用电导频散法研究Cl-、SO42-和H2PO4-阴离子与土壤的相互作用

本文介绍了采用电导频散装置测量分别含有10^-4mol/LHCl、5×10^-5mol/L H₂SO₄和10^-4mol/L H₃PO₄的黄棕壤、棕壤、黑土和砖红壤悬液(20-30g/kg)的电导频散曲线,频散曲线上均呈现频率范围相当宽的坪区,频散曲线的特性分析结果表明,黄棕壤和棕壤在3种酸溶液中的始散频率(0.6-1kHz)低于黑土悬液(16-28kHz),而砖红壤的始散频率最高(25-47kHz;Cl^-、SO₄^2-和H₂PO₄^-离子与4种土壤的相对亲合力(REC_1.5/REC_tp-1)顺序为Cl^- < SO₄^2- < H₂PO₄^-,在不同土壤之间的顺序则随酸溶液而异.     

土-水体系中电导频散的影响因素

用红壤、赤红壤和砖红壤3种土壤胶体,测定胶体悬液在不同频率时的电导和直流电导,用以观察频散现象。结果表明,各种胶体的电导频散能力因土壤类型而异,红壤最强,赤红壤次之,砖红壤最弱。呈现明显频散所需要的频率,红壤和赤红壤为10千赫左右,砖红壤约为100千赫。可变电荷土壤的类型对电导频散的影响与土壤胶体所带的电荷总量密切相关。对于同一种胶体,悬液相对电导率(某一频率时的电导率与300赫时的电导率之比)随胶体浓度的增加而变大。红壤悬液在各种电解质存在时的电导频散曲线的形状不同,其中KCl者为一斜上直线,Ca(NO₃)₂,和CaCl₂,者则为上翘的曲线。在1到100千赫之间,频散的顺序为:KCl>Ca(NO₃)₂>CaCl₂。呈现明显频散所需要的频率,对KCl者为1千赫左右,Ca(NO₃)₂者约为10千赫,CaCl₂者高达100千赫左右。在同一频率下,红壤胶体悬液的相对电导率随KCl溶液浓度的增加(10^-5—10^-3mol/L)而减小。     

阴离子对可变电荷土壤吸附铜离子的影响机理

根据NO-3、Cl-和SO24-对可变电荷土壤和恒电荷土壤吸附Cu2+的影响的比较,探讨了阴离子对可变电荷土壤吸附Cu2+的影响机理。结果表明,当3种阴离子的浓度相同时,在SO24-体系中铁质砖红壤对Cu2+的吸附率较在NO3-和Cl-体系中大得多,而在浓度相同的3种阴离子体系中,黄棕壤对Cu2+的吸附率相差不大。在离子强度相近的NaCl体系中,砖红壤对Cu2+的吸附率相近。在3种阴离子体系中,随着pH升高,砖红壤对Cu2+的吸附率均增大;但在NO-3体系和Cl-体系中Cu2+的吸附率相近;而在SO24-体系中Cu2+的吸附率最大。随着Na2SO4浓度的增大,铁质砖红壤和砖红壤对Cu2+的吸附率减小。但在0.005 mol L-1和0.05 mol L-1Na2SO4体系中,Cu2+的吸附率大于在不含Na2SO4的体系中者。而在0.5 mol L-1Na2SO4体系中,Cu2+吸附率小于在不含Na2SO4体系中者。在3种浓度的Na2SO4体系中,黄棕壤对Cu2+的吸附率均小于在不含Na2SO4体系中者。总之,阴离子可通过离子强度、专性吸附和形成离子对影响土壤对Cu2+的吸附。在可变电荷土壤中,阴离子对Cu2+吸附的影响机理较在恒电荷土壤中复杂得多。     

硫酸根离子添加顺序对可变电荷土壤吸附铜离子的影响

研究了SO2-4添加顺序对三种可变电荷土壤(昆明铁质砖红壤、徐闻砖红壤和江西红壤)吸附Cu2+的影响,作为对照,也研究了其对恒电荷土壤(黄棕壤、棕壤)以及两种不同矿物(高岭石与针铁矿)吸附铜离子的影响。实验结果表明,在同等条件下,SO2-4添加顺序对两类表面性质不同的土壤吸附Cu2+有着不同的影响。对于恒电荷土壤,SO2-4添加顺序对土壤吸附Cu2+几乎没有影响。同等pH条件下,对可变电荷表面而言,加入CuSO4者具有最高的Cu2+吸附率;对昆明砖红壤、徐闻砖红壤以及针铁矿和高岭石而言,先加入Cu2+者相对先加入SO2-4者Cu2+吸附率更高;对江西红壤而言,上述这个次序则刚好相反。SO2-4浓度和有机质去除对同等pH条件下铜离子吸附率高低的排序并无实质性影响。     

