Chromium Speciation in Water by Sorption on Calcite and Determination by Electrothermal Atomic Absorption Spectrometry

Abstract

A rapid, sensitive, and accurate method for the separation and speciative determination of chromium (Cr)(VI) and Cr(III) in water samples has been developed using sorption as the separation technique in conjunction with final determination by electrothermal atomic absorption spectroscopy (ETAAS). The present method, where granular calcite is used as selective sorbent, separates Cr(III) with retention values up to 99%, resulting in high accuracy determination of Cr(VI). Total Cr was likewise determined by ETAAS after an efficient reduction of Cr(VI) to Cr(III) using ascorbic acid as reducing agent, deriving Cr(III) concentration from the difference between total Cr and Cr(VI). The parameters of the separation technique, solution pH (4.5–5.5), solution flow rate through the calcite column (0.14–0.42 mL min^?1), and calcite column internal diameter (1.5–3.0 cm), were evaluated. Best results were achieved with pH of 5.5, flow rate of 0.42 mL min^?1, and column internal diameter of 1.5 cm. Optimum determination conditions were found using magnesium nitrate [Mg(NO₃)₂] as chemical modifier, pyrolysis, and atomization temperatures of 1400 and 2200°C, respectively. In such conditions, the detection limits (n=10) were 1.5 and 0.8 µg L^?1 for Cr(III) and Cr(VI), respectively.     

Application of Novel Fulvic Acid-Coated Magnetite Nanoparticles for CO<Subscript>2</Subscript><Superscript>−</Superscript>-Mediated Photoreduction of Cr(VI)

We here isolate fulvic acids from vermicompost to prepare and characterize novel fulvic acid-coated magnetite nanoparticles. UV-A irradiation of suspensions of the nanoparticles under different experimental conditions led to photo-reduction of Cr(VI). In anoxic conditions in the presence of formic acid, after 60 min of irradiation ca. 100% of Cr(VI) was reduced. Under these conditions, the carbon dioxide radical anions, CO₂ ^.- , mediated the photo-reduction of Cr(VI). However, the high reduction potential of Cr(VI) and the variety of reactive species generated upon UV-A irradiation make this nanomaterial also suitable for Cr(VI) photo-reduction also under aerobic conditions in the presence of formic acid or under anoxic conditions without the addition of formic acid. The possible photodegradation routes involved are discussed in detail.     

Chemical Behavior of U(VI) in the Presence of Soil Components

Soil components from different environments (forest (OF), semiarid (SZ), and sand (AS)) were separated from fulvic and humic substances, characterized by DRX, EDS(SEM), and zero-charge points were determined. The sorption of U(VI) by these materials was determined considering contact time, concentration of U(VI), pH, ionic strength, and presence of sodium chloride and humic acids. The time to reach the kinetic sorption equilibrium was ca. 1 min for the components of the SZ and AS soils, whereas those from OF required longer times. The zero-charge points of the materials indicate that in the experimental conditions, the surfaces of the materials are positively charged, as are uranyl ions. The sorption kinetic data were well fitted to the pseudo-second-order model, which indicates chemical sorption. The maximum sorption capacities for U(VI) obtained from data fitted to the Langmuir model of OF and SZ were 49 and 19.8 mg g^?1 respectively. Sorption isotherm data for AS were best fitted to the Freundlich model (q_e?=?5.4 mg g^?1). The maximum values of distribution coefficients (K_d) were 23?±?7 L kg^?1, 545?±?64 L kg^?1, and 1178?±?229 L kg^?1 for AS, SZ, and OF, respectively; these values may depend on pH, contact time, initial concentration of U(VI), and the composition of the materials. Sodium chloride in the aqueous solutions affects U(VI) sorption by the materials SZ and AS. The effect of humic acids depends on pH, only in acid media soluble humate complexes may be formed.     

