微生物降解褐煤产生的腐植酸化学特性研究

本文对微生物降解褐煤产生的腐植酸的化学特性进行了分析.结果表明,褐煤经微生物降解后其腐植酸与降解前相比,氢和氧百分含量增加,碳百分含量减少,分子量减小 ,而絮凝极限明显增大,红外吸收光谱也发生明显变化.     

硝化褐煤对铬离子溶液的吸附研究

利用硝酸与龙口褐煤反应制得硝化褐煤，使其有效吸附质腐植酸含量提高。用该湖化褐煤对铬离子进行吸附试验，研究吸附剂的吸附量、吸附动力学、吸附模型和溶液的pH值对吸附的影响。结果表明：硝化褐煤对铬离子具有良好的吸附特性，其静态等温吸附符合Langmuir等温议程。     

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。     

First determination of Cu adsorption on soil humin

Humic substances are heterogeneous mixtures of organic compounds occurring in huge amounts mainly in waters, soils, sediments and organic wastes. They are formed during the decay of living organisms. They play a very important role in many environmental processes including carbon sequestration, water cleaning and retention, soil erosion, fertility and pollutant retention. However, due to their complex nature, humic substances are still poorly characterized and much less known than living matter. Humin is the most insoluble and, in turn, the least understood fraction of humic substances. To our knowledge, no information is currently available on the adsorption and desorption behaviors of metal ions on soil humin. Here, we report the adsorption and desorption properties of Cu(II) on humin and humic acids isolated from a forest soil in northeast China using the batch equilibration method. Solid-state ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (¹³C CPMAS NMR) spectroscopy was used to characterize and compare the chemical structures of humin and humic acid. The batch experiments’ results show that humin has a lower adsorption capacity and higher adsorption reversibility for Cu(II) than humic acid. The adsorption isotherms well fitted both the Langmuir and Freundlich equations. Humin, therefore, plays an important role in controlling the fate, transport and bioavailability of Cu(II) in the environment. The ¹³C CPMAS NMR spectra showed that compared with humic acid, humin was higher in alkyl C, carbohydrate C and phenolic C and was lower in methoxyl C, aryl C and carbonyl C. These findings mean that humin was less alkylated, more aliphatic and more hydrophobic.     

Reduction of Cr(VI) by peat and coal humic substances

The reduction of Cr(VI) by humic substances from leonardite and peat was investigated by capillary zone electrophoresis at various pHs. Both humic materials reduced Cr(VI) at pH 5.4, but not at basic pH. The capacity of leonardite humic substances to reduce Cr(VI) was lower than that of peat humic substances. Fe(III) accelerated the reduction of Cr(VI) by peat humic substances, but not by leonardite humic substances. Cr(VI) reduction mechanisms are proposed. The coal humic substances seem more suitable for remediation of Cr(VI)-contaminated sites.     

Ammonia removal properties of lightweight aggregates from Si–Al–Fe and Si–Ca rocks

Lightweight aggregates commonly used as construction materials contain high percentages of metal oxides and thus are potential sorbents in aqueous systems. Here, ammonia is used as the model compound to be removed by aggregates since it is toxic for the aquatic life and is regulated in physical systems. The point of zero charge of aggregates is determined at pH values higher than 9. The aggregates made with raw materials from Larisa, Milos, and Samos presented ammonia sorptive capacities of 210, 220 and 400 μmol/kg, respectively. However, the LWA made from wollastonite (Samos) resulted in high pH (10.6) solutions and thus, production of toxic unionized ammonia. Thus, a combination of high sorptive uptake and neutral pH in solution is desired and can be achieved in future studies by selecting the appropriate raw materials for the preparation of aggregates.     

