低分子有机酸去除土壤中重金属条件的研究

采用化学萃取实验,以湖南郴州柿竹园和湖南衡阳水口山矿区的重金属污染农田土壤为研究对象,采用柠檬酸、草酸、酒石酸作为低分子有机酸萃取剂,在一定的条件下对污染土壤中重金属进行萃取实验,确定各个单因素的适宜条件。结果表明,对于湖南郴州和衡阳两个污染地区土壤运用化学萃取技术萃取重金属来进行土壤修复是实际可行的;柠檬酸、酒石酸、草酸对各种土壤中的重金属都表现出了良好的萃取能力,是高效的土壤重金属萃取剂;单因素的适宜萃取条件为100mmol·L^-1有机酸溶液,固液比1∶5,恒定温度35℃,pH为3,反应时间24h,且萃取率随着电解质浓度的增大而提高;土壤中重金属存在形态与萃取效果有一定的相关性,稳定态（残渣态、硫化物和有机结合态、铁-锰氧化物结合态）金属含量高,表现为较低的萃取率;反之,萃取率高;柠檬酸、草酸、酒石酸3种萃取剂均能有效地降低衡阳污染土壤中的重金属浓度,3种萃取剂的萃取效率依次为酒石酸〉草酸〉柠檬酸。     

低分子量有机酸对土壤磷活化影响的研究

研究两种低分子量有机酸（柠檬酸和苹果酸）对土壤磷活化影响,并用修正的Hedley法测定土壤磷活化前后磷组分的变化。结果表明,低分子量有机酸能持续活化土壤磷,活化强度随低分子量有机酸浓度的增大而增强,并且柠檬酸活化土壤磷的能力强于苹果酸。低分子量有机酸能促进作物有效态无机磷组分（H2O-P和NaHCO3-Pi）的释放;同时还促进有机磷组分（NaHCO3-Po和NaOH-Po）的矿化。在低分子量有机酸浓度达到0.5 mmol/L以上时,其对土壤磷组分的活化量的顺序为:NaOH-Pi HCl-P NaHCO3-Pi H2O-P,即铁铝结合态磷 钙结合态磷 作物有效态磷。低分子量有机酸活化土壤磷的过程中伴有大量铁、铝释放,且铁或铝的释放量与磷活化量之间显著正相关（P0.05）。说明铁、铝结合态磷是低分子量有机酸活化土壤磷的主要磷源,并且其活化机制可能与铁、铝结合态磷的螯合溶解有关。     

不同浓度和pH对茶多酚活化土壤硅、铝、铁的影响

通过浸提试验研究了不同浓度茶叶提取物、儿茶素和表没食子儿茶素没食子酸脂(EGCG)3种茶多酚(TPs)和不同p H下EGCG对漂洗水稻土和黄壤Si、Al和Fe活化的影响。结果表明:(1)随TPs浓度升高,土壤Si活化量在茶叶提取物和儿茶素作用下总体上均增加,在EGCG作用下却先增后减;Al、Fe活化量在各TP作用下均增加。同一浓度下,各TP活化Si的量均为漂洗水稻土黄壤,活化Al或Fe的量均为黄壤漂洗水稻土。(2)随EGCG溶液p H升高,Si活化量为漂洗水稻土降低,黄壤增加;Al、Fe活化量为2种土壤均增加。同一p H下,EGCG活化Si的量p H≤5.5时为漂洗水稻土黄壤,p H=6.5时为黄壤漂洗水稻土;活化Al、Fe的量均为黄壤漂洗水稻土。综上,TPs浓度和p H对不同土壤Si、Al和Fe的活化有不同影响。     

低分子有机酸对土壤中重金属的解吸及影响因素

研究了柠檬酸、草酸、酒石酸和苹果酸对矿区土壤中重金属Pb、Cd、Cu和Zn的解吸行为,并探讨了介质pH值对其解吸土中重金属的影响。振荡解吸试验结果表明四种低分子有机酸对供试污染土壤中Pb、Cd、Cu和Zn都具有一定的解吸能力。由于土壤中重金属有效态含量较低,各重金属的解吸率都不高。在对Pb和Cd的解吸中,各低分子有机酸能力大小顺序为柠檬酸>酒石酸≈苹果酸>草酸;Cu的解吸顺序为柠檬酸>草酸>酒石酸≈苹果酸;Zn的解吸顺序为酒石酸>柠檬酸≈苹果酸>草酸。低分子有机酸随浓度的增加,其解吸能力提高。低分子有机酸对重金属的解吸量随pH值的降低而增加。     

