膨润土对土壤腐殖质特性的影响

砂质土壤腐殖质含量低,影响了土壤肥力.文章通过田间条件下砂滤管试验,利用膨润土的吸附和粘结功能,研究了膨润土不同用量对土壤腐殖质特性的影响.结果表明:膨润土在促进松结态腐殖质分解、加速紧结态腐殖质合成方面发挥了重要作用,有利于增加土壤系统的内稳性.施用膨润土促进了紧结态和稳结态腐殖质中HA的积累,提高了HA/FA比.胡敏酸红外吸收光谱表明,膨润土能使其脂肪族物质增多、芳化度降低.膨润土具有提高土壤腐殖质含量,改善土壤腐殖质特性,从而提高了土壤肥力.     

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     

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。     

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。     

盐碱地农-渔开发对土壤环境的影响

在东北苏打盐碱地进行了稻-鱼-苇-蒲开发试验,并探讨了该模式对盐碱土壤环境的影响。结果表明,开发后土壤有机质含量增加96.8%(平均值,以下同),盐分含量下降43.6%,全量和速效N、P、K质量分数分别增加142.8%和188.2%;阳离子交换量、盐基总量分别增加8.21%及27.71%;土壤腐殖质以富里酸为主,w(HA)/w(FA)比值提高36.15%;养鱼稻田的土壤微生物总量明显高于未养鱼田(P<0.01);优势种为放线菌。土壤酶活性进一步加强。系统废水的盐分质量浓度降至1.0 g/L左右,碱浓度低于水源(7.0~10.0 mmol/L)。该模式不会造成土壤次生盐碱化。     

冻融交替对高寒草甸土壤微生物量氮和有机氮组分的影响

采用Bremner氮素分级方法,研究冻融交替对高寒草甸土壤微生物量氮和有机氮组分的影响.结果表明:随着冻融时间的变化,微生物量氮含量先减少后增加,在冻融1 d后达到最小值,4℃、-4℃、-4～4℃和-20～4℃处理下分别下降了50.37%、57.47%、37.79%和37.51%;氨基酸氮和氨基糖氮变化趋势相同,先增加后减少,均在冻融1 d后达到最大值,各处理氨基酸氮含量分别为处理前的1.6倍、1.47倍、1.44倍和1.5倍,氨基糖分别为处理前的1.66倍、1.58倍、1.65倍和1.91倍;氨态氮含量先增加后减少,-20～4℃处理在冻融1 d后为处理前的1.25倍,其余3个处理在冻融3 d后达到最大值;各处理酸解未知氮的变化趋势大体相同,在冻融25 d后达到最小值.研究表明冻融时间对微生物量氮和有机氮组分影响显著,微生物量氮含量是有机氮组分变化的主要原因.     

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.     

椰纤维生物炭对砖红壤水稻土Pb形态及水稻产量和品质的影响

为研究椰纤维生物炭(CFB)对铅(Pb)污染水稻土中Pb形态和生物有效性的影响,以及对水稻(Oryza sativa L.)生长和品质的调控效果,以热带(海南)具有代表性的花岗岩和玄武岩母质发育的砖红壤水稻土为供试土壤,在6种Pb污染土壤(Pb质量分数为0、50、250、500、2 500、5 000 mg·kg~(-1))中添加质量分数为3%的CFB,并进行水稻盆栽试验,分析土壤EDTA有效态Pb含量和Pb形态,及糙米Pb含量、水稻产量和农艺性状的变化。结果表明:随Pb污染量的增加,两种水稻土中各化学形态和有效态Pb含量显著增加(P0.05);CFB的施用降低了土壤交换态、碳酸盐结合态和铁锰氧化物结合态Pb含量,增加了有机结合态和残渣态含量;降低了供试土壤有效态Pb含量,且玄武岩母质水稻土较花岗岩母质水稻土效果更显著。Pb质量分数(250、500 mg·kg~(-1))未超过国家农业用地风险管制值(GB15618—2018;≤500 mg·kg~(-1))时,花岗岩水稻土、玄武岩水稻土中糙米Pb含量依次超过食品安全国家标准(0.2mg·kg~(-1));Pb胁迫未对水稻生长和农艺性状造成明显影响;而质量分数为5 000 mg·kg~(-1)时,Pb胁迫抑制水稻生长、降低农艺性状,此时花岗岩和玄武岩中糙米Pb含量分别超过国家食品安全标准14、10倍。CFB能够缓解Pb对水稻产量和品质的影响;Pb质量分数为500mg·kg~(-1)时,CFB的施用使玄武岩水稻土中糙米Pb含量降低38.4%,符合食品安全国家标准。因此,椰纤维生物炭能够促使土壤中Pb向水稻难吸收的有机结合态和残渣态转化,降低有效态Pb含量,减轻Pb对水稻生长的毒害及在糙米中的累积。     

