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1.
1,5-bis(p-Hydroxybenzaldene)thiocarbohydrazone (BHBTZ) had been synthesized and used as a new kind of substrate for horseradish peroxidase (HRP). The experiment results showed that ascorbic acid (AsA) had strongly inhibiting effect on the BHBTZ-H(2)O(2)-HRP reaction system, so AsA had been spectrophotomericly determined as the inhibitor by enzymatic inhibition method. Under experimental conditions, the linear relationship between DeltaA(386) and AsA concentration was in the range of 0.82-18.0 microg ml(-1) with a detection limit of 0.245 microg ml(-1). The effect of interferences on AsA determination was investigated. The proposed method was successfully applied to the determination of AsA in tea drink.  相似文献   

2.
The photochemical formation of Fe(II) and hydrogen peroxide (H 2O 2) coupled with humic acids (HA) was studied to understand the significance of iron cycling in the photodegradation of atrazine under simulated sunlight. The presence of HA significantly enhanced the formation of Fe(II) and H 2O 2, and their subsequent product, hydroxyl radical ( (*)OH), was the main oxidant responsible for the atrazine photodegradation. During 60 h of irradiation, the fraction of iron presented as Fe(II) (Fe(II)/Fe(t)) decreased from 20-32% in the presence of the Fe(III)-HA complex to 10-22% after adding atrazine. The rate of atrazine photodegradation in solutions containing Fe(III) increased with increasing HA concentration, suggesting that the complexation of Fe(III) with HA accelerated the Fe(III)/Fe(II) cycling. Using fluorescence spectrometry, the quenching constant and the percentage of fluorophores participating in the complexation of HA with Fe(III) were estimated by the modified Stern-Volmer equation. Fourier transform infrared spectroscopy (FTIR) offered the direct evidence that Fe(III)-carboxylate complex could be formed by ligand exchange of HA with Fe(III). Based on all the information, a possible reaction mechanism was proposed.  相似文献   

3.
The kinetics of Cr(Ⅵ) reduction by sulfide in soil suspensions with various pHs, soil compositions, and Fe(Ⅱ) concentrations was examined using batch anaeroblc experimental systems at constant temperature. The results showed that the reaction rate of Cr(Ⅵ) reduction was in the order of red soil 〈 yellow-brown soil 〈 chernozem and was proportional to the concentration of HCl-extractable iron in the soils. Dissolved and adsorbed iron in soil suspensions played an important role in accelerating Cr(Ⅵ) reduction. The reaction involved in the Cr(Ⅵ) reduction by Fe(Ⅱ) to produce Fe(ⅡI), which was reduced to Fe(Ⅱ) again by sulfide, could represent the catalytic pathway until about 70% of the initially present Cr(Ⅵ) was reduced. The catalysis occurred because the one-step reduction of Cr(Ⅵ) by sulfide was slower than the two-step process consisting of rapid Cr(Ⅵ) reduction by Fe(Ⅱ) followed by Fe(Ⅲ) reduction by sulfide. In essence, Fe(Ⅱ)/Fe(Ⅲ) species shuttle electrons from sulfide to Cr(Ⅵ), facilitating the reaction. The effect of iron, however, could be completely blocked by adding a strong Fe(Ⅱ)-complexing ligand, 1,10-phenanthroline, to the soil suspensions. In all the experiments, initial sulfide concentration was much higher than initial Cr(Ⅵ) concentration. The plots of In e[Cr(Ⅵ)] versus reaction time were linear up to approximately 70% of Cr(Ⅵ) reduction, suggesting a first-order reaction kinetics with respect to Cr(Ⅵ). Elemental sulfur, the product of sulfide oxidation, was found to accelerate Cr(Ⅵ) reduction at a later stage of the reaction, resulting in deviation from linearity for the In c[Cr(Ⅵ)] versus time plots.  相似文献   