低分子有机酸离子对降低土壤铝毒的作用

对低分子有机酸离子在降解土壤铝毒中的作用进行研究的结果表明，许多低分子有机酸离子可以对铝进行络合，使铝的活性降低，从而削弱铝毒。几种低分子有机酸离子削弱土壤铝毒的能力大小为：草酸〉乙酸〉柠檬酸。在玉米的贫栽试验中，土壤中施信柠檬酸盐，可以显著地降低土壤高活性铝的含量促进玉米生长，从百起到很好的改良结果。     

低分子有机酸对土壤中Pb形态的影响

为探讨螯合诱导修复技术的作用机制,研究2种低分子有机酸即柠檬酸和苹果酸对土壤中重金属Pb各形态的影响。结果表明,对于人工模拟不同污染程度的PbⅠ～PbⅣ土壤,随着柠檬酸和苹果酸添加浓度的升高,土壤中最具活性的可交换态Pb百分含量均有不同程度的提高,从而达到了活化重金属Pb的目的;Pb活化效果随柠檬酸浓度升高而升高,随苹果酸浓度升高呈先上升后基本不变趋势,当有机酸浓度为10,20 mmol/kg时,苹果酸和柠檬酸活化Pb效果分别达到最优;二者相比,柠檬酸活化Pb效果优于苹果酸的活化效果。     

低分子有机酸/盐对复合污染土壤中Pb、Zn、As有效性的影响

模拟森林凋落物淋洗液中草酸/草酸盐和柠檬酸/柠檬酸盐浓度范围.研究了不同浓度草酸/草酸盐和柠檬酸/柠檬酸盐溶液对复合污染土壤中Pb、Zn、As有效性的影响和机制.研究表明,除较低浓度低分子有机酸和有机盐抑制As的释放外,所有浓度的草酸/草酸盐和柠檬酸/柠檬酸盐均促进A1层和B层污染土壤中Pb、Zn、As的活化释放,其中5.0 mmol/L时Pb释放作用最强.25.0 mmol/L时Zn和As活化效果最显著,且Pb和Zn的释放效果强于As.低分子有机盐对Pb、Zn、As的释放效果强于相应的低分子有机酸,即草酸盐强于草酸、柠檬酸盐强于柠檬酸,所以低分子有机酸/盐类物质促进重金属释放的主要机理在于低分子有机酸阴离子反应,H+在此过程中并不起主要作用.不同种类的低分子有机酸和有机盐对Pb、Zn、As有效性的影响也不同,表现为柠檬酸强于草酸,柠檬酸盐强于草酸盐,这与两种有机酸/有机盐的化学结构、离解常数及其和重金属形成络合物的稳定性大小有关.几种浸提剂对A1层土壤Pb、Zn、As的释放效应明显强于B层.     

低分子量有机酸对红壤无机磷活化的作用

采用室内模拟试验研究了低分子量有机酸,如草酸、柠檬酸、酒石酸和苹果酸在红壤无机磷活化中的作用。结果表明,相同浓度下,有机酸活化土壤磷的能力为柠檬酸酒石酸苹果酸。低浓度(0.5mmolL-1)时,草酸活化能力最小;高浓度(≥5mmolL-1)时,其活化能力最大。对同一种有机酸而言,土壤各无机磷形态活化量均随pH的升高而降低;且在同一酸度下,其活化量以铝磷(Al-P)为最多,铁磷(Fe-P)和钙磷(Ca-P)次之,闭蓄态磷(O-P)则最少。有机酸活化土壤无机磷酸盐应该是质子酸效应和有机酸阴离子络合效应共同作用的结果,且与磷酸盐的溶度积常数密切相关。研究结果对根系土壤无机磷素循环研究有着重要的意义。     

