不同类型堆肥中腐殖酸与富里酸的光谱特性和分子量分布

以中药渣(HR)、小麦秸秆(WS)和稻壳(RH)为辅料工业化生产的鸡粪堆肥中的腐殖酸(HA)和富里酸(FA)为研究对象,系统对比分析了不同类型堆肥腐殖质(HSs)的光谱特性和分子量分布。结果表明,3类堆肥中HA的芳香性均高于FA,HR和RH堆肥中HA和FA的芳香化程度均高于WS堆肥。三维荧光区域体积积分结果显示,HA的类腐殖质含量(Ⅲ+Ⅴ,86%～91%)高于FA(56%～64%),而FA的类蛋白物质(Ⅰ+Ⅱ,28%～37%)远高于HA(5%～9%),表明HA具有更高的腐殖化程度和分子量特征;其次,RH和WS堆肥中FA分别含有更多的类富里酸和类腐殖酸,而HR堆肥中FA的类络氨酸组分更多。傅里叶红外光谱分析发现,FA比HA含有更多的酰胺和羧酸,其中HR、WS和RH堆肥中FA分别富含芳香族羧酸、酰胺和多糖结构。元素分析结果显示,与FA相比,堆肥HA具有较高的C/N比和较低的O/C比,表明HA具有更多的不饱和结构,而FA具有更多的含氧官能团。添加不同辅料的堆肥中,WS堆肥HSs的脂肪化程度最高。高效体积排阻色谱结果显示,HA比FA具有更宽的高分子量分布(>2×10⁴     

松花江腐殖酸的提取、表征及与重金属的络合作用

本文提得了第二松花江水及底泥中的黄腐酸(FA)和棕腐酸(HA),测定了总酸性基、羧基、醌基等官能团并进行了元素分析,研究了红外、紫外及荧光光谱,与一般水体腐殖酸的特征相同。 选用凝胶过滤法研究了腐殖酸与汞、镉、锌的络合作用,测定了水及底泥的FA和HA对Zn、Cd、Hg的络合容量,其趋势为Hg>Cd>Zn,计算了条件稳定常数,logA值显示出汞与腐殖酸的稳定性高于汞与水体中除S~(2-)及SH-外的其它配位络合物,合成了腐殖酸汞固体络合物,用红外光谱确定其络合作用,测定了腐殖酸汞在水中的溶解度。     

草炭溶解态有机物质与Cu2+、Cd2+络合稳定性的研究

研究了由草炭提取的胡敏酸(HA)、富里酸(FA)、水溶解态有机物质(WSOM)的基团特征,分子量分布及其与Cu2+、Cd2+两种金属离子之间的络合稳定性。对HA、FA及WSOM的红外光谱研究显示三者的官能团组成相似,只是含量略有不同。固态13C-NMR对HA、FA及WSOM结构特征的描述以及水相凝胶色谱法对三种有机质样品的分子量及分子量分布的测定结果显示HA分子最大且含有大量的长链烷烃,而FA分子小得多,结构以碳水化合物及多糖为主,WSOM的分子量略低于FA,结构与FA相近。离子交换平衡法对三种有机质样品与Cu2+、Cd2+的络合配位数和稳定常数的测定结果显示两种介质条件下络合配位数(x)、络合稳定常数(logk)的次序均为:Cu2+>Cd2+;同一介质条件下,对不同有机质而言均满足:M-HA>M-FA>M-WSOM。     

土壤有机质级份的红外和热重特性

用红外分析(FTIR)和热失重分析法对从三种不同利用方式下的黄泥土中提取出的FA,HA及用酸性二甲基亚砜(DMSO)和HF—HCl两种方法提取胡敏素的元素组成及结构特征进行分析,结果表明：胡敏素占腐殖质总碳的60—70％,FA和HA分别占10％和15％左右;不同利用方式下土壤的DMSO-humin,HF-humin 1．HF-humin2在波数2930／1640处的吸收强度比分别为1．18—1．44,0．32—0．43,0．37—0．41;DMSO．humin在78—86℃和264-282℃出现了主要的失重峰,HF-humin1和HF—humin2的主要失重峰在333—338℃和438—458℃之间,FA和HA的主要失重峰分别在300℃和359℃左右,说明用DMSO提取的胡敏素脂肪族类物质较多,缩合程度较低;而用HF—HCl提取的则含较多的芳香族类物质,缩合程度较高．     