腐殖质的光化学降解及其对环境污染物环境行为的影响

腐殖质是地表环境中最重要的有机组分,也是生态环境中最主要的吸光物质之一,对环境污染物的形态、迁移、毒性和生物可利用性有着重要的影响。文章综述了腐殖质的结构特征和光化学降解反应过程和机理,指出腐殖质的光敏化和光化学降解过程对环境污染物的环境行为和归宿有重要的影响。通常,腐殖质的光敏化作用在低质量浓度下,尤其在一定铁离子的协同作用下可促进有机污染物的降解,但高质量浓度的腐殖质由于其本身的吸光作用以及参与自由基的竞争则抑制有机污染物的降解。腐殖质的光化学降解过程降低了环境体系的pH和腐殖质的分子量、破坏了腐殖质的芳环结构、改变了紫外和可见光区域的吸收等,导致其与重金属离子和有机污染物结合能力的下降,造成水体或颗粒态中游离的污染物质量浓度增加,对生态系统将造成更大的危害。目前对腐殖质和环境污染物本身的光化学降解机理已较为清晰,今后应加强对自然水体或土壤系统中腐殖质光化学降解的影响因素,腐殖质光化学降解过程中结构特性的变化机理,以及腐殖质的结构特性与环境污染物结合性质之间的构效关系等方面的研究。特别是随着平流层臭氧空洞的增加,增强了到达地球表面的紫外线强度,研究紫外线增强对腐殖质和有机污染物的降解以及对生态系统的影响可进一步深刻理解太阳光辐射对污染物环境行为和归宿的影响。     

Organic compounds in water extracts of coal: links to Balkan endemic nephropathy

The Pliocene lignite hypothesis is an environmental hypothesis that has been proposed to explain the etiology of Balkan endemic nephropathy (BEN). Aqueous leaching experiments were conducted on a variety of coal samples in order to simulate groundwater leaching of organic compounds, and to further test the role of the Pliocene lignite hypothesis in the etiology of BEN. Experiments were performed on lignite coal samples from endemic BEN areas in Romania and Serbia, and lignite and bituminous coals from nonendemic regions in Romania and the USA. Room temperature, hot water bath, and Soxhlet aqueous extraction experiments were conducted between 25 and 80 °C, and from 5 to 128 days in duration. A greater number of organic compounds and in higher concentrations were present in all three types of leaching experiments involving endemic area Pliocene lignite samples compared to all other coals examined. A BEN causing molecule or molecules may be among phenols, PAHs, benzenes, and/or lignin degradation compounds. The proposed transport pathway of the Pliocene lignite hypothesis for organic compound exposure from endemic area Pliocene lignite coals to well and spring drinking water, is likely. Aromatic compounds leached by groundwater from Pliocene lignite deposits in the vicinity of endemic BEN areas may play a role in the etiology of the disease. A better understanding of organic compounds leached by groundwater from Pliocene lignite deposits may potentially lead to the identification and implementation of effective strategies for the prevention of exposure to the causative agent(s) for BEN, and in turn, prevention of the disease.     

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.     

Sorption of pyrene from water by oil shale ash and mineral particles

The aim of this work was to estimate the sorption of pyrene from water solutions on mineral substrates, e.g., alumina, silica, and oil shale ash, from the Estonian thermal plant. Results obtained from this study indicate that the sorption of pyrene on mineral oxides and oil shale ash particles from water can be described with a linear equation. The sorptive capacity per weight of oil shale ash in aqueous systems was significantly lower compared with mineral adsorbents. The distribution coefficient (K_d) for pyrene in the system with particles of oil shale ash was 10–12 times lower as than for mineral adsorbents.     

Strong adsorption of DNA molecules on humic acids

Analysing soil microbial communities is often hampered by DNA adsorption on soil organic compounds such as humic acids. However the role of humic acids in DNA adsorption and stability in soils remains controversial. To characterize DNA–humic acid interactions, we studied DNA adsorption on two commercially available humic acids and a soil humic acid extracted from an Andosol. Desorption of the adsorbed DNA using 4 different solutions—distilled water, 0.1 M NaCl, 0.1 M sodium phosphate buffer (pH 6.0), and 1% sodium dodecyl sulfate solution—was also studied to understand the mechanism of DNA adsorption on humic acids. Here, we show that humic acids play an important role in DNA adsorption to soils. DNA molecules were adsorbed on the humic acids, with adsorption increasing proportionally with the DNA concentrations in the solution. The adsorption on all humic acid samples was fitted with Freundlich equation, and the parameters obtained from the equation indicated a high affinity between the humic acids and DNA molecules. The total amount of DNA desorbed by the 4 solutions was less than 2% of the total DNA adsorbed on all the humic acids. The results demonstrate that DNA molecules are able to bind strongly to humic acids by ligand binding, hydrophobic interaction, aggregation, or precipitation.     

