Phenanthrene sorption to structurally modified humic acids

Several studies emphasize the importance of soil organic matter characteristics in hydrophobic contaminant sorption and outline the strong dependence of sorption on organic matter aromaticity. In this study, the role of organic matter aromaticity in phenanthrene sorption was investigated using humic acids (HAs) from compost, peat, and soil that were structurally modified by bleaching, hydrolysis, oximation, and subcritical water extraction. The HAs were characterized with cross polarization magic angle spinning carbon-13 nuclear magnetic resonance (CPMAS 13C NMR) spectroscopy and used in batch equilibrations with phenanthrene. Bleaching substantially reduced the aromaticity of the samples whereas the other treatments increased the relative aromaticity. Phenanthrene sorption increased, even though there was a substantial reduction in sorbent aromaticity with some samples. The HAs that exhibited comparable CPMAS 13C NMR spectra and aromaticity did not behave similarly with respect to phenanthrene sorption. When the sorption data (K(oc) values) were correlated to sample aromaticity, the correlation coefficients (r2) did not exceed 0.39. Comparisons with the atomic H to C ratio provided slightly better r2 values (up to 0.54). This study demonstrates that macroscopic sorbent characteristics could not explain the observed phenanthrene sorption coefficients, aliphatic structural components of HAs can contribute appreciably to phenanthrene sorption, and organic matter physical conformation may regulate access to organic matter structures. Therefore, the use of only macroscopic sorbent properties, such as aromaticity, to predict and rationalize sorption values cannot solely be used to explain the behavior of organic contaminants in soil environments.     

Chemical and carbon-13 cross-polarization magic-angle spinning nuclear magnetic resonance characterization of logyard fines from British Columbia

Phasing out beehive burners and rising costs for landfilling have increased the need to widen options for utilization of the smaller size fractions of woody wastes generated during log handling and sawmilling in British Columbia. We characterized several size classes of logyard fines up to 16 mm sampled from coastal and interior operations. Total C, total N, ash, and condensed tannin concentrations were consistent with properties derived largely from wood, with varying proportions of bark and mixing with mineral soil. Especially for < 3-mm fractions, the latter resulted in high ash contents that would make them unsuitable for fuel. Solid-state 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectra were consistent with the chemical data, with high O-alkyl intensity and similarity to naturally occurring woody forest floor; no samples were high in aromatic or phenolic C. Aqueous extracts of two < 16-mm fines, which accounted for only a small proportion of the total C, were enriched in alkyl C and had low or undetectable tannins. Application to forest sites might cause short-term immobilization of N, but also might include possible longer-term benefits from reduction of N loss after harvesting and restoration of soil organic matter in degraded sites.     

The effect of pyrolysis atmosphere on bio-oil yields and structure

A food industry waste, almond shell, was pyrolyzed under three different environment static, nitrogen, and steam to produce bio-oil and its derivatives. The oil yield obtained at pyrolysis temperature of 600°C was 24.23% in a static atmosphere, whereas it increased to 27.25% and 33.05% in nitrogen and steam atmospheres, respectively. The bio-oil obtained under steam atmosphere is very efficient due to the production of high liquid and gas yields. Moreover, co-feeding steam during the pyrolysis altered the bio-oil structure by increasing the aliphatics and reducing the asphaltenes. Moreover, steam treatment also increases H/C and heating value of bio-oils. According to the obtained results, steam pyrolysis is an alternative option for future applications in refineries.     

Bioconversion of sugarcane bagasse into a protein-rich product by white rot fungus

The fungus Pleurotus ostreatus NRRL-2366 degraded 56.7% and 45.9% of untreated and chemically pretreated (delignified) sugarcane bagasse, respectively, during 14-day incubation in a submerged fermentation process. The biodegradation percentages of cellulose, hemicellulose and lignin were 33.0%, 72.5% and 14.5%, respectively. An increment of 22.6% of crude protein content in the residual fermented material was observed. Chemical composition of the end-product and its amino acids profile were reported.     