水稻砷吸收的分子机制与矿质元素调控研究

结合稻田砷污染现状和已发现水稻砷吸收的分子机制,本文阐述了不同矿质元素对水稻砷吸收的影响及其调控机制的研究进展,为水稻砷的污染防控以及降低稻米中砷积累提供参考依据。     

低分子量有机酸类物质对红壤和黑土磷有效性的影响

在20℃恒温培养条件下,研究低分子量有机酸类的钠钙盐(LA)和低分子量有机酸类与混合氨基酸的钠钙盐(LAA)不同用量水平对红壤和黑土磷有效性的影响。研究表明,两种低分子量有机酸类混合物在各不同水平下均能显著提高红壤和黑土磷有效性;随着培养的进行,添加有LA、LAA的各处理对红壤和黑土中磷有效性均有明显提高。无论是LA或LAA,红壤中以半量处理对提高磷有效性作用效果更为明显,而黑土中则以LAA作用效果更好,且以常量LAA处理的效果最好,常量LA和LAA处理间差异显著。在添加磷肥的基础上,与不加有机酸物质处理(CKp)相比,添加常量LA、LAA和半量LA(0.5 LA)、LAA(0.5 LAA)处理,在红壤中磷固定率平均值分别降低10.5%、22.3%和11.3%、19.4%;在黑土中分别降低8.6%、10.6%和14.1%、11.8%。LA和LAA对降低红壤和黑土磷固定率效果显著,红壤以半量处理的效果较好,黑土则以常量LAA处理效果最好。     

Effect of organic and mineral fertilizers on some soil properties

Abstract

NPK was applied to a Haynie, very fine, sandy loam as 89.6 MT/ha (40 T/ac) of OF (organic fertilizer as feedlot manure at 45% water content) and as MF (mineral fertilizer) with nutrients equivalent to the manure during 18 months.

Organic fertilizer increased soil organic matter content 0.25% more than the MF and 0.2% more than the control. Organic fertilizer increased the CEC 0.3 m.e./100 g more than the MF and 0.4 m.e./100 g more than the control. Organic fertilizer increased exch. Mg by 32 kg/ha while MF decreased exch. Mg slightly.     

低分子量有机酸对红壤和黄褐土K+吸附动力学的影响

采用连续流动法研究了低分子量有机酸影响下供试土壤的钾素吸附动力学特征,探讨了描述土壤K 吸附动力学的最优模型。结果发现,有机酸（苹果酸、柠檬酸）作用下,红壤吸附的K 量均低于对照（不加有机酸）处理,0.1 mmol/L草酸处理除外。黄褐土对K 的吸附因K 浓度的不同而差异明显。当K 浓度为0.1 mmol/L时,有机酸作用下黄褐土吸附的K 量低于对照,而当K 浓度为1.0 mmol/L时,有机酸作用下的黄褐土K 吸附量高于对照。K 吸附反应速度与时间的自然对数lnt间存在良好的线性关系（R0.05=0.754,R0.01=0.874）。1.0 mmol/L KCl处理的初始吸附速率较高,反应速度降低的较快。对红壤、黄褐土吸附K 的数据进行拟合,双常数方程、指数方程和Elovich方程拟合效果较好,都达到了极显著水平,一级动力学方程拟合效果不好。双常数方程的相关系数（R）高于Elovich方程和指数方程,双常数方程是描述红壤和黄褐土在有机酸作用下K 吸附动力学的最优模型。结果表明,有机酸对两种土壤吸附能力的影响均表现为草酸＞柠檬酸＞苹果酸。有机酸作用下红壤和黄褐土的K 吸附过程主要受土壤电荷的影响。     

Effect of pruned material,extracts, and polyphenols of tea on enzyme activities and microbial community structure in soil

