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.     

亚热带茶园土壤的某些生物化学性状研究

茶园土壤的有机质含量、腐殖质组成、有机碳的循环与平衡特点、酶活性及其在施肥条件下的变化情况与土壤肥力密切相关．试验结果表明：亚热带茶园土壤有机质含量水平较低，腐殖质组成中以富里酸为主，HA／FA比、酶活性均比起源土壤略低；高产茶园土壤有机碳库的循环水平较高，在不施有机肥的情况下仍能保持平衡；低产茶园土壤有机碳库的循环水平较低，输出大于输入，施用有机肥可以较快地提高茶园土壤有机质含量和酶活性水平．增施有机肥和实行茶林复合是培肥茶园土壤、提高茶园生产力的有效措施．     

垃圾填埋场渗滤液回流处理技术研究进展

垃圾渗滤液回流处理后，CODcr去除率最高达95％，在半好氧状态下NH3-N质量浓度降低至10mg/L几以下，渗滤液水质得到改善；渗滤液回流增加了湿度，使有机物的降解速率加快；渗滤液同流处产甲烷速率是不回流处产甲烷速率的2倍多：渗滤液回流处的总沉降幅度可达填埋场深度的20％，而不回流处仅为8％。回流处理技术分为直接回流至垃圾层、表面喷灌或浇灌至填埋场表面、地表下回流或内层回流技术。在填埋场处于产酸阶段早期，回流的渗滤液量宜少不宜多：在产气阶段则可逐渐增加。应将稳定化程度高的垃圾层区(产甲烷区)排出的渗滤液回流至新填人的垃圾层(产酸区)，将新垃圾层所产生的渗滤液回流至老的稳定化区。通过控制垃圾的组成、回流的时间、渗滤液的pH值等手段可改善回流处理效果。     

土壤和沉积物中非水解有机碳对菲的吸附

采用改进的酸水解方法对土壤和沉积物中的有机质组分进行了分离和提取,用固体13C核磁共振（13CNMR）表征了非水解有机碳（NHC）,同时研究了不同有机质组分对菲的吸附行为,结果表明,菲的吸附等温线都呈现出明显的非线性,能很好地拟合Freundlich方程;而且NHC和碳黑（BC）比其原始和去矿样品的吸附容量都有明显提高.这些结果揭示了NHC和BC主要控制着菲在土壤和沉积物中的吸附行为.沉积物及其NHC对菲的吸附容量要高于土壤及其NHC,这与土壤和沉积物中有机质的不同来源有关.     

高温堆肥碳氮循环及腐殖质变化特征研究

堆肥化处理，是指依靠自然界广泛分布的细菌、放线菌、真菌等微生物，对有机物有控制地进行生物降解，使之转化为腐殖质的生物化学处理技术。作者采用畜禽粪便条垛式高温堆肥实验方法，研究了堆肥过程中碳氮循环及腐殖质变化特征。结果表明，堆肥过程中，碳素和氮素变化最大，表现为二者总量的减少，其中以碳素总量减少较多，氮素总量次之，从而导致碳氮质量分数比降低。腐殖酸总量、胡敏酸和富里酸总量均呈下降趋势，但腐殖酸占有机碳的比例以及胡敏酸与富里酸质量分数比却在提高，速效养分含量也在升高，表明堆肥过程是一个有机质数量减少、有机质质量提高的过程。     

利用矿化垃圾层预防和控制渗滤液导排系统堵塞

在卫生填埋场中,垃圾渗滤液导排系统堵塞普遍存在,悬浮固体形成的物理堵塞、有机物降解和金属离子沉淀导致的生物-化学堵塞是引起导排系统堵塞的关键因素.本文构建了"矿化垃圾+砾石层导排"的渗滤液下渗装置,通过矿化垃圾预处理渗滤液中悬浮固体和有机物以控制导排系统发生的物理和生物-化学堵塞.结果表明,在矿化垃圾层,渗滤液中化学需氧量(COD)和悬浮固体(SS)去除较多,去除率分别达到了85%和87%,并且Ca²⁺浓度也出现了波动较大的现象;然而,渗滤液在砾石层下渗过程中,其COD、SS和Ca²⁺浓度保持稳定.并且,砾石层可排水孔隙率在长期运行的过程中没有明显变化,表明渗滤液在砾石导排层没有形成明显的沉淀.与此同时,在没有添加矿化垃圾的对照组发现,砾石层可排水孔隙率减少最多的区段是渗滤液的进水点位(可排水孔隙率减少达到了53%),即渗滤液有机负荷最大处的饱和砾石层堵塞最为严重,其无机堵塞物主要是碳酸钙等.因此,在渗滤液流入砾石层前,采用矿化垃圾层部分饱和的方式对渗滤液中有机物和悬浮固体进行预处理,可以预防和控制渗滤液在砾石层形成沉淀堵塞.研究为填埋场的运行管理渗滤液导排系统堵塞提供了新的思路和方法.     