土壤—水体系中离子反应平衡时间的电导法检测

采用电导法检测了土壤—水体系中离子反应达到平衡所需的时间。5种土壤和硝酸盐溶液(10-4/3z mol L-1)配制的20种悬液(30 g kg-1)的电导率时间变化曲线表明,所有悬液的电导率均呈下降趋势,在平衡100~300 h后不再变化。含Cu(NO3)2和Pb(NO3)2溶液(10-4mol L-1)的黄棕壤悬液(10 g kg-1)的Wien效应曲线的位置和形状随平衡时间而变,但当平衡时间≥480 h,曲线出现重叠。含NaNO3和KNO3溶液(2×10-4mol L-1)的黄棕壤悬液(10 g kg-1)的电导率与离心清液中Na 和K 离子浓度随平衡时间呈同步变化趋势,平衡初期均不断下降,分别在平衡70 h和30 h后趋达稳定。这些实验结果表明,电导法确是一种检测土壤—水体系中离子反应平衡时间的简易手段。     

聚丙烯酰胺对H_2PO_4~-和HPO_4~(2-)在土壤中吸附-解吸特性的影响

采用批量平衡法研究聚丙烯酰胺(PAM)对两种形态磷(HPO2-4、H2PO-4)在土壤中吸附和解吸特性的影响,以明确PAM对输入土壤中肥料磷素的固持效果。结果表明:施入PAM土壤对磷的吸附动力学过程符合二级动力学方程(平均R2=0.998 4),包括快速反应和慢速平衡两个阶段。在低(20mg/kg)和高(100mg/kg)磷浓度条件下,原土或施入PAM处理土壤对HPO2-4、H2PO-4的吸附均可在反应进行12h时达到平衡,仅高浓度磷条件的H2PO-4处理需要24h达到吸附平衡。Langmuir模型可对等温吸附数据进行很好的拟合(平均R2=0.940 4)。相比原土对照处理,PAM处理可提高土壤对H2PO-4吸附,降低对HPO2-4的吸附,使得HPO2-4的最大吸附量和吸附强度降低,而H2PO-4的最大吸附量和吸附强度升高。PAM处理土壤对磷的解吸受施磷量影响不同,中低施磷条件(磷含量低于80mg/kg)下,NaCl和柠檬酸对PAM处理土壤中磷解吸率均低于原土对照,而在高施磷量条件下,NaCl和柠檬酸对PAM处理土壤中磷素的解吸率均高于原土对照,说明中低施磷条件下,施用PAM不利于土壤对H2PO-4和HPO2-4的释放。PAM施入土壤后,H2PO-4的解吸率(NaCl、柠檬酸)始终高于HPO2-4,说明H2PO-4较不易被土壤固定。     

pH对砖红壤和黄棕壤Cu~(2+)吸附与解吸的影响

对砖红壤和黄棕壤在不同浓度、不同pH下吸附和解吸Cu2+进行了测定。结果表明, 2种土壤Cu2+吸附量均随平衡液中Cu2+浓度增加而增大,两者关系较好地符合Langmuir吸附方程。Cu2+吸附量随pH升高而增加,Cu2+分配系数的对数与pH呈极显著的线性正相关,吸附一个Cu2+所释放H+的平均数砖红壤(1. 19)大于黄棕壤(1. 01)。可解吸Cu2+的数量随pH升高和吸附Cu2+的数量增加而增加,在pH4~6下,黄棕壤吸附Cu2+及可解吸Cu2+的比例(平均为10. 5% )大于砖红壤(平均为3. 1% )。由此认为, 2种土壤吸附Cu2+虽以专性吸附为主,但砖红壤的表面吸附点位较少,专性吸附点位的比例较高,对Cu2+的亲和性或专性吸附性大于黄棕壤。     

