红壤中镉在有机酸作用下的解吸行为

采用平衡批处理法,研究了3种有机酸及其两两混合液在序列pH值梯度下（pH 3.0～7.0）对华南山地红壤Cd解吸行为的影响.结果表明,草酸与苹果酸不利于Cd的解吸,反而促进了吸附,其中草酸只是在较高浓度(20 mmol·L^-1)且土壤溶液pH＞5.0时促进解吸.随着pH值升高,草s酸、苹果酸以及不含有机酸的对照溶液对红壤中Cd的解吸率都快速下降.柠檬酸在pH＜5.0时不利于Cd解吸;在pH＞5.0时显著促进Cd解吸,但两种浓度柠檬酸解吸特征有所不同,在低浓度(2 mmol·L^-1)下对镉的解吸率呈降低-升高-降低变化,在高浓度(20 mmol·L^-1)下呈降低-升高变化.在低pH条件下（pH 3.0、4.0）,苹果酸最有利于Cd的解吸,但3种酸对Cd解吸率差别不大,在较高pH条件下(pH 5.0～7.0),柠檬酸最有利于解吸,且解吸率大大高于草酸与苹果酸.有机酸混合没有明显的交互作用,对Cd的解吸率介于相应单独有机酸之间.     

Comparison of GC and HPLC for the quantification of organic acids in coffee

A GC and an HPLC method for the quantification of organic acids OAs in coffee have been compared. The GC procedure, employing trimethylsilyl derivatives, was found to be very tedious. The HPLC method, which employed an ion exchange column using a flow gradient of water containing 1% phosphoric acid and UV detection (210 nm), was found to be much simpler for the quantification of eight organic acids (oxalic, succinic, fumaric, malic, tartaric, citric, quinic and fumaric acids) in four representative coffee samples. The HPLC procedure was more convenient than that described in the literature since no pre-purification was required for quantification of the OAs.     

有机酸对Pb、Cd的土壤化学行为和植株效应的影响

有机酸对Pb、Cd的络合作用将其对土壤吸附Pb、Cd的影响和植株效应差异的研究表明,柠檬酸、草酸与Pb、Cd络合能力的大小与重金属本身的性质有关,络合作用影响土壤对Pb、Cd的吸附量,柠檬酸降低土壤对Pb、Cd的吸附,草酸则增加土壤对Pb、Cd的吸附.水培试验表明,柠檬酸可减轻Pb对小麦、水稻幼苗的毒害.柠檬酸对Cd的植株外观毒性效应影响不显著,但能促使植株茎叶、根中Cd含量下降.Pb和Cd复合处理条件下,Cd存在促使水稻植株对Pb吸收量增加,Pb存在抑制水稻植株对Cd的吸收.     

有机酸对Pd 、Cd的土壤化学行为和植株效应的影响

有机酸对Pd,Cd的络合作用将其对土壤吸附Pd,Cd的影响和植株效应差异的研究表明,柠檬酸,草酸与Pd,Cd络合能力的大小与重金属本身的性质有关,络合作用影响土壤对Pd,Cd的吸附量,柠檬酸降低土壤对Pd,Cd的吸附,草酸则增加土壤对Pd,Cd的吸附,水培试验表明,柠檬酸可减轻Pb对小麦,水稻幼苗的毒害,柠檬酸对Cd的植株外观毒性效应影响不显著,但能促使植株茎叶,根中Cd含量下降,Pd和Cd复合处理条件下,Cd存在促使水稻植株对Pd吸收量增加,Pd存在抑制水稻植株对Cd的吸收。     

有机酸对菜地土壤磷素活化的影响

实验室模拟研究两种有机酸(柠檬酸、草酸)对菜地土壤磷素活化的影响。结果表明:有机酸对菜地土壤磷的活化效果较明显,且随有机酸浓度的增加,土壤磷活化效果越显著。两种有机酸的活化效果为草酸>柠檬酸。有机酸对磷的活化效果与土壤Olsen- P含量、有机质含量呈显著正相关关系。土壤中有效磷的释放随着有机酸浸提时间的延长而逐渐增加。     

柠檬酸、草酸和乙酸对污泥中镉、铅、铜和锌的去除效果

研究了柠檬酸、草酸和乙酸对污泥中Cd、Pb、Cu和Zn等重金属的去除效果,并分析了污泥中重金属的形态变化和生物有效性.结果表明,随着反应时间和酸浓度的增加,污泥中重金属（Cu除外）的去除率也相应增加.污泥加入柠檬酸溶液反应7 h即可去除污泥中52.0%的Pb和74.2％的Zn, 24 h后可去除76.0%的Pb和92.5%的Zn,草酸和乙酸对重金属的去除率较低.柠檬酸去除的Pb和Zn主要以稳定态存在,并导致污泥中不稳定态重金属的比例上升,其中可交换态重金属浓度有不同程度的增加.虽然有机酸对Cd和Cu的去除率较低,但反应后可交换态Cd和Cu的浓度仍有小幅增加.     

