Effect of low-molecular-weight organic acids on the distribution of mobilized Al between soil solution and solid phase

Low-molecular-weight (LMW) organic acids occur widely in soils. Results in pure mineral systems and podzols suggest that LMW organic acids can promote the dissolution of Al from kaolinite, Al oxides and soils, but limited information is available concerning the role of these organic acids on Al mobilization in variable charge soils as yet. This paper deals with the effect of LMW organic acids on Al mobilization and mobilized Al distributed between the solution phase and exchangeable sites in two acidic variable charge soils. The results indicated that LMW organic acids accelerated Al mobilization through proton- and ligand- promoted reactions. The ability of different organic acids to mobilize Al followed the order: citric acid > oxalic acid > malonic acid > malic acid > tartaric acid > salicylic acid > lactic acid > maleic acid. This order was in general agreement with the magnitude of the stability constants of Al–organic acid complexes. The ratio of soluble Al to exchangeable Al also increased as the stability constants increased. These results showed that the organic acids with strong Al-complexation capacity were most effective in Al mobilization, whereas the weak organic acids promoted the retention of mobilized Al by the soil exchangeable sites. Increase in both organic acid concentration and solution pH promoted Al mobilization and also increased the ratio of soluble Al to exchangeable Al due to the increase in the concentration of the effective organic ligands, especially in the strong organic acid systems. These findings may have their practical significance for establishing more effective amelioration procedures for variable charge soils with increased acidity and higher mobility of Al.     

Mechanism of aluminum release from variable charge soils induced by low-molecular-weight organic acids: Kinetic study

The kinetic curves of aluminum release from two variable charge soils and a kaolinite within 48 h can be divided into three stages: the first stage located within the initial 30 min, at which the release rate of Al was the fastest one and the released Al dominantly originated from exchangeable Al and amorphous Al pools. The Elovich equation fit the kinetics data at this stage fairly well. The moderate and the slow stages occurred within 0.5-2 and 2-48 h, respectively. During these two stages, the released Al was mainly attributed to Al oxides, poorly crystalline kaolinite and easily weathered hydrous mica. The different linear equations also fit the kinetics data at these two stages well. The rate of Al release decreased sharply with time during the fast stage, but the rate remained constant during the moderate and slow stages. In Ultisol, Al oxides were the more important pool for Al release than poorly crystalline kaolinite and easily weathered hydrous mica during the latter two stages. In Oxisol, poorly crystalline kaolinite was the more important Al pool. Compared to the control system, the presence of organic acids increased the rate and quantity of Al release from variable charge soils. The ability of organic acids to accelerate Al release followed the order: oxalic acid > citric acid > malic acid > lactic acid. This is generally in consistent with the magnitude of the stability constants of the Al-organic complexes. The release rate of Al also increased with the rise in concentration of organic acids.     

Carboxylate-containing chelating agent interactions with amorphous chromium hydroxide: Adsorption and dissolution

Anthropogenic chelating agents and biological chelating agents produced by indigenous organisms may dissolve Cr^III (hydr)oxides in soils and sediments. The resulting dissolved Cr^III-chelating agent complexes are more readily transported through porous media, thereby spreading contamination. With this work, we examine chelating agent-assisted dissolution of amorphous chromium hydroxide (ACH) by the (amino)carboxylate chelating agents iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), tricarballylic acid (TCA), citric acid (CIT), ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediaminetetraacetic acid (CDTA), and trimethylenediaminetetraacetic acid (TMDTA). The extent of chelating agent adsorption onto ACH increased quickly over the first few hours, and then increased more gradually until a constant extent was attained. The extent of chelating agent adsorption versus pH followed “ligand-like” behavior. All chelating agents with the exception of TCA and IDA effectively dissolved significant amounts of ACH within 10 days from pH 4.0 to 9.4. IDA dissolved ACH below pH 6.5 and above pH 7.5. Rates of ACH dissolution normalized to the extent of chelating agent adsorption were pH dependent. IDA, NTA, CIT, and CDTA exhibited an increase in normalized dissolution rate with decreasing pH. EDTA and TMDTA exhibited a maximum in normalized dissolution rate near pH 8.5. Use of acetic acid as a pH buffer in experiments decreased the extent of chelating agent adsorption for IDA, NTA, and CIT but increased normalized rates of chelating agent-assisted dissolution for all chelating agents except EDTA. The results from this study provide the necessary information to calculate the extents and time scales of ACH dissolution in the presence of (amino)carboxylate chelating agents.     

