Hydroxycinnamic acids as affected by different fertilization of Rebula grapevines

The phenolic composition of white grapes is important since browning reactions may dramatically compromise the overall quality of musts and wines. Only few scientific contributions are available, which investigated how fertilization can influence this class of compounds. Thus, the aim of this work was to examine the effects of NPK soil fertilization coupled with soil or foliar applications of Mg, Fe, and Zn on the concentrations of K, Mg, Fe, and Zn of grape berries and leaf petioles of potted Rebula grapevines (Vitis vinifera L.), also revealing the change of hydroxycinnamic acids in grape juice. The results obtained over the three‐year study (2009–2011) showed that NPK fertilization positively affected K and Zn concentrations of petioles and grape berries, and negatively Mg. In addition, K (synergistic) and Mg (antagonistic) had an influence on Zn uptake. Our findings suggest that the supply of NPK was profitable for a reduction of trans‐caftaric acid in grape juice, while only few differences were observed with further application of nutrients.     

Root exudation of sugars,amino acids,and organic acids by maize as affected by nitrogen,phosphorus, potassium,and iron deficiency

Root exudates play a major role in the mobilization of sparingly soluble nutrients in the rhizosphere. Since the amount and composition of major metabolites in root exudates from one plant species have not yet been systematically compared under different nutrient deficiencies, relations between exudation patterns and the type of nutrient being deficient remain poorly understood. Comparing root exudates from axenically grown maize plants exposed to N, K, P, or Fe deficiency showed a higher release of glutamate, glucose, ribitol, and citrate from Fe‐deficient plants, while P deficiency stimulated the release of γ‐aminobutyric acid and carbohydrates. Potassium‐starved plants released less sugars, in particular glycerol, ribitol, fructose, and maltose, while under N deficiency lower amounts of amino acids were found in root exudates. Principal‐component analysis revealed a clear separation in the variation of the root‐exudate composition between Fe or P deficiency versus N or K deficiency in the first principal component, which explained 46% of the variation in the data. In addition, a negative correlation was found between the amounts of sugars, organic and amino acids released under deficiency of a certain nutrient and the diffusion coefficient of the respective nutrient in soils. We thus hypothesize that the release of dominant root exudates such as sugars, amino acids, and organic acids by roots may reflect an ancient strategy to cope with limiting nutrient supply.     

Characterization by LC-MS(n) of four new classes of chlorogenic acids in green coffee beans: dimethoxycinnamoylquinic acids, diferuloylquinic acids, caffeoyl-dimethoxycinnamoylquinic acids, and feruloyl-dimethoxycinnamoylquinic acids

LC-MS4 has been used to detect and characterize in green coffee beans 12 chlorogenic acids not previously reported in nature. These comprise three isomeric dimethoxycinnamoylquinic acids (7-9) (Mr 382), three caffeoyl-dimethoxycinnamoylquinic acids (22, 24, and 26) (Mr 544), three diferuloylquinic acids (13-15) (Mr 544), and three feruloyl-dimethoxycinnamoylquinic acids (28, 30, and 32) (Mr 558). Structures have been assigned on the basis of LC-MS4 patterns of fragmentation and relative hydrophobicity and, in the case of the dimethoxycinnamoylquinic acids, by comparison with authentic standards. Several new structure-diagnostic fragmentations have been identified for use with diacyl-chlorogenic acids, for example, m/z 299 and 255 for C4 caffeoyl, m/z 313 and 269 for C4 feruloyl, nearly equal elimination of both cinnamoyl residues for vic-3,4-diacyl, and an increasing ratio of "dehydrated" ions to "non-dehydrated" ions at MS2 with increasing methylation of those cinnamoyl residues. Possible mechanisms have been proposed to account for the fragmentations observed. The mass spectrometric resolution of six isomeric chlorogenic acids (Mr 544) in a crude plant extract by fragment-targeted LC-MS2 and LC-MS3 experiments illustrates the analytical power and advantage of ion trap mass spectroscopy.     

