Studies on hexavalent chromium biosorption by chemically-treated biomass of Ecklonia sp

The biomass of the brown seaweed, Ecklonia sp., is capable of reducing Cr(VI) to Cr(III). However, very little is known about the mechanism of Cr(VI) reduction by the biomass. The aims of the present investigation were to enhance the Cr(VI)-reducing capacity of the biomass using various chemical treatments and to elucidate the mechanisms governing Cr(VI) reduction. Among the various chemical treatments, acid-treatment showed the best performance with regards the improvement of Cr(VI) removal from the aqueous phase, while organic solvent-treatment significantly improved the removal efficiency of total Cr in the equilibrium state. Based on FTIR study, the biomass was subjected to chemical modification of its amino and carboxyl groups, to examine their roles in the Cr(VI) removal from the aqueous phase. Methylation of the amino group significantly decreased the Cr(VI) removal rate, but amination of the carboxyl group significantly increased the Cr(VI) removal rate. Meanwhile, esterification of the carboxyl group and carboxylation of the amino group decreased the Cr(VI) removal rate, but the former showed a more negative effect than the latter. These findings indicated that the amino and carboxyl groups take part in the Cr(VI) removal from the aqueous phase. In conclusion, mechanisms for direct and indirect Cr(VI) removal are proposed, and some aspects for the application of this biomass to Cr(VI) detoxification are discussed.     

Comparative study of chromium biosorption by red, green and brown seaweed biomass

Dried biomass of the macroalgae Fucus vesiculosus and Fucus spiralis (brown), Ulva spp. (comprising Ulva linza, Ulva compressa and Ulva intestinalis) and Ulva lactuca (green), Palmaria palmata and Polysiphonia lanosa (red) were studied in terms of their chromium biosorption performance. Metal sorption was highly pH dependent with maximum Cr(III) and Cr(VI) sorption occurring at pH 4.5 and pH 2, respectively. Extended equilibrium times were required for Cr(VI) binding over Cr(III) binding (180 and 120min, respectively) thus indicating possible disparities in binding mechanism between chromium oxidation states. The red seaweed P. palmata revealed the highest removal efficiency for both Cr(III) and Cr(VI) at low initial concentrations. However, at high initial metal concentrations F. vesiculosus had the greatest removal efficiency for Cr(III) and performed almost identically to P. lanosa in terms of Cr(VI) removal. The Langmuir Isotherm mathematically described chromium binding to the seaweeds where F. vesiculosus had the largest q(max) for Cr(III) sorption (1.21mmol g(-1)) and P. lanosa had the largest Cr(VI) uptake (0.88mmol g(-1)). P. palmata had the highest affinity for both Cr(III) and Cr(VI) binding with b values of 4.94mM(-1) and 8.64mM(-1), respectively. Fourier transform infrared analysis revealed interactions of amino, carboxyl, sulphonate and hydroxyl groups in chromium binding to Ulva spp. The remaining seaweeds showed involvement of these groups to varying degrees as well as ether group participation in the brown seaweeds and for Cr(VI) binding to the red seaweeds.     

Enhanced adsorption of hexavalent chromium by a biochar derived from ramie biomass (<Emphasis Type="Italic">Boehmeria nivea</Emphasis> (L.) Gaud.) modified with β-cyclodextrin/poly(L-glutamic acid)

This paper explored biochar modification to enhance biochar’s ability to adsorb hexavalent chromium from aqueous solution. The ramie stem biomass was pyrolyzed and then treated by β-cyclodextrin/poly(L-glutamic acid) which contained plentiful functional groups. The pristine and modified biochar were characterized by FTIR, X-ray photoelectron spectroscopy, specific surface area, and zeta potential measurement. Results indicated that the β-cyclodextrin/poly(L-glutamic acid) was successfully bound to the biochar surface. Batch experiments were conducted to investigate the kinetics, isotherm, thermodynamics, and adsorption/desorption of Cr(VI). Adsorption capacities of CGA-biochar were significantly higher than that of the untreated biochar, and its maximum adsorption capacity could reach up to 197.21 mg/g at pH 2.0. Results also illustrated that sorption performance depended on initial solution pH; in addition, acidic condition was beneficial to the Cr(VI) uptake. Furthermore, the Cr(VI) uptake was significantly affected by the ion strength and cation species. This study demonstrated that CGA-biochar could be a potential adsorbent for Cr(VI) pollution control.     