交替冻融对东北典型土壤腐殖质的影响

以受季节性冻融过程影响显著的东北地区的黑土、暗棕壤和水稻土为例,采用实验室模拟的方法,研究交替冻融循环过程（分别在-20℃和20℃下处理）对土壤腐殖质的影响。研究表明：交替冻融后,黑土和暗棕壤松结态腐殖质质量分数分别增加了39%和28%,HA/FA分别上升了45%和35%;水稻土松结态腐殖质质量分数和HA/FA分别下降了18%和31%。三维荧光结果进一步验证,黑土、暗棕壤在交替冻融中土壤芳香化程度增高,HA/FA上升,而水稻土则相反。黑土和暗棕壤松结态腐殖质和HA/FA升高,主要是微生物分解作用和土壤大团聚体破坏等原因造成,水稻土松结态腐殖质和HA/FA降低,主要是水稻土的缺氧环境造成。     

堆肥处理对污泥腐殖物质组成和光谱学特征的影响

采用凝胶(Sephadex G-75)色谱、荧光光谱和红外光谱法研究了污泥堆肥的HA和FA在堆制前后的组成与结构特征变化．凝胶色谱分析表明,污泥经过63d堆腐后,HA中大分子组分含量明显提高;而FA则由不同分子量物质组成,其中小分子量物质占主要部分,在堆腐以后,FA中大分子物质含量下降30％,小分子量物质含量则相对增加．同时,荧光光谱、红外光谱的结果表明：随着污泥堆肥的进行,HA中有机物不饱和结构的多聚化或联合程度增大,芳香结构物质含量增加;但经过堆制的FA具有更多的结构简单的低分子量物质和更低的芳构化水平．     

胡敏酸、富里酸对土壤-地下水系统中BDE-47迁移的影响

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是土壤-地下水系统中广泛存在的有机污染物,研究土壤组分对其迁移行为的影响是解决土壤-地下水系统中多溴联苯醚归趋问题的关键。以典型多溴联苯醚同系物2,2',4,4'-四溴联苯醚(2,2',4,4'-tetrabromodiphenyl ether,BDE-47)为研究对象,选取胡敏酸(humic acid,HA)、富里酸(fulvic acid,FA)2种代表性土壤有机组分,配制不同浓度的FA、HA溶液(150 mg·L~(-1)、50 mg·L~(-1)),分别对不同浓度的BDE-47(100μg·g~(-1)、10μg·g~(-1))污染土壤进行土柱淋滤实验,探讨FA、HA对土壤-地下水系统中BDE-47迁移的影响。结果表明,HA作用下,实验组下层土壤中BDE-47的残留比例分别为0.62%和0.40%,分别低于对照组的0.72%和3.36%;FA作用下,实验组下层土壤中BDE-47的残留比例分别为6.40%和6.71%,分别高于对照组的0.72%和3.36%。结合HA和FA的元素组成和结构特征分析可知,疏水性强的HA能够促进BDE-47随水流迁移进入地下水系统;亲水性强的FA促进BDE-47在土壤系统中的分布,阻滞了土壤系统中BDE-47进入地下水系统。本文为评估HA、FA对土壤-地下水系统中BDE-47迁移的影响提供依据。     

城市污染河道沉积物有机质的氧化稳定性

为了研究城市河道沉积物有机质的氧化稳定性,以氧化稳定系数(Kos)和腐殖化程度(HA/FA)作为评价指标,在用H2O2处理沉积物的基础上,探讨城市污染河道有机质含量、有机质组成等对氧化稳定性的影响.结果显示,污染河道沉积物有机质含量明显高于自然水生态系统沉积物有机质含量;富里酸(FA)、胡敏酸(HA)、胡敏素(HM)是污染河道沉积物有机质主要赋存形式,其中胡敏素是主体,占全部有机质的65%以上;易氧化有机质(OMr)和难氧化有机质(OMd)与总有机质含量均显著正相关(P0.05);OMd的含量可以更直观地反映河道污染程度;重污染河道沉积物有机质去除量较高;随着有机质的去除,沉积物Kos在总体上有上升的趋势;不同形态有机组分其Kos差异性明显(P0.05),以HM为主的紧结态腐殖质的Kos值最高;用HA/FA和OMr可从大体上表征沉积物的氧化稳定性;HA、FA是影响城市河道沉积物氧化稳定性的主要因素.     