4.
The effect of sixteen metal ions: Al, Cd, Co(II), Cr(III), Cr(VI), Cu(II), Fe(III), Li, Mg, Mn(II), Mo(VI), Ni(II), Pb(II), Se(IV), V(V), and Zn on the mortality and infectivity ofHeterorhabditis bacteriophora were observed over a 96 hr period. All ions except Pb(II) even at naturally unrealistic concentrations did not cause the mortality of the nematodes. A weak vitalizing effect could eventually be observed with Mn(II), Mg, Fe(III) and Ni(II) (Table 1). However, such treatment generally lowered infectivity of the nematodes with respect to wax moth caterpillars.Galleria mellonella. This effect was particularly significant with Ni(II) and Pb(II).  相似文献   

5.
In spite of a lack of acute toxicity of single metal ions, in 96 hour laboratory tests there was a long term toxicity againstS. carpocapsae andH. bacteriophora nematodes. The 96 hour laboratory tests were carried out in order to prove possible synergistic and antagonistic interactions between pairs of metal ions. Thus, the pairs of ions were arranged from each of Al, Cd, Co(II), Cr(III), Cr(VI), Cu(II), Fe(III), Li, Mo(VI), Ni(II), Sc(IV), V(V) and Zn on one side and Mn(II) and Mg on the other. Mn(II) and Mg ions considerably reduced the nematode mortality and increased their infectivity againstGalleria mellonella caterpillars.  相似文献   

6.
The competing ligand exchange method was used to investigate the competitive binding of Ni(II) by Al(III) and Fe(III) in model aqueous solutions and freshwaters. Graphite furnace atomic absorption spectrometry and adsorptive cathodic stripping voltammetry were used to monitor the rate of uptake of the Ni by Chelex 100 chelating resin and dimethylglyoxime as the competing ligands, respectively. The results have revealed that Ni(II)–humate complexes were more labile in presence of the mixture of Al(III) and Fe(III), compared to the lability of the Ni(II)–humate complexes when only one of the two, Al(III) or Fe(III), was present. The environmental significance of this work is that in model solutions simulating freshwater containing humic substances and the target trace metal Ni(II) and cations, Al(III) and Fe(III), the competitive binding of Ni(II), Al(III) and Fe(III) by humic substances makes Ni(II)–humate complexes labile, releasing free Ni2+–aqua complex, which reported to be toxic.  相似文献   

7.
Lactic acid (LA) has been proposed to be an enhancer for dietary iron absorption, but contradictory results have also been reported. In the present study, fully differentiated Caco-2 cell monolayers were used to evaluate the effects of LA (1-50 mmol/L) on the cellular retention and transepithelial transport of soluble non-heme iron (as ferric nitrilotriacetate). Our data revealed a linear decline in Fe(III) retention with respect to the concentration of LA added. In the presence of 50 mmol/L LA, retention of Fe(III) and Fe(II) decreased 57% and 58%, respectively. In contrast, transfer of Fe(III) across the cell monolayer was doubled, while Fe(II) transfer across the cell monolayer decreased 35%. We conclude that LA reduces cellular retention and transepithelial transport of Fe(II) by Caco-2 cells in a dose-dependent manner. However, while LA also reduces retention of Fe(III) by Caco-2 cells, the transfer of Fe(III) across cell monolayers is enhanced, possibly due to effects on paracellular transport.  相似文献   

8.
Three continuous assays are described for lipoxygenase (LOX), hydroperoxide lyase (HPL) and alcohol dehydrogenase (ADH) in leek tissue. The catalytic activity of LOX showed significant difference (significance level 5%) between linolenic acid (9.43 x 10(-)(4) katals per kg protein) and linoleic acid (2.53 x 10(-)(4) katals per kg protein), and the pH-optimum of LOX was 4.5-5.5 against linoleic acid. The catalytic activity of HPL was statistically the same for 9-(S)-hydroperoxy-(10E,12Z)-octadecadienoic acid (1.01 x 10(-)(2) katals per kg protein) and 13-(S)-hydroperoxy-(9Z,11E)-octadecadienoic acid (7.69 x 10(-)(3) katals per kg protein). ADH showed a catalytic activity of 5.01 x 10(-)(4) katals/kg of protein toward hexanal. Model experiments with crude enzyme extract from leek mixed with linoleic acid or linolenic acid demonstrated differences in the amount of produced aroma compounds. Linoleic acid resulted in significantly most hexanal, heptanal, (E)-2-heptenal, (E)-2-octenal, (E,E)-2,4-decadienal, pentanol, and hexanol, whereas linolenic acid resulted in significantly most (E)-2-pentenal, (E)-2-hexenal, (E,Z)-2,4-heptadienal, (E,E)-2,4-heptadienal, and butanol. Leek LOX produced only the 13-hydroperoxide of linoleic acid and linolenic acid.  相似文献   