Cr(VI) uptake mechanism of Bacillus cereus

In this study, we investigated the Cr(VI) uptake mechanism in an indigenous Cr(VI)-tolerant bacterial strain -Bacillus cereus through batch and microscopic experiments. We found that both the cells and the supernatant collected from B. cereus cultivation could reduce Cr(VI). The valence state analysis revealed the complete transformation from Cr(VI) into Cr(III) by living B. cereus. Further X-ray absorption fine structure and Fourier transform infrared analyses showed that the reduced Cr(III) was coordinated with carboxyl and amido functional groups from either the cells or supernatant. Scanning electron microscopy and atomic force microscopy observation showed that noticeable Cr(III) precipitates were accumulated on bacterial surfaces. However, Cr(III) could also be detected in bacterial inner portions by using transmission electron microscopy thin section analysis coupled with energy dispersive X-ray spectroscopy. Through quantitative analysis of chromium distribution, we determined the binding ratio of Cr(III) in supernatant, cell debris and cytoplasm as 22%, 54% and 24%, respectively. Finally, we further discussed the role of bacterium-origin soluble organic molecules to the remediation of Cr(VI) pollutants.     

A comparative study on metal sorption by brown seaweed

This study compared the sorption of Ag, Cd, Co, Cd, Mn, Ni, Pb and Zn by a Ca-treated Sargassum biomass at pH 5.0, under low and high ionic strength (IS) conditions. The sorption isotherms of As [As(V)] and Cr [Cr(III) and Cr(VI)] were also determined at low IS. The isotherm data for the eight cationic metals and Cr(III) were well fitted by Langmuir equations. Generally, the maximum metal uptake (Umax) followed: Cr(III) > Pb approximately Cu > Ag approximately Zn approximately Cd > Ni approximately Mn approximately Co > Cr(VI) > As(V) at low IS and Pb > Cu > Co > Mn approximately Cd > Zn approximately Ag > Ni at high IS. As(V) did not bind to the seaweed at pH 5.0. The results indicated that sorption of Pb was not affected by the increasing IS, though the percentage of free Pb ions in the water was greatly reduced as predicted by the speciation model. High IS lowered Umax by 10-36% (except Co and Pb), and lowered the affinity constant of the metal by 33-91% for all cationic metals, as compared to low IS. Moreover, the removal efficiency of the cationic metals and Cr decreased exponentially with initial metal concentrations and was lower at high IS. Ion-exchange was the mechanism responsible for the cationic metal sorption onto the seaweed, and Na ion interfered with the cationic metal binding through electrostatic interaction. In conclusion, this study showed the differential binding capacity of the Sargassm biomass for different metals and oxidation states and the differential effects of IS. According to the present results, Sargassum may be considered a good biosorbent for cationic metals (especially Pb) in both low and high-salt containing wastewater.     