Pruning is a regular management practice performed in tea fields, but its effects on soil properties and microbial community structures have not been well explored. Effects of tea pruned material, tea extracts, and tea polyphenols application on soil properties and microbial characteristics, including pH, soil enzyme activities, culturable microbial population, and bacterial community, were investigated in a pot-incubation experiment lasting for 10 weeks. Results indicated that returning of tea pruned material or its extracts significantly increased the soil pH as compared to control. The soil invertase and urease activities, as well as the culturable microbial population treated with pruned material were much higher than those in control, while polyphenol oxidase activity was similar among different treatments. Denaturing gradient gel electrophoresis analysis of bacterial community indicated that the Shannon’s diversity index (H) of all nine treatments receiving additives slightly decreased as compared to control. Pruning returning specifically induced several beneficial bacterial species, including Brevibacterium sp. and Burkholderia sp. In conclusion, pruning returning alleviated soil acidification, induced soil enzyme activities, stimulated culturable microbial population, and reshaped the microbial community. This research suggests that this management could be applied as an alternative agricultural practice in tea cultivation.     

植茶年限对土壤pH值、有机质与酚酸含量的影响

土壤pH值和有机质是土壤肥力的重要指标,土壤中的酚酸类物质也是一类重要的有机物质,与pH值和有机质关系复杂。本文以四川省名山区茶园土壤为对象,研究植茶年限对土壤pH值、有机质和酚酸含量的影响,并探讨它们之间的相互关系。结果显示:随着植茶年限的延长,各土层土壤的pH值均呈现不同程度的下降趋势,即植茶10年植茶7年植茶5年植茶3年水稻土,表层土壤酸化明显;随着植茶年限的延长,土壤有机质、总酚和水溶性酚含量均呈增加趋势。相关分析表明,0~10 cm土层土壤中,总酚与土壤pH值呈负相关;10~20和30~40 cm土层土壤中,水溶性酚与土壤pH值呈负相关;10~20 cm土层土壤中,总酚与土壤有机质呈正相关;在10~20、20~30和30~40 cm土层土壤中,水溶性酚与土壤有机质呈正相关。说明植茶土壤酚酸含量的增加是影响土壤pH值下降和有机质含量升高的重要因素。     

Sulfate adsorption by variable charge soils: Effect of low-molecular-weight organic acids

Sulfate (SO₄ ^2–) movement and transport in soils has received considerable attention in recent years. In most soils, SO₄ ^2– coexists with a variety of natural organic compounds, especially organic acids. Studies were conducted to assess the effect of low-molecular-weight organic acids (eight aliphatic and five aromatic acids) on SO₄ ^2– adsorption by variable charge soils from Chile and Costa Rica. The effects of type of organic acid, pH, type of soil, and organic acid concentration were investigated. In one experiment, a 1.0 g soil sample was equilibrated with 25 ml 0, 0.5, 1.0, 2.0, 4.0, or 6.0 mM K₂SO₄ in 1 mM NaCl in the presence or absence of 5 mM citric acid. In the second set of experiments, the adsorption of 2 mM SO₄ ^2– in soils at pH 4 or pH 5 in the presence or absence of one of 13 organic acids at a concentration of 2 mM or 5 mM was studied. Results showed that citric acid significantly decreased SO₄ ^2– adsorption by the two soils. Sulfate adsorption decreased with increasing pH of the equilibrium solution. Aliphatic acids, with the exception of cis-aconitic acid, decreased the amount of SO₄ ^2– adsorbed by the two soils, with oxalic, tartaric, and citric acid showing the greatest effect. The differences in pH values of the equilibrium solutions in the presence and absence of organic acids were significantly, but negatively, correlated with the amount of SO₄ ^2– adsorbed, suggesting chemisorption of SO₄ ^2– and the release of hydroxide ions. The ionization fraction values of the organic acids at the equilibrium pH were correlated with the amounts of SO₄ ^2– adsorbed, suggesting that the protonation of surface hydroxyl groups of the mineral phase increased as the strength of the ionization of the acid increased, thus creating more positively charged surfaces. Received: 12 February 1997     