Removal of Natural Organic Matter from River Water Using Potassium Ferrate(VI)

In this research, we have investigated the removal efficiency of natural organic matter (NOM) from river and stream water using potassium ferrate(VI). For the study, ferrate was added in 100-ml water sample mixed either with humic acid or with fulvic acid. The removal efficiency at the ferrate dose of 2–46 mg/l (as Fe) was 21–74% for 10 mg/l humic acid and 48–78% for 10 mg/l fulvic acid. NOM was more effectively removed either at lower pH or at higher temperature. The removal performance by ferrate was comparable to that by traditional coagulants (i.e., alum, FeSO₄·7H₂O, and FeO(OH)). In addition, the removal rate of humic acid using traditional coagulants was improved by pretreatment with a very small dose of ferrate. The reaction between ferrate and humic acid was completed within 60 s, while showing first-order kinetic, and then reached a steady state.     

Inorganic pyrophosphatase activity of soils

A simple method to assay inorganic pyrophosphatase activity in soils is described. It involves extraction and colorimetric determination of the orthophosphate (Pi) released when 1 g soil is incubated with buffered (pH 8) pyrophosphate (PPi) solution at 37°C for 5 h. The 1 n H₂SO₄ used to extract Pi gives quantitative recovery of Pi added to soils, and the colorimetric method used to determine the Pi extracted in the presence of PPi is specific for Pi. The inorganic pyrophosphatase activity of the six soils studied ranged from 50 to 450 μg Pi released·g^?1 soil·5 h^?1. Steam sterilization (121°C for l h), formaldehyde, fluoride, oxalate, and carbonate inhibited and toluene, Na⁺, K⁺, NH⁺₄, Cl^?, NO^?₃, NO^?₂, SO^2?₄, and EDTA had no effect on the activity of this enzyme in soils. The initial rates of Pi released obeyed zero-order kinetics. The temperature dependence of the rate constant conformed to the Arrhenius equation up to the point of enzyme inactivation (55°C). The activation energy of pyrophosphatase activity of the six soils studied ranged from 32.5 to 43.2 (av 36.1) kJ·mole^?1. Application of the three linear transformations of the Michaelis-Menten equation indicated that the K_m values of PPi for pyrophosphatase in four soils ranged from 20 to 51 (avg. 35) mM and that the V_max ranged from 130 to 830 (av 500) μg Pi released g^?1 soil·5 h^?1. Studies of other properties of inorganic pyrophosphatase activity in soils are reported.     

Kinetics of the reaction between the hydroxyl radical and organic matter standards from the International Humic Substance Society

Purpose

The objective of this study was to evaluate the effect of the physicochemical properties of five dissolved organic matter (DOM) isolates on their reactivity with the hydroxyl radical (HO·) in water.

Materials and methods

Five DOM isolates were purchased from the International Humic Substance Society (IHSS). Weight average molecular weight (M _W) of these samples was quantified using size exclusion chromatography based on polyethylene glycols as reference standards. Functional group and elemental composition of the DOM samples were available from the IHSS website. Room temperature rate constants were measured using electron pulse radiolysis.

Results and discussion

Five IHSS standards were examined in this study: two soil organic and three aquatic organic matters. The composition varied from samples that had primarily aliphatic carbon (Pony Lake fulvic acid) to mostly aromatic carbon moieties (Elliot Soil humic acid). The M _W values of the five samples ranged from 2,400 to 4,100 Da, with an average value of 3,060 Da. Second-order reaction rate constants between DOM and HO· (k _DOM-HO·) were measured using thiocyanate competition kinetics, giving values ranging from 1.21 to 10.36?×?10⁸ M_C ^?1?s^?1. The k _DOM-HO· values were not found to correlate with either M _W or the aliphatic-aromatic carbon ratio, which is consistent with previous reports looking at natural organic matter (NOM), but is different to reports on size-fractionated (ultrafiltration through 15–1 kDa membranes) effluent organic matter (EfOM). We attribute this difference to the larger molecular weight distributions in size-fractionated EfOM compared to NOM.

Conclusions

The k _DOM-HO· values in this study ranged over a factor of 10, suggesting that hydroxyl radical reactivity does depend on the sample composition; however, no major correlation was found between the measured reactivity and bulk physicochemical properties of DOM.     

Formation constants of cu2+ complexes with humic and fulvic acids

Formation constants for Cu²⁺ complexes with humic and fulvic acids were determined by a modification of the well-known Bjerrum potentiometric titration method. Highly stable complexes were formed with formation constants of the order of those observed for synthetic polycarboxylic acids. Overall formation constants for a two-step process (B₂) ranged from 2.5 · 10^?4 to 7.9 · 10^?3.     