Humic acid formation in artificial soils amended with compost at different stages of organic matter evolution

A composting process was conducted under optimal conditions for 150 d, obtaining three biomasses at different levels of maturity: raw material (RM), fresh compost obtained after 11 d of composting (FC), and evolved compost (EC) obtained after 150 d of composting. During the composting process, HAs were extracted and fully characterized by mass balance, DRIFT, and 1H and 13C-nuclear magnetic resonance spectroscopy. Each compost sample was incubated for 180 d in an artificial soil, after which HA extraction was repeated and characterized. To compare composts containing different amounts of labile organic matter (OM), an equal amount of unhydrolyzable OM was added to the soils. Our results indicated that compost HAs consist of a biologically and chemically stable fraction (i.e., the unhydrolyzable HA [U-HA]) and a labile fraction, whose relative contents depended on the composting duration. Humic acid from more EC contained a higher amount of recalcitrant fraction (aromatic carbon) and a lesser amount of labile fraction (aliphatic carbon) than HA from RM and FC. These results suggest that the humification process during composting preserves the more recalcitrant fraction of the compost-alkali soluble/acid insoluble fraction (HA-fraction). Incubation of composts in soil showed that due to the higher labile fraction content, HAs from raw material were more degraded than those from EC. The abundance of labile carbon of soil amended with less-evolved compost (RM and FC) allowed the more recalcitrant fractions of U-HA to be more preserved than in EC. These results suggest that less-evolved compost could contribute more than well evolved compost to the stable soil OM.     

Characterization of high-tannin fractions from humus by carbon-13 cross-polarization and magic-angle spinning nuclear magnetic resonance

Condensed tannins can be found in various parts of many plants. Unlike lignin there has been little study of their fate as they enter the soil organic matter pool and their influence on nutrient cycling, especially through their protein-binding properties. We extracted and characterized tannin-rich fractions from humus collected in 1998 from a black spruce [Picea mariana (Mill.) Britton et al.] forest in Canada where a previous study (1995) showed high levels (3.8% by weight) of condensed tannins. A reference tannin purified from black spruce needles was characterized by solution 13C nuclear magnetic resonance (NMR) as a pure procyanidin with mainly cis stereochemistry and an average chain length of four to five units. The colorimetric proanthocyanidin (PA) assay, standardized against the black spruce tannin, showed that both extracted humus fractions had higher tannin contents than the original humus (2.84% and 11.17% vs. 0.08%), and accounted for 32% of humus tannin content. Consistent with the results from the chemical assay, the aqueous fraction showed higher tannin signals in the 13C cross-polarization and magic-angle spinning (CPMAS) NMR spectrum than the emulsified one. As both tannin-rich humus fractions were depleted in N and high in structures derived from lignin and cutin, they did not have properties consistent with recaldtrant tannin-protein complexes proposed as a mechanism for N sequestration in humus. Further studies are needed to establish if tannin-protein structures in humus can be detected or isolated, or if tannins contribute to forest management problems observed in these ecosystems by binding to and slowing down the activity of soil enzymes.     

Solid-state carbon-13 nuclear magnetic resonance of humic acids at high magnetic field strengths

Use of solid-state 13C nuclear magnetic resonance (NMR) spectroscopy has become commonplace in studies of humic substances in soils and sediments, but when modern high-field spectrometers are employed, care must be taken to ensure that the data obtained accurately reflect the chemical composition of these complex materials in environmental systems. In an effort to evaluate the quality of solid-state 13C NMR spectra obtained with modern high-field spectrometers, we conducted a series of experiments to examine spectra of various humic acids taken under a variety of conditions. We evaluate conditions for obtaining semiquantitative cross polarization magic angle spinning (CPMAS) 13C NMR spectra of humic acids at high magnetic field and spinning frequency. We examine the cross polarization (CP) dynamics under both traditional and ramp CP conditions on Cedar Creek humic acid. Fitted equilibrium intensities from these CP dynamic studies compare to within 3.4% of the intensities determined from a Bloch decay spectrum of the same sample. With a 1-ms contact time, ramp CP and traditional CP spectra were acquired on this sample and were found to compare to within 5.4% of the Bloch decay spectrum; however, the signal-to-noise ratio per hour of data acquisition was found to double under ramp CP conditions. These results demonstrate the power of applying modern solid-state NMR techniques at high magnetic field strengths. With these techniques, high-quality, semiquantitative spectra can be quickly produced, allowing the application of solid-state NMR techniques to more environmentally relevant samples, especially those where the quantity is limited.     

