Studies of Thermal Transformations of Humic and Fulvic Acids in Soils I. Infrared Spectroscopy and Temperature-Programmed Pyrolysis Mass Spectrometry

Temperature-programmed pyrolysis mass spectrometry and Fourier-transform infrared spectroscopy have been used to monitor structural changes of humic and fulvic acids isolated from soils in China, in the temperature range of 25-550°C. in this work, we found that decarboxylation is obvious as the main reaction with dehydration reaction from 150°C to 400°C, the anhydride can be identified from FT-IR spectra at temperature range from 200°C to 400°C; there are evident changes of the aromatic nucleus of humic and fulvic acids above 400°C, even remaining up to 550°C. Besides, some changes of adsorption water can be distinguished before 200°C, and the mass signal of sulphur dioxide was detected.     

Studies of Thermal Transformation of Humic and Fulvic Acids in Soils Ii. Thermogravimetry

The thermogravimetry and differential curves of the humic and fulvic acids in the soils from five areas of China were determined and the peaks of these curves were classified according to the results of infra-red (IR) spectra at high temperature and pyrolysis-mass spectra (Py/Ms). the kinetic parameters for heat-degradation of these humic and fulvic acids were calculated by the Coast-Redfern method. the initial temperatures, the final temperatures, and the peaks of DTG curves, the activation energies, the reaction orders and the percentages of weight loss at different reaction stages for these samples were analysed. Thus, the similarity of thermal transformation of humic and fulvic acids in the soils from different areas of China was demonstrated. in addition, the DTA curves of red earth HA and FA were determined.     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

A steam dried municipal solid waste gasification and melting process

Considering high-moisture municipal solid waste (MSW) of China, a steam dried MSW gasification and melting process was proposed, the feasibility was tested, and the mass and energy balance was analyzed. Preliminary experiments were conducted using a fixed-bed drying apparatus, a 200 kg per day fluidized-bed gasifier, and a swirl melting furnace. Moisture percentage was reduced from 50% to 20% roughly when MSW was dried by slightly superheated steam of 150°C?C350°C within 40 min. When the temperature was less than 250°C, no incondensable gas was produced during the drying process. The gasifier ran at 550°C?C700°Cwith an air equivalence ratio (ER) of 0.2?C0.4. The temperature of the swirl melting furnace reached about 1240°C when the gasification ER was 0.3 and the total ER was 1.1. At these conditions, the fly ash concentration in the flue gas was 1.7 g·(Nm³)^?1, which meant over 95% fly ash was trapped in the furnace and discharged as slag. 85% of Ni and Cr were bound in the slag, as well as 60% of Cu. The mass and energy balance analysis indicates that the boiler heat efficiency of an industrial MSW incineration plant reaches 86.97% when MSW is dried by steam of 200°C. The boiler heat efficiency is sensitive to three important parameters, including the temperature of preheated MSW, the moisture percentage of dried MS Wand the fly ash percentage in the total ash.     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.     

褐煤风化过程中化学特性的变化

本文测定了６种不同风化程度褐煤的化学性状。结果表明，随着在自然界堆积风化时间的延长，褐煤的总碳，总氮含量及碳氮比都下降，灰分含量则增大，可提取的腐植酸及黄腐酸量明显增大，且紫外吸光值呈系统变化，尤其是黄腐酸中聚乙烯吡咯烷酮树脂可吸附部分（黄腐酸中腐植部分）随风化加深而降低，各种不同风化程度褐煤中腐植酸的红外吸收光谱变化不是很明显，且与土壤腐植吸收光谱相似。     

A Cu-modified active carbon fiber significantly promoted H2S and PH3 simultaneous removal at a low reaction temperature