低分子量有机酸对促进可变电荷土壤中铝溶解的影响

Low-molecular-weight （LMW） organic acids exist widely in soils and play an important role in soil processes such as mineral weathering, nutrient mobilization and A1 detoxification. In this research, a batch experiment was conducted to examine the effects of LMW organic acids on dissolution of aluminum in two variably charged soils, an Ultisol and an Oxisol. The results showed that the LMW organic acids enhanced the dissolution of A1 in the two investigated soils in the following order： citric 〉 oxalic 〉 malonic 〉 malic 〉 tartaric 〉 salicylic 〉 lactic 〉 maleic. This was generally in agreement with the magnitude of the stability constants for the Al-organic complexes. The effects of LMW organic acids on Al dissolution were greater in the Ultisol than in the Oxisol as compared to their controls. Also, the accelerating effects of citric and oxalic acids on dissolution of A1 increased with an increase in pH, while the effects of lactic and salicylic acids decreased. Additionally, when the organic acid concentration was less than 0.2 mmol L-I, the dissolution of A1 changed Iittle with increase in acid concentration. However, when the organic acid concentration was greater than 0.2 mmol L^-1,the dissolution of A1 increased with increase in acid concentration. In addition to the acid first dissociation constant and stability constant of Al-organic complexes, the promoting effects of LMW organic acids on dissolution of A1 were also related to their sorption-desorption equilibrium in the soils.     

外源低分子量有机酸对碳酸钙预处理的酸性土壤中活性铝钙镁影响的研究

通过在所研究的第四纪红黏土发育的红壤中混入CaCO3,研究在pH缓冲体系中外加低分子量有机酸对土壤中Al、Ca和Mg的影响。结果表明:无论加CaCO3与否,在pH 4.5的条件下外源草酸、柠檬酸、苹果酸的加入均使土壤可溶性Al显著提高,交换性Al显著下降和交换性Ca显著升高;加入CaCO3的情况下,3种有机酸处理的交换性Mg均显著提高。3种有机酸促进Al溶解能力的大小顺序为:柠檬酸>草酸>苹果酸,这一结果与有机酸和Al形成络合物的稳定常数大小一致。另一方面,3种有机酸处理下,CaCO3预处理均引起可溶性Al的显著升高和交换性Al的下降。双因素方差分析表明,有机酸通过络合作用或沉淀作用对可溶性和交换性Al、Ca和Mg均具有绝对的影响优势,CaCO3仅对可溶性和交换性Al、交换性Ca有显著影响,由于实验中pH缓冲体系的控制,这种影响主要通过Al与Ca、Mg的竞争交换作用实现。总体来说,外源低分子量有机酸的加入使土壤活性Al显著升高,活性Ca、Mg略有升高,有机酸在酸性土壤中的作用需从有机酸溶解阳离子的角度进一步评价。     

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。     

有机物质阴阳离子对调节土壤pH的作用

The process of organic materials increasing soil pH has not yet been fully understood. This study examined the role of cations and organic anions in regulating soil pH using organic compounds. Calcareous soil, acid soil, and paddy soil were incubated with different simple organic compounds, pH was determined periodically and CO2 emission was also measured. Mixing organic acids with the soil caused an instant decrease of soil pH. The magnitude of pH decrease depended on the initial soil acidity and dissociation degree of the acids. Decomposition of organic acids could only recover the soil pH to about its original level. Mixing organic salts with soil caused an instant increase of soil pH. Decomposition of organic salts of sodium resulted in a steady increase of soil pH, with final soil pH being about 2.7-3.2 pH units over the control. Organic salts with the same anions （citrate） but different cations led to different magnitudes of pH increase, while those having the same cations but different anions led to very similar pH increases. Organic salts of sodium and sodium carbonate caused very similar pH increases of soil when they were added to the acid soil at equimolar concentrations of Na^＋. The results suggested that cations played a central role in regulating soil pH. Decarboxylation might only consume a limited number of protons. Conversion of organic salts into inorganic salts （carbonate） was possibly responsible for pH increase during their decomposition, suggesting that only those plant residues containing high excess base cations could actually increase soil pH.     