Feasibility of using microalgal biomass cultured in domestic wastewater for the removal of chromium pollutants

The feasibility of obtaining and using the biomass of a microalga, Chlorella miniata, from domestic wastewater (DW) cultures for the removal of chromium(III) [Cr(III)] and chromium(VI) [Cr(VI)] was compared with that from commercial Bristol medium (BM). Results showed that Chlorella miniata cultured in DW under 16-8 hours light-dark cycle [DW(16-8)] had similar growth to that in BM [BM(16-8)], but these two biomass had different biochemical compositions, and the former one had lower carbohydrate and higher protein content. When cultured in domestic wastewater, a higher biomass was obtained under continuous illumination [DW(24-0)], and the cells had higher carbohydrate and lower protein concentrations than that of DW(16-8). The spectra of the Fourier transform infrared spectrometer revealed that the functional groups on the surface of the three kinds of biomass--DW(16-8), DW(24-0), and BM(16-8)--were comparable, except an additional peak at 1731 cm(-1) was found in the biomass cultured in domestic wastewater, which was probably the result of bacterial contamination. Although biochemical differences were found among the three kinds of microalgal biomass, similar biosorption performances to chromium pollutants were recorded, with approximately 75% Cr(III) and 100% Cr(VI) removed at equilibrium in Cr(III) and Cr(VI) experiments, respectively, when dead biomass was used as a biosorbent. Therefore, it is possible to culture Chlorella miniata in domestic wastewater and use the biomass for the removal of chromium pollutants.     

Chromate reduction on humic acid derived from a peat soil--exploration of the activated sites on HAs for chromate removal

Humic substances are a major component of soil organic matter that influence the behavior and fate of heavy metals such as Cr(VI), a toxic and carcinogenic element. In the study, a repetitive extraction technique was used to fractionate humic acids (HAs) from a peat soil into three fractions (denoted as F1, F2, and F3), and the relative importance of O-containing aromatic and aliphatic domains in humic substances for scavenging Cr(VI) was addressed at pH 1. Spectroscopic analyses indicated that the concentrations of aromatic C and O-containing functional groups decreased with a progressive extraction as follows: F1>F2>F3. Cr(VI) removal by HA proceeded slowly, but it was enhanced when light was applied due to the production of efficient reductants, such as superoxide radical and H(2)O(2), for Cr(VI). Higher aromatic- and O-containing F1 fraction exhibited a greater efficiency for Cr(VI) reduction (with a removal rate of ca. 2.89 mmol g(-1) HA under illumination for 3 h). (13)C NMR and FTIR spectra further demonstrated that the carboxyl groups were primarily responsible for Cr(VI) reduction. This study implied the mobility and fate of Cr(VI) would be greatly inhibited in the environments containing such organic groups.     

Transient behavior of heavy metals in soils during electrokinetic remediation

This paper presents a systematic bench-scale laboratory study performed to assess the transient behavior of chromium, nickel, and cadmium in different soils during electrokinetic remediation. A series of laboratory electrokinetic experiments was conducted using two different clayey soils, kaolin and glacial till. For each type of soil, four electrokinetic experiments with 1, 2, 4, and 10 d of treatment time were performed. In all tests, the contaminants were Cr(VI), Ni(II), and Cd(II) combined in the soil. A geochemical assessment was performed using the geochemical model MINEQL(+) to determine the partitioning of the heavy metals in soils as precipitated, adsorbed, and aqueous forms. Results showed that in kaolin, the extent of Ni(II) and Cd(II) migration towards the cathode increased as the treatment time increased. Unlike kaolin, in glacial till treatment time had no effect on nickel and cadmium migration because of its high buffering capacity. In both kaolin and glacial till, the extent of Cr(VI) migration towards the anode increased as the treatment time increased. However, Cr(VI) migration was higher in glacial till as compared to kaolin because of the high pH conditions that existed in glacial till. In all tests, some Cr(VI) was reduced to Cr(III), and the Cr(VI) reduction rate to Cr(III) as well as the Cr(III) migration were significantly affected by the treatment time. Overall, this study showed that the electroosmotic flow as well as the direction and extent of contaminant migration and removal depend on the polarity of the contaminant, the type of soil, and the treatment duration.     

