminate the adsorbed organic molecules (interference materials) coating the HA structure.     

猪粪堆肥中铜锌与腐殖质组分的结合竞争

为研究猪粪堆肥中铜锌与腐殖质组分的结合竞争,以猪粪和秸秆为堆腐原料,进行了为期36 d的好氧堆肥实验,研究猪粪堆肥过程中腐殖质组分(胡敏酸和富里酸)、胡敏酸结合态铜锌、富里酸结合态铜锌含量的变化。结果表明,堆肥结束后,腐殖化程度提高,胡敏酸碳含量增加394.4%,富里酸碳含量降低64.9%,腐殖化指数从0.24增加到3.33;随着堆肥的进行,胡敏酸结合态铜锌含量分别增加394.3%和56%,而富里酸结合态铜锌含量分别下降17.5%和28.4%;相关分析表明,胡敏酸结合态铜、富里酸结合态锌与胡敏酸、富里酸碳含量及腐殖化指数均成显著相关(P<0.01);堆肥过程中,胡敏酸结合态铜与富里酸结合态铜之比大于1,而胡敏酸结合态锌与富里酸结合态锌小于1,另外,胡敏酸中的Cu/Zn大于1,而富里酸中的Cu/Zn小于1,表明在腐殖质中铜主要与胡敏酸结合,而锌主要与富里酸结合。研究揭示了猪粪堆肥中重金属铜锌与不同腐殖质组分的结合竞争关系,为畜禽粪便堆肥土地利用的风险评估和风险控制提供科学依据。     

Advantages and risks of using steel slag in preparing composts from raw organic waste

It had been reported that iron and manganese oxides in steel slag enhanced the production of humic acid (HA) from low-molecular-weight compounds, such as phenolic acids, amino acids, and saccharides. In the present study, this function of steel slag was applied to the composting of raw organic wastes (ROWs). The degree of humification of HAs is an important factor in evaluating compost quality. Thus, HAs were extracted from the prepared composts and the humification parameters were determined, in terms of elemental compositions, acidic functional group contents, molecular weights, spectroscopic parameters from UV–vis absorption and ¹³C NMR spectra. The timing for adding steel slag affected the degree of humification of HAs in the composts. The weight average molecular weight of a HA when slag was added initially (29 kDa) was significantly higher than when slag was added after elevating the temperature of the compost pile (17–18 kDa). These results show that ROWs are decomposed to low-molecular-weight compounds after the pile temperature is elevated and the presence of slag enhances the polycondensation of these compounds to produce HAs with a higher degree of humification. Because the slag used in the present study contained several-tens ng g^?1 to several μg g^?1 of toxic elements (B, Cu, Cr, and Zn), leaching tests for these elements from the prepared composts were carried out. Levels for leaching boron from composts prepared by adding slag (0.2–0.4 mg L^?1) were obviously higher than the corresponding levels without slag (0.05 mg L^?1).     

Co-composting of spent coffee ground with olive mill wastewater sludge and poultry manure and effect of Trametes versicolor inoculation on the compost maturity

The co-composting of spent coffee grounds, olive mill wastewater sludge and poultry manure was investigated on a semi-industrial scale. In order to reduce the toxicity of the phenolic fraction and to improve the degree of composting humification, composts were inoculated with the white-rot fungus Trametes versicolor in the early stages of the maturation phase.During composting, a range of physico-chemical parameters (temperature and both organic matter and C/N reduction), total organic carbon, total nitrogen, elemental composition, lignin degradation and spectroscopic characteristics of the humic acids (HAs) were determined; impacts of the composting process on germination index of Hordeum vulgare and Lactuca sativa were assessed. The coffee waste proved to be a highly compostable feedstock, resulting in mature final compost with a germination index of 120% in less than 5 months composting. In addition, inoculation with T. versicolor led to a greater degree of aromatization of HA than in the control pile. Moreover, in the inoculated mixture, lignin degradation was three times greater and HA increased by 30% (P < 0.05), compared to the control pile. In the T. versicolor inoculated mixture, the averages of C and N were significantly enhanced in the HA molecules (P < 0.05), by 26% and 22%, respectively. This improvement in the degree of humification was confirmed by the ratio of optical densities of HA solutions at 465 and 665 nm which was lower for HA from the treated mixture (4.5) than that from the control pile (5.4).     