用悬液Wien效应研究阳离子与土壤粘粒间的能量关系

从能量关系研究土壤带电粘粒与电解质离子间的相互作用一直是土壤化学家希望解决的课题。本文介绍阳离子与带电粘粒间的平均结合自由能和平均吸附自由能的计算公式,并用悬液Wien效应法研究K 、NH4 、Ca2 和Cd2 与黄棕壤、棕壤和黑土粘粒间的能量关系。研究结果表明:K 和NH4 的平均结合自由能范围为6.3~7.1kJmol-1,K 的结合能稍大于NH4 的;Ca2 和Cd2 的结合能范围为7.2~9.4kJmol-1。同一阳离子与不同土壤的结合能顺序如下:黄棕壤<棕壤<黑土。它们在同一高场强(如150kVcm-1)下的平均吸附能ΔGad值:K 和NH4 在黄棕壤和棕壤粘粒上的很接近,分别为0.9和0.8kJmol-1,而在黑土粘粒上,NH4 的较K 的大0.1kJmol-1;Ca2 在黄棕壤和黑土上的吸附能较Cd2 的分别大0.3和0.6kJmol-1;二价阳离子的平均吸附自由能约为一价阳离子的2~2.5倍。     

红壤交换性碱和交换性酸的研究Ⅰ.与中性盐(Na2SO4, NaClO4和KClO4)的关系

用自动控制pH的装置定量研究了两种红壤类土壤胶体在三种中性盐溶液中的交换性碱和交换性酸的变化.发现在Na2SO4溶液中在pH低时出现交换性碱,pH高时出现交换性酸.砖红壤胶体的交换性碱比红壤胶体的大,并且在pH5.6附近还出现不受Na2SO4浓度影响的交换中性点.NaClO4和KClO4溶液中,在测定pH范围内只出现交换性酸,红壤胶体的数量比砖红壤胶体的大.同一土壤胶体在KClO4中的数量比NaClO4中的多.二者都有一峰值,对于砖红壤胶体前者在pH4.3,后者在pH5.8.提出了测定SO2-4-交换性碱的方法.     

SO42-和Cl-对稻田土壤养分及其吸附解吸特性的影响

利用长期定位试验 ,比较了长期施用含SO42-和Cl- 化肥 22年后稻田土壤的 pH值、养分状况及其吸附解吸特性。结果表明 ,长期施用含SO42-化肥 ,土壤有机质、速效氮和速效钾的含量较高 ,但全量氮磷钾的含量较低 ;长期施用含Cl- 化肥 ,土壤全量氮磷钾和速效磷的含量较高 ,但pH值相对较低。长期施用含上述二种阴离子的化肥后 ,土壤对H2PO4-的最大吸附量均较大 ,且在Cl- 处理下土壤对H2PO4-吸附的结合能较大 ,而SO42-处理下土壤在同等吸附量时对H2PO4-的解吸量相应较多。长期施用含SO42-的化肥亦使土壤对钾素的供应强度较大 (K0的绝对值较大 )、缓冲能力增强 (AR0值较高 ) ,而长期施用含Cl- 的化肥时则与SO42-相反     

Gipslöslichkeiten in wässerigen Systemen mit NaCl,MgCl2, Na2SO4 und MgSO4

Gypsum solubilities in aqueous systems containing NaCl, MgCl₂, Na₂SO₄, and MgSO₄ Solubilities of Gypsum (CaSO₄·2H₂O) have been determined within the systems MgSO₄–MgCl₂–NaCl–H₂O and MgSO₄–Na₂SO₄–NaCl–H₂O at 21 different compositions of solutions per concentration range (0.01, 0.05, 0.1, 0.15, 0.5, and 1.0mol/l) of total easily soluble salt. Lines of equal solubilities of gypsum can be constructed form these data. They make possible to estimate gypsum solubility in solutions of similar composition. Small quantities of KCl or KNO₃ may be taken as NaCl. Solubilities measured under percolation conditions deviate sometimes to lower, those measured at supersaturation to higher values. The tendency to supersaturation lowers with increasing content of crystal-solution interfaces within the system. At concentrations of easily soluble salts from 0,01 to 0,15mol/l the solubility of gypsum is governed by the CL^?:SO⁼ ₄-ratio. Concentration of solution or Na⁺:Mg⁺⁺ -ratio are of lower efficiency.     