壬基酚在土壤中的吸附和淋溶特性

为探究壬基酚在土壤中的吸附迁移规律,分别采用振荡平衡法和柱淋溶法研究了壬基酚在南京黄棕壤、江西红壤、常熟乌栅土、太湖水稻土、东北黑土5种不同土壤中的吸附特性、移动特性,并通过比较其在不同土壤中的吸附和淋溶来分析壬基酚在土壤中吸附和淋溶性的影响因素。吸附试验表明,壬基酚在南京黄棕壤、江西红壤、常熟乌栅土、太湖水稻土、东北黑土中的吸附性均较符合Freundlich方程,Kd值分别为18.89、26.64、44.15、47.49、69.92;吸附性大小次序为:南京黄棕壤江西红壤常熟乌栅土太湖水稻土东北黑土;以有机碳含量表示的土壤吸附常数KOC在2 534.50~4 860.65之间;影响壬基酚土壤吸附性的主要因素为土壤有机质含量,土壤有机质含量增加,吸附增强;壬基酚在5种土壤中的吸附自由能为-21.02~-19.77 k J·mol~(-1),表明吸附机理主要是物理吸附。土柱试验表明,壬基酚在土壤中具有难淋溶性质,壬基酚在5种供试土壤的1~3 cm深度的淋溶滞留量最大;影响其在土壤中淋溶性的主要因素为土壤有机质含量,与吸附试验相一致。壬基酚在土壤中易吸附难淋溶,移动性弱的特点对地表土壤层具有潜在的污染风险,应该引起足够重视。     

丁噻隆在土壤中的吸附和淋溶特性

分别利用振荡平衡法和土柱淋溶法研究了丁噻隆在不同土壤中的吸附和淋溶特性及其影响因素。结果表明,丁噻隆在5种供试土壤中的吸附特性能较好地用线性模型拟合,吸附能力顺序为:东北黑土>太湖水稻土>江西红壤>南京黄棕壤>陕西潮土,吸附常数Kd为0.19~2.87 mL.g-1,吸附性能较差。丁噻隆在3种典型土壤中的淋溶试验表明其具有较强的淋溶性,淋溶速率为:江西红壤>太湖水稻土>东北黑土。影响丁噻隆吸附和淋溶的主要因素是土壤有机质含量。     

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.     

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.     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

荧光猝灭法测定菲、苊、芘与腐殖酸的结合常数

用荧光猝灭法测定了胡敏酸（Fluka）与苊、菲和芘相互作用的结合常数（KDOC），其lgKDOC值分别为4．4，4．48和4．89．用同样方法测得长江水生FA以及黑龙江水生FA和HA的KDOC之间有显著差别．HA的KDODC一般高于FA．黑龙江水生FA的KDOC高于长江．对同一来源的腐殖酸，三种多环芳烃的KDOC与KOW呈线性相关．     

Electrochemical oxidation of humic acid at the antimony- and nickel-doped tin oxide electrode

This work investigated the degradation of humic acid （HA） in aqueous solution by electrochemical oxidation with Antimony- and Nickel-doped Tin oxide electrode （Ni-Sb-SnO2/Ti electrode） as the anode. Initial concentrations of HA ranged from 3 to 9 mg-L 1. Under such a concentration scope, the degradation of HA was a mass transfer controlled process. Degradation rate increased with the increase of HA initial concentration. Test on the effect of tert-butanol revealed that · OH played an important role in the oxidation of HA. The absence of cation Ca2＋ was beneficial to HA degradation, which suggested that both indirect and direct electrolyze happened during the whole electrochemical oxidation process. Alkaly （pH = 12） and neutral （pH = 7） conditions were benefical to HA degradation.     