低磷胁迫下AM真菌对枳实生苗吸磷效应及根系分泌有机酸的影响

在温室沙培灭菌条件下,以Al-P为磷源、枳为试材、Glomus mosseae (G.m)和G.versiforme (G.v)为菌剂,研究低磷胁迫下AM真菌对枳实生苗干物重、吸磷效应及根系分泌有机酸的影响。结果表明,接种AM真菌显著增加枳地上部、地下部干物重,增幅16.79%~135.25%;同时显著增加其吸磷量,菌丝对植株的吸磷贡献率为17.04%~71.95%(G.m>G.v),施Al-P显著提高菌丝吸磷贡献率。接种AM真菌的根系分泌的有机酸种类与对照有所不同,未接种处理枳分泌的有机酸有草酸、苹果酸、乳酸、乙酸、顺丁烯二酸和柠檬酸等6种,而接种G.m的则检测到草酸、酒石酸、苹果酸、乳酸、乙酸、柠檬酸、丁二酸等7种,G.v处理的检测到酒石酸,接种处理均未检测到顺丁烯二酸;接种丛枝菌根真菌增加了枳根系分泌有机酸的量(比未接种处理增加19.80~56.87 mg/kg,且施用AlPO₄后有机酸含量显著增加(增加20.06~21.84 mg/kg);未接种植株根系仅分泌少量有机酸;接种植株根系分泌的有机酸以苹果酸(42.87%)、柠檬酸(39.22%)和草酸(12.06%)为主。     

Nickel sorption capacity of ground xylem of Quercus ilex trees and effects of selected ligands present in the xylem sap

In this work the influence of four different ligands present in the xylem sap of Quercus ilex (histidine, citric, oxalic and aspartic acids) on Ni(II) adsorption by xylem was investigated. Grinded xylem was trapped in acrylic columns and solutions of Ni(II), in the absence and presence of the four ligands prepared in KNO(3) 0.1molL(-1) at pH 5.5, were percolated through the column. Aliquots of solutions were recovered in the column end for Ni determination by graphite furnace atomic absorption spectrometry (GFAAS). The experimental data to describe Ni sorption by xylem in both the presence and absence of ligands was better explained by the Freundlich isotherm model. The decreasing affinity order of ligands for Ni was: oxalic acid>citric acid>histidine>aspartic acid. On the other hand, the Ni(II) adsorption by xylem increased following the inverse sequence of ligands. Potentiometric titrations of acidic groups were carried out to elucidate the sorption site groups available in Q. ilex xylem. The potentiometric titration has shown three sorption sites: pK(a) 2.6 (57.7% of the sorption sites), related to monobasic aliphatic carboxylic acids or nitrogen aromatic bases, pK(a) 8.1 (9.6%) and pK(a) 9.9 (32.7%), related to phenolic groups.     

黑麦草生长过程中有机酸对镉毒性的影响

研究了低分子量有机酸草酸、柠檬酸、乙酸及高分子量有机酸胡敏酸对黑麦草(Lolium Loinn)生长过程中Cd毒性的影响.结果表明,随着低分子量有机酸浓度增加,Cd毒性有所增强,致使黑麦草中的叶绿素含量降低及黑麦草的生物量降低,递降顺序是草酸＜乙酸＜柠檬酸.而施入胡敏酸后,Cd毒性逐渐减弱,黑麦草中的叶绿素含量及黑麦草生物量逐渐增加.对低分子量有机酸而言,无论迁移到黑麦草茎叶中,还是迁移到黑麦草根系中的Cd,随着施入的有机酸浓度增加,增加顺序为柠檬酸＞乙酸＞草酸.对胡敏酸而言,迁移到黑麦草茎叶和根系中的Cd,随着施入的胡敏酸浓度增加,Cd含量减少,说明其具有降低Cd毒性的作用.另外,根系中Cd含量明显高于茎叶中Cd含量,由此得知,黑麦草根系对Cd有较强的富集作用,并阻止Cd向茎叶中迁移.     