Interaction of organic acids and pH on multi-heavy metal extraction from alkaline and acid mine soils

Vegetation at mining sites can produce increased heavy metal leaching by the organic acids and protons originating from root secretion and litter degradation. Batch experiments were conducted to investigate the effects of organic acids and pH on the extraction of Pb, Cd, Zn and Cu from an alkaline mine soil (sampled from a mining site of Chenzhou City, Hunan Province) and an acid mine soil (sampled from a mining site of Daxin county, Guangxi Province). The results showed that in the presence of organic acids (acetic, oxalic, malic, fumaric, tartaric and citric acids) at pH 7, the extraction of Pb, Cd, Zn and Cu from the acid mine soil was much higher than that from the alkaline mine soil, in which only citric acid with higher concentration was capable of extracting some heavy metals. Citric acid had the strongest ability in extracting heavy metals, followed by oxalic acid. Heavy metal extraction dramatically decreased with increasing pH. Moreover, at low pH, oxalic acid promoted the risk of Cu leaching; at high pH, the leaching of Pb, Zn, Cd and Cu was enhanced by both oxalic and citric acids. This indicated that those plants, which can produce substantial citric acid or oxalic acid by root secretion and litter degradation, should not be selected for the revegetation of mining sites.     

Tracing subsurface migration of contaminants from an abandoned municipal landfill

This paper aims at determining of inorganic leachate contamination for a capped unsanitary landfill in the absence of hydrogeological data. The 2D geoelectrical resistivity imaging, soil physicochemical characterization, and surface water analysis were used to determine contamination load and extent of selective heavy metal contamination underneath the landfill. The positions of the contaminated subsoil and groundwater were successfully delineated in terms of low resistivity leachate plumes of <10 Ωm. Leachate migration towards the reach of Kelang River could be clearly identified from the resistivity results and elevated concentrations of Fe in the river downslope toe of the site. Concentration of Fe, Mn, Ca, Na, K, Mg, Cu, Cr, Co, Ni, Zn, and Pb was measured for the subsoil samples collected at the downslope (BKD), upslope (BKU), and the soil-waste interface (BKI), of the landfill. The concentration levels obtained for most of the analyzed heavy metals significantly exceed the normal range in typical municipal solid waste landfill sites. The measured heavy metal contamination load in the subsoil is in the following order Fe ? Mn > Zn > Pb > Cr > Cu. Taking into consideration poor physical and chemical characteristics of the local soil, these metals first seem to be attenuated naturally at near surface then remobilize unavoidably due to the soil acidic environment (pH 4.2-6.18) which in turn, may allow an easy washing of these metals in contact with the shallow groundwater table during the periodic fluctuation of the Kelang River. These heavy metals are believed to have originated from hazardous industrial waste that might have been illegally dumped at the site.     

Remediation of soil co-contaminated with pyrene and cadmium by growing maize (Zea mays L.)

Sites co-contaminated with organic and metal pollutants are common and considered to be a more complex problem as the two components often causes a synergistic effect on cytotoxicity. Phytoremediation has been proposed as a cost-effective technology for treating heavy metal or organic contamination and may be suitable for remediation of co-contaminated soil. This study investigated the concurrent removal of pyrene and cadmium in co-contaminated soil by growing maize in a pot experiment. At the end of 60 day culture, pyrene in spiked soil diminished significantly, accounting for 21–31 % of the initial extractable concentration in unplanted soil and 12–27 % in planted soil. With the increment of cadmium level, the residual pyrene both in unplanted and planted soil tended to increase. Although the presence of cadmium increased the accumulation of pyrene in maize, plant accumulation only account for less than 0.30 % of the total amount of the dissipated pyrene in vegetated soils. It implied that plant-promoted microbial biodegradation was the predominant contribution to the plant-enhanced dissipation of pyrene in co-contaminated soil. Unlike pyrene, heavy metal cadmium cannot be degraded. It was observed that maize can concurrently removed about on the average 0.70 % of the total cadmium amount in soil by plant uptake, but cadmium phytoextraction would be inhibited under contamination of pyrene. Maize CT38 can normally grow in the co-contaminated soil with high level cadmium and pyrene and can effectively remedy the sites co-contaminated with these two types of contamination, which suggest the possibility of simultaneous phytoremediation of two different contaminant types.     