PBS降解过程对植物发芽和生理特性的影响研究

采用青菜（Green vegetables）和生菜（Romaine lettuce）的种子发芽和室外盆栽实验,通过考察植物的种子发芽、生物量以及叶绿素质量浓度等指标,研究了可生物降解材料聚丁二酸丁二醇酯（PBS）对青菜和生菜发芽和生长过程中生理特性（植株地上鲜、干质量,地下鲜、干质量,株高,根长,叶片数,叶绿素质量浓度）的影响。研究结果表明：（1）土壤中加入PBS有利于青菜种子的发芽,较大幅度的提高了其发芽率、苗长、根长等,并且随着PBS质量分数的增加这种促进作用越发明显,PBS×100处理组的苗长和根长较空白对照组分别增长了12.9%和26.1%;（2）低质量分数的PBS对青菜和生菜的发芽、生长以及叶绿素的合成具有一定的促进作用,但是高质量分数的PBS则会产生轻微的抑制作用。     

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.     

施肥对不同肥力春玉米田土壤溶解性有机质的影响

选取辽河灌区不同肥力水平春玉米（Zea mays ssp. mays L.）农田土壤为研究对象,通过连续3年田间定位试验,采用三维荧光光谱法分析了不同层次土壤溶解性有机质组分含量,研究施肥对不同肥力农田土壤溶解性有机质组分（DOM、DOC、DON、DOP）的影响,分析土壤DOM及其组分的土壤肥力效应。结果表明,施肥使高（产量12.75±0.75 t·hm^-2）、中（产量10.50±0.75 t·hm^-2）、低（产量8.25±0.75 t·hm^-2）产田土壤DOM的∑Fex/em分别增加了2.84%、3.56%和-1.52%,平均增加了1.08%,土壤w（DOC）分别增加了20.43%、16.43%和-29.11%,平均增加了9.36%,土壤w（DOP）分别增加了-22.87%、10.30%和4.15%,平均增加了-3.39%,土壤 w（DON）分别增加了-20.63%、6.97%和-8.41%,平均增加了-7.54%。施肥显著增加中产田土壤中w（DOM）,中产田底层（20-40 cm）和高产田表层（0-10 cm）、中层（10-20 cm）土壤w（DOC）,中产田中层和低产田表层土壤w（DOP）,中产田中层土壤w（DON）。施肥增加了低产田土壤FI值（荧光指数）,降低了高产田土壤FI值,施肥增加了高产田土壤HIX（腐殖化指数）,降低了中低产田土壤HIX。施肥显著增加中产田土壤DOM组分含量,降低高、低产田土壤DOM组分含量。施肥主要增加10-20 cm土壤DOM组分含量,耗损20-0 cm土壤DOM组分。施肥促进高产田土壤DOM陆源化,低产田土壤DOM生物源化,施肥使中低产田土壤DOM腐殖化程度降低。施肥不仅是土壤DOM的重要来源,同时通过影响微生物及作物根系活力促进土壤DOM的耗损,因农田土壤质地的差异,施肥对土壤DOM的影响不同。DOM荧光强度与产量呈显著正相关,具有土壤肥力指示作用。     

改性腐殖酸对铀的吸附的试验研究

通过静态吸附实验,探讨了改性HA对U(Ⅵ)吸附影响。考查pH值、时间、U(Ⅵ)的初始浓度和温度等对吸附的影响。结果表明:pH值对改性腐殖酸的吸附效果影响较大,改性腐殖酸吸附U(Ⅵ)的最佳pH值为6,最大去除率为99.37%,吸附在60 min内基本达到平衡。UO22+在改性腐殖酸上的吸附是放热过程,符合Freundlich等温吸附方程,相关系数达0.99以上,表明IHA对铀的吸附是以表面为主要吸附位,并不是均匀的单层吸附。图8,参9.     

Studies of Thermal Transformation of Humic and Fulvic Acids in Soils Ii. Thermogravimetry

The thermogravimetry and differential curves of the humic and fulvic acids in the soils from five areas of China were determined and the peaks of these curves were classified according to the results of infra-red (IR) spectra at high temperature and pyrolysis-mass spectra (Py/Ms). the kinetic parameters for heat-degradation of these humic and fulvic acids were calculated by the Coast-Redfern method. the initial temperatures, the final temperatures, and the peaks of DTG curves, the activation energies, the reaction orders and the percentages of weight loss at different reaction stages for these samples were analysed. Thus, the similarity of thermal transformation of humic and fulvic acids in the soils from different areas of China was demonstrated. in addition, the DTA curves of red earth HA and FA were determined.