Antifungal activity of 4-methyl-6-alkyl-2H-pyran-2-ones

A number of 4-methyl-6-alkyl-alpha-pyrones were synthesized and characterized on the basis of 1H NMR and mass spectroscopy. These compounds were tested in vitro against pathogenic fungi, namely, Sclerotium rolfsii Saccardo, Rhizoctonia bataticola (Taub.) Butler, Pythium aphanidermatum (Edson) Fitz., Macrophomina phaseolina (Tassi), Pythium debaryanum (Hesse), and Rhizoctonia solani Nees. Lower homologues were less effective, whereas compounds such as 4-methyl-6-butyl-alpha-pyrone, 4-methyl-6-pentyl-alpha-pyrone, 4-methyl-6-hexyl-alpha-pyrone, and 4-methyl-6-heptyl-alpha-pyrone were found effective against all of the test fungi. They inhibited mycelial growth by approximately 50% (ED50) at 15-50 microg/mL. 4-Methyl-6-hexyl-alpha-pyrone, which was found most effective, was tested against S. rolfsii in a greenhouse at 1, 5, and 10% concentrations. The 10% aqueous emulsion of 4-methyl-6-hexyl-alpha-pyrone suppressed disease development in tomato by 90-93% as compared with the untreated infested soil in the greenhouse after 35 days of treatment.     

Degradation of 2, 4-D, 2, 4, 5-T,and picloram in two Philippine soils

The degradation of 2, 4-D, 2, 4, 5-T, and picloram in two Philippine soils was investigated under upland and flooded (submerged) conditions. These herbicides degraded in both upland and flooded Maahas clay and Luisiana clay soils. The rate of degradation of the herbicides was more rapid in the Maahas clay soil than in the Luisiana clay soil. Among the three herbicides, 2, 4-D was the least persistent and picloram was the most persistent in both soils under both submerged and upland conditions. 2, 4, 5-T degraded more actively in the two Philippine soils in this study than studies previously reported in the available literature. The fact that both the 2, 4-D and 2, 4, 5-T did not degrade in sterilized soils during the incubation period suggests that the degradation is due to the microbial activity in the soils.     

2-羟基-4-甲氧基苯甲醛和2-羟基-4-甲氧基苯甲酸对菜粉蝶多酚氧化酶的抑制作用

测定了2羟-基-4-甲氧基苯甲醛和2羟-基-4-甲氧基苯甲酸两种效应物对菜粉蝶多酚氧化酶(po lypheno lox idase,简称PPO,EC.1.14.18.1)催化L-多巴(L-DOPA)氧化活力的抑制作用。结果表明,这两种效应物对该酶的活性均有明显的抑制作用,抑制中浓度(IC50)分别为2.71和5.66 mm o l/L,抑制常数分别为2.82和3.35 mm o l/L;2羟-基-4-甲氧基苯甲醛对该酶的抑制作用显著高于2羟-基-4-甲氧基苯甲酸的;这两种抑制剂对酶的抑制作用机理完全不同,2羟-基-4-甲氧基苯甲醛对酶的作用表现为混合型抑制,而2羟-基-4-甲氧基苯甲酸对酶的作用表现为竞争性抑制。研究结果为设计以该酶为靶标的杀虫剂提供理论依据。     

Anthracene influence on (15NH4)2SO4 fertilization of wheat seedlings

The influence of the addition of anthracene (1 μg anthracene g^?1 soil) in N transformations following (¹⁵NH₄)₂SO₄ fertilization (200 mg N g^?1 soil) was investigated in wheat pots by quadrapole mass-spectrometry. The dry matter yield at harvesting (after 16 days) was not statistically affected (P=0.05) by anthracene addition. The total amount of N from the fertilizer taken up by wheat seedings in 16 days was 29 and 26.8% of the added N in the absence and in the presence of anthracene, respectively, but the difference was not significantly different at level P=0.05. In order to investigate more deeply the effect of anthracene on the N cycle in the soil-plant system, the first-order rate constants of N mineralization, N immobilization, nitrification and N plant uptake have been determined according to a ¹⁵N + ¹⁴N soil-plant model. The comparison of the constants showed that organic N mineralization, nitrification and plant uptake proceeded at the same rate, while a small different rate (P=0.05) was shown by N immobilization. In fact, the N immobilization constant increased from 0.14±0.012 to 0.21±0.014 day^?1 as a consequence of anthracene addition.     