Distribution and incorporation mode of the herbicide MCPA in soil derived organo-clay complexes

The incorporation of xenobiotics into soil, especially via covalent bonds or sequestration has a major influence on the environmental behavior including toxicity, mobility, and bioavailability. The incorporation mode of 4-chloro-2-methylphenoxyacetic acid (MCPA) into organo-clay complexes has been investigated under a low (8.5 mg MCPA/kg soil) and high (1000 mg MCPA/kg soil) applied concentration, during an incubation period of up to 120 days. Emphasis was laid on the elucidation of distinct covalent linkages between non-extractable MCPA residues and humic sub-fractions (humic acids, fulvic acids, and humin). The cleavage of compounds by a sequential chemical degradation procedure (OH^?, BBr₃, RuO₄, TMAH thermochemolysis) revealed for both concentration levels ester/amide bonds as the predominate incorporation modes followed by ether linkages. A possible influence of the soil microbial activity on the mode of incorporation could be observed in case of the high level samples. Structure elucidation identified MCPA as the only nonextractable substance, whereas the metabolite 4-chloro-2-methylphenol was additionally found as bioavailable and bioaccessible compound.     

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.     

Spectroscopic studies of the progress of humification processes in humic substances extracted from refuse in a landfill

Humic acids (HA) and fulvic acids (FA) extracted from refuse in a landfill at different landfill ages were characterized by elemental composition, GPC, FTIR, and (13)C CP/MAS NMR. The elemental composition analysis revealed high O/C and low H/C ratios in the FA, indicating a high proportion of O-alkyl and carboxylic acids in the FA. The M(w) and M(n) values and M(w)/M(n) ratios indicated that the HA had a higher molecular weight and were more homogeneous with respect to molecular weight. FTIR spectra showed that the FA had relatively more intense bands assigned to aliphatic structures and were abundant in oxygen-containing function groups. The analytical results of (13)C CP/MAS NMR suggested that there were more oxygenated aliphatic carbons and fewer aromatic carbons in the FA than in the HA. All the results demonstrated that the degree of humification increased with landfill age.     

Concentrations of monosaccharides in humic substances in the early stages of humification.

Deteriorated liquid packaging board (LPB) and biowaste compost are matrices, mainly consisting of cellulose, in the early stages of humification. Degradative studies on these matrices allow an examination of the role of carbohydrates in the synthesis of humic substances. Samples of different age were collected and divided by extraction into hot water extract (HWE), bitumen, humic acid (HA), fulvic acid (FA) and humin or residual fibre fractions. The following monosaccharides were identified in these fractions: L-arabinose, D-ribose, D-xylose, L-fucose, D-mannose, D-fructose, D-galactose, D-glucose, L-rhamnose and xylitol. The main component in all fractions was glucose. The concentrations of monosaccharides in humic acids (HAs) of LPB ranged from 67 to 503 mg/g of organic matter, and the concentrations in HAs of compost from 52 to 101 mg/g. As a general trend, the concentrations of monosaccharides decreased during LPB degradation and composting in all fractions. At the same time the relative amounts of D-xylose, D-mannose and D-galactose increased in HAs of compost samples.     

Characterization of the humic material formed by composting of domestic and industrial biowastes Part 1. HPLC of the cupric oxide oxidation products from humic acids

The changes induced by humification of anaerobically digested sewage sludge, source separated biowaste, and pulp mill biosludge were determined by extracting the fractions of bitumen and humic and fulvic acids from the samples of fresh and humified composts. In all cases, a distinct decrease in the amount of bitumen could be detected during humification. The amount of humic acids increased in sewage sludge and biowaste samples, but decreased in pulp mill biosludge sample during humification. The humic acids were degraded by CuO oxidation and the phenolic degradation products were analysed by reversed-phase high-performance liquid chromatography. The yield of these aromatic degradation products was in the range 0.9–2.0 % for each sample. The main phenolic degradation products were 4-hydroxybenzoic acid, vanillic acid, 4-hydroxybenzaldehyde, vanillin, syringaldehyde, and acetovanillone. Two lignin dimers, dehydrodivanillin and dehydrodiacetovanillone, were also identified.     