不同有机酸对铅胁迫小麦幼苗的缓解作用

研究了在铅胁迫条件下,加入外源有机酸对小麦铅毒害的缓解效应。结果表明,低浓度的草酸和乙酸能增加铅胁迫小麦叶绿素含量,不同程度地提高SOD、CAT、POD活性,降低MDA含量,而高浓度草酸和乙酸及柠檬酸对此则无明显的缓解作用;乙酸处理减少根系活跃吸收面积,柠檬酸能明显提高根系活力。草酸对铅胁迫的缓解效果最明显。     

Formation and biliary excretion of glutathione conjugates of bile acids in the rat as shown by liquid chromatography/electrospray ionization-linear ion trap mass spectrometry

There is yet to be a reliable prediction of urolithiasis. To facilitate early diagnosis, a simple and rapid high performance liquid chromatography method with electrochemical detection using disposable copper-nanoparticle-plated electrodes (Cuⁿ-SPE) was developed for multiple detection of creatinine and 4 urolithic organic acids. A total of 206 normal and urolithic human and canine urines and urolith samples were collected for direct analysis of creatinine, cystine, uric acid, oxalic acid, and citric acid without sample cleanup and derivatization processes. Urinary organic acids were separated in 11 min and were devoid of ascorbic acid interference. The detection limits (S/N > 3) were at the nanomolar level with linear dynamic ranges spanning 2–3 orders of magnitude. Recoveries in urine ranged from 99.5% for creatinine to 86.5% for citric acid. The analytical variations (RSD) were less than 6.2% in phosphate buffer and 7.7% in urine. Important differences in organic acid levels/profiles between animal species and among normal and urolithic urines/urolith were unveiled and corresponded well (70–90%) with the urolithic risk in a retrospective assessment. The simplicity and reproducibility of this method using disposable Cuⁿ-SPE has made routine urine analysis possible and can be of great clinical and diagnostic potential in the screening of urolithiasis and abnormal states related to excess secretion of organic acids and amino acids in humans and animals.     

Roles of Organic Acids and Nitrate in the Long-Distance Transport of Cobalt in Xylem Saps of <Emphasis Type="Italic">Alyssum murale</Emphasis> and <Emphasis Type="Italic">Trifolium subterraneum</Emphasis>

Roles of organic acids and nitrate in the long-distance transport of cobalt (Co) in xylem saps of hyperaccumulator Alyssum murale and non-hyperaccumulator Trifolium subterraneum were studied under hydroponic conditions. Organic acids (oxalic, malic, malonic, citric, and fumaric) and nitrate in xylem sap samples were separated and determined simultaneously by reversed-phase high performance liquid chromatography after solid-phase extraction with nanosized hydroxyapatite. Results indicated that Co treatment significantly increased the concentrations of xylem oxalic and malic acids for the hyperaccumulator A. murale compared to the control but significantly decreased the concentrations of xylem nitrate and malonic acid; concentrations of citric acid in xylem sap samples did not show significant difference between the control and Co treatments. By analyzing the relationship between the concentrations of organic acids, nitrate, and concentrations of Co in xylem saps, it could be concluded that oxalic and malic acids in xylem saps seemed to participate in the long-distance Co translocation process, and citric acid did not relate to the xylem Co transport of A. murale and T. subterraneum. Our work might be very useful for understanding the mechanism of long-distance transport of heavy metals in hyperaccumulator.     

Detection and quantification of ligands involved in nickel detoxification in a herbaceous Ni hyperaccumulator Stackhousia tryonii Bailey

Field-collected, young plants of Ni hyperaccumulator Stackhousia tryonii, grown in a glasshouse for 20 weeks, were exposed to low- (available Ni concentration in the native serpentine soil, i.e. 60 microg g(-1) dry soil) and high- (external application of 1000 ppm) Ni concentrations in the substrate. Nickel concentration in the freeze-dried leaf tissues increased from 3700 microg g(-1) to 13 700 microg g(-1) with soil Ni supplementation, of which >60% was extracted with dilute acid (0.025 M HCl). Nickel supplementation also elicited a 575%, 211%, and 37% increase in the final concentrations of oxalic, citric, and malic acids, respectively, in leaf tissues. Malic acid was the dominant organic acid, followed by citric and oxalic acids. The molar ratio of Ni to malic acid was 1.0, consistent with a role for malate as a ligand for Ni in hyperaccumulating plants, supporting detoxification/transport and storage of this heavy metal in S. tryonii. The total amino acid concentrations in the xylem sap did not change with Ni supplementation (21.7+/-3.7 mM and 17.9+/-5 mM, respectively, for low- and high-nickel-treated plants). Glutamine was the major amino acid in both the low- and high-Ni-treated plants. The concentration of glutamine decreased by >60%, with a corresponding increase in alanine, aspartic acid, and glutamic acid, on exposure to high Ni. A role of amino acids in Ni complexation and transport in S. tryonii is not immediately apparent.     