内源性土壤苏云金杆菌(BRC-ZYR2)对含氧铬还原的影响研究

Chromium（Cr） may cause losses in the yield of field plant, which is one of the favorite habitats of Bacillus thuringiensis（Bt）. The purposes of our study were to assess the Cr（VI）-resistance and Cr（VI）-reducing abilities of an indigenous soil isolate of Bt and to determine the factors governing Cr（VI） reduction. Towards this end a novel dichromate-reducing Bt BRC-ZYR2, characterized with insecticidal crystal proteins（ICPs）, was isolated from a uranium deposit. Minimum inhibitory concentrations（MICs） of Cr（VI） were determined by broth dilution method and the concentrations of Cr（VI） and total Cr in the supernatant were quantified colorimetrically using 1,5-diphenylcarbazide（DPC） reagent and a mixture of sulfuric-nitric acids, respectively. The isolate contained five ICP genes（cry1Ba, cry1 Bb, cry1Be/cry1 Bf, cry9 Ca and cry9Da） and exhibited a high level of Cr（VI） resistance with MICs of 150 mg L-1at pH 7.0 and 30？C, and 500 mg L-1under optimal conditions（pH 9.0 and 40？C）. The total Cr concentration was similar to initial concentration of Cr（VI） under the optimal condition, suggesting that the essential removal of the Cr（VI） was dependent on Bt reduction. Under optimal conditions, the initial Cr（VI） concentrations from 25 to 75 mg L-1significantly decreased in 24 h after incubation. Addition of Mn2＋, Co2＋, Mo2＋and Cu2＋activated Bt-mediated Cr（VI） reduction, while Zn2＋, Ni2＋and glucose were found to inhibit the reduction. Our results indicated that this isolate could be a promising biopesticide with the potential for both insect biocontrol and Cr bioremediation in the field.     

Hexavalent Chromium Removal by Candida sp. in a Concentric Draft-Tube Airlift Bioreactor

The main purpose of this work was to conduct a kinetic study on cell growth and hexavalent chromium [Cr(VI)] removal by Candida sp. FGSFEP in a concentric draft-tube airlift bioreactor. The yeast was batch-cultivated in a 5.2-l airlift bioreactor containing culture medium with an initial Cr(VI) concentration of 1.5 mM. The maximum specific growth rate of Candida sp. FGSFEP in the airlift bioreactor was 0.0244 h^?1, which was 71.83% higher than that obtained in flasks. The yeast strain was capable of reducing 1.5 mM Cr(VI) completely and exhibited a high volumetric rate [1.64 mg Cr(VI) l^?1 h^?1], specific rate [0.95 mg Cr(VI) g^?1 biomass h^?1] and capacity [44.38 mg Cr(VI) g^?1 biomass] of Cr(VI) reduction in the airlift bioreactor, with values higher than those obtained in flasks. Therefore, culture of Candida sp. FGSFEP in a concentric draft-tube airlift bioreactor could be a promising technological alternative for the aerobic treatment of Cr(VI)-contaminated industrial effluents.     

Influence of humic substances on photolysis of divalent mercury in aqueous solution

Mercury (II) solutions were irradiated by a simulated sunlight in the presence of humic acid (HA) or fulvic acid (FA). Results show that, under the experimental conditions and the FA and HA chosen, less than 20% of the Hg in solution was photolysed with a rate of (1.63±0.29)×10^?2 s^?1 (n=23) and the rest of (2.38±0.40)×10^?4 s^?1 (n=23) depending on the substitutes of humic substances to which Hg were bond. The sunlight photolysis lifetimes were estimated to be 4 and 250 sunlight hours respectively under summer conditions at Stockholm latitude.     

Complexation of Cu2+ and Pb2+ by peat and humic acid

The binding of metal to humic substances is problematical. The approaches for studying metal binding to organic matter are briefly reviewed. Ion-selective electrodes (Cu²⁺ and Pb²⁺) were used to measure metal complexation by a whole peat and an extracted humic acid (HA) fraction. Scatchard plots and calculation of incremental formation constants were used to obtain values for the binding constants for the metals onto both peat and HA. Both the peat and the humic acid had a larger maximum binding capacity for Pb²⁺ than for Cu²⁺ (e.g. at pH = 5 HA gave 0·188 mmol Cu²⁺ g^?1 and 0·564 mmol Pb²⁺ g^?1: peat gave 0·111 mmol Cu²⁺ g^?1 and 0·391 mmol Pb²⁺ g^?1). Overall, the humic acid had a larger metal binding capacity, suggesting that extraction caused conformational or chemical changes. The binding constants (K₁) for Cu²⁺ increased with increasing pH in both peat and humic acid, and were larger in the peat at any given pH (e.g. at pH = 5 HA gave log K₁= 2·63, and peat gave log K¹= 4·47 for Cu²⁺). The values for Pb²⁺ showed little change with pH or between peat and humic acid (e.g. at pH = 5 HA gave log K¹= 3·03 and peat gave log K¹= 3·00 for Pb²⁺). In the peat, Cu²⁺ may be more able to bind in a 2:1 stoichiometric arrangement, resulting in greater stability but smaller binding capacity, whereas Pb²⁺ binds predominantly in a 1:1 arrangement, with more metal being bound less strongly. Whole peat is considered to be more appropriate than an extracted humic acid fraction for the study of heavy metal binding in organic soils, as this is the material with which metals introduced into an organic soil would interact under natural conditions.     

Treatment of Cr(VI)-spiked soils using sulfur-based amendments

The objective of this research was to assess the hexavalent chromium (Cr(VI)) reducing efficiency of sulfur-based inorganic agents including calcium polysulfide (CPS), iron sulfide (FeS), pyrite (FeS₂) and sodium sulfide (Na₂S) in three soils. An alkaline soil (soil 1), a neutral soil (soil 2) and a slightly acid soil (soil 3) constituted the investigated soils. The soils were spiked with two levels of Cr(VI) (100 and 500 mg Cr(VI) kg^?1 soil) and incubated at field capacity (FC) for one month. Then, CPS, FeS, FeS₂ and Na₂S were added at 0, 5 and 10 g kg^?1 and the concentrations of exchangeable Cr(VI) were measured after 0.5, 4, 48 and 168 h in a batch experiment. The pH and organic carbon content of the soils played predominant role in Cr(VI) self-reduction by the soil itself. Complete self-reduction of Cr(VI) from soils 1, 2 and 3 was achieved at maximum Cr(VI) levels of 1, 50 and 500 mg kg^?1, respectively. Therefore, the concentration of Cr(VI) should not exceed the given levels in order to ensure that Cr(VI) is not released into the environment from contaminated sites. Moreover, decreasing pH in the alkaline soil caused significant increase of Cr(VI) reducing efficiency. Na₂S, CPS and FeS, in contrast to FeS₂, were efficient Cr(VI) reducing agents in all three soils. For all added amendments the following order of Cr(VI) reducing capacity was observed: Na₂S > CPS > FeS > FeS₂ in soil 1, Na₂S ? CPS ~ FeS > FeS₂ in soil 2 and Na₂S ? FeS > CPS ~ FeS₂ in soil 3.     

The role of amino acids and nucleic bases in turnover of nitrogen and carbon in soil humic fractions

Incorporation of labelled ¹⁵N and ¹⁴C amino acids and nucleic bases into soil humus fractions as well as humus turnover was investigated under field conditions. The dynamics of ¹⁵N and ¹⁴C incorporation into organic matter was characterized by the following main steps: rapid incorporation of the labelled substance prevailing for the first 1–3 weeks, and decomposition of included labelled fragments prevailing beyond one month after substance addition. The annual turnover rates of N and C in humus fractions due to incorporation of amino acids and nucleic bases were calculated. The turnover rate of N in humus is two to three times that of C. The contribution of amino acids to organic matter generation is about twice as great as that of nucleic bases and other N-containing organic substances. This indicates the important role of amino acids in the humification process and humus turnover. Turnovers of humic acids (0·002 year^?1 for C and 0·02 for N) are the most rapid of humic fractions investigated, and humin is characterized by the slowest turnover (0·0002 year^?1 for C and 0·007 for N). There are no significant differences in the turnover rates of fulvic acid fractions (0·0002 year^?1 for C) with different molecular weight.     