• Cu_0.15-ACF performs the best for H₂S and PH₃ simultaneous removal. • 550°C and 90°C are separately calcination and reaction temperatures. • The reason why Cu_0.15/ACF shows better performance was found. • The accumulation of H₂PO₄⁻ and SO₄²⁻(H₂O)₆ is the deactivation cause of Cu_0.15/ACF. Poisonous gases, such as H₂S and PH₃, produced by industrial production harm humans and damage the environment. In this study, H₂S and PH₃ were simultaneously removed at low temperature by modified activated carbon fiber (ACF) catalysts. We have considered the active metal type, content, precursor, calcination, and reaction temperature. Experimental results exhibited that ACF could best perform by loading 15% Cu from nitrate. The optimized calcination temperature and reaction temperature separately were 550°C and 90°C. Under these conditions, the most removal capacity could reach 69.7 mg/g and 132.1 mg/g, respectively. Characterization results showed that moderate calcination temperature (550°C) is suitable for the formation of the copper element on the surface of ACF, lower or higher temperature will generate more cuprous oxide. Although both can exhibit catalytic activity, the role of the copper element is significantly greater. Due to the exceptional dispersibility of copper (oxide), the ACF can still maintain the advantages of larger specific surface area and pore volume after loading copper, which is the main reason for better performance of related catalysts. Finally, increasing the copper loading amount can significantly increase the crystallinity and particle size of copper (oxide) on the ACF, thereby improving its catalytic performance. In situ IR found that the reason for the deactivation of the catalyst should be the accumulation of generated H₂PO₄⁻ and SO₄²⁻(H₂O)₆ which could poison the catalyst.     

Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions

The mobility of phenanthrene (PHE) in soils depends on its sorption and is influenced by either the existing soil humus or exogenous humic substances. Exogenous humic acids (HAs) were added to soil to enhance the amount of soil organic carbon (SOC) by 2.5, 5.0, and 10.0 g kg⁻¹. PHE desorption of the treated soils was determined at two pH levels (3.0 and 6.0) and temperatures (15 and 25 °C). Soil PHE adsorption was related to pH and the type and quantity of added HAs. Humic acid (HA) and fulvic acid (FA) derived from peat had different effects on adsorption of PHE. Adsorption increased at first and then decreased with increasing quantity of exogenous FA. When the soil solution pH (in 0.005 M CaCl₂) was 4.5 or 3.0, the turning points were 2.5 g FA kg⁻¹ at pH 3.0 and 5 g FA kg⁻¹ at pH 4.5. When soil solution pH was 6, the amount of adsorbed PHE was enhanced with increasing exogenous HAs (HA or FA) and amount of adsorption by soil treated with FA was higher than with HA. Adsorption of PHE in the FA treatment at 10.0 g kg⁻¹ was lower than the controls (untreated soil or treatment with HAs at 0 g kg⁻¹) when the soil solution pH was 3.0. This suggests that FA adsorbed by soil was desorbed at low pH and would then increase PHE solubility, and PHE then combined with FA. PHE adsorption was usually higher under lower pH and/or lower temperature conditions. PHE sorption fitted the Freundlich isotherm, indicating that exogenous humic substances influenced adsorption of phenanthrene, which in turn was affected by environmental conditions such as pH and temperature. Thus, exogenous humic substances can be used to control the mobility of soil PAHs under appropriate conditions to decrease PAH contamination.     

Scanning Electron Microscopy of Humic Substances Produced During Cellulose Decomposition

Humic substances (HS) produced during the aerobic decomposition of polysaccharides still need to be recognized as such and characterized. Humic (HA) and fulvic (FA) acids extracted at different time intervals during composting of cotton residues from carding, where no decomposition of lignin occurred, were investigated by scanning electron microscopy (SEM) size exclusion chromatography and infrared spectroscopy. Throughout the experiment, fulvic acids possessed a larger number of carboxyl groups but a lower number of weak acidic groups (negatively charged acid groups at pH 11) than humic acids. the number of carboxyl groups increased with time in both fulvic and humic acids, while that of phenolic groups decreased. Infrared spectra showed that the ratio between carboxyl and methyl groups decreased from 8.5 to 4 in FA after 18 days. This change corresponded with the disappearance of flat sheet structures observed by SEM at pH 6. Our results suggest that the shape of humic molecules as observed by SEM reflects the strength of hydrophilic/hydrophobic interactions with the solvent molecules. About 80% of FA molecules had a molecular weight lower than 3500 as deduced from column calibration with HS standards obtained by ultrafiltration. About 40% of humic acids were composed of small molecules; only 20% HA had a molecular weight larger than 45000. Polysaccharide-derived HS may not be limited to the high molecular weight poorly transformed fraction containing bonded polysaccharide structures, but may also consist of low molecular weight components with no structural similarity to the original material.     