Soil Fertility,Sugarcane Yield Affected by Limestone,Silicate, and Gypsum Application

The aim of this study was to verify if the application of silicate or lime, in association with gypsum, on sugarcane residue can lead to amendment of subsurface soil acidity, increasing sugarcane yield and profitability. The treatments were: 1 – control (without application of amendments), 2 – gypsum, 3 – dolomitic limestone, 4 – silicate, 5 – dolomitic limestone + gypsum, and 6 – silicate + gypsum. The surface application of gypsum led to reduction in Al (aluminum) contents and Al saturation, and increase in Mg⁺², Ca⁺², K⁺, S–SO₄^?, and base saturation in deeper soil layers, as well as increased yield of stalks, sugar, trash, bagasse, and energy, and greater profit. The application of limestone and silicate, alone or in association with gypsum, amend soil acidity throughout the soil profile. It likewise leads to an increase in stalk, sugar, trash, bagasse, and energy yield, however, application of silicate in association with gypsum leads to the greatest profitability.     

酚酸化合物对土壤酶活性和土壤养分的影响

研究了酚酸化合物对连作西瓜土壤酶活性和土壤养分的影响。结果表明,添加外源酚酸入土刺激了土壤酶活性,土壤过氧化氢酶活性、脲酶活性均比对照提高,土壤呼吸强度增加,施入酚酸化合物2周时,500.mg/kg浓度的苯丙烯酸和对羟基苯甲酸土壤呼吸强度分别比同期对照增加了22.5%和20.0%;处理4周时,750.mg/kg浓度的苯丙烯酸和对羟基苯甲酸脲酶活性分别比对照提高了34.4%和29.0%。苯丙烯酸和对羟基苯甲酸类酚酸化合物降低了土壤碱解氮、速效磷、速效钾含量,有机质含量也降低,250.mg/kg苯丙烯酸处理2周时,碱解氮、速效钾、速效磷和有机质含量分别比对照降低了9.6%,18.4%,20.7%和11.0%。     

Comparisons of soil test phosphorus by Olsen,Bray P1, Mehlich I and Mehlich III methods

Abstract

A study was undertaken to evaluate the agreement among different university laboratories performing the Olsen, Bray P1, and Mehlich I tests for P on a diverse group of noncalcareous agricultural soils and to develop relationships among the Olsen, Bray P1, Mehlich I, and Mehlich III soil tests. For each test, the results from the individual laboratories were highly correlated (r² ≥ 0.90) and in almost all instances the slopes of the equations describing the relationships among laboratories approached one, The results indicate that the Olsen, Bray P1 and Mehlich I soil tests may be performed with a high degree of precision when standard soil test procedures are followed.

Of the three most commonly performed tests in the U.S. (Olsen, Bray P1, and Mehlich I), the Olsen and Mehlich I tests were the most highly correlated (r² = 0.87) although the Mehlich I test removed approximately one and one half times more P than did the Olsen test. Bray P1 and Olsen and Mehlich I P were less highly correlated (r² ≤ 0.72) and the relationships between these variables were influenced by the texture of the soils. The quantity of P removed by the Bray P1 test was on the order of two and three times greater than that removed by the Olsen and Mehlich I tests, respectively. The Bray P1 and Mehlich III soil tests were highly correlated (r² = 0.97) and similar quantities of P were extracted from the soil by the two tests.     