Isolation and characterization of multi-potential Rhizobium strain ND2 and its plant growth-promoting activities under Cr(VI) stress

Soil contaminated by chromium (Cr) is a major concern for sustainable agriculture. Considering this as a basis, the present study was designed to isolate Cr(VI)-reducing and plant growth-promoting bacterial strain from contaminated sampling sources. In this study, Rhizobium strain ND2 was isolated from the root nodules of Phaseolus vulgaris grown in leather industrial effluent contaminated soil. The strain ND2 exhibited strong resistance to different heavy metals and reduced 30 and 50 µg ml^?1 concentrations of Cr(VI) completely after 80 and 120 h of incubation, respectively, as well as chromium adsorption and immobilization were confirmed by scanning electron microscopic equipped with energy X-ray spectroscopy. In addition, the strain produced 21.73 and 36.86 µg ml^?1 of indole-3-acetic acid at 50 and 100 µg ml^?1 of L-tryptophan supplimentations, respectively. Strain ND2 positively affected the exo-polysaccharide, ammonia, protease and catalase production and stimulated root length of various test crops under Cr(VI) stress. Moreover, Rhizobium strain ND2 has the potential to colonize the diverse agricultural crops. Thus, the present findings strongly suggested that the multipotential properties of ND2 could be exploited for bioremediation of contaminated sites with Cr(VI) as well as potential bio fertilizer for enhancing the agricultural productivity.     

Development of Analytical Procedure for the Determination of Exchangeable Cr(VI) in Soils by Anion-exchange Fast Protein Liquid Chromatography with Electrothermal Atomic Absorption Spectrometry Detection

Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄–K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l^?1), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l^?1 and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g^?1 of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g^?1.     

Soil organic carbon storage and quality are impacted by corn cob biochar application on a tropical sandy loam

Purpose

Humic substances, which are integral components of total organic carbon (TOC), influence soil quality. The study aimed to investigate whether humic and non-humic fractions exhibit early, consistent, and measurable changes and affect TOC sensitivity and storage in a tropical sandy loam soils amended with corn cob biochar.

Materials and methods

There were four treatments with four replicates established in a randomized complete block design. Composite soil samples were taken from plots without biochar (CT), from plots incorporated with 15 t biochar ha^?1 (BC-15), and 30 t biochar ha^?1 without or with phosphate fertilizer (BC-30 and BC-30+P). The TOC, and humin, humic acid (HA), and fulvic acid (HA) fractions of soil organic carbon were determined for each treatment. The optical densities (400–700 nm) were measured on the soil-free extracts by spectrophotometry; the densities measured at 465 and 665 nm were used to calculate the E₄₆₅/E₆₆₅ ratios.

Results and discussion

The BC-30 and BC-30+P plots recorded the highest TOC, humin, humic acid (HA), and fulvic acid (FA) contents with respect to the lowest in the CT. The total exchangeable carbon stratification was significantly higher in all the biochar-treated plots relative to the CT. Spectral analysis showed higher values of E₄₆₅/E₆₆₅ (5.02 and 5.15) in the CT and BC-15-treated soils, respectively, compared with the BC-30 and BC-30+P-amended soils with E₄₆₅/E₆₆₅ ratios of 2.76 and 2.98, respectively.

Conclusions

Corn cob biochar applied to a tropical sandy loam:

? increased the concentrations of HA and FA and led to increased stratification of TOC, with a stronger effect on HA compared with FA;

? significantly lowered E₄₆₅/E₆₆₅ at the high biochar application rate of 30 t ha^?1, implying the dominance of high molecular weight humic acid-like substances, and increased degree of aromaticity of the TOC.

     

Influence of natural and synthetic humic substances on the activity of urease

The activity of a purified urease, obtained from Bacillus pasteurii, was inhibited by humic and fulvic acids obtained from an agricultural soil. Enzyme kinetic studies showed that the humic substances affected the affinity of the enzyme for its substrate (K_m) and the maximum velocity of the reaction (V_max). The V_max was inhibited to the same extent by both humic (HA) and fulvic (FA) acids, the precise effect depending on the pH and concentration of humic substance. At pH 4.0, HA concentrations of 25 pg cm^?3 and 10 μg cm^?3 inhibited the V_max by 38.5% and 20% respectively. HA and FA had similar effects on the K_m but in this case the lowering of the affinity of the enzyme for its substrate was not concentration dependent in the range 0–25 μg cm^?3 of humic substance. Typically, the affinity was decreased from a K_M of 50 mM in the control to 67 mM in the presence of HA and FA. The effects were not due primarily to the ash or N contents of the humic substances because de-ashed humic acid and synthetic model humic (made from catechol, guaiacol, pyrogallol, resorcinol and protocatechuic acid) and fulvic acid (made from polymaleic acid), containing virtually no ash or N, were equally as effective. The effect was not related to the phenolic monomers which, before polymerization, had no effect on urease activity.     