Bioleaching of spent fluid catalytic cracking catalyst using Aspergillus niger

The use of the fungus Aspergillus niger for the bioleaching of heavy metals from spent catalyst was investigated, with fluid catalytic cracking (FCC) catalyst as a model. Bioleaching was examined in batch cultures with the spent catalysts at various pulp densities (1-12%). Chemical leaching was also performed using mineral acids (sulphuric and nitric acids) and organic acids (citric, oxalic and gluconic acids), as well as a mixture of organic acids at the same concentrations as that biogenically produced. It was shown that bioleaching realised higher metal extraction than chemical leaching, with A. niger mobilizing Ni (9%), Fe (23%), Al (30%), V (36%) and Sb (64%) at 1% pulp density. Extraction efficiency generally decreased with increased pulp density. Compared with abiotic controls, bioleaching gave rise to higher metal extractions than leaching using fresh medium and cell-free spent medium. pH decreased during bioleaching, but remained relatively constant in both leaching using fresh medium and cell-free spent medium, thus indicating that the fungus played a role in effecting metal extraction from the spent catalyst.     

Untersuchungen zum Säurestoffwechsel von Aspergillus niger

Zusammenfassung Entwickelt sich das Mycel von Aspergillus niger ausgehend von Conidien bei 43, 30 bzw. 10° C auf einer Nährlösung mit Glucose (5%) als C-Quelle und KNO₃ (1%) als N-Quelle, so kann durch Zusatz von Glucon- bzw. Citronensäure vor und nach dem Zeitpunkt des fast völligen Glucoseverbrauches eine Mehranhäufung von Oxalsäure erzielt werden. Die auf die Kultur und auf den Verbrauch an Citronensäure bezogene Ausbeute ist von der Temperatur und dem Zeitpunkt des Zusatzes abhängig. Bei 43° C wurde für die Zeit nach dem fast völligen Glucoseverbrauch ein Einbau von C¹⁴ aus Gluconsäure-C¹⁴ (U) und Citronensäure-1,5-C¹⁴ in die Oxalsäure nachgewiesen. Unter diesen Bedingungen können also beide Säuren als C-Quelle für die Oxalsäureanhäufung dienen. Es wird vermutet, daß die Mehranhäufung von Oxalsäure durchweg mit einem Umsatz von Glucon- und Citronensäure u. a. in Oxalsäure verknüpft ist.

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Summary Aspergillus niger has been grown from conidia at 43, 30 or 10° C on a medium containing glucose (5%) as a source of carbon and KNO₃ (1%) as a source of nitrogen. Gluconic and citric acid have been added before and after glucose in the medium has been used up almost completely. By addition of each of the acids yield of oxalic acid related to flask could be increased. Yield of oxalic acid related to flask and to citric acid consumed depends on temperature and on time of addition. Incorporation of C¹⁴ from gluconate-C¹⁴ (U) and citric acid-1,5-C¹⁴ into oxalic acid has been demonstrated at 43° C for cultures having used up glucose almost completely. By this it is proofed that under these conditions gluconic and citric acid can be used as a source of carbon for accumulation of oxalic acid. It is suggested that increase of oxalic acid yield caused by addition of gluconic or citric acid is due to conversion of the two acids into oxalic acid (among other products) under all conditions investigated.

     

有机酸去除污泥重金属前后硝态氮和铵态氮浓度变化

研究了柠檬酸、草酸和乙酸溶液对污泥中重金属(Cd、Pb、Cu和Zn)的去除效果,以及处理前后析出液和污泥中硝态氮和铵态氮的浓度变化.结果表明,0.8mol.L-1柠檬酸溶液可去除污泥中76.0%的Pb和92.5%的Zn,是较好的重金属去除剂.污泥经有机酸处理后,有大量的硝态氮和铵态氮溶解于析出液中,与加入蒸馏水的对照处理相比,有机酸可大幅度增加析出液中铵态氮的含量,减少硝态氮含量.由于污泥处理过程中有其他形态的氮的转化,处理后污泥中仍含有较高浓度的硝态氮和铵态氮.0.5mol.L-1草酸处理的析出液中硝态氮和铵态氮浓度分别为2.8和888.1mg.L-1,且重金属含量不高,可作为较好的液体肥料进行回收利用.     