PAH Growth from the pyrolysis of CPD, indene and naphthalene mixture

In this study, the addition of cyclopentadienyl (CPDyl) moieties to aromatic rings has been investigated experimenNaphthalene was selected as the representative aromatic compound and its pyrolytic reactivity was studied first to obtain background information for the pyrolysis of cyclopentadiene-indene-naphthalene mixture. The experiments were conducted in a 5 s laminar flow reactor over the temperature range of 700-850 degrees C with 50 degrees C increments. PAH growth from naphthalene pyrolysis is mainly attributed to aryl-aryl addition of naphthyl radicals and naphthalene fragmentation, with lower product formation rates comparing with hydrocarbons with CPDyl moieties. The results indicate that naphthalene is less reactive than the CPDyl containing hydrocarbon radical-molecule addition of CPDyl radicals to naphthalene results in phenanthrene, which can also be formed substantially from other growth pathways. This addition occurs mainly at low temperatures and is less favored due to the competition from more reactive indenyl and CPDyl radicals. CPDyl radical addition to naphthalene exhibits limited aromatic growth due to the aromaticity restrictions of naphthalene. The studies of hydrocarbons with and without CPDyl moieties suggest that the reaction pathways of CPDyl bearing hydrocarbons are different from those without these moieties and cannot be adequately accounted for by the existing acetylene addition and aryl-aryl addition mechanisms.     

Characterization of non-extractable residues of the fungicide dithianon in soil using 13C/14C-labelling techniques

The fate of the (14)C-labelled fungicide dithianon in soil is characterized by the formation of non-extractable, "bound" residues of approximately 63% of applied amount in 64 d. Humic acids containing these "bound" residues were isolated after conducting degradation studies of the active ingredient in an orthic luvisol under standardized conditions. In the same way, (13)C-labelled dithianon was incubated in an artificial soil which was produced by humification of (13)C-depleted straw in an incinerated soil. The "bound" residues of the (13)C-labelled dithianon in the humic acid fraction of the artificial soil were analyzed using (13)C-NMR techniques. There was no evidence of a covalent bonding of the residues to the humic substances. Results of polarity gradient high performance thin layer chromatography (AMD-HPTLC) of "bound" residues of the (14)C-labelled dithianon in the humic acid fraction indicate a sequestration process of metabolites into the humic substance as a possible binding mechanism.     

Humic complexes of diethyl phthalate: molecular modelling of the sorption process

The sorption mechanisms and complex formation between humic acid (HA) and a successively increasing number of diethyl phthalate (DEP) molecules have been studied theoretically using molecular mechanics, the number (n) of DEP molecules being varied from 1 to 30. The energy components of the single HA x nDEP complexes have been used as explanatory variables in a principal component analysis for exploring the presence of similarities/dissimilarities in the energetic properties of the individual xenobiotic complexes. The sorption can be explained in terms of a two-step mechanism. Absorption takes place as long as the host humic acid structure offers (a) enough internal docking space and (b) favorable interactions (energy release) with the guest molecule. This takes place for up to 7 DEP molecules. Further increase in the number to 30 DEP molecules will, due to the lack of free available internal voids, lead to surface controlled adsorption. The two-step sorption process apparently results in (a) a linear increase in energy gain by DEP bonds, and similarly (b) a constant incremental rise in molecular properties of the complexes such as volume and surface area. Three outstanding observations emerge: (1) Structural features at the atomic level (nanochemistry), such as partial atomic charges and high aromaticity of the humic acid, are observed to be dominating the intermolecular interactions in the complexes at the specific sorption sites. (2) Torsional relief and favorable changes in bonding energy also prevail for the growing complex. The latter indicates both the structural flexibility of the HA host and the stabilizing effect of DEP on the complex, by filling of the voids within the HA molecule. (3) The intermolecular forces are described mainly by hydrogen bonds (electrostatic energy) and interactions between dipole-dipole, such as carboxylic functions and uncharged moieties such as aromatic rings (van der Waals energy).