垃圾渗滤液中有机物分子量的分布及在MBR系统中的变化

利用凝胶层析方法分析了垃圾渗滤液中有机物分子量的分布情况,并考察了利用膜生物反应器(MBR)处理垃圾渗滤液系统中有机污染物分子量的分布以及水溶性腐殖质(AHS)含量的变化．研究发现,垃圾渗滤液中的有机物主要由两部分组成,即分子量大于6000的大分子物质和分子量小于1500的小分子物质．大分子物质主要是水溶性腐殖质,而小分子物质主要由挥发性有机酸及水溶性腐殖质组成．大分子的AHS难以被微生物降解,但能被微滤膜截留．大部分小分子的AHS既难以被微生物降解,又不能被膜截留,是构成MBR处理出水COD的主要成分．     

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。     

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.     

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.     

北京市非正规垃圾填埋场垃圾成分特性

通过北京市3处典型非正规垃圾填埋场与1处正规垃圾卫生填埋场对比研究,结果表明,非正规垃圾填埋场与正规垃圾填埋场陈腐垃圾物理组成相近,但非正规垃圾填埋场有机物含量更低,同时垃圾分布不均匀;以建筑渣土为主的区域有机质含量一般低于5%;以生活垃圾为主的区域有机质含量与正规垃圾场相近,一般高于10%,内部最高温度可达42℃左右。     

Fungal diversity and its mechanism of community shaping in the milieu of sanitary landfill

• Ascomycota was the predominant phylum in sanitary landfill fungal communities. • Saprophytic fungi may be of special importance in landfill ecology. • Both richness and diversity of fungal community were lower in leachate than refuse. • Physical habitat partly contributed to the geographic variance of fungal community. • NO₃⁻ was considered the most significant abiotic factor shaping fungal community. Land filling is the main method to dispose municipal solid waste in China. During the decomposition of organic waste in landfills, fungi play an important role in organic carbon degradation and nitrogen cycling. However, fungal composition and potential functions in landfill have not yet been characterized. In this study, refuse and leachate samples with different areas and depths were taken from a large sanitary landfill in Beijing to identify fungal communities in landfills. In high-throughput sequencing of ITS region, 474 operational taxonomic units (OTUs) were obtained from landfill samples with a cutoff level of 3% and a sequencing depth of 19962. The results indicates that Ascomycota, with the average relative abundance of 84.9%, was the predominant phylum in landfill fungal communities. At the genus level, Family Hypocreaceae unclassified (15.7%), Fusarium (9.9%) and Aspergillus (8.3%) were the most abundant fungi found in the landfill and most of them are of saprotrophic lifestyle, which plays a big role in nutrient cycling in ecosystem. Fungi existed both in landfilled refuse and leachate while both the richness and evenness of fungal communities were higher in the former. In addition, fungal communities in landfilled refuse presented geographic variances, which could be partly attributed to physical habitat properties (pH, dissolved organic carbon, volatile solid, NH₄⁺, NO₂⁻ and NO₃⁻), while NO₃⁻ was considered the most significant factor (p<0.05) in shaping fungal community.     

免耕与常规耕作下黑土腐殖酸含量与结构的差异

以东北农业科学院长期耕作定位实验为研究对象,结合元素分析和红外光谱来研究免耕与翻耕两种耕作方式对黑土腐殖酸含量与胡敏酸结构的影响。结果表明：免耕处理的腐殖酸含量高于常规耕作处理18.28%,两种耕作处理间HA/FA值差异很小;免耕处理的碳、氮和氢元素含量分别高于翻耕处理5.48%、36.49%和27.65%,N/C和H/C值也高于翻耕处理,而翻耕处理的O/C值高于免耕处理;不同耕作处理的红外光谱吸收带表现相似趋势,其中2920、2580、1620、1420和1220σ·cm-1处吸光度免耕信号高于翻耕,而1026、721σ·cm-1处吸光度相反。免耕增加了腐殖酸、胡敏酸及富里酸含量;免耕增加了黑土胡敏酸的芳香度、脂肪化程度和聚合程度,而翻耕作增加了黑土胡敏酸的氧化程度,这说明经过长达26年的免耕处理使黑土腐殖质结构趋于稳定,而翻耕处理使黑土腐殖质结构趋于简单。     

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.     