Evaluation of municipal solid waste composting kinetics

Most modern municipal solid waste (MSW) composting operations have emphasized the enhancement of decomposition of the organic fraction of the waste to comply with strict environmental regulations. This can be achieved once the composting process kinetics are well understood. This study examined process kinetics through experimentation with bench-scale reactors under controlled composting conditions to show the interdependence between biological, chemical and physical factors during composting of MSW. The effects of temperature, moisture content, waste particle size and carbon to nitrogen (C/N) ratio on process kinetics were evaluated. The results obtained revealed that these factors should be carefully controlled in order to achieve optimum process performance. It has been found that the organic matter degradation during composting follows a first-order kinetic model.     

Antibiotic degradation during manure composting

On-farm manure management practices, such as composting, may provide a practical and economical option for reducing antibiotic concentrations in manure before land application, thereby minimizing the potential for environmental contamination. The objective of this study was to quantify degradation of chlortetracycline, monensin, sulfamethazine, and tylosin in spiked turkey (Meleagris gallopavo) litter during composting. Three manure composting treatments were evaluated: a control treatment (manure pile with no disturbance or adjustments after initial mixing), a managed compost pile (weekly mixing and moisture content adjustments), and vessel composting. Despite significant differences in temperature, mass, and nutrient losses between the composting treatments and the control, there was no difference in antibiotic degradation among the treatments. Chlortetracycline concentrations declined rapidly during composting, whereas monensin and tylosin concentrations declined gradually in all three treatments. There was no degradation of sulfamethazine in any of treatments. At the conclusion of the composting period (22-35 d), there was >99% reduction in chlortetracycline, whereas monensin and tylosin reduction ranged from 54 to 76% in all three treatments. Assuming first-order decay, the half-lives for chlortetracycline, monensin, and tylosin were 1, 17, and 19 d, respectively. These data suggest that managed compositing in a manure pile or in a vessel is not better than the control treatment in degrading certain antibiotics in manure. Therefore, low-level manure management, such as stockpiling, after an initial adjustment of water content may be a practical and economical option for livestock producers in reducing antibiotic levels in manure before land application.     

Enzymatic transformation and binding of labeled 2,4,6-trinitrotoluene to humic substances during an anaerobic/aerobic incubation

Organic pollutants are degraded in soil and simultaneously nonextractable residues are formed. However, proof is lacking that this fixation has a detoxifying effect. We investigated the transformation and binding of 2,4,6-trinitrotoluene (TNT) with catechol or soil humic acid as cosubstrates. Carbon-14-labeled TNT and its reaction products were quantified by radiocounting; extractable compounds were identified by high performance liquid chromatography (HPLC). Bound and extractable residues of 15N-labeled TNT and metabolites were studied by 15N nuclear magnetic resonance spectroscopy (15N NMR). Since TNT is not easily transformed under oxidizing conditions an anaerobic/aerobic treatment was used. Anaerobic microorganisms from cow manure were used to reduce TNT during the anaerobic phase and subsequently, a laccase from Trametes villosa was used in the aerobic phase to oxidatively couple the metabolites to humic matter. Seventy-four percent of TNT was immobilized with catechol as cosubstrate, but only 25% with humic acid. With catechol the main extractable component was TNT, while with humic acid it was mostly the metabolite 4-aminodinitrotoluene. For both co-substrates, the spectra of immobilized metabolites obtained by solid-state 15N-cross polarization magic angle spinning (CPMAS) NMR spectroscopy showed signals in the chemical shift region for protonated aromatic amino compounds. However, in the presence of catechol, an additional signal from nonextractable nitro groups was found, which could represent sequestered TNT. The partially reduced metabolites of TNT that formed nonextractable residues in humic acid are not likely to be remobilized easily and are thus regarded as detoxified.     

