天然有机质和金属离子在矿物表面的共吸附

天然有机质(NOM)在土壤、沉积物和水体等环境中无处不在,其中富里酸和胡敏酸是主要形态。富里酸及胡敏酸活性高,易与天然矿物颗粒和金属离子发生相互作用,影响矿物的表面化学特性以及金属离子的形态与迁移性,进而在控制环境中金属离子的生物有效性和毒性等方面起重要作用。本文主要综述了富里酸和胡敏酸等NOM和金属离子在矿物表面共吸附特性与主要影响因素,归纳了表面络合模型和现代光谱技术在上述三元体系研究中的应用及其反应机制研究进展。NOM在较大程度上改变了金属离子在矿物表面的吸附特性和反应机制,并受体系pH、金属离子类型和浓度、NOM浓度、NOM和金属离子的添加顺序、矿物类型等因素的影响。低pH时,NOM通常促进矿物对金属离子的吸附。NOM和金属离子在矿物表面的共吸附机制包括:NOM和金属离子竞争吸附表面活性吸附位点;在溶液中形成NOM-金属离子络合物;形成金属离子桥接矿物表面位点与NOM的A型三元络合物(矿物-金属离子-NOM)或NOM联接矿物表面与金属离子的B型三元表面络合物(矿物-NOM-金属离子);静电作用改变表面电荷特征。最后展望了天然有机质等配体与金属离子在矿物表面共吸附有关的研究热点和方向。     

施用腐殖酸对煤矸石养分释放的影响

煤矸石是一种潜在的资源,在现有技术条件下无法快速处理的大量煤矸石裸露堆放造成占地及生态环境问题,已成为矿区生态环境治理关注的热点。煤矸石山的植被恢复是其原位保存的最有效办法。腐殖酸作为腐殖质的主要组成成分对改善不利的植物生长环境具有积极作用。为探讨腐殖酸对煤矸石养分释放的影响,采用室内培养试验方法,研究了添加不同浓度腐殖酸及不同培养时间下煤矸石的pH、电导率(EC)变化及氮、磷、钾速效养分的释放特征。结果表明:相对于不添加腐殖酸处理(CK),添加腐殖酸的煤矸石pH明显升高,最高达到7.77,而EC急剧下降,平均为126.13μS/cm,比CK的平均EC下降77.81%;添加腐殖酸的煤矸石速效磷和碱解氮均大幅度增加,速效磷含量平均为CK的2.33倍,碱解氮含量最高达到CK的1.94倍;速效钾含量相对于CK也有一定增加;添加的腐殖酸浓度越大,促进煤矸石养分释放效果越好;在培养期间,各项研究指标值总体表现"V"和"N"形,在后期逐渐呈现稳定作用趋势。煤矸石具有一定养分供给潜力,腐殖酸添加到煤矸石中可以提高其植物养分可获得性。     

腐殖酸-高岭石胶体对铀(VI)在饱和多孔介质中迁移过程的影响

为探讨可溶性有机质存在条件下黏土矿物胶体对铀（VI）在饱和多孔介质中迁移的影响,选取2种石英砂（细砂和粗砂）分别构建均质构型的石英砂柱,研究了饱和水流条件下腐殖酸存在时高岭石胶体对铀在2种不同粒径石英砂中迁移的影响。结果表明,示踪溶质在2种均质石英砂柱中的穿透曲线相似且分布对称。当在石英砂柱中只通入铀（VI）溶液时,铀（VI）在2种粒径石英砂柱中的穿透量均较小（<25%）,此时大量的铀（VI）通过络合作用吸附在石英砂表面上。当通入溶液中存在腐殖酸和高岭石胶体时,铀（VI）在2种石英砂柱中的穿透量增加,且在600~850 μm石英砂中（58.36%）比250~425 μm石英砂中（42.68%）穿透量更多。这充分表明腐殖酸—高岭石胶体和石英砂粒径是影响铀（VI）在地下环境中迁移的重要因素。     