UV light induces Ag nanoparticle formation: roles of natural organic matter,iron, and oxygen

Nanoparticles occurring in the environment originate either from engineered, synthetically produced nanoparticles, or from naturally produced nanoparticles. The latter can be formed in natural media by light-induced reduction of metal ions in presence of natural organic matter, such as humic substances occurring widely in waters, soils and sediments. There is actually few knowledge on the effect of sunlight and of the nature of organic matter on nanoparticle formation. Therefore, we studied here the photoreduction of silver(I) ion to silver nanoparticles with and without ferrous ion under oxic and anoxic conditions, using humic and fulvic acids as proxies of natural organic matter. UV light-induced formation of silver nanoparticles was monitored up to 60 min by measuring surface plasmon resonance in air-saturated mixture and nitrogen-saturated mixture of silver(I) ion–organic matter. Results show that the surface plasmon resonance intensity was about 2.5 times higher in the nitrogen-purged solution mixture than the air-saturated solution. This finding suggests the oxygen-containing species had no major role in forming silver nanoparticles. Therefore, photo-driven formation of silver nanoparticles most likely involved photoactivation of silver(I) ion and natural organic matter complexes. We observed also that both iron(II) and iron(III) ions highly modified the surface plasmon resonance spectra of the particles with broader features. Results also reveal that in the presence of humic acid, the intensity of the surface plasmon resonance peak decreased by at least 50 %, while almost no change in the intensity was seen when fulvic acid was used. Overall, our findings demonstrate that the ligand–metal charge transfer process, affected by the nature of organic matter, i.e., humic acid versus fulvic acid, was influenced by redox iron species.     

Molecular changes of aquatic humic substances formed from four aquatic macrophytes decomposed under different oxygen conditions

Aquatic macrophytes’ decomposition is a source of recalcitrant carbon in the long term contributing to humic substances (HS) formation. Understanding the influence of plant detritus quality and oxygen availability over molecular changes of these compounds provides ecological information related to their cycling. This study described the molecular variation of dissolved HS from Eichhornia azurea, Egeria najas, Oxycaryum cubense and Salvinia molesta decomposition under aerobic and anaerobic conditions. The aquatic HS formed from the four aquatic macrophytes showed similar features (e.g. molecular weight and aromaticity). This fact indicates little influence of the detritus quality or availability of oxygen on the fulvic acids (FA) and humic acid characteristics. Under aerobic condition a decrease in the polysaccharides content in FA occurred. HS from E. najas were related to less-recalcitrant features, while HS from S. molesta were related to recalcitrant.     

Characterization of fulvic acids during olive mill waste composting (Elemental,Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Soil organic matter chemistry. Part 1. Characterization of several humic preparations by proton and carbon‐13 nuclear magnetic resonance spectroscopy

Both laboratory and commercial preparations of humic substances (HSs) such as fulvic acids and humic acids along with HC1‐HF preparation of Manitoba peat soil organic matter were characterized using Fourier Transformation (FT) proton (¹H) and carbon‐13 (¹³C) nuclear magnetic resonance (NMR) spectroscopy. All the samples were dissolved in a solution of 0.4 N NaOD in D₂O. In the case of ‘H‐NMR spectroscopy, all the investigated humic samples displayed resonance absorption peaks in the region of 1–4 ppm indicating the likely presence of aliphatic protons in the preparations. However, with the exception of one fulvic acid preparation (extracted from Manitoba Carrol clay‐loam soil with 0.5 N NaOH), ¹H‐NMR spectra of all other samples provided evidence for strong aromatic character. The aliphatic and aromatic characteristics of such samples of HSs were further confirmed with the aid of ¹³C‐NMR spectra.     

Veränderung von Biokonzentration und Wirkung vom PSM in Anwesenheit von Huminstoffen

Humic substances, in aqueous bodies primarily fulvic acids, may demonstrate an inhibitory as well as an activating influence on organisms. We present evidence with bacteria-containing algal cultures and with cultures of the nematodeCaenorhabditis elegans. Structural elements of the fulvic acids which may be responsible for such effects are not yet known. Furthermore, the presence of fulvic acids may lead to increases in bioconcentration of xenobiotics. Increase in the toxicity of xenobiotics in the presence of humic substances have also been described. We present studies applying lethal as well as sublethal toxicity endpoints.     