Preparation of jet engine range fuel from biomass pyrolysis oil through hydrogenation and its comparison with aviation kerosene

The Bio-oil was produced from the pyrolysis of agricultural wastes (Eucalyptus sawdust) and discarded soybean frying oil. The temperature of the pyrolysis system was initiated at 28°C and increased to 850°C. Atmospheric distillation of crude bio-oil was performed and a fraction at a temperature range 160–240°C (pyrolysis oil) was separated and subjected to GC-MS, ¹H-NMR, TGA and FTIR analysis to identify the different properties and compounds present in pyrolysis oil. It was noticed that there was an abundance of oxygen and nitrogen containing compounds as well as other reactive species in pyrolysis oil. To reduce the amount of these species, the pyrolysis oil was subjected to hydrogenation in the presence of NiMo as a catalyst. After hydrogenation, the atmospheric distillation of hydrogenated bio-oil was performed and another fraction at temperature range 160–240°C (hydrogenated bio-oil) was separated and analyzed by the same techniques. It was noticed that during hydrogenation, more than 60% oxygenated and other reactive species were converted into hydrocarbons. Hydrogenated bio-oil showed very similar physico-chemical properties such as distillation curve, density, viscosity, freezing point, flash point, the presence of hydrocarbons and enthalpy of combustion as aviation kerosene also known as QAV-1.     

Attenuation of methane and volatile organic compounds in landfill soil covers

The potential for natural attenuation of volatile organic compounds (VOCs) in landfill covers was investigated in soil microcosms incubated with methane and air, simulating the gas composition in landfill soil covers. Soil was sampled at Skellingsted Landfill at a location emitting methane. In total, 26 VOCs were investigated, including chlorinated methanes, ethanes, ethenes, fluorinated hydrocarbons, and aromatic hydrocarbons. The soil showed a high capacity for methane oxidation resulting in very high oxidation rates of between 24 and 112 microg CH4 g(-1) h(-1). All lower chlorinated compounds were shown degradable, and the degradation occurred in parallel with the oxidation of methane. In general, the degradation rates of the chlorinated aliphatics were inversely related to the chlorine to carbon ratios. For example, in batch experiments with chlorinated ethylenes, the highest rates were observed for vinyl chloride (VC) and lowest rates for trichloroethylene (TCE), while tetrachloroethylene (PCE) was not degraded. Maximal oxidation rates for the halogenated aliphatic compounds varied between 0.03 and 1.7 microg g(-1) h(-1). Fully halogenated hydrocarbons (PCE, tetrachloromethane [TeCM], chlorofluorocarbon [CFC]-11, CFC-12, and CFC-113) were not degraded in the presence of methane and oxygen. Aromatic hydrocarbons were rapidly degraded giving high maximal oxidation rates (0.17-1.4 microg g(-1) h(-1)). The capacity for methane oxidation was related to the depth of oxygen penetration. The methane oxidizers were very active in oxidizing methane and the selected trace components down to a depth of 50 cm below the surface. Maximal oxidation activity occurred in a zone between 15 and 20 cm below the surface, as this depth allowed sufficient supply of both methane and oxygen. Mass balance calculations using the maximal oxidation rates obtained demonstrated that landfill soil covers have a significant potential for not only methane oxidation but also cometabolic degradation of selected volatile organics, thereby reducing emissions to the atmosphere.     