Chromium species behaviour in the activated sludge process

The purpose of this research was to compare trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) removal by activated sludge and to investigate whether Cr(VI) reduction and/or Cr(III) oxidation occurs in a wastewater treatment system. Chromium removal by sludge harvested from sequencing batch reactors, determined by a series of batch experiments, generally followed a Freundlich isotherm model. Almost 90% of Cr(III) was adsorbed on the suspended solids while the rest was precipitated at pH 7.0. On the contrary, removal of Cr(VI) was minor and did not exceed 15% in all experiments under the same conditions. Increase of sludge age reduces Cr(III) removal, possibly because of Cr(III) sorption on slime polymers. Moreover, the decrease of suspended solids concentration and the acclimatization of biomass to Cr(VI) reduced the removal efficiency of Cr(III). Batch experiments showed that Cr(III) cannot be oxidized to Cr(VI) by activated sludge. On the contrary, Cr(VI) reduction is possible and is affected mainly by the initial concentration of organic substrate, which acts as electron donor for Cr(VI) reduction. Initial organic substrate concentration equal to or higher than 1000 mgl(-1) chemical oxygen demand permitted the nearly complete reduction of 5 mgl(-1) Cr(VI) in a 24-h batch experiment. Moreover, higher Cr(VI) reduction rates were obtained with higher Cr(VI) initial concentrations, expressed in mg Cr(VI) g(-1) VSS, while decrease of suspended solids concentration enhanced the specific Cr(VI) reduction rate.     

Kinetics of the reduction of hexavalent chromium with the brown seaweed Ecklonia biomass

The dead biomass of the brown seaweed, Ecklonia sp., is capable of reducing toxic Cr(VI) into less toxic or nontoxic Cr(III). However, little is known about the mechanism of Cr(VI) reduction by the biomass. The objective of this work was to develop a kinetic model for Cr(VI) biosorption, for supporting our mechanism. The reduction rate of Cr(VI) increased with increasing total chromate concentration, [Cr(VI)], and equivalent concentration of organic compounds, [OCs], and decreasing solution pH. It was found that the reduction rate of Cr(VI) was proportional to [Cr(VI)] and [OCs], suggesting the simple kinetic equation -d[Cr(VI)]/dt=k[Cr(VI)][OCs]. When considering the consumption of organic compounds due to the oxidation by Cr(VI), an average rate coefficient of 9.33 (+/-0.65)microM(-1)h(-1) was determined, at pH 2. Although the function of the pH could not be expressed in a mechanistic manner, an empirical model able to describe the pH dependence was obtained. It is expected that the developed rate equation could likely be used for design and performance predictions of biosorption processes for treating chromate wastewaters.     

Mobility and recalcitrance of organo-chromium(III) complexes

Hexavalent chromium [Cr(VI)] is a major industrial pollutant. Bioremediation of Cr(VI) to Cr(III) is a viable clean-up approach. However, Cr(VI) bioreduction also produces soluble organo–Cr(III) complexes, and little is known about their behavior in the environment. When tested with soil columns, citrate–Cr(III) showed little sorption to soil; malate–Cr(III) had limited partitioning with soil; and histidine–Cr(III) exhibited significant interaction with soil. It appears that the mobility varies depending on the organic ligand. Further, Ralstonia eutropha JMP 134 and Pseudomonas aeruginosa pAO1 readily degraded malate, citrate, and histidine, but not the corresponding organo–Cr(III) complexes. The recalcitrance is not due to toxicity, but the complexes are likely to cause hindrance to enzymes, as malate dehydrogenase and amino acid oxidase could not use malate–Cr(III) and histidine–Cr(III), respectively. The data are in agreement with the reports of soluble organo–Cr(III) complexes in the environment.     

Influence of complex reagents on removal of chromium(VI) by zero-valent iron

The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).     