Growth and metal accumulation response of <Emphasis Type="Italic">Vigna radiata</Emphasis> L. var PDM 54 (mung bean) grown on fly ash-amended soil: effect on dietary intake

Plants of Vigna radiata L. var. PDM 54 (mung bean) were grown in soil amended with different amounts (10 and 25%) of fly ash (FA). Although total metal content increased with increasing FA amendment, DTPA-extractable metals were higher for 10% FA. Accumulation of metals by the plants increased with increasing FA amendment and was greater in shoots than in roots (except for Mn and Cu) and seeds (except Mn). The total daily intake (TDI) of all the tested metals in seeds was within the recommended dietary allowance (RDA)/provisional tolerable daily intake (PTDI) for adults, except for Cd, which was higher than recommended values. Principal-components analysis (PCA) based on studies of physicochemical properties, DTPA-extractable metals, and metal accumulation in the different parts of V. radiata showed that physicochemical properties such as cation-exchange capacity, organic carbon, and organic matter had significant positive effects on accumulation of Cd, Co, Ni, and Pb by the plant, whereas EC had a significant negative effect. Although addition of fly ash (10%) initially increased the rate of growth, toxic symptoms were observed for 25% FA. Results from analysis of antioxidants (carotenoids, ascorbic acid, non-protein thiol, and free proline) revealed that these increased more in plants grown in 10% FA than in those grown in garden soil. Cysteine and malondialdehyde (MDA) content increased with increasing FA amendment. PCA also showed that all the antioxidants studied behaved similarly except cysteine, for which there was a close relationship with MDA content. Thus, the results obtained during this study revealed that V. radiata L. var. PDM 54 may be grown in 10% FA and/or contaminated agricultural soil.     

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．     

垃圾渗滤液对土壤铁锰有效性及地下水质的影响

受垃圾渗滤液影响,垃圾场周边土壤有机物含量增加。试验结果显示,随着土壤有机物含量的增加,土壤中有效态铁锰含量增大。垃圾场周边土壤中渗滤液有机物和金属铁锰共存时,大量的有机物质能活化土壤中的铁锰,增加其有效性,增强其在土壤中的迁移能力。从而造成垃圾场地下水较严重的铁锰污染。     

垃圾渗滤液对斑马鱼的毒性及抗氧化酶活性的影响

在室内模拟条件下,以斑马鱼（Daniorerio）为受试动物,探讨生活垃圾渗滤液对斑马鱼的急性毒性及对其鱼鳃、肝脏中的过氧化物歧化酶（SOD）、还原型谷胱甘肽（GSI-I）及Na＋,K＋-ATP酶等3种酶的影响。结果表明,垃圾渗滤液对斑马鱼的96hLC50为13．2％。垃圾渗滤液对斑马鱼的急性毒性相对较高,斑马鱼对垃圾渗滤液毒性的敏感性强。慢性毒性测试结果显示,垃圾渗滤液对斑马鱼肝脏中SOD活性和GSH质量分数的诱导作用明显,对Na＋,K＋-ATP酶活性影响并不明显;垃圾渗滤液对斑马鱼鱼鳃中SOD活性影响显著（P〈0．05）。除Na＋,K＋-ATP酶外,斑马鱼的抗氧化防御相关生物标志物对渗滤液染毒胁迫具有相对较高的敏感性,SOD和GSH均可用作垃圾渗滤液慢性胁迫的有效生物标志物。     

垃圾渗滤液浇灌对红壤原生动物群落的影响

采用“非浸没培养皿法”（non-flooded petri dish method)培养,对李坑垃圾填埋汤垃圾渗液淋灌的土壤中的原生动物群落进行了分析。实验发现4属4种纤毛虫：膨胀肾形虫（Colpoda inflata)、有肋薄咽虫（Leptopharynx costatus)、莫式拟肾形虫（Paracolpoda maupasi)、恼斜板虫（Plagiocampa difficils)。随淋灌中垃圾渗滤液浓度的上升,出现的纤毛虫种类呈递减趋势,从定量实验的结果来看,即使是较低浓度的垃圾渗滤液,也对土壤原生动物群落造成了较大的伤害。25％浓度的垃圾渗滤液淋灌的土样中,原生动物数量仅为CK组的30％;超过50％浓度的渗滤液稀释液淋灌土样,则仅为CK组的10％左右。数据表明污染本身并没有被降解,而是全部（或至少大部分）转移到了受渗滤液影响的土壤中,从而导致土壤中的原生动物群落的结构无论是从数量上还是从种类上均曹到相当大的破坏。表4参15