Experimental investigation on aluminum release from haplic acrisols in southeastern China

A sequential dissolution technique and a prolonged extraction method were used to investigate aluminium (Al) release from 4 Haplic Acrisols in southeastern China. The results show that the order of acidification of the 4 soils is: Tunxi soil>Yongchun soil>Shengxian soil>Ninghai soil. The amount of exchangeable Al is directly proportional to the extent of soil acidification. Al was released from both organically bound and inorganic Al pools after acid input. During several initial cycles of extraction the release of Al was mainly from the weakly organically bound Al pool. After prolonged extraction, Al release from the inorganic Al pool became more important to the total dissolved Al due to a rapid depletion of the weakly organically bound Al pool. The sizes of readily reactive Al pools in the Ninghai soil and Shengxian soil are larger than in the Yongchun soil and Tunxi soil. Al released from the inorganic Al pool in the Ninghai soil, Shengxian soil and Yongchun soil after 20 cycles of extraction was higher than from the organically bound Al pool, whereas the opposite was the case for the Tunxi soil. A low saturation of Al binding on soil organic matter (SOM) does not necessarily lead to a low Al release as in the case of the Shengxian soil. Also a relatively high saturation does not necessarily ensure a large Al release from the Al pool as in the case of the Tunxi soil and Yongchun soil. Once both organically bound and inorganic Al pools are depleted of readily reactive Al phases due to high soil acidification, Al dissolution would be small even under strong acid input. The high concentration of aqueous Al after rapid Al release from the weakly organically bound Al pool and subsequent depletion of the pool may have significant ecological and environmental effects.     

Exploring Cd,Cu, Pb,and Zn dynamic speciation in mining and smelting-contaminated soils with stable isotopic exchange kinetics

The exchange kinetics of Cd, Cu, Pb, and Zn in seven mining and smelting-contaminated soils and the other two anthropogenically contaminated soils was investigated by using multi-elementary stable isotopic exchange kinetic (SIEK) method, and the experimental results were successfully interpreted by modelling using a sum of pseudo first order kinetics equations. SIEK results show that in the studied soils the isotopic exchange of Cd is a relatively fast process, and the exchange almost reaches an apparent plateau after 3-d equilibration; whereas for Cu, Pb, and Zn, the exchange is more sluggish, suggesting that it is important to understand the time-dependent metal mobility for risk assessment and management of contaminated soils. In most of the soils, the total isotopically exchangeable pool is divided, for all the metals, into two distinct pools: a fast exchangeable pool (E₁) with a kinetic rate constant k₁ having values around 1 min⁻¹ and a much slower exchangeable pool (E₂) with k₂ ranging from 0.0001 min⁻¹ to 0.001 min⁻¹. The distribution of the two exchangeable pools varies significantly among metals. The amount of isotopically exchangeable Cd related to the fast pool is dominant, accounting for on average 60% of total isotopically exchangeable pool in the soils; whereas this pool is smaller for Cu, Zn, and Pb. The sequence of average k₁ values is Cd > Pb ≈ Zn > Cu, consistent with the reported sequence of stability constants of metal-humic substances (HS) complexes while the average k₂ values follow the order: Cd > Pb > Cu > Zn, probably controlled by the slow desorption of metal ions associated with soil organic matter (SOM) fraction. Our results imply that further study on the exchange kinetics of metals on each individual sorption surface in soils, especially SOM, is critical to help understanding the overall exchange kinetics of heavy metals in whole soils.     

Speciation of heavy metals in electroplating industry sludge and wastewater residue using inductively coupled plasma