Improvement of biochar capability in Cr immobilization via modification with chitosan and hematite and inoculation with Pseudomonas putida

ABSTRACT

Modification of biochar using chitosan and hematite made the biochar product more effective for hexavalent chromium (Cr (VI)) reduction in contaminated soils. Release experiment was conducted to examine Cr (VI) reduction in different treatments (control, unmodified biochar and two modified biochars with chitosan or hematite). The results indicated that the application of all treatments significantly decreased the release rate of Cr in comparison to the control treatment. Chitosan-modified biochar application increased Cr (VI) reduction from 28.53% (biochar) to 46.23%. In the case of hematite-modified biochar, it increased Cr (VI) reduction from 28.55% (biochar) to 38.95%. Two kinetic equations including pseudo-first-order and pseudo-second-order models employed to describe the time-dependent Cr release data. Between the kinetic equations estimated, the pseudo-second order best fitted to experimental data. In the presence of Pseudomonas putida, cumulative Cr release rate decreased by 2.38 mg kg^?1 (50.29%) in hematite–biochar and 1.768 mg kg^?1 (39.73%) in unmodified biochar as compared with control (4.43 mg kg^?1). According to results reported herein, modification of biochar with chitosan or hematite is promising since made biochar more effective in removing Cr from Cr-polluted calcareous soils.     

氮磷用量对豫北地区小麦产量的交互效应研究

采用盆栽试验研究了氮磷不同用量与配比对小麦产量的影响,分析了产量与小麦不同生育期各生理指标之间的关系。结果表明:氮磷施用存在最佳配比,当氮磷肥用量分别相当于220kg(N)·hm-2和160kg(P2O5)·hm-2时,小麦产量最高。小麦产量与根系活力、开花期酸性磷酸酶活性和拔节期硝酸还原酶活性密切相关,根系活力、酸性磷酸酶和硝酸还原酶活性与小麦吸收的氮磷总量呈显著正相关关系。根系活力、酸性磷酸酶和硝酸还原酶活性随着磷肥用量增加而提高,随着氮肥用量增加先提高后下降,因此过多的氮肥施用通过降低小麦根系活力、酸性磷酸酶和硝酸还原酶活性等,减少小麦对氮磷吸收,进而降低产量。     

Growth, Net Photosynthetic Rate, Nutrient Status and Secondary Xylem Anatomical Characteristics of Fagus Crenata Seedlings Grown in Brown Forest Soil Acidified with H2SO4 Solution

Dry matter production, net photosynthetic rate, leaf nutrient status and trunk anatomical characteristics of Fagus crenata seedlings grown in brown forest soil acidified by adding H₂SO₄ solution were investigated. The soil acidification leaded to decreased (Ca+Mg+K)/Al molar ratio in the soil solution. Dry mass per plant of the seedlings grown in the soil treated with H⁺ at 120 mg·L^?1 was significantly reduced compared with the control value at 0 mg·L^?1. When net photosynthetic rate was reduced in the seedlings grown in the soil treated with H⁺ at 120 mg·L^?1, the carboxylation efficiency and maximum net photosynthetic rate at saturated CO₂-concentration were lower than the control values. The addition of H⁺ to the soil at 120 mg·L^?1iinduced a reduction in the concentration of Ca in the leaf. By contrast, the concentration of Al in the leaf was increased with increasing the amount of H⁺ added to the soil. The annual ring formed in the seedlings grown in the soil treated with H⁺ at 120 mg·L^?1 was significantly narrower than that at 0 (control), 10, 30, 60 or 90 mg·L^?1. Based on the results obtained in the present study, we conclude that Fagus crenata is relatively sensitive to a reduction in the (Ca+Mg+K)/Al molar ratio of soil solution compared with Picea abies.