快生型大豆根瘤菌(Rhizobium fredii)内源质粒在培养及共生过程中的稳定性

以湖北洪湖公离的快生型大豆根瘤菌为材料，考察了它们的内源质粒在培养过程及共生过程中的稳定性．结果表明，所有供试菌株的质粒在培养条件下比较稳定，传代50次后没有明显变异．对其中2个菌株与4种不同的大豆宿主共生过程中质粒的稳定性研究，发现HA12－1－12的共生质粒和隐性质粒高度构定，HA7－2－2的质粒却发生了不同程度的变异．质粒检测的结果及RFLP分析表明，HA7－2－2共生质粒的稳定性高于隐性质粒，而且共生质粒上携带的nodDABC和nifHDK基因相当保守，不易受宿主的影响而产生变异．盆栽试验的结果也说明，虽然HA7－2－2的内源质粒在共生过程中发生了遗传重排，但它的共生性状没有明显的变异．     

太湖水-沉积物界面磷、pH及碱性磷酸酶的时空特征及相关性

于2011年3、6和9月通过对太湖不同营养化湖区的5个标准采样位点进行采样分析,探讨了界面沉积物间隙水和上覆水中磷含量、pH及碱性磷酸酶活性的时空分布特征及相关性。结果表明,上覆水及沉积物间隙水中的总磷（TP）、可溶性正磷酸盐（SAP）、pH及碱性磷酸酶（ALP）活性均表现出明显的空间异质性和季节变化趋势。间隙水总磷（PW-TP）、间隙水可溶性正磷酸盐（PW-SAP）高于上覆水,分别最高高出0．082、0．042mg·L-1;上覆水pH值高于间隙水pH值,最高高出O．35个单位;间隙水中碱性磷酸酶（PW-ALP）活性高于上覆水中碱性磷酸酶（W-ALP）活性,最高高出13．244μg·mL·h-1。TP、SAP、pH及ALP活性在3、6、9月份中均以16#样品最高,其中6月份16#样品PW-TP、PW-SAP、上覆水pH及PW-ALP活性分别O．527、0．132、7．46和61．090μg·mL·h-1。参数相关性分析结果表明,W-TP与W-SAP、W-pH显著相关。W-SAP与PW-TP、PW-SAP、W-ALP、PW-ALP均显著相关。PW-TP与PW-pH显著相关性,与PW-ALP活性存在一定的相关性,但不显著。PW-SAP与PW-ALP显著相关。     

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.     

Characterization of humic substances in bio-treated municipal solid waste landfill leachate

Considerable organic matter remains in municipal solid waste landfill leachate after biological treatments. Humic substances (HSs) dominate the organic matter in bio-treated landfill leachate. In this study, the HSs from landfill leachate treated by membrane bioreactor (MBR-HSs) were analyzed via elemental analysis, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, and charge polarized magic-angle spinning-¹³C-nuclear magnetic resonance. The characteristic absorption in the UV wavelength range indicated the presence of high C=C and C=O double bonds within the MBR-HSs. Compared with commercial HSs, MBR-HSs had lower carbon content [48.14% for fulvic acids (FA) and 49.52% for humic acids (HA)], higher nitrogen content (4.31% for FA and 6.16% for HA), lower aromatic structure content, and higher carbohydrate and carboxylic atoms of carbon content. FA predominantly had an aliphatic structure, and HA had less condensed or substituted aromatic ring structures than natural HA. The aromatic carbon content of MBR-HSs was lower than that of humus-derived HSs but higher than that of waste-derived HSs, indicating that MBR-HSs appeared to be more similar to humus-derived HSs than waste-derived HA.     

Quantitative characterization of Cu binding potential of dissolved organic matter （DOM） in sediment from Taihu Lake using multiple techniques

Dissolved organic matter （DOM） plays an important role in heavy metal speciation and distribution in the aquatic environment especially for eutrophic lakes which have higher DOM concentration. Taihu Lake is the third largest freshwater and a high eutrophic lake in the downstream of the Yangtze River, China. In the lake, frequent breakout of algae blooms greatly increased the concentration of different organic matters in the lake sediment. In this study, sediment samples were collected from various part of Taihu Lake to explore the spatial difference in the binding potential of DOM with Cu. The titration experiment was adopted to quantitatively characterize the interaction between Cu（II） and DOM extracted from Taihu Lake sediments using ion selective electrode （ISE） and fluorescence quenching technology. The ISE results showed that the exogenous DOM had higher binding ability than endogenous DOM, and DOM derived from aquatic macrophytes had a higher binding ability than that derived from algae. The fluorescence quenching results indicated that humic substances played a key role in the complexation between DOM and Cu（II） in the lake. However, because of the frequent breakout of algae blooms, protein-like matters are also main component like hnmic matters in Taihu Lake. Therefore, the metals bound by protein-like substances should be caused concern as protein-like substances in DOM were unstable and they will release bound metal when decomposed.     

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.     

不同填埋年龄的矿化垃圾中胡敏酸的分子荧光光谱研究

对上海市老港填埋场封场6-10年矿化垃圾中的胡敏酸(HA)进行荧光光谱分析,结果表明,不同封场时间的矿化垃圾中HA的荧光光谱均为宽带峰型,pH值对HA荧光光谱的影响较小.而且随着矿化垃圾封场时间的加长,荧光特征峰波长缓慢增加.     