Patterns of metals and arsenic poisoning in Vibrio fischeri bacteria

The Microtox bioassay was used to establish dose-response curves for some toxic elements in aqueous solutions, namely, Zn(II), Pb(II), Cu(II), Hg(II), Ag(I), Co(II), Cd(II), Cr(VI), As(V) and As(III). Experiments were carried out at either pH 6.0 or pH 7.0 to indicate that pH may influence the measured toxicity of some elements due to pH-related changes of their chemical speciation. EC20 values, which represent a measurable threshold of toxicity, were determined for each element and were found to rank as Pb(II)>Ag(I)>Hg(II) approximately Cu(II)>Zn(II)>As(V)>Cd(II) approximately Co(II)>As(III)>Cr(VI). These values were compared to the limit concentrations allowed in industrial wastewater according to the official regulations in Catalonia (Spain). It appears that the Microtox test is sensitive enough for detecting some of the tested elements with respect to official regulations of Catalonia (Spain) dealing with pollution control, with the exception of cadmium, mercury, arsenate, arsenite and chromate.     

Chromium accumulation by the hyperaccumulator plant Leersia hexandra Swartz

Leersia hexandra Swartz (Gramineae), which occurs in Southern China, has been found to be a new chromium hyperaccumulator by means of field survey and pot-culture experiment. The field survey showed that this species had an extraordinary accumulation capacity for chromium. The maximum Cr concentration in the dry leaf matter was 2978 mg kg(-1) on the side of a pond near an electroplating factory. The average concentration of chromium in the leaves was 18.86 times as that in the pond sediment, and 297.41 times as that in the pond water. Under conditions of the nutrient solution culture, it was found that L. hexandra had a high tolerance and accumulation capacity to Cr(III) and Cr(VI). Under 60 mg l(-1) Cr(III) and 10 mg l(-1) Cr(VI) treatment, there was no significant decrease of biomass in the leaves of L. hexandra (p>0.05). The highest bioaccumulation coefficients of the leaves for Cr(III) and Cr(VI) were 486.8 and 72.1, respectively. However, L. hexandra had a higher accumulation capacity for Cr(III) than for Cr(VI). At the Cr(III) concentration of 10 mg l(-1) in the culture solution, the concentration of chromium in leaves was 4868 mg kg(-1), while at the same Cr(VI) concentration, the concentration of chromium in leaves was only 597 mg kg(-1). These results confirmed that L. hexandra is a chromium hyperaccumulator which grows rapidly with a great tolerance to Cr and broad ecological amplitude. This species could provide a new plant resource that explores the mechanism of Cr hyperaccumulation, and has potential for usage in the phytoremediation of Cr-contaminated soil and water.     

Mechanisms of chromium and arsenite adsorption by amino-functionalized SBA-15

The adsorption of Cr(VI) and As(III) by amino-functionalized SBA-15 (NH₂-SBA-15) from single and binary systems were investigated in this work. The effects of pH and temperature on the adsorption of NH₂-SBA-15 were studied. Adsorption kinetics, isotherm model, and thermodynamics were studied to analyze the experimental data. pH 2 was the optimum condition for the adsorption of Cr(VI) and pH 4 for As(III) adsorption. Increasing temperature had a positive effect on the removal of both Cr(VI) and As(III). The Freundlich isotherm model can depict the adsorption process best. The pseudo-second-order kinetic model fitted well with the kinetic data of Cr(VI) and As(III) in the single-component system. In the binary system, the adsorption of As(III) by NH₂-SBA-15 was slightly enhanced with the presence of Cr(VI); however, As(III) had no obvious effect on the removal of Cr(VI). Regeneration experiments indicated that 0.1 mol/L NaHCO₃ was an efficient desorbent for the recovery of Cr(VI) and As(III) from NH₂-SBA-15; the desorption rates for Cr(VI) and As(III) were 91.6 and 33.59 %, respectively. After five recycling cycles, the removal rates were 88 and 7 % for Cr(VI) and As(III) adsorption by NH₂-SBA-15, respectively.     