Effects of glucose,cellulose, and humic acids on soil microbial eco‐physiology

Microbial eco‐physiology in soils is regulated by substrate quality of the organic matter. This regulation was studied for a forest and an agricultural soil by the combination of activity and biomass techniques. Soil respiration was stimulated by the substrate quality in the order, humic acid < cellulose < glucose over 20 days. Concurrently, substrate addition increased the respiratory quotient (RQ), defined as the ratio of mol CO₂ evolution per mol O₂ uptake. Anabolic processes were mainly induced by glucose addition. Soil preconditioned with glucose showed a decrease in the RQ value during glucose‐induced microbial growth in comparison to non‐amended control. The decrease in the RQ value induced by preconditioning with cellulose and humic acid was lower. Glucose, cellulose, and humic acid addition modified the microbial biomass as estimated by fumigation‐extraction (FE), substrate‐induced respiration (SIR), and ATP content. Since each biomass estimate refers to specific microbial components, shifts in microbial eco‐physiology and community structure induced by substrate quality were reflected by SIR : FE and SIR : ATP ratios. The active and glucose‐responsive biomass in the forest soil which was earlier suggested as being dominated by K‐strategists was increased in the order, humic acid < cellulose < glucose.     

Absorption spectra of humic acids

For the purpose of explaining the forming process of soil humic acids, the author determined the absorption spectra of various humic acids. From soils and peats which were pretreated with 5% HCl at 70°C for 30 minutes or from those which were not, humic acids were extracted by treating with 0.5% NaOH at boiling temperature for 30 minutes. In these humic acids, the one which is extracted after acid pretreatment is provisionally designated as SrL humic acid and the other as L humic acid. The supernatant alkaline solutions obtained by centrifuging the above mentioned extracts were acidified with hydrochloric acid, and precipitated humic acids were filtered and washed with water until Cl' free. Humic acids were dissolved in 0.1% NaOH and ultrafiltered using collodion membrane. The filtrates were acidified with hydrochloric acid and humic acids were collected by centrifuging, transferred on the filter paper, washed with dilute hydrochloric acid and water successively, then air-dried and pulverized.     

有机酸对污染土壤中镉释放的影响

There is limited information on the release behavior of heavy metals from natural soils by organic acids. Thus, cadmium release, due to two organic acids (tartrate and citrate) that are common in the rhizosphere, from soils polluted by metal smelters or tailings and soils artificially contaminated by adding Cd were analyzed. The presence of tartrate or citrate at a low concentration (≤ 6 mmol L^-1 for tartrate and ≤ 0.5 mmol L^-1 for citrate) inhibited Cd release, whereas the presence of organic acids in high concentrations (≥ 2 mmol L^-1 for citrate and ≥ 15 mmol L^-1 for tartrate) apparently promoted Cd release. Under the same conditions, the Cd release in naturally polluted soils was less than that of artificially contaminated soils. Additionally, as the initial pH rose from 2 to 8 in the presence of citrate, a sequential valley and then peak appeared in the Cd release curve, while in the presence of tartrate the Cd release steadily decreased. In addition, Cd release was clearly enhanced as the electrolyte concentration of KNO₃ or KCl increased in the presence of 2 mmol L^-1 tartrate. Moreover, a higher desorption of Cd was shown with the KCl electrolyte compared to KNO₃ for the same concentration levels. This implied that the bioavailability of heavy metals could be promoted with the addition of suitable types and concentrations of organic acids as well as reasonable field conditions.     

Biogeochemistry of aluminum in a forest catchment in the Czech Republic impacted by atmospheric inputs of strong acids