环丙氨嗪在Aldrich胡敏酸中吸附-解吸特征的研究

采用批平衡法,研究了不同温度下环丙氨嗪在Aldrich胡敏酸中的吸附与解吸特征。结果表明：环丙氨嗪吸附和解吸过程都包含极快速、快速和缓慢阶段。伪二级动力学方程能较好地描述不同温度下环丙氨嗪的吸附动力学特性,表明吸附速率决定于胡敏酸表面吸附位点的可用度,而不是溶液中环丙氨嗪的浓度。环丙氨嗪在极快速吸附阶段的吸附速率随温度的升高而增大,但平衡时的吸附量却随温度的增加而降低。吸附等温线和解吸曲线符合Langmuir方程和Freundlich方程。环丙氨嗪在胡敏酸上的解吸速率小于吸附速率,表明存在滞后效应。吸附焓变、熵变和自由能都为负值,表明环丙氨嗪在胡敏酸上的吸附是一个自发、熵减小的放热过程。-Go〈40 kJ.mol^-1表明环丙氨嗪在胡敏酸表面以物理吸附为主。     

Antioxidant effect of lignite humic acids and its salts on the thermo-oxidative stability/degradation of polyvinyl alcohol blends

We demonstrate the antioxidant potential of humic acids in (green) polymer chemistry. Lignite humic acids and its sodium and ammonium salts were mixed at different concentrations with polyvinyl alcohol and thermogravimetry was used to assess the influence on the thermo-oxidative stability of resulted blends. Both protonized form and ammonium salt of humic acids caused increased stability of investigated polymers in the studied concentration range (0.5–10% of humic acids in polymer). In contrast to protonized form, the ammonium salt also showed moderating effect on polymer degradation kinetics. Sodium salts caused substantially lower stabilizing effect and presence of 10% of humic matter caused even destabilization. In all cases, however, when the degradation has already started, the presence of humic acids and its salts caused more intensive polymer decomposition, which resulted in lower weight of char.     

Adsorptive behaviors of humic acid onto freshly prepared hydrous manganese dioxides

This study focused on the adsorptive behaviors of humic acid onto freshly prepared hydrous MnO₂(s) (δMnO₂), and investigated the feasibility of employing δMnO₂ for humic acid removal from drinking water. Effects of such parameters as molecular mass of humic acid, kinds of divalent cations on adsorptive behaviors and possible mechanisms involved were investigated. This study indicated that humic acid with higher molecular mass exhibited more tendency of adsorbing onto δMnO₂ than that with lower molecular mass. Ca²⁺ facilitated more humic acid adsorption than Mg²⁺; UV-Vis spectra analysis indicated higher capabilities of Ca²⁺ coordinating with acidic functional groups of humic acid than that of Mg²⁺. Additionally, ζ potential characterization indicated that Ca²⁺ showed higher potential of increasing gz potential of δMnO₂ than Mg²⁺. Ca²⁺ of 1.0 mmol/L increased ζ potential of δMnO₂ from ?37 mV (pH 7.9) to +7 mV (pH 7.2), while 1.0 mmol/L Mg²⁺ increased to lower value as ?9 mV (pH 6.5), correspondingly. Fourier transform infrared (FTIR) spectra demonstrated the adsorption of humic acid onto δMnO₂, showing the important roles of-COO^? functional groups and surface Mn-OH in the adsorption of humic acid onto δMnO₂.     

Physico-chemical processes of humic acid-trace element interactions

Experiments were carried out under various pH conditions since this factor may strongly influence the equilibrium of various physico-chemical forms in which a certain trace element may occur in the aquatic environment. Pick-up processes were investigated for iron, cobalt, zinc, ruthenium and mercury under various experimental conditions. The rate and type of bonding or association of trace metals in humic acids was investigated by means of their replacement with other ions. For this reason the pick-up of a radionuclide of a certain trace metal by humic acid was performed, and when equilibrium was reached, the humic acids were transferred to another system where a known concentration of another ion was present. Replacement reactions took place and their yields were followed by radioactivity measurements in the liquid phase. The shape of each curve indicates the specific kinetics of the interaction of a particular trace element with humic acids under experimental conditions. Speed, total yield and time needed to reach equilibrium are specific for each particular case. The purpose of our work is to investigate the nature of trace-element interactions with humic acids. Having in mind the large variations that may occur in the constitution of humic acids, our attention focussed primarily on the search for the role these chemical variations and the different processes of their formation play on the ability of humic acids to bind trace elements. Our results demonstrated that charge-dependent processes, such as ion exchange and sorption-desorption, present a major interaction mechanism in humic acidtrace element interaction. Another important mechanism by which some trace elements are associated with humic acids seems to be chelation.     