9.
Cattle manure vermicompost has been used for the adsorption of Al(III) and Fe(II) from both synthetic solution and kaolin industry wastewater. The optimum conditions for Al(III) and Fe(II) adsorption at pH?2 (natural pH of the wastewater) were particle size of ≤250?µm, 1 g/10 mL adsorbent dose, contact time of 4 h, and temperature of 25°C. Langmuir and Freundlich adsorption isotherms fitted reasonably well in the experimental data, and their constants were evaluated, with R 2 values from 0.90 to 0.98. In synthetic solution, the maximum adsorption capacity of the vermicompost for Al(III) was 8.35 mg g?1 and for Fe(II) was 16.98 mg g?1 at 25°C when the vermicompost dose was 1 g 10 mL?1, and the initial adjusted pH was 2. The batch adsorption studies of Al(III) and Fe(II) on vermicompost using kaolin wastewater have shown that the maximum adsorption capacities were 1.10 and 4.30 mg g?1, respectively, at pH?2. The thermodynamic parameter, the Gibbs free energy, was calculated for each system, and the negative values obtained confirm that the adsorption processes were spontaneous.  相似文献   

10.
Chromium (Cr)-contaminated soils pose a great environmental risk, with high solubility and persistent leaching of Cr(VI). In this study, hydroxysulfate green rust (GRSO4), with the general formula Fe(II)4Fe(III)2(OH)12SO4·8H2O, was evaluated for its efficiency in Cr(VI) stabilization via Cr(VI) reduction to Cr(III) in four representative Cr(VI)-spiked soils. The initial concentrations of phosphate buffer-extractable Cr(VI) (Cr(VI)b) in soils 1, 2, 3, and 4 were 382.4, 575.9, 551.3, and 483.7 mg kg-1, respectively. Reduction of Cr(VI) to Cr(III) by structural Fe(II) (Fe(II)s) in GRSO4 in all studied soils was fast, wherein the application of GRSO4 markedly decreased the amount of Cr(VI)b at the Cr(VI)b/Fe(II)s stoichiometric mole ratio of 0.33. The kinetics of Cr(VI) reduction by GRSO4 could not be determined as this reaction coincided with the release of Cr(VI) from soil during the experiment. The concentration of Cr(VI)b decreased, as the Cr(VI)b/Fe(II)s ratio decreased from 0.46 to 0.20, generally to below 10 mg kg-1. Back-transformation of the generated Cr(III) was examined in the presence of manganese oxide birnessite at the birnessite/initial Cr(III) mole ratio of 4.5. The results of batch tests showed that only 5.2% of the initial Cr(III) was converted to Cr(VI) after two months, while under field capacity moisture conditions, less than 0.05% of the initial Cr(III) was oxidized to Cr(VI) after six months. The results illustrated that remediation of Cr(VI)-contaminated soils would be fast, successful, and irreversible with an appropriate quantity of fresh GRSO4.  相似文献   

11.
The environmental degradation of a mixture of domoic acid (DA) and kainic acid (KA) in seawater with and without added transition metals is reported. The association constants for kainic acid with Fe (III) and Cu (II) were determined using (1)H nuclear magnetic resonance (NMR; K1,Fe(III) = 2.27 x 10(12), K2,Fe(III) = 8.99 x 10(8), K1,Cu(II) = 1.38 x 10(10), and K2,Cu(II) = 4.35 x 10(7)). The photochemical half-life of kainic acid has been determined to be significantly longer (40-100 h) than that of domoic acid in corresponding marine systems (12-34 h). The significance of this finding was highlighted by a comparison of the quantification of a mixture of kainic and domoic acids during photodegradation by liquid chromatography-tandem mass spectrometry (LC-MS/MS) techniques and the widely used competitive enzyme-linked immunosorbent assay (cELISA; Biosense Laboratories) method. The MS-based analysis showed that approximately 50% of the DA was photodegraded within 15 h. In contrast, the domoic acid cELISA assay reported that the concentration essentially remained unchanged over this period. The possibility of interference from naturally occurring kainic acid during cELISA measurements could lead to the overestimation of total domoic acid, especially if they occur in mixtures in sunlit waters.  相似文献   

12.
Strategy II plants respond to Fe stress by releasing a phytosiderophore and are believed to absorb Fe as Fe(III). Gallium(III) has chemical characteristics which have made it useful as a substitute for Fe(III) in biological systems. The objectives of our study were to: 1) determine if Ga(III) acts competitively to reduce Fe(III) uptake or otherwise substitutes for Fe(III) in barley (Hordeum vulgare L.), and 2) determine if the competition for Fe(III) between EDDHA or BPDS and barley further elucidates the form of Fe absorbed by barley. Chlorosis ratings, phytosiderophore production, and tissue Fe contents were indexes of Fe stress.

Gallium was absorbed and translocated by the plant both in the presence and absence of Fe, and slightly alleviated Fe stress in the absence of Fe. However, Fe uptake was not affected by the presence of Ga. Thus, Ga(III) did not seem to compete with Fe(III) for uptake. Increasing EDDHA in solution intensified chlorosis and phytosiderophore production and reduced root Fe, but did not reduce leaf Fe concentration. Increased BPDS had no influence on either chlorosis or leaf Fe, but did cause phytosiderophore production to increase and root Fe to decline. The presence of Fe(II) in solutions containing BPDS suggests a potential for reducing Fe(III) in the roots of barley.  相似文献   

13.
The toxicity of single metal ions: Al, Co(II), Cr(III), Cu(II), Fe(III), Mg, Mn(II), Mo(VI), Ni(II), Se(VI), V(V) and Zn and the following pairs of them: Al-Co, Al-Mg, Al-Mo, Al-Se, Al-Zn, Cr-Co, Cr-Mg, Cr-Mo, Cr-Se, Cr-Zn, Cu-Co, Cu-Mg, Cu-Mo, Cu-Se, Cu-Zn, Fe-Co, Fe-Mg, Fe-Mo, Fe-Se, Fe-Zn, Mn-Co, Mn-Mg, Mn-Mo, Mn-Se, Mn-Zn, Ni-Co, Ni-Mg, Ni-Mo, Ni-Se, Ni-Zn, V-Co, V-Mg, V-Mo, V-Se, V-Zn, Zn-Co, Zn-Mg, Zn-Mo, and Zn-Se on Daphnia magna was examined. The most prominent antagonism in the toxicity was observed in the following ion pairs: Al-Mo(VI), Cr(III)-Co(II), Cr(III)-Mg, Cr(III)-Mo(VI), Cr(III)-Se(VI), Cr(III)-Zn, Fe(III)-Se(VI), Mn(II)-Mg, Mn(II-Se(VI), Zn-Mg and Zn-Mo(VI). The strong synergism was found for the following ion systems: Cr(III)-Se(VI), Cr(III)-Zn, Fe(III)-Se(VI), Mn(II)-Zn, Mn(II)-Se(VI), Ni(II)-Co(II), Ni(II)-Mo(VI), Ni(II)-Se(VI), Ni(II)-Zn, V(V)-Co(II), V(V)-Mo(VI), V(V)- Se(VI), and V(V)-Zn. Synergism and antagonism in toxicity were dependent on water hardness as well as on the ion concentration. Adaptive procesess of the animals to the toxic environment could also be observed. Thus, the toxicity of the single ions and their pairs was not linear with respect to time.  相似文献   

14.
Fulvic acids have been isolated from a sandy loam (Countesswells series) and a clay soil (Tipperty series) and the products of their reaction with different amounts of iron over a range of pH from 0.5 to 11 analyzed by Mössbauer spectroscopy. Three distinct types of spectral component were detected at 77 K, a sextet from magnetically dilute Fe(III) and doublets from Fe(II) and Fe(III), the last arising from both organic complexes and poorly crystalline oxide species. In iron-fulvic acid mixtures the proportion of iron as Fe(II) increased as the pH was lowered from 5 to 1 by the addition of hydrochloric or nitric acid at all Fe to fulvic acid ratios (1:5 to 1:500). When the pH was lowered below 1 the amounts of Fe(II) decreased with the lower Fe to fulvic acid ratios, but increased with the higher ratios. The amounts of the Fe(III) component contributing to a doublet signal decreased with decreasing Fe:fulvic acid ratios. At low iron concentrations the iron appears to be strongly bound to the fulvic acid, but when the iron content is of the order of 1–2% uncomplexed Fe(III) species can be present. At pH > 2 these are hydrolysed ions which form poorly-crystalline oxides at higher pH. This was confirmed by analysis of spectra at 4.2 K. At pH < 2 free ions are present in solution. In solutions with high fulvic acid contents (greater than 100-fold excess) the reactions with iron are completely reversible, but in solutions with a lower proportion of fulvic acid to iron, where free ions are present, there is a lack of reversibility.  相似文献   

15.
《Journal of plant nutrition》2013,36(10-11):1909-1926
Abstract

Phenolic substances in the soil–plant system can be oxidized by metal ions, inorganic components, molecular oxygen as well as by phenoloxidases, giving rise to the formation of products of low or high molecular weight. Interactions of these products with iron, in both reduced and oxidized form, can affect the iron mobility in soil and rhizosphere, and thus its availability to plants. Here we report the results of a study on the complexing and reducing activity of the oxidation products from caffeic acid (CAF), obtained via electrochemical means, towards Fe(III) and Fe(II) in aqueous solution in the 3.0–6.0 pH range. The HPLC analysis of the filtered solutions after the CAF oxidation showed the formation of two main groups of products: (i) CAF oligomers formed through radicalic reactions which do not involve the double bond of the CAF lateral chain and (ii) products where this bond is involved. These oxidation products (COP) were found to interact with both Fe(III) and Fe(II) with formation of soluble and insoluble Fe(III)‐, and Fe(II)‐COP complexes. The COP were found to be able to reduce Fe(III) to Fe(II) mainly at pH < 4.0. A low redox activity was observed at pH ≥ 4.5 due to Fe(III) hydrolysis reactions as well as to the decrease in the redox potential of the Fe(III)/Fe(II) couple. Formation of hydroxy Fe(III)‐COP polymers occurs at pH > 3.5.  相似文献   

16.
Anaerobic benzene biodegradation was performed in batch experiments using Rhine River sediment as inoculum and amorphous Mn(IV) or Fe(III) as independent final electron acceptors. Benzene (4.5 μmol) was degraded in 80 and 710 days in batch experiments under Mn(IV) and Fe(III) reducing conditions, respectively. Highest benzene degradation rate, 0.07 μmol/day, was obtained under Mn (IV) reducing conditions, with soluble Mn(II) and CO2 recoveries of 71.5% and 93% regarding to the stoichiometric values, respectively. Likewise, benzene biodegradation was performed in a continuous column coupled to the reduction of Mn(IV). Efficiency of benzene biodegradation was up to 97% under steady state operation in a sediment column operated continuously for more than 160 days. The carbon dioxide and Mn(II) recoveries were 88% and 77%, respectively, of the theoretical ratio according to the stoichiometry for benzene biodegradation.  相似文献   

17.
Phytotoxicity of Thallium (Tl) in Culture Solution Part 2: Effects of Tl(III) on the Growth and Heavy Metal Contents of Pea and Field Bean Plants The effects of Tl(NO3)3 and Tl(III)EDTA on growth and heavy metal contents of pea plants (Pisum sativum L. cv. Aromata) and field bean plants (Vicia faba L. cv. Hangdown) were compared in hydroponic culture experiments. In the presence of Tl(NO3)3, the essential heavy metals were available to the plants in their ionic forms. When Tl(III)EDTA was present the essential heavy metals were available as chelated complexes. Dry matter production of the pea plants was inhibited to a greater extent by TI(II1)EDTA than by Tl(NO3)3. The distribution of TI within the plant was unaffected by the accompanying anion, however an increase of the TI content of the stems and the leaves was observed in the presence of TI(II1)EDTA. The micronutrients exhibited different interactions with TI(II1). In the presence of increasing concentrations of Tl(NO3)3 the Mn content of each organ and the Zn content of the roots were lowered, but the Zn content of the stems was increased. Increasing concentrations of TI(II1)EDTA resulted only in a decrease of the Mn content of the roots, but in an increase of the contents of Fe and Mn within the stems, and Fe, Mn, Zn, and Cu within the leaves. The increases may be due to concentration by growth inhibition. In contrast to pea plants, growth of field bean plants was inhibited only by TI(N03)). The field bean plants retained most of the TI within the roots independent of the TI compound in the solution. Chelation of TI(II1) resulted in higher TI contents of both the roots and the stems, but equal or reduced TI contents of the leaves. Whereas increasing concentrations of Tl(NO3)3 reduced the Mn content of each organ as well as the Zn content of the roots and the leaves, TI(II1)EDTA only reduced the Mn content of the roots.  相似文献   