4HQL-2型全喂入花生联合收获机的研制

针对中国花生的种植特点,借鉴已有的设计经验,研制成功了一种适于中国花生主产区收获作业的4HQL-2型全喂入花生联合收获机。该机利用挖拔组合式工作原理,为保证挖拔效果和稳定性,设计了一种全新的挖拔组合装置;夹持输送部件首次采用了三带夹持原理（普通V型带）,利用柔性夹持方式大大降低了花生的机械掉果率;去土部件采用了上下摆拍式去土方式,去土效果好,损失低;摘果装置采用全喂入式,利用甩捋式工作原理提高了鲜湿花生的摘净率;清选装置采用风筛组合式,逐稿器和振动筛作反向摆动可有效地减轻整机振动。经田间检测摘果率为99.6%,总损失率3.3%,破损率2.0%,含杂率2.2%,达到了设计和相关标准要求,并已通过农业部鉴定。     

FeSO_4-ZnSO_4-H_2O水盐体系相图及其应用

采用等温溶解平衡法研究了ZnSO4-FeSO4-H2O体系平衡关系,以Zn2+、Fe2+浓度为坐标轴,在直角坐标系中制出了0℃、10℃和25℃时ZnSO4-FeSO4-H2O体系相图,在相图中单相区和c(Fe2+)+c(Zn2+)=100 g/L直线上方的重合区域就是Zn-Fe微量元素水溶肥料的配方区。多温相图分析及实验表明:根据10℃时ZnSO4-FeSO4-H2O相图配方区制备出来的Zn-Fe微量元素水溶肥料具有良好的储存性能。     

Comparison of 4-Mercapto-4-methylpentan-2-one contents in hop cultivars from different growing regions

Contributions of hop-derived thiols were examined. Extremely strong fruity, black currant-like aromas were detected in beers hopped with some U.S. cultivars. 4-Mercapto-4-methylpentan-2-one (4MMP) was supposed to be the main contributor to the fruity aroma, and the contents between cultivars were investigated. In hop pellets, a negative correlation between 4MMP concentration and copper ion content in hops was observed. 4MMP was detected only in U.S., Australian, and New Zealand cultivars, but no European ones, which are treated with copper-containing fungicides (Bordeaux mixture) and therefore have a high content of copper ions. The 4MMP content was highest in Simcoe cultivars, followed by Summit, Apollo, Topaz, Cascade pellets, and also differed between crop years. It was indicated that most 4MMP exists freely in wort or in hop pellets with only small amounts formed from precursors and that the amounts increased during the fermentation process.     

Dynamics of aqueous aluminum species in a podzol affected by experimental MgSO4 and (NH4)2SO4 treatments

Chemistry of aqueous Al in a podzol on a Norway spruce (Picea abies [L.] Karst.) site in the Black Forest (SW Germany) and changes induced by experimental applications of MgSO₄ were studied. Soil solution taken from the O, E and BC horizons were analyzed for the fractions ‘labile monomeric Al’, ‘non-labile monomeric Al’, and ‘acid-reactive Al’. The activities of ‘inorganic monomeric Al’ species and the saturation indices (SI) of the soil solution with respect to Al-bearing minerals were calculated using the equilibrium speciation model WATEQF. On the untreated plot, soil leachates are characterized by Al_tot concentrations of 0.1 mg L^?1 (mineral soil). In the O horizon, the fractions ‘acidsoluble Al’ and ‘non-labile monomeric Al’ (mainly organically complexed Al) together comprise 80% of Al_tot. In the leachates from the mineral soil Al³⁺ prevails, being 50% of Al_tot. Al-F-complexes make up 5 to 10% in all horizons. MgSO₄ and (NH₄)₂SO₄ treatments resulted in an intense Al mobilization up to 50 mg L^?1. In this situation, 60% of Al_tot is covered by Al³⁺ and 40% by non-phytotoxic Al-SO₄-complexes. After rainfall events, mobilized Al is quickly translocated into the subsoil, with water flow through macropores then appearing to be an important mechanism. In both treatments, soil solution chemistry was favorable for the precipitation of the Al(OH)SO₄-type minerals alunite and jurbanite. However, a control of Al solubility by this process is not likely due to kinetic restraints. Application of MgSO₄ was followed by an increase of the Mg/Al molar ratio in the soil solution, whereas the Ca/Al ratio decreased. After treatment with (NH₄)₂SO₄ both the Ca/Al and the Mg/Al ratios deteriorated.