The role of soil humic and fulvic acid in the sorption of endosulfan (alpha and beta)

The sorption behaviour of alpha- and beta-endosulfan in soil organic matter was investigated using standard soil humic acid (HA) and soil fulvic acid (FA) with a modified solubility enhancement method and a dialysis bag technique. For HA, all the experiments were conducted at an ionic strength of 0.001 mol/L, in both the presence and absence of calcium and at an ionic strength of 0.01 mol/L. For FA, the experiments were conducted at two ionic strengths: 0.001 mol/L (with calcium) and 0.01 mol/L. This study is the first to describe the striking differences in the sorption behaviours of the two stereoisomers of endosulfan in HA and in FA. The sorption coefficients of alpha-endosulfan in HA and FA were significantly higher than those of beta-endosulfan. Beta-endosulfan has comparable sorption coefficients (1.5–5.4 L/g) in HA and in FA. Ionic strength and the presence of calcium have no significant effect on the sorption of beta-endosulfan in HA. However, calcium can significantly (p=0.01) enhance the solubility of alpha-endosulfan in HA. Changes in ionic strength by one order of magnitude also affect the solubility of alpha-endosulfan in HA. The sorption coefficients of alpha-endosulfan in HA (10–36 L/g) were greater than those in FA (9–14 L/g). The chirality of the alpha-isomer was hypothesised to be the primary reason behind its higher sorption in soil organic matter relative to the beta-isomer. In the presence of dissolved HA and FA found in natural soil environments, solubility of endosulfan can be increased by five times than the aqueous solubility of endosulfan without HA and FA.     

腐殖酸存在下镉和铅对土壤脱氢酶活性的影响

采用室内培养试验研究Cd和Pb污染红壤添加不同组分腐殖酸后,其脱氢酶活性的变化,结果表明,红壤遭受镉和铅污染后,脱氢酶活性显著降低,然而腐殖酸特别是胡敏酸的存在能够使脱氢酶活性得到显著回升,说明腐殖酸与重金属的相互作用对重金属污染土壤微生物活性的改善和修复功能,对土壤有一定的去污降毒作用.不同腐殖酸组分的效应大小为:灰色胡敏酸(GHA)>棕色胡敏酸(BHA)>富里酸(FA),表明分子量愈大、芳构化程度愈高的腐殖酸组分,其对重金属的钝化愈强,从而解除土壤重金属对生物毒害的能力愈强.     

Spatio-temporal variations of fluorescence properties of dissolved organic matter along the River Têt (Pyrénées-Orientales,France)

Fluorescence excitation-emission matrices showed the spectral signature of dissolved organic matter (DOM) downstream in the River Têt at all seasons corresponding to humic substances with maximum fluorescence emission λem=420–460 nm for excitations of λex=340–360 nm and the occasional presence of tryptophan, tracer of anthropogenic pressure, spectroscopically identified by λex/λem=310/350 nm. A factorial discriminant analysis, performed using the parameters selected (λex/λem pairs of wavelength), succeeded in a better discrimination of seasons than stations, and clearly showed the presence of two fluorophores. Fluorophore 1, with two absorption bands: λex=260–320 nm and 330–390 nm for λem=440–500 nm, and Fluorophore 2, with one absorption band: λex=300–360 nm for λem=410 nm, which are attributed to humic acid (HA) and fulvic acid (FA), respectively. Variations of DOM relative contents downstream in the River Têt, according to seasons and stations, showed high amounts of DOM (pedogenic character) along the river in the humid period, with the highest value obtained in the mountain section. In contrast, in summer, the DOM contents were low (aquagenic character). Moreover, DOM presents a relatively constant composition with a percentage of FA ranging from 40% at the mountain station to 48% at the mouth river, whatever the season.     

不同时期添加蘑菇渣对落叶堆肥过程的影响

研究不同时期添加蘑菇渣对落叶堆肥过程的影响.结果表明:堆肥降温期添加蘑菇渣有利于提高有机质的降解率,堆肥末期各处理有机质降解率分别为15.85%,10.17%,12.90%和15.16%;有利于吸收固定堆肥中的氨,减少氨的挥发,降低堆肥的pH值.在堆肥初始一次性添加蘑菇渣,有利于堆肥总氮的积累,提高堆肥产品中胡敏酸和腐殖质含量,降低堆肥总氮损失率.在堆肥初始和降温期分次添加蘑菇渣有利于堆肥硝态氮的合成,富里酸的分解以及HA/FA的增加.在整个堆肥过程中,各处理HA和HA/FA均呈增加趋势,FA呈降低趋势,较好地反映了落叶堆肥的腐熟程度.在堆肥不同阶段添加蘑菇渣各有其优点,综合后认为在堆肥初始添加蘑菇渣的效果最为理想.