Antimutagenic and/or genotoxic effects of processed humic acids as tested upon S. cerevisiae D7

Humic acids (HAs) are formed during decomposition of organic matter. Their adsorption, dispersion or emulsification properties attract the interest of medical science and pharmacy. The aim of this work was to study antimutagenic effects of processed HA. Yeast strain Saccharomyces cerevisiae D7 was first used for HA antimutagenicity testing. The highest antimutagenic activity was found in potassium and sodium humates. Humates isolated from lignite pre-treated by HNO₃ exhibited slightly lower antimutagenic activity; this effect is caused probably by their higher oxidation degree. Sodium humate processed at 250°C exhibited genotoxic effect, which is probably connected with accelerated formation of reactive oxygen species such as superoxide anion by HA at higher temperature.     

Possible linkages between lignite aquifers, pathogenic microbes, and renal pelvic cancer in northwestern Louisiana, USA

In May and September, 2002, 14 private residential drinking water wells, one dewatering well at a lignite mine, eight surface water sites, and lignite from an active coal mine were sampled in five Parishes of northwestern Louisiana, USA. Using a geographic information system (GIS), wells were selected that were likely to draw water that had been in contact with lignite; control wells were located in areas devoid of lignite deposits. Well water samples were analyzed for pH, conductivity, organic compounds, and nutrient and anion concentrations. All samples were further tested for presence of fungi (cultures maintained for up to 28 days and colonies counted and identified microscopically) and for metal and trace element concentration by inductively-coupled plasma mass spectrometry and atomic emission spectrometry. Surface water samples were tested for dissolved oxygen and presence of pathogenic leptospiral bacteria. The Spearman correlation method was used to assess the association between the endpoints for these field/laboratory analyses and incidence of cancer of the renal pelvis (RPC) based on data obtained from the Louisiana Tumor Registry for the five Parishes included in the study. Significant associations were revealed between the cancer rate and the presence in drinking water of organic compounds, the fungi Zygomycetes, the nutrients PO₄ and NH₃, and 13 chemical elements. Presence of human pathogenic leptospires was detected in four out of eight (50%) of the surface water sites sampled. The present study of a stable rural population examined possible linkages between aquifers containing chemically reactive lignite deposits, hydrologic conditions favorable to the␣leaching and transport of toxic organic compounds from the lignite into the groundwater, possible microbial contamination, and RPC risk.     

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.     

Diuron herbicide degradation catalyzed by low molecular weight humic acid-like compounds

Phenylureas such as diuron are major herbicides used worldwide to control undesirable weeds. The environmental fate of phenylureas is of great interest because massive amounts of those herbicides are used. It is known that abiotic degradation of phenylureas in soil–water systems is catalyzed by humic acids. However, due to the chemical heterogeneity and large molecular sizes of humic acids, the specific effects of functional groups during catalysis have not been elucidated. Therefore, we studied here for the first time the kinetics of diuron degradation in the presence of low molecular weight humic acid-like compounds such as benzoic acid derivatives. Experiments were carried out at various pH and temperature, and monitored by high-performance liquid chromatography. Results show that all benzoic acid derivatives efficiently catalyzed diuron hydrolysis. The catalytic efficiency decreased in the following order: 0.88 M^?1 day^?1 for 3,4-dihydroxybenzoic acid, 0.72 M^?1 day^?1 for 4-hydroxybenzoic acid, 0.23 M^?1 day^?1 for phthalic acid, 0.11 M^?1 day^?1 for 2-hydroxybenzoic acid, and 0.09 M^?1 day^?1 for 2,4-dihydroxybenzoic acid. These differences in the catalytic efficiency are explained by steric hindrance affecting the accessibility of reactive sites and hence influencing the rate of the overall process. Steric factors are therefore expected to control the catalytic activity of humic acids because of the chemical similarities between humic acids and low molecular weight humic acid-like compound. Our results should help predict more accurately the fate and abiotic degradation mechanism of phenylureas in the environment.