低分子量有机酸作用下土壤中菲和芘的残留及形态

采用微宇宙试验方法,以菲和芘为多环芳烃(PAHs)代表物,研究了几种低分子量有机酸作用下黄棕壤中菲和芘的残留和形态。结果表明,老化60 d后土壤中菲和芘的残留含量明显减少;不施加有机酸的对照土壤中,菲和芘的残留含量为10.13和29.18 mg kg-1,去除率为87.33%和63.50%。与对照相比,供试浓度(0～64 mg kg-1)范围内,柠檬酸、草酸、酒石酸等3种低分子量有机酸作用下土壤中PAHs残留含量提高,去除率减小,表明供试条件下有机酸抑制土壤中菲和芘的降解;进一步分析发现,少量(≤4 mg kg-1)的有机酸即可对PAHs降解产生高的抑制效果。微生物降解在PAHs的去除中起重要作用,且芘比菲更抗微生物降解。供试条件下,可脱附态和有机溶剂提取态是土壤中菲和芘存在的主要形态,而结合态残留占总残留的比例很小(<8.5%)。3种有机酸均提高了土壤中可脱附态和有机溶剂提取态菲和芘的残留含量,施加有机酸使土壤中菲和芘的可脱附态含量较对照分别提高了46.67%～749.1%和1.83%～80.20%,有机溶剂提取态则提高了8.73%～375.2%和22.63%～114.3%;低分子量有机酸作用下结合态的菲和芘含量仍很小。     

Impact of low-molecular-weight organic acids on the availability of phenanthrene and pyrene in soil

The impact of low-molecular-weight organic acids (LMWOAs) on the availability of phenanthrene and pyrene was investigated using laboratory batch assays. Experiments were conducted with two types of soil with different organic contents. The LMWOAs used were citric and oxalic acid. A mild solvent extraction procedure and a sorption-desorption experiment were used to predict the availability of phenanthrene and pyrene. Results showed that the extractable amounts of phenanthrene and pyrene in both soil types increased with increased citric or oxalic acid concentration. Citric acid addition promoted phenanthrene and pyrene extraction to a greater degree than oxalic acid. Compared with freshly spiked soils, the extractable amounts of phenanthrene and pyrene with the addition of LMWOAs decreased significantly after 60 days of cultivation. Soils with higher values of soil organic carbon content (f_oc) showed decreased phenanthrene and pyrene availability after the addition of LMWOAs. The sorption and desorption results also demonstrated the enhanced availability of PAHs with LMWOA addition. Phenanthrene sorption could be described using a linear model, regardless of the addition of LMWOAs. The simulated distribution constants (K_d) for phenanthrene sorption decreased significantly with the addition of LMWOAs. In contrast, phenanthrene desorption clearly increased with the addition of LMWOAs. These results suggest that the availabilities of phenanthrene and pyrene can be increased with the addition of suitable LMWOAs.     

外源胡敏酸对土壤有机质组分变化的影响及其与茶树铅有效性的关系

盆栽试验分析了胡敏酸输入土壤6个月后茶树根际和非根际土壤有机质SOM及其组分,包括水溶性物质WSS、富啡酸FA、胡敏酸HA以及土壤微生物生物量SMB的变化,并对不同土壤有机质组分碳含量和茶树不同组织铅含量作了相关性分析。外源胡敏酸设置3个浓度水平（0、300、600 mg kg-1）,铅设置2个浓度水平（0、300 mg kg-1）,试验共有6个处理。茶苗置于温室培养,6个月后分新叶、老叶、新茎、老茎、根收获。结果表明：根际并非总是富含有机质,未加铅处理根际SOM含量低于非根际;而加铅处理根际SOM含量高于非根际。HA加入土壤能够显著增加根际和非根际SOM和SMB的含量,但是加铅处理和不加铅处理增加幅度不同。高浓度HA显著增加了根际FA的含量,可能是HA部分裂解所致。非根际有机质各组分与茶树铅含量无显著相关关系;根际SOM、HA和茶树不同组织铅含量没有显著相关关系。根际WSS、FA与茶树嫩叶、老叶、嫩茎、老茎以及根部铅含量均存在显著或极显著正相关关系;而根际SMB与茶树各个组织铅含量存在显著负相关关系。总之,胡敏酸施入土壤改变了土壤有机质及其各个组分的含量,而根际某些土壤有机质组分的改变又显著影响了茶树不同组织铅的吸收和分布。