Differences between calcifuge and acidifuge plants in root exudation of low-molecular organic acids

The nature and quantity of low-molecular organic acids (LOAs) exuded by the roots of nine species of calcifuge and nine species of acidifuge wild plants from northern Europe were determined by ion chromatography. Particular attention was paid to differences between the calcifuge and the acidifuge species in the proportions of different LOAs in their root exudates. Great differences in mol% root exudation between the calcifuge and the acidifuge species were found in some acids. The calcifuge species exuded more acetic acid, the acidifuge species more oxalic acid and much more citric acid. In three calcifuge species, however, root exudation of oxalic acid was appreciable, whereas acetic acid exudation was low in these species. The phosphate- and Fe-solubilizing ability of eight LOAs in a rhizosphere limestone soil was also tested. Oxalic acid was the most efficient phosphate solubilizer and citric acid, by far, the most efficient Fe-solubilizer at the concentration (10 mM) tested. It might be hypothesized that acidifuge species use oxalate to solubilize phosphate and citrate to solubilize Fe, in limestone soil. The inability of calcifuge species to grow in limestone soil might, therefore, be due to low root exudation of these acids and, as a result, inability to solubilize phosphate and Fe in limestone soil.     

Oxalic acid production by citric acid-producing Aspergillus niger overexpressing the oxaloacetate hydrolase gene oahA

The filamentous fungus Aspergillus niger is used worldwide in the industrial production of citric acid. However, under specific cultivation conditions, citric acid-producing strains of A. niger accumulate oxalic acid as a by-product. Oxalic acid is used as a chelator, detergent, or tanning agent. Here, we sought to develop oxalic acid hyperproducers using A. niger as a host. To generate oxalic acid hyperproducers by metabolic engineering, transformants overexpressing the oahA gene, encoding oxaloacetate hydrolase (OAH; EC 3.7.1.1), were constructed in citric acid-producing A. niger WU-2223L as a host. The oxalic acid production capacity of this strain was examined by cultivation of EOAH-1 under conditions appropriate for oxalic acid production with 30 g/l glucose as a carbon source. Under all the cultivation conditions tested, the amount of oxalic acid produced by EOAH-1, a representative oahA-overexpressing transformant, exceeded that produced by A. niger WU-2223L. A. niger WU-2223L and EOAH-1 produced 15.6 and 28.9 g/l oxalic acid, respectively, during the 12-day cultivation period. The yield of oxalic acid for EOAH-1 was 64.2 % of the maximum theoretical yield. Our method for oxalic acid production gave the highest yield of any study reported to date. Therefore, we succeeded in generating oxalic acid hyperproducers by overexpressing a single gene, i.e., oahA, in citric acid-producing A. niger as a host.     

Effects of several organic acids on the feeding behavior of Tilapia nilotica

Automatic recording of the frequency of feeding ‘bites’ was used to evaluate the effects of several organic acids (citric, metacectonic, lactic, acetic, and oxalic) on the stimulatory feeding behavior of Tilapia nilotica. Some of these acids are added to food stocks to retard spoilage. The results showed that citric acid at a concentration of 10^?2 to 10^?6 m , metacetonic acid at 10^?4 to 10^?6 m , and lactic acid at 10^?2 to 10^?5 m stimulated feeding. Fish tended to avoid metacetonic acid at 10^?3 m and acetic acid at 10^?3 m . Acetic acid at 10^?5 m and oxalic acid at 10^?6 m had no significant effects on fish feeding.     

Highly Simple Deep Eutectic Solvent Extraction of Manganese in Vegetable Samples Prior to Its ICP-OES Analysis

In the present work, simple and sensitive extraction methods for selective determination of manganese have been successfully developed. The methods were based on solubilization of manganese in deep eutectic solvent medium. Three deep eutectic solvents with choline chloride (vitamin B4) and tartaric/oxalic/citric acids have been prepared. Extraction parameters were optimized with using standard reference material (1573a tomato leaves). The quantitative recovery values were obtained with 1.25 g/L sample to deep eutectic solvent (DES) volume, at 95 °C for 2 h. The limit of detection was found as 0.50, 0.34, and 1.23 μg/L for DES/tartaric, DES/oxalic, and DES/citric acid, respectively. At optimum conditions, the analytical signal was linear for the range of 10–3000 μg/L for all studied DESs with the correlation coefficient >0.99. The extraction methods were applied to different real samples such as basil herb, spinach, dill, and cucumber barks. The known amount of manganese was spiked to samples, and good recovery results were obtained.