腐植酸对土壤氮素转化及氨挥发损失的影响

采用培养试验方法研究腐植酸添加量(0、5%、10%、25%、50%、75%HA)对土壤氮素转化及其损失的影响。结果表明:与CK对比,1)腐植酸可显著降低氨挥发量,各处理平均降低12.08%,且随着腐植酸添加量的增加对氨挥发的抑制作用增大;2)培养前期,5%~50%添加量范围内腐植酸能提高土壤脲酶活性,至5 d时平均提高了35.13%,75%腐植酸添加量的土壤脲酶活性降低了13.23%,但培养后期(14 d后)腐植酸处理均能提高土壤脲酶活性;3)添加腐植酸使土壤铵态氮含量增加,且随着腐植酸添加量的增大,土壤铵态氮含量呈增加趋势,至培养112 d时,腐植酸处理的土壤铵态氮含量平均增加了39.63%;4)在整个培养期间,腐植酸处理的土壤表观硝化率平均降低了17.20%,且腐植酸的添加量越大,土壤表观硝化率越低。这些结果充分表明腐植酸能够调控土壤氮素去向、减少氮素损失,对提高氮肥利用率具有重要意义。     

Effects of dietary humic acid on growth performance,haemato‐immunological and physiological responses and resistance of Rainbow trout,Oncorhynchus mykiss to Yersinia ruckeri

This study investigated the effects of dietary humic acid sodium salt on growth performance, haemato‐immunological and physiological responses, and resistance of rainbow trout, Oncorhynchus mykiss to Yersinia ruckeri. The experimental fish were divided into four groups; three of them were fed with humic acid incorporated diets (0.3% H3, 0.6% H6, 1.2% H12) and an additive free basal diet served as the control. Growth performance and haematological parameters of rainbow trout were not affected by humic acid supplemented diets (p > 0.05). However, dietary humic acid especially with 0.6% incorporation significantly increased stomach pepsin, intestinal trypsin and lipase activities p < 0.05. Following 60 days of feeding trial, fish were challenged with Yersinia ruckeri for 20 days. At the end of the challenge period, significantly higher (p < 0.05) survival rates were found in the 6% humic acid group compared to all other experimental treatment. Thus humic acid might replace antibiotics in diets for rainbow trout to control yersiniosis.     

橡胶树死皮防治缓释颗粒调理剂造粒工艺的研究

橡胶树死皮已成为制约天然橡胶生产发展的重要因子之一,研发轻简、高效的死皮防治技术是目前橡胶生产中亟需解决的问题。以腐植酸为载体,对橡胶树死皮防治缓释颗粒调理剂的圆盘造粒工艺进行了研究。通过设计正交试验,分析了圆盘倾斜角度、圆盘转速及粘结剂对缓释颗粒调理剂的粒度、颗粒强度及颗粒崩解率的影响,确定了合理的造粒工艺：圆盘转速为60 r/min、倾角30°,粘结剂为壳聚糖。最优工艺条件下制备的缓释颗粒调理剂的粒度为91.5%、颗粒强度为34.1 N、崩解率为10%,粒度及颗粒强度已达国家复合肥标准相关要求;从崩解率看,所制备的调理剂颗粒具有一定的缓释性能。本研究的开展可为实现轻简、高效的橡胶树死皮防控提供技术支撑。     

增施腐殖酸及减施化肥对盐碱地粳稻品质的影响

基于盐碱地土质差、稻米品质低的问题,开展了增施腐殖酸及减施化肥对水稻品质影响的研究。结果表明：增施腐殖酸明显提高了垦粳7号糙米率、精米率,降低水稻直链淀粉,对整精米率、蛋白质影响不明显,腐殖酸A2（15.84 g/盆）显著提高了垦粳7号的食味评分,明显改善了食味品质;减施化肥明显提高了垦粳7号食味品质,以B4（减量30%）施肥水平的食味评分最高,且对加工品质和营养品质影响不明显,但增加了垦粳7号垩白粒率与垩白度,导致稻米外观品质变劣。通过增施腐殖酸（15.84 g/盆）配施化肥（减量30%）可明显提升垦粳7号的食味品质,但降低了其外观品质。     