The Lysina catchment in the Czech Republic was studied to investigate the biogeochemical response of Al to high loadings of acidic deposition. The catchment supports Norway spruce plantations and is underlain by granite and podzolic soil. Atmospheric deposition to the site was characterized by high H⁺ and SO₄ ^2– fluxes in throughfall. The volume-weighted average concentration of total Al (Al_t) was 28 mol L^–1 in the O horizon soil solution. About 50% of Al_t in the O horizon was in the form of potentially-toxic inorganic monomeric Al (Al_i). In the E horizon, Al_t increased to 71 mol L^–1, and Al_i comprised 80% of Al_t. The concentration of Al_t (120 mol L^–1) and the fraction of Al_i (85%) increased in the lower mineral soil due to increases in Al_i and decreases in organic monomeric Al (Al_o). Shallow ground water was less acidic and had lower Al_t concentration (29 mol L^–1). The volume-weighted average concentration of Al_t was extremely high in stream water (60 mol L^–1) with Al_i accounting for about 60% of Al_t. The major species of Al_i in stream water were fluorocomplexes (Al-F) and aquo Al³⁺. Soil solutions in the root zone were undersaturated with respect to all Al-bearing mineral phases. However, stream water exhibited Al_i concentrations close to solubility with jurbanite. Acidic waters and elevated Al concentrations reflected the limited supply of basic cations on the soil exchange complex and slow weathering, which was unable to neutralize atmospheric inputs of strong acids.     

Cleaning heavy metal contaminated soil with soluble humic substances instead of synthetic polycarboxylic acids

Abstract

Soils contaminated with heavy metals constitute a serious and widespread ecological problem but to clean such soils requires strong chemicals such as polycarboxylates; frequently ethylenediaminetetraacetic acid and nitrilotriacetic acid are used. However, these compounds are synthetic and toxic and their replacement by natural products such as soluble humic substances as washing agents for cleaning heavy metal polluted soils would be environmentally very attractive. In fact, such a replacement seems possible at least on cadmium and copper contaminated soil inasmuch as humic substances, depending on the concentration, were found to extract up to 45% and 54% of total cadmium and copper from a highly contaminated calcareous soil. Even though higher amounts of the two metals were extracted by ethylenediaminetetraacetic acid and nitrilotriacetic acid, the humic substances undoubtedly extracted the most reactive fractions. However, the humic substances extracted only 4% of total lead and 17% of total nickel, whereas the percentages for the synthetic polycarboxylates were about 30% for nickel and lead. Ethylenediaminetetraacetic acid and nitrilotriacetic acid may therefore be replaced by humic substances as washing agents for cadmium, copper and maybe nickel contaminated soils, whereas they seem unsuited for cleaning lead contaminated soils, at least if the soils are as calcareous as the soil tested.     

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。     

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。     

Soil Phosphorus Remediation by Bahia Grass,Common Bermuda Grass,Crab Grass,and Switch Grass

Soil phosphorus (P) removal by harvest may be a practical remediation strategy. Small plots of bahia grass (BG) (Paspalum notatum Flügge), common bermuda grass (CB) (Cynodon dactylon (L.) Pers.), crab grass (CG) (Digitaria ciliaris (Retz.) Koel.), and switch grass (SG) (Panicum virgatum L.) were established on a coastal plain soil (Mehlich 3P, 100–500+ mg kg^?1) . Yield, tissue P concentration, and uptake P were determined in 2002–2005, and surface (0–15 cm) soil P were determined in 2002 and 2005. The uptake decreased, SG > CG > BG = CB (range 230–90 kg ha^?1), paralleling the decrease in surface soil P. Uptake depended on soil P (P < 0.01–0.10), with uptake > surface soil P decrease at low soil P due to uptake from subsoil but decrease > uptake at high soil P due to leaching. Soil P concentration did not affect SG tissue P nor did multiple harvests decrease its relative productivity.     

土壤培肥过程中氯离子累积与分布规律研究

以陕西杨凌杜寨村为中心,沿南、西、北3条辐射线分别采取耕层和剖面土样,探讨土壤中Cl^-的累积与垂直分布情况,揭示受人类生活影响历史较长的杜寨村农田土壤中Cl^-的累积状况与迁移规律。结果表明,在半干旱偏湿润气候地区,由于受自然环境因素和人为因素的强烈影响,Cl^-在村庄附近的土壤耕层呈现出累积趋势,随着离村庄距离的增加而明显减少;土壤剖面上Cl^-的含量随着土壤深度的增加也逐渐减少;Cl^-在土壤耕层虽然表现出一定的累积趋势,但累积量并不高,暂时不会影响作物的产量和品质。