Characterization of fulvic acids during olive mill waste composting (Elemental, Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Contribution of black carbon to nonlinearity of sorption and desorption of acetochlor on sediment

In order to investigate the contribution of various black carbon (BC) contents to nonlinearity of sorption and desorption isotherms for acetochlor on sediment, equilibrium sorption and desorption isotherms were determined to measure sorption and desorption of acetochlor in sediment amended with various amounts of BC. In this paper, two types of BC referred to as BC400 and BC500 were prepared at 400°C and 500°C, respectively. Higher preparation temperature facilitated the formation of micropores on BC to enhance its sorption capacity. Increase of the BC content obviously increased the sorption amount and reduced the desorption amount for acetochlor. When the BC500 contents in total organic carbon (TOC) increased from 0 to 60%, Freundlich sorption coefficient (K _f) increased from 4.07 to 35.74, and desorption hysteresis became gradually obvious.When the content of BC in TOC was lower than 23%, the sorption isotherm had a significant linear correlation (p = 50.05). In case of desorption, a significant nonlinear change could be observed when the content of BC was up to 13%. Increase of BC content in the sediment would result in shifting the sorption-desorption isotherms from linearity to nonlinearity, which indicated that contribution of BC to nonlinear adsorption fraction became gradually remarkable.     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well.     

氯化消毒饮用水中强致突变物MX[3-氯-4-(二氯甲基)-5-羟基-2(5H)-呋喃酮]的形成

利用一系列XAD吸附树脂及大孔阴、阳离子交换树脂,将太湖水中溶解态有机物分离为溶解态富里酸类、腐殖酸类、憎水弱酸类、憎水碱类、憎水中性物类、亲水酸类、亲水碱类七种组分,分别对不同组分的有机物进行氯化处理后,用GC/MS选择离子峰面积法测定了产物中的MX[3-氯-4-（二氯甲基）-5-羟基-2（5H）-呋喃酮]。结果表明,太湖水体中的溶解态腐殖酸类可能是生成MX的重要前驱物。     

Chemical Approach to Study the Environmental Implications of Humic Acid and Gamma-Hch Interaction

Pesticide-humic interactions are known to have environmental significance in modifying the toxicity and mobility of agricultural chemicals. to test this, interaction between gamma-hexachlorocyclohexane (gamma-HCH) released from the sand coated with gamma-HCH and humic acid was investigated using thin layer chromatography and spectral studies such as UV (ultraviolet), IR (infrared), mass and FAB (fast atom bombardment) mass spectrometry. These studies revealed the evidence of loose interchelation between gamma-HCH and humic acid. the significance of the results in relation to detoxification of gamma-HCH in aquatic ecosystems are discussed.     

Photoreactivity of humic substances: relationship between fluorescence and singlet oxygen production

Humic substances are natural compounds abundantly present in the environment. They play a significant role in the natural attenuation of pollution in surface water due to their capacity to generate reactive species upon solar light excitation. Finding physico chemical parameters related to this property would be of a great help in the prediction studies of the organic pollutants fate. In this work, we investigated relationships between the ability of the humic substances to produce singlet oxygen and their fluorescence properties. For this, a series of sixteen humic acids, fulvic acids, and water-extractable organic matter from soils were studied. The steady-state singlet oxygen concentrations in the irradiated humic substances solutions were measured by monitoring the loss of furfuryl alcohol added as a singlet oxygen scavenger. The emission spectra of the sixteen samples were also recorded. Values of the steady-state singlet oxygen concentrations and the emission intensities showed significant variations among the humic samples and a parallel increase. Thus, here we demonstrate that the rate of singlet oxygen production and the emission intensity of the humic samples are correlated, the best correlation being obtained for emission wavelengths between 500 and 580 nm. This correlation which was never reported until now can be used to estimate the singlet oxygen-production capacity of the humic substances based on their fluorescent properties.