18.
Pulse and steady state radiolysis techniques have been used to determine the bimolecular rate constants and to investigate the spectral nature of the intermediates and the degradation induced by hydroxyl radicals ((*)OH) with 1,3,5-triazine (T), 2,4, 6-trimethoxy-1,3,5-triazine (TMT), and 2,4-dioxohexahydro-1,3, 5-triazine (DHT) in aqueous medium. A competitive kinetic method with KSCN as the (*)OH scavenger was used to determine the rate constants for the reaction of (*)OH with T, TMT, and DHT. The bimolecular rate constants are 3.4 x 10(9), 2.06 x 10(8), and 1.61 x 10(9) dm(3) mol(-)(1) s(-)(1) respectively, for T, TMT, and DHT at pH approximately 6. The transient absorption spectra obtained from the reaction of (*)OH with T, TMT, and DHT have single absorption maxima at 320, 300, and 300 nm, respectively, and were found to undergo a second-order decay. The formation of TOH(*) [C(6)OH-N(5)-yl radical], TMTOH(*) [N(5)OH-C(6)-yl radical], and DHT(*) [C(6)-yl radical] is proposed from the initial attack of (*)OH with T, TMT, and DHT, respectively. A complete degradation of TMT (10(-3) mol dm(-3)) was obtained after absorbed doses of 5 kGy in N(2)O-saturated solutions and 16 kGy in aerated solutions. A similar degradation pattern was obtained with DHT in N(2)O-saturated solutions. Complete degradation was observed with an absorbed dose of 7 kGy. On the basis of the results from both pulse and steady state radiolysis, a possible reaction mechanism involving (*)OH-mediated oxidative degradation is proposed. A complete photodecomposition of DHT was also observed in the presence of ferric perchlorate using ultraviolet light at low pH. Photoinduced electron transfer between Fe(III) and DHT in the Fe(III)-DHT complex and subsequent formation of DHT(*) are proposed to be the major processes that lead to the complete degradation of DHT at pH 3.  相似文献   

19.
The free radical scavenging capacity (RSC) of antioxidants from sesame cake extract was studied using the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH(*)()) on a kinetic model. Pure lignans and lignan glycosides isolated from methanolic extract by preparative HPLC were used in the study. To understand the kinetic behavior better and to determine the RSC of sesame antioxidants, the second-order rate constant (k(2)) was calculated for the quenching reaction with [DPPH(*)] radical. The k(2) values of the sesame antioxidants were compared with those of butylated hydroxytoluene and alpha-tocopherol. The k(2) values for sesamol, sesamol dimer, sesamin, sesamolin, sesaminol triglucoside, and sesaminol diglucoside were 4.00 x 10(-)(5), 0.50 x 10(-)(5), 0.36 x 10(-)(5), 0.13 x 10(-)(5), 0.33 x 10(-)(5), and 0.08 x 10(-)(5) microM(-)(1) s(-)(1), respectively.  相似文献   

20.
Arsenic(As) contamination in soil and water poses a serious threat to the ecosystem health and human beings, and is of widespread concern. The main As species found in soil and water are arsenite As(Ⅲ) and arsenate As(Ⅴ). Because As(Ⅲ) is more toxic and often more mobile than As(Ⅴ), many remediation strategies aim to oxidize As(Ⅲ) to As(Ⅴ). In the environment, the reduction of As(Ⅴ) under anaerobic conditions is mainly mediated by microorganisms, but the oxidation of As(Ⅲ) under aerobic conditio...  相似文献   

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