Weed seed viability in composted beef cattle feedlot manure

Manure composting has gained increased acceptance by the beef cattle (Bos taurus) feedlot industry in southern Alberta, Canada. Unlike fresh manure, compost is often promoted as being "weed-free." Studies were conducted with five weed species in 1997 and thirteen in 1999 to examine the effect of feedlot manure composting on weed seed viability. Weed seeds were buried in open-air compost windrows and recovered at various times during the thermophilic phase of composting. Windrow temperature and water contents were also measured. Germinability was zero for all composted weed seeds at all sampling times in 1997. However, some seeds remained viable (positive tetrazolium test denoting respiration) on Day 70. In 1999, only one of the thirteen species retained germinability on Day 21 and only two species had respiring seeds on Day 42. Time-viability relationships during composting were defined by exponential decay models. Lethal temperatures to eliminate viability was species-dependent. In 1999, four weed species were killed in the initial 7 d of composting at a lethal temperature of 39 degrees C while temperatures of > 60 degrees C were required for two species. Regression analysis on weed seed viability versus windrow temperature resulted in significant R2 values, which showed that only 17 to 29% of the variation in viability was accounted for by temperature. The lack of definitive relationships between temperature and weed seed viability demonstrated that factors other than temperature may play a role in eliminating weed seeds during composting.     

A simple numerical model for predicting organic matter decomposition in a fed-batch composting operation

Using dog food as a model of the organic waste that comprises composting raw material, the degradation pattern of organic materials was examined by continuously measuring the quantity of CO2 evolved during the composting process in both batch and fed-batch operations. A simple numerical model was made on the basis of three suppositions for describing the organic matter decomposition in the batch operation. First, a certain quantity of carbon in the dog food was assumed to be recalcitrant to degradation in the composting reactor within the retention time allowed. Second, it was assumed that the decomposition rate of carbon is proportional to the quantity of easily degradable carbon, that is, the carbon recalcitrant to degradation was subtracted from the total carbon remaining in the dog food. Third, a certain lag time is assumed to occur before the start of active decomposition of organic matter in the dog food; this lag corresponds to the time required for microorganisms to proliferate and become active. It was then ascertained that the decomposition pattern for the organic matter in the dog food during the fed-batch operation could be predicted by the numerical model with the parameters obtained from the batch operation. This numerical model was modified so that the change in dry weight of composting materials could be obtained. The modified model was found suitable for describing the organic matter decomposition pattern in an actual fed-batch composting operation of the garbage obtained from a restaurant, approximately 10 kg d(-1) loading for 60 d.     

Evaluation of extracted organic carbon and microbial biomass as stability parameters in ligno-cellulosic waste composts

Extracted organic C and microbial biomass were evaluated as stability parameters in 3 different ligno-cellulosic waste composts. Organic C was extracted by both water and alkali and further separated in humic-like carbon (HLC) and nonhumic carbon (NHC). Conventional humification parameters, such as humification index and degree of humification were calculated from NHC and HLC. Microbial biomass carbon (B(C)) was determined as an indicator of the degree of biochemical transformation, whereas ninhydrin reactive N (B(NIN)) was measured to obtain the stability parameter B(NIN)/N(TOT) (N(TOT), total N). The water-extracted organic C did not provide reliable information on the transformations underwent by the ligno-cellulosic wastes during composting, since its content remained almost unaltered during the whole process. In contrast, parameters based on the alkali-extracted organic C and microbial biomass clearly reflected organic matter (OM) changes during the process. There was an increase in the net amount of HLC in the alkali extracts throughout composting, especially in the first 7 to 12 wk of the process, as well as a relative enrichment of HLC with respect to NHC. Values of humification index and degree of humification in end products were consistent with an adequate level of compost stability. The stability parameter B(NIN)/N(TOT) showed to be a reliable indicator of stability in ligno-cellulosic wastes. Parameters based on the alkali-extracted C and microbial biomass clearly reflected the transformation of the OM during composting and can be used as stability parameters in ligno-cellulosic waste composts.     