腐植酸对水体中五价钒的吸附

采用批次实验法,研究了腐植酸浓度、钒离子浓度、吸附时间、温度、溶液p H、离子强度、电解质等对腐植酸吸附水体中五价钒的影响。结果表明,钒溶液浓度为90.91 mg·L~(-1)条件下,腐植酸的浓度为1.09 g·L~(-1)时,腐植酸对钒的吸附量最大。随着钒溶液浓度的增加,吸附率逐渐降低并趋于0;而吸附量呈增加-缓慢增加-平衡的趋势;在腐植酸浓度为1.09 g·L~(-1)条件下,钒溶液浓度为1 818.18 mg·L~(-1)时,吸附量达到最大值,吸附等温线与Langmuir模型基本吻合。随着溶液pH、温度的增加,腐植酸对钒的吸附量逐渐减少,即在酸性、温度较低的条件下更有利于腐植酸对钒的吸附。随着溶液电解质浓度的增加,腐植酸对钒的吸附量逐渐降低。红外光谱和扫描电镜的结果显示,腐植酸对钒的吸附机制为钒在腐植酸的表面和内部形成稳定的络合物,这与腐植酸的O-H(或N-H)的氢键、C-O和C-H键的伸缩振动有关。因此,可以考虑用适量的腐植酸作吸附剂,去除水体中的钒,并调整环境条件增强吸附效果。     

Humic Acids Derived from Leonardite-Affected Growth and Nutrient Uptake of Corn Seedlings

Using organic fertilizer or soil amendment such as humic substances is an important component for sustainable agriculture. The objective of this study was to determine the effects of different factions of humic acids (HAs) on corn seedling growth and nutrient uptake. The experiment was carried out with both an agar culture in root boxes and a hydroponic culture to which 400 mg/L of different factions of humus acids, mixed HAs, and raw Leonardite were added. The experiments were repeated twice with three replications for each treatment. The results showed that applications of HAs significantly improved the leaf and root growth of corn seedlings compared with the control (no HA addition). In the agar culture, seedlings treated with HAs with relatively low molecular weights had more leaves and twice long of roots compared to control and other treatments. In the hydroponic culture, the mixture of three factions was the best treatment for both shoot and root growth of seedlings.     

Lignite pre-treatment and its effect on bio-stimulative properties of respective lignite humic acids

Humic acids originating from South-Moravian lignite were subjected to a comparative study with the aim to assess the alteration of their physico-chemical properties after various lignite pre-treatments. Physical modification was achieved with two organic acids, such as acetic acid and citric acid and chemical modification by nitric acid and hydrogene peroxide in various concentrations. Elemental analysis, solid-state NMR, GC–MS analysis of polyols and size exclusion chromatography were carried out for chemical–physical characterization of obtained humic acids. Their biological effect, in form of potassium and ammonium humates, was tested on maize (Zea mays) seedlings. In these tests, potassium humates achieved far better overall results than ammonium humates. Results were inter-correlated in order to appraise the influence of humic acids physical and chemical properties on biological activity. Surprisingly, fractions with the lowest molecular size (0–35 kDa) showed no correlation with bioactivity results (Pearson coefficient from 0.05 to −0.4). On the contrary, middle-sized fractions (35–175 kDa) showed highly significant positive correlation (Pearson coefficient up to 0.92) and the highest molecular-size-fractions (275–350 kDa) showed negative correlation (Pearson coefficient up to −0.75). These findings were identical for both potassium and ammonium humates. No connection was found between bioactivity of humates and polyols content which was remarkably high; it reached 150 mg per g of humic acids in the most extreme case of 5% hydrogene peroxide pre-treatment. In the final analysis, the preparation mode bore pivotal responsibility for the control of humic acids biological effect and showed the best results for potassium humates obtained from lignite pre-treated by acetic acid and by 2% hydrogen peroxide.