Electro-migration of heavy metals in an aged electroplating contaminated soil affected by the coexisting hexavalent chromium

Cr(VI) was often reported to oxidize soil organic matter at acidic environments due to its high ORP, probably thus changing cationic metal species bound to soil organic matter, and influencing their electro-migration patterns. However, such an effect on the electro-migration was not confirmed in most previous studies. Therefore, this study applied a fixed voltage direct current field on an aged electroplating contaminated clayed soil, with a special interest in the direct or indirect influence of Cr(VI) on the electro-migration of other coexisting metals. After 353 h electrokinetic process, 81% of Zn, 53% of Ni and 22% of Cu in the original soil were electro-migrated into the electrolyte, and most of the remaining concentrated near the cathode. The Cr(VI) oxidized some soil organic matter along its migration pathway, with a pronounced reaction occurred near the anode at low pHs. The resulting Cr(III) reversed its original movement, and migrated towards the cathode, leading to the occurrence of a second Cr concentration peak in the soil. Metal species analyses showed that the amount of metals bound to soil organic matter significantly decreased, while a substantial increase in the Cr species bound to Fe/Mn (hydro-)oxides was observed, suggesting an enhancement of cationic metal electro-migration by the reduction of Cr(VI) into Cr(III). However, the Cr(VI) may form some stable lead chromate precipitates, and in turn demobilize Pb in the soil, as the results showed a low Pb removal and an increase in its acid-extractable and residual fractions after electrokinetic remediation.     

In situ remediation of soils contaminated with toxic metal ions using microwave energy

Following onto our work on the in situ remediation of soils contaminated with PAH's, PCB's and other polychlorinated organic compounds using microwave energy, we now report a preliminary investigation on the in situ remediation of soils contaminated with toxic metal ions: Cd(II), Mn(II), Th(IV), Cr(III) and mainly Cr(VI). The soil is partially vitrified in the process, and extraction with hot (70 degrees C) 35% nitric acid for 4.5 h leads to the recovery of very small amounts of the metals which had been spiked into the clean soil: Cd, Mn, and Cr(III) are completely immobilized (unextractable), Th is mostly unextractable, and Cr(VI) partially extractable at very high levels of spiking, but almost completely unextractable using the US EPA Toxicity Characteristic Leaching Procedure. This suggests that contaminated soils which are not going to be used for agricultural purposes can be remediated safely to preset depths without fear of the toxic metal ions leaching out for a long time.     

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.     

Tessier连续提取法用于土壤铬分析的Cr(Ⅵ)-Cr(Ⅲ)转化及适用性

为揭示Tessier连续提取法应用于土壤总铬(TCr)和六价铬[Cr(Ⅵ)]结合态分析的适用性,通过液相和土壤相实验,分别研究了提取液自身还原性组分及土壤残留还原剂在各个提取步骤中导致的Cr(Ⅵ)-Cr(Ⅲ)转化问题。结果表明,提取液中还原性组分会在铁锰氧化物结合态和有机结合态的检测中导致Cr(Ⅵ)被还原为Cr(Ⅲ),可还原的Cr(Ⅵ)最大量分别为50.88和0.54 mg;经还原修复后的铬污染土壤中残留还原剂会在可交换态和碳酸盐结合态的检测中导致Cr(Ⅵ)的还原。提取过程中Cr(Ⅵ)-Cr(Ⅲ)的转化限制了Tessier连续提取法在铬污染土壤中的应用。当用于了解铬污染土壤TCr、Cr(Ⅵ)结合态的分布时,Cr(Ⅵ)铁锰氧化物结合态和有机结合态检测结果均显著低于真实值,TCr结合态的检测结果重现性较差。当用于评价修复后土壤中Cr(Ⅵ)结合态变化时,可交换态、碳酸盐结合态、铁锰氧化物结合态和有机结合态的检测结果均可能显著低于真实值。研究可为利用Tessier连续提取法准确评估铬污染土壤修复效果提供参考。