超声辅助电催化氧化降解水杨酸的研究

通过对水杨酸降解的UV扫描吸收光谱的研究表明,在水杨酸的电催化氧化和超声辅助电催化氧化降解过程中,都有吸收紫外光的中间体生成,对吸光度峰值随降解反应时间的变化关系进行非线性最小二乘法拟合(NLSF),发现其衰减均符合表观一级反应动力学规律;而COD值的衰减也都符合表观一级反应动力学规律。GC-MS检测到水杨酸超声辅助电催化氧化降解60 min后,有中间产物甲酸、乙酸、苯酚,认为是水杨酸在.OH的作用下,开环氧化降解生成乙酸和甲酸等小分子有机物,最后降解为二氧化碳和水。     

Land management in rural Burkina Faso: the role of socio‐cultural and institutional factors

Farmers in the Sahel have been acknowledged for reclaiming degraded lands and improving food security by ingeniously modifying traditional agroforestry, water, and soil management practices. Despite the advantages offered by this range of farming techniques, their adoption rate is influenced by several factors. Using multivariate probit models and a correlation coefficient, this article examines the factors influencing the adoption of five land management practices based on 220 household and 40 farm surveys in four adjacent rural communities in southern Burkina Faso. The model results indicate that household labor force, education of household head, land tenure security, livestock holding, and membership in farmers’ groups influence the adoption of zaï practice, composting, improved fallow, stone bunds, and live hedges. However, two of the surveyed factors ‐ number of farms and visit by agricultural extension staff during the 12 months prior to the survey ‐ were not significant. Furthermore, a significant correlation was found between different land management practices, e.g., the decision to practice zaï is significantly linked to that of live hedges and composting. Zaï practice and stone bunds are considered labor intensive, which explains their significant correlations with household labor force at the 1% and 5% levels of significance, respectively.     

Advanced solid-state carbon-13 nuclear magnetic resonance spectroscopic studies of sewage sludge organic matter: detection of organic "domains"

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.     

Degradation of greenhouse twines derived from natural fibers and biodegradable polymer during composting

Commercial composting operations generally do not accept organic wastes with plastic twines from the greenhouse vegetable industry and the bulk of the waste materials ends up in landfills. The objectives of this paper are to identify environmentally compatible substitutes that could replace the current use of petrochemically derived plastic twines in greenhouse vegetable production, thus diverting them from landfills, and to assess the extent of their degradation via composting. Physical properties of the twines, including linear density, percent weight loss and tensile strength were monitored for the biodegradation tests. A pilot-scale composting trial was conducted in an in-vessel composting system. Results showed that the three biodegradable twine materials (cotton, jute and EcoPLA) could degrade readily in a composting environment within a reasonable time frame. Specifically, at the end of 105 days of composting, 85.3%, 84.8% and 81.1% of weight loss was observed for cotton, jute and EcoPLA, respectively. Furthermore, EcoPLA exhibited a slower decline in tensile strength with time, when compared to jute and cotton.     

Olfactory response to mushroom composting emissions as a function of chemical concentration

Odor pollution is a major problem facing mushroom [Agaricus bisporus (Lange) Imbach] compost production. Techniques for quantifying mushroom composting odors are needed to assess the effectiveness of odor control measures. Odor samples were obtained in nalophane bags from 11 mushroom composting sites. Samples were collected 0.2 m downwind from the pre-wetting heaps (aerated or unaerated) of raw composting ingredients (wheat straw, poultry and horse manures, and gypsum) and subsequent Phase I composting windrows or aerated tunnels. The odor concentrations (OCs) of the samples were assessed using serial dilution olfactometry and the chemical composition of the samples was determined using gas chromatography-mass spectrometry (GC-MS), both 24 h after sampling. Gas detector tubes were used for on-site measurement of gaseous compounds. Odorants that exceeded their published olfactory detection thresholds by the greatest order of magnitude, in decreasing order, were: H2S, dimethyl sulfide (DMS), butanoic acid, methanethiol, and trimethylamine. Concentrations of NH3 were not significantly correlated with OC, and they were not significantly affected by the use of aeration. Aeration reduced the OC and the combined H2S + DMS concentrations by 87 and 92%, respectively. There was a very close correlation (r = 0.948, P < 0.001) between the OC of bag samples and the combined H2S + DMS concentrations, measured on-site with detector tubes. This relationship was unaffected by the NH3 concentration or the type of compost: aerated or unaerated, pre-wet or Phase I, poultry manure-based or horse and poultry manure-based compost. Prediction of the OC will enable rapid and low-cost identification of odor sources on mushroom composting sites.