The speciation of metals in environmental samples is a critical factor in assessing the potential environmental impacts, before their disposal. The distribution and speciation of toxic heavy metals in plating wastewater residues and sludge was investigated for four samples using sequential extraction method. Tessier method was used to fractionate the metal content into exchangeable, acid extractable, reducible and oxidizable fractions. Residual and total metal contents were determined in aqua regia digest. The extracts were analysed for metals using inductively coupled plasma -atomic emission spectrometry. The bioavailable fraction (exchangeable and acid extractable fractions) is comprised less than the other forms. The oxidisable and reducible forms are dominants for all the four samples studied. The major metal constitute in the samples is iron, the wastewater residue contains (12.3 and 7.4 g/Kg respectively on dry basis) and the sludge contains (31.5 and 41.6 g /Kg) respectively. Cr concentration is higher in wastewater residue of second electroplating industry. The descending order of the average total metal contents for these four samples were Fe > Cr > Sn > Zn >Cu > Ni > Mn > Pb > Cd > Ag. Based on the average of absolute values for the four samples the highest bioavailability order of metals is Cr (39 %) in wastewater residues and Zn (32 %) in sludge samples. Metal recovery was good, with < 10 % difference between the total metal recovered through the extractant steps and the total metal determined using aqua regia extract.     

Heavy metal relationships in a Pennsylvania soil

Soils of loamy sand on weathered, sandy dolomite were cored from six holes up to 70 ft beneath a municipal waste landfill in central Pennsylvania. Mn, Fe, Ni, Co, Cu, Zn, Cd, Pb, and Ag were determined in exchangeable and non-exchangeable forms in total and < 15 μm soil samples. Most of these metals were bound in Mn oxides, non-exchangeable with 0.5 M CaCl₂. The Mn oxides (often X-ray amorphous) identified when crystalline as todorokite occurred chiefly as coatings on quartz grains.Somewhat higher amounts of acid leachable trace metals were found in the < 15 μm size fraction than in the total soil samples; however, trace metal/Mn ratios were similar in both. In general, the initial mild soil leaching, which dissolved chiefly Mn oxides, gave MnFeX>Co>Ni>Pb>Zn> Cu>Cd>Ag. The final leaching, which dissolved chiefly ferric oxides, gave Fe>Mn>Ni>Zn>Co> Cu>Pb>Cd>Ag. Samples taken from an unpolluted site and from the same soils affected for seven years by leachate from the refuse had similar metal contents.Soil extractable Co, Ni, Cu, and Zn could be predicted from the Mn extracted. Based in part on factor analysis of the data, Mn-rich oxides had at least tenfold higher heavy metal percentages than Fe-rich oxides (crystalline component goethite), reflecting their greater coprecipitation potential. Because of this potential and because of the generally higher solubility of Mn than Fe oxides, more heavy metals may be released from Mn-rich than from Fe-rich soils by disposal of organic-bearing wastes. However, leaching of the moisture-unsaturated soils in situ is rarely severe enough to completely dissolve both Mn and Fe oxides. Based on the Mn content, Cd, Cu, and Pb were depleted in soil moisture beneath the landfill relative to their amounts in the soil. This depletion may reflect factors including heterogeneity in metal content of the soil oxides; preferential resorption of these metals; and removal of the Cd, Cu, and Pb as organic precipitates or as inorganic precipitates such as carbonates.     

Efficiency of chelating agents in retaining sludge-borne heavy metals in intensively applied agricultural soils

This paper presents an evaluation of different chelating agents for their effectiveness in removing Cu, Co and Zn in three distinctly different types of sludge-amended soils. Soil types (Luvisol, Arenosol and Vertisol) were each mixed with an anaerobically digested sludge at a 1:1 ratio followed by leaching with three types of chelating agents, namely: ethylenediamine tetra acetic acid, nitrilotriacetic acid and acetic acid. Aqua regia method was used to quantify pseudo total metal before and after treatment. Generally, chelating agents can be out competed by soil colloids in attracting cations. The efficiency of chelating agents was found to follow this order ethylenediamine tetra acetic acid?<?nitrilotriacetic?=?acetic acid in all the three metals, with ethylenediamine tetra acetic acid being the most effective chelating agent. More heavy metals were removed in Luvisol and Arenosol than in Vertisol implying that soils rich in clay fraction retain more cations than soils with minimal clay fraction. Similarly, copper responded positively to chelation than zinc and cobalt in Luvisols and Arenosols, although the results were not conclusive for Vertisols.     

Amelioration of soil acidity,Olsen-P,and phosphatase activity by manure- and peat-derived biochars in different acidic soils

To increase soil productivity, ameliorate nutrient scarcity, and reduce metal toxicity in highly weathered acidic soils usually requires fertilizer and lime application. Effects of three biochars on soil acidity, Olsen-phosphorus (P), phosphatase activities, and heavy metal availability were investigated to test potential of these biochars as soil amendments in highly weathered acidic soils. