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1.
胡敏酸的酒精分级沉淀法分级   总被引:13,自引:2,他引:13  
卓苏能  文启孝 《土壤学报》1994,31(3):251-258
本文利用酒精分级沉淀法,将胡敏酸分成12个级分,并对各级分的结构进行了表征。结果表明,随着溶液中乙醇浓度的增大,各级分胡敏酸的腐殖化程度大体上逐渐由强变弱,分子量逐渐变小,全氮,水解性总氮和氨基酸氮的含量逐渐增大,而氨基糖氮和铵态氮逐渐减少 ,同时还讨论了本法与凝胶分级法所获得的结果不同的可能原因。  相似文献   

2.
为探究不同分子量腐植酸组分的结构特征,本研究利用褐煤粉提取腐植酸进行超滤分级,获得四个不同分子量的腐植酸组分。研究发现,分子量大于50 kDa和小于1 kDa的腐植酸分别占总腐植酸的49.66%、47.07%,中间两个组分占比很小;腐植酸的理化性质和功能主要是由1 kDa以下的腐植酸和50 kDa以上的腐植酸所决定的。1 kDa以下的腐植酸总酸性基、羧基和酚羟基官能团含量最高,酚羟基占总酸性基的比例也较高,腐植酸的芳香化程度、缩合度随分子量的增大而增大,含氧官能团含量、E4/E6值随分子量的增大而减少。通过盆栽试验,探索了不同分子量腐植酸对土壤镉有效性的影响,土壤对镉的吸附量随腐植酸分子量的增大而减少,各处理均在500 mg/L时达到吸附平衡;土壤镉的解吸量亦随腐植酸分子量的增大而减少。小分子量腐植酸的酸性官能团丰富,对土壤重金属的吸附络合能力更强,可以降低土壤对镉的吸持能力,提高其移动性和生物有效性;大分子腐植酸则主要起吸持和固定作用,降低重金属的移动性和生物有效性。  相似文献   

3.
The effects of humic acid (HA) and phosphorus (P) applications on plant growth and nutrient content of lettuce, together with available soil phosphorus remaining after harvest were examined. The amounts of phosphorus used were 0, 120, and 240 kg ha?1 and those of humic acid were 0, 100, 200, and 300 kg ha?1. Phosphorus increased the nitrogen content of lettuce significantly (P<0.01) while the application of humic acid did not have significant effect. Humic acid, phosphorus, and HA×P interaction increased the nitrogen content of lettuce significantly (P<0.05). All effects were not significant for plant K, Ca, Mg, Fe, Cu, and Mn contents. Application of phosphorus decreased Zn content significantly (P<0.05). Increased amount of phosphorus caused significant increases in residual soil phosphorus (P<0.01). It was concluded that the application of 120 kg ha?1 of phosphorus together with 300 kg ha?1 of humic acid was convenient for the head weight of lettuce.  相似文献   

4.
To investigate the chemical heterogeneity of humic substances in relation to molecular size, fulvic and humic acids were extracted and purified from the surface horizon of a Humic Gleysol in northern Switzerland. A fractionation scheme using hollow‐fibre ultrafiltration cartridges was developed and used to obtain four size fractions of the humic acid with nominal molecular weight ranges > 300 kDa, 100–300 kDa, 30–100 kDa, and 10–30 kDa. The fulvic acid and all humic acid fractions were characterized by size exclusion chromatography, elemental analysis (C, H, N, S), as well as spectroscopic techniques including UV‐VIS, CP‐MAS 13C‐NMR, FT‐IR, and fluorescence spectroscopy. Clear chemical differences between the humic acid size fractions were observed. Smaller size fractions of the soil humic acid contained more chargeable functional groups and a larger percentage of aromatic carbon than the larger size fractions. Conversely, the percentage of aliphatic carbon increased with increasing apparent molecular weight. The chemical composition of the smallest humic acid fraction differed clearly from the fulvic acid fraction, despite similar apparent molecular size and carboxyl carbon content. Small humic acids contained much more aromatic carbon and less aliphatic carbon than the fulvic acid fraction. Apparently, humic size fractions differ in their chemical composition, which can have important implications for their environmental behaviour.  相似文献   

5.
腐植酸和氮肥用量及其互作对植烟土壤质量的影响   总被引:3,自引:0,他引:3  
以中烟100为材料,采用腐植酸和氮肥双因子盆栽试验,研究了腐植酸和氮肥用量及其互作对植烟土壤团聚体组成、养分及酶活性的影响。结果表明:干、湿筛法测定的土壤团聚体的平均重量直径均以T3处理(腐植酸900 mg/kg+氮肥40 mg/kg)最高,与其他处理相比提高幅度分别为15.3%~23.2%和6.5%~20.0%;方差分析显示,腐植酸与氮肥互作对土壤pH、有机质影响不显著,但对土壤碱解氮、有效磷、速效钾含量的影响达到极显著水平(P0.01);二者互作对烤烟各生育期土壤脲酶、蔗糖酶活性影响不同。由此,腐植酸和氮肥用量及其互作对提高土壤团聚体稳定性、土壤主要养分含量及酶活性具有显著效果。  相似文献   

6.
Summary Lettuce and tomato seeds were treated in Petri dishes with a humic acid derived from an oxidized coal and with fractions of the same humic acid obtained by ultrafiltration through membranes of known molecular cutoff and by extracting with buffers set at pH 4 and pH 5. The unfractionated humic acid was applied at 40, 100, 1000, and 5000 mg l-1 whereas the humic fractions were applied at 40, 100, and 200 mg l-1. Germination parameters such as the number of total germinated seeds, the velocity of seed germination, the fresh weight and dry weight of total seedlings were measured and related to the chemical and physicochemical properties of the humic material. No increase in the germination percentage or the germination rate was observed for either lettuce or tomato seeds. The fresh weight of total seedlings and per seedling increased in treatments with unfractionated humic acid with increasing concentrations for both lettuce and tomato plants without showing signs of growth inhibition up to 5000 mg l-1. This was attributed to cell elongation and more efficient water uptake. For the lettuce, the fresh weight both of total seedlings and per seedling was enhanced by treating the seeds with fractions of low molecular weight and high content of acidic functions, whereas the dry weight both of total seedlings and per seedling did not change with the humic fraction used. For the tomato seeds in contrast, the dry weight both of total seedlings and per seedling was increased by the use of unfractionated humic acid and by some of the humic fractions. An uptake of humic material by growing tomato seedlings was inferred.  相似文献   

7.
通过对华北平原小麦–玉米轮作农田生态系统18年田间施肥试验,研究了长期不同施肥处理对耕层(0—20 cm)土壤腐殖质及活性腐殖质组分碳和氮的影响。试验设化肥NPK不同组合(NPK、NP、NK、PK),全部施用有机肥(OM),一半有机肥+化肥NPK(1/2OMN)及不施肥(CK)共7个处理。结果表明,各施肥处理均能在不同程度上增加土壤腐殖质(胡敏酸、富里酸和胡敏素)及活性腐殖质(活性胡敏酸和活性富里酸)组分碳和氮含量,提高可浸提腐殖质(胡敏酸和富里酸)及活性腐殖质组分碳和氮分配比例;但施肥对土壤活性腐殖质组分碳和氮含量的增加率均分别高于腐殖质组分碳和氮。各处理土壤腐殖质及活性腐殖质组分碳和氮含量均为OM处理最高,且有机肥与化肥NPK配施高于单施化肥各处理;而化肥处理中NPK均衡施用效果最好。说明施用有机肥、有机肥与化肥NPK配施及化肥NPK均衡施用是增加土壤腐殖质及活性腐殖质组分碳和氮的关键;活性腐殖质组分碳和氮较腐殖质组分碳和氮对施肥措施的响应更灵敏。  相似文献   

8.
不同产地的腐植酸对小白菜养分利用的影响   总被引:2,自引:0,他引:2  
以小白菜为材料进行土壤盆栽试验,研究等腐植酸量的4种不同产地(内蒙古、新疆、山西、江西)的风化煤腐植酸与氮磷钾配施对小白菜养分利用的影响。结果表明,不同产地的腐植酸对小白菜不同生育期植株和土壤中氮、磷、钾含量的影响存在差异。在小白菜苗期,植株钾含量存在差异,其中山西和江西腐植酸处理植株含钾量分别提高了12.58%、6.08%,而内蒙古和新疆腐植酸处理植株含钾量分别降低了18.24%、23.48%;土壤中除山西腐植酸处理,其他各腐植酸处理均提高了土壤中有效磷和速效钾的含量,提高幅度分别为44.88%~60.89%和15.04%~24.78%。在旺盛生长期,除内蒙古腐植酸,其余各腐植酸处理均显著提高了小白菜植株中的氮含量,提高幅度为11.52%~40.45%;各腐植酸处理均显著提高了土壤中有效磷含量,提高幅度为19.12%~51.24%。不同产地的腐植酸均提高了肥料的当季利用率,且腐植酸对小白菜N、P、K吸收利用的促进作用是多种官能团在特定结构中协同作用的结果,而不是哪一个官能团单独起作用,其中,山西腐植酸处理的肥料当季利用率最高。  相似文献   

9.
不同分子量风化煤腐殖酸对玉米植株主要代谢物的影响   总被引:1,自引:1,他引:0  
【目的】腐殖酸的分子量决定了其功能特性,研究不同分子量腐殖酸对玉米生长发育的影响,可为腐殖酸资源的高效利用提供理论依据。【方法】选用‘郑单958’为供试玉米品种,以霍格兰营养液为基础溶液进行水培试验。选择分子量为> 50 kDa (HA_H)、10 kDa~50 kDa (HA_M)和<10 kDa (HA_L)三种腐殖酸,添加量均为碳10 mg/L,以不添加腐殖酸为对照(CK),共四个处理。幼苗生长20 d后收获,分为根、茎和叶样品,烘干称重,采用傅里叶变换红外光谱仪(型号VERTEX 70,德国Bruker公司)检测玉米植株根、茎和叶的光谱特征。【结果】腐殖酸处理玉米根、茎和叶的干物质重较对照分别显著提高了91.07%、89.27%和88.53%。三种腐殖酸处理,以小于10 kDa分子量腐殖酸(HAL)对玉米植株生长的促进作用最大,根、茎和叶的干物质重分别提高了143.14%、123.41%和150.54%,其次为10~50 kDa分子量腐殖酸(HA_M),大于50 kDa分子量腐殖酸(HAH)效果又次之。腐殖酸处理的玉米根系FTIR光谱在3420 cm–1和1655 cm–1波数附近的透射率均低于对照,茎FTIR光谱在3420 cm–1和1655 cm–1波数附近的透射率均高于对照,表明腐殖酸处理能增加玉米根系碳水化合物、蛋白质、多肽和氨基酸类物质的含量,减少其在茎中的积累,腐殖酸各处理玉米叶片在3420、2920、1735、1655、1518、1380、1250和1050 cm–1波数附近的透射率均低于对照,小于10 kDa分子量腐殖酸表现尤为明显。这表明不同分子量(尤其是小于10 kDa分子量)腐殖酸能够增加玉米叶片碳水化合物、脂类物质、蛋白质、多肽、氨基酸类物质和核酸等的含量。【结论】外源添加腐殖酸能够增加玉米干物质重,引起玉米植株不同器官中碳水化合物、脂类物质、蛋白质、多肽、氨基酸类物质及核酸发生变化,小分子量(<10 kDa)的腐殖酸对玉米植株生长的促进作用大于大分子量的,在生产中应尽量选择小分子腐殖酸产品,以充分发挥其促生作用。  相似文献   

10.
通过凝胶层析法对土壤腐植酸进行了分组提取,并对其各分子量分级组成及其与Cd、Zn的络合特性进行了研究.结果表明:土壤胡敏酸通过G-50可以分成3个较集中的组分,分子量分别为M=78180、M=48339及M=22863;通过G-100可以得到2个组分,分子量分别为M=63343和M=19870.富里酸通过G-50、G-100层析,则从总体上成为单一的宽带,分子量约为M=2300.腐植酸对Cd、Zn络合量的测定显示:胡敏酸对Cd、Zn的络合量呈2个明显的峰值,而富里酸只有1个峰值.两者对Cd、Zn络合量随洗脱体积的变化曲线与其吸光值随洗脱体积的变化曲线相一致.65Zn示踪技术研究65Zn与胡敏酸、富里酸络合的结论与常规方法一致.  相似文献   

11.
A method is described for the extraction and analysis of various nitrogen‐, phosphorus‐ and carbon‐containing fractions from plant material. Lipids were extracted with chloroform/methanol and chloroform/methanol/water. Soluble nitrogen (nitrate, ammonia, and amino acid), phosphorus (inorganic and sugar phosphate) and carbon (sugar and tannin) fractions were extracted with cold trichloracetic acid. Hot soluble nitrogen and phosphorus (nucleic acid) and carbon (starch and tannin) fractions were extracted with hot trichloracetic acid. Protein remained in the residue. A detailed automated scheme is described for the analysis of each of the above fractions. Also included are methods for analyzing triglyceride, hydrolyzable ester phosphate and phytic acid.  相似文献   

12.
施用腐殖酸对提高玉米氮肥利用率的研究   总被引:17,自引:1,他引:17       下载免费PDF全文
试验研究腐殖酸与尿素配合施用对玉米养分吸收、产量与N肥利用率的影响结果表明,腐殖酸能明显促进玉米植株对N、P、K养分的吸收,滞留在茎叶的N和K2O明显增加。在尿素中添加腐殖酸能明显提高玉米产量和N肥利用率。在尿素中添加10%的腐殖酸玉米产量和N肥利用率综合效果较好。  相似文献   

13.
盆栽试验结果表明 ,施钼和缺钼时 ,氮肥对冬小麦的增产率分别为 319.9%和 174.0% ;冬小麦子粒中蛋白氮、清蛋白氮、醇溶蛋白氮含量 ,面粉蛋白质氨基酸总量及其氨基酸组分的含量以及谷氨酸、脯氨酸的比例等随氮肥水平提高而增加 ;但冬小麦面粉中游离天门冬氨酸和苏氨酸的含量和比例降低 ,游离氨基酸含量在缺钼时提高了 38.3% ,施钼时则下降了 37.1%。在高、低氮肥水平下施钼 ,冬小麦子粒中蛋白质含量没有明显影响 ,但分子量小的蛋白质含量及其占总量的比例下降 ,清蛋白比例分别下降 14.5、6.6个百分点 ;而大分子量蛋白质含量和比例均提高。在不同施氮水平下缺钼冬小麦子粒中游离氨基酸含量比施钼分别高 48.0%和 15.26% ,且亲水性氨基酸比例增加。缺钼冬小麦子粒中低分子量蛋白质、游离氨基酸以及亲水性氨基酸的增加 ,可能是诱发缺钼冬小麦子粒低休眠度以及出现收获前萌芽的重要原因。  相似文献   

14.
Pyrophosphate (140 mM, pH 7.1) extracts of two arable soils and one pasture soil were ultrafiltrated separating the extracted material into three fractions: AI with nominal molecular weight (nmw) > 100 kD, AII with nmw between 10 kD and 100 kD and R with nmw < 10 kD. Protease activity was determined in the fractions by using three different substrates: N-benzoyl-l-argininamide (BAA), specific for trypsin; N-benzyloxy-carbonyl-l-phenylalanyl l-leucine (ZPL), specific for carboxypeptidases; and casein, essentially a non-specific substrate. The derivative fractions were also analysed for their amino acid N and humic (HA) and fulvic (FA) acid contents. The organic matter of extracts and derivative fractions obtained from the pasture soil was analysed by isoelectric focusing (IEF) and that of fractions analysed by pyrolysis gas chromatography (Py-GC). Activities of the extract were monitored for their thermal stability and those of the extract and derivative fractions for their optimal pH.Due to the mechanical disintegrating action of sodium pyrophosphate over the humic substances during the fractionation process the amount of total organic C and FA in the fractions was ranked as R > AII > AI. The lowest amino acid N/organic C was found in the R fraction, whereas AII fraction was rich in humic acids, carbohydrates and amino acid N and AI fraction showed the lowest carbohydrate content. At least 70% of the total BAA- and ZPL-hydrolysing activity was associated to particles with nmw higher than 10 kD and at least 30% of these activities were present in particles with nmw higher 100 kD. Casein-hydrolysing activity was quite evenly distributed among the three fractions (AI, AII and R). The extracted protease-organic complexes were resistant to thermal denaturation and some of them showed optimal activity at pH values higher than 10 as a result of the polyanionic characteristics of the humic material surrounding enzyme molecules and of the presence of alkaline protease. Comparison of data obtained in Py-GC analyses and in protease activity suggests that BAA-hydrolysing activity was associated to a highly condensed humic matter and ZPL-hydrolysing activity to less resistant humic substances, while at least some of the extracted casein-hydrolysing activity was present as glyco-proteins not associated to humus. BAA-hydrolysing activity was probably inhibited by fresh organic matter of carbohydrate origin whereas lignin derived organic matter probably inhibited ZPL- and casein-hydrolysing activity.  相似文献   

15.
In acidic soils, phosphorus availability is affected by its strong affinity for mineral surfaces, especially Fe‐ and Al‐hydroxides. Plant roots have developed adaptive strategies to enhance the availability of phosphorus, including producing and exuding low molecular weight organic acids with a high affinity for phosphorus that competes with high molecular weight organic ligands formed during humification and mineralization. The aim of this study was to characterize the kinetics and mechanism of phosphorus desorption from Fe‐ and Al‐hydroxides of variable crystallinity, as well as binary Fe:Al‐hydroxide mixtures. Long‐term desorption experiments (56 days) were conducted with CaCl2, CaSO4, citric acid, and humic acid as competitive sorptives. CaCl2 and CaSO4 were selected as general inorganic sorptives and citric and humic acids were selected as organic ligands produced by organisms in the rhizosphere or following humification. The cumulative phosphorus desorption increased following the order CaCl2 < CaSO4 < humic acid < citric acid. Amorphous ferrihydrite and Fe‐rich Fe:Al‐hydroxides exhibited much less desorption when exposed to inorganic solutions than the crystalline and Al‐rich Fe:Al‐hydroxide mixtures. Models of the desorption data suggest phosphorus desorption with citric acid is diffusion‐controlled for ferrihydrite and Fe‐rich amorphous Fe:Al‐hydroxides. When humic acid was the sorptive, metal‐organic complexes accumulated in the solution. The results suggest organic compounds, especially citric acid, are more important for liberating phosphorus from Fe‐ and Al‐minerals than inorganic ions present in the soil solution.  相似文献   

16.
腐植酸对番茄苗期氮素代谢的影响   总被引:2,自引:0,他引:2  
腐植酸对肥料具有改性增效的作用,以番茄为供试材料,研究腐植酸增效剂不同添加量对番茄苗期生长及氮素代谢酶活性的影响,为腐植酸的开发应用提供参考依据。采用砂培试验方法,设置了向霍格兰营养液分别加入腐植酸增效剂0(HA0),1(HA1),2(HA2),5(HA3),10(HA4) mL/L处理。培养30天后,测定番茄的生长指标、植株养分含量、硝酸还原酶活性、谷氨酰胺合成酶和谷氨酸脱氢酶活性。添加适量腐植酸增效剂能促进番茄苗期生长,HA3处理番茄根系干重比HA0提高了31.68%,HA1处理番茄地上部干重最大。添加腐植酸可以提高番茄苗期叶片叶绿素含量,HA3处理番茄苗期叶片叶绿素总量和类胡萝卜素含量最高,分别比HA0提高了17.11%,24.04%。添加适量腐植酸增效剂能增加番茄苗期根系和地上部对氮素的吸收,HA3处理的番茄根系、地上部及总氮素积累量比HA0分别提高了30.61%,20.24%,21.54%。添加腐植酸增效剂可以调控番茄根系和叶片氮素代谢过程,提高了氮素代谢酶活性,与HA0相比,HA4处理根系硝酸还原酶活性最大,HA3处理根系谷氨酰胺合成酶活性最高,HA2处理根系谷氨酸脱氢酶的活性最大;HA3处理番茄苗期叶片中硝酸还原酶、谷氨酰胺合成酶和谷氨酸脱氢酶活性最大,与HA0处理相比分别提高了38.27%,64.54%,106.63%。添加腐植酸增效剂可以促进番茄苗期的生长和对氮素的吸收,提高氮素代谢酶活性,处理中以在营养液中添加5 mL/L腐植酸增效剂效果最佳,腐植酸增效剂添加量低于5 mL/L时,对番茄苗期的生长及氮素代谢具有明显的促进作用。  相似文献   

17.
采用Bowman和Cole提出的有机磷分组方法,对施入外源腐殖酸条件下,不同时期棕壤有机磷的组成变化进行测定。结果表明,施入外源腐殖酸,在培养的各个时期,有机磷各组分所占比例的基本格局没有改变,依然是中等活性有机磷>中等稳定性有机磷>高稳性有机磷>活性有机磷。施入外源腐殖酸后,在培养的30 d,活性有机磷均下降;在培养的60 d和90 d,施入高量腐殖酸的土壤,活性有机磷升高。施入外源腐殖酸,在培养的各个时期均可明显增加中等活性有机磷的含量,特别是在施入高量腐殖酸时增加的最多;同时还可降低中等稳定性有机磷的含量,在施入高量腐殖酸时降低的最多。  相似文献   

18.
王景燕  龚伟  胡庭兴 《水土保持学报》2012,26(2):155-160,164
通过对川南坡地进行退耕试验,研究坡地退耕成慈竹林、杂交竹林、桤木+慈竹林和弃耕地对土壤腐殖质及团聚体碳和氮的影响。结果表明,坡地退耕5年后土壤腐殖质(胡敏酸、富里酸和胡敏素)、活性腐殖质(活性胡敏酸和活性富里酸)及团聚体碳和氮含量、胡敏酸与富里酸比值和胡敏酸E4/E6值,以及可浸提腐殖质(胡敏酸和富里酸)、活性腐殖质及>0.25mm各粒径团聚体碳和氮分配比例均增加,并呈现出慈竹林>杂交竹林>桤木+慈竹林>弃耕地>农耕地的变化规律。土壤团聚体有机碳(氮)含量及其分配比例随土壤团聚体粒径的增加呈现出"V"形变化,其最小值分别出现在2~1mm和0.5~0.25mm粒径。说明川南坡地退耕对增加土壤腐殖质及团聚体碳和氮含量、改善土壤肥力状况和促进土壤碳固定具有重要的作用和意义。  相似文献   

19.
Abstract

Different molecular weight fractions obtained by ultrafiltration of a humic acid (HA) extracted from a Mollisol were analyzed by chemical, infrared, electron microscopy, and isotachophoresis methods. The results showed that the different HA fractions did not differ substantially in characteristics from each other, although each fraction was composed of subfractions exhibiting different electromobilities. It appeared that fractionation of HA would yield molecular weight fractions as imposed by any exclusion limits used in the procedure. However, the elemental composition, infrared spectra, and electron micrographs showed that the fractions, separated by molecular weight limits, contained similar compounds. These results do not support the concept of humic acids as a heterogeneous mixture of compounds, but show instead that humic acids may possess a composition more homogeneous in nature than previously postulated.  相似文献   

20.
Soil samples were fractionated by sedimentation in water and by flotation in heavy liquids to separate complexed and uncomplexed organic and inorganic components. Flocculation of clays in heavy organic liquids was delayed by addition of a surfactant. Heavy liquids and surfactants sorbed by soil components were removed by washing with acetone-water mixtures.In a sample of a red-brown earth, the organic carbon and nitrogen contents were highest in the finest separates. In samples of a ground-water rendzina and a chernozemic soil, the coarse clay and silt separates had the highest organic carbon and nitrogen contents. Organic matter was concentrated in low density fractions in all separates. Carbon/nitrogen ratios were lowest in the finer and heavier separates. Calcium, and to a lesser extent manganese, iron and phosphorus, were concentrated in low density fractions: thus these elements appear to be associated with organic matter and may be important in organo-mineral complex formation. Carbonates, titanium, iron, silicon and potassium were concentrated at the highest densities.Organic fractions < 2.06 g cm?3 from sand size separates were insoluble in alkali and had wide carbon/nitrogen ratios characteristic of plant debris. The light fractions from fine silt and coarse clay separates were more soluble in alkali but showed high ratios of humic to fulvic materials and high absorption at 280 nm. Such materials were considered to be microbial cell debris and were associated with high contents of disordered aluminium and iron oxides and expanding lattice silicates in 1 to 5 μm aggregates.Heavier fractions, particularly of finer clay separates, contained more fulvic and humic materials of a more aliphatic nature than those in < 2.06 g cm?3 fractions. It is suggested that physical sorption on clay surfaces may be more important in these fractions. Ellite and kaolinite were concentrated in medium density fractions, and contents of some iron oxides and titanium minerals were highest in fractions > 2.06 g cm?3. Such minerals plus quartz and feldspars were associated with minor amounts of organic matter or possibly were not involved in organo-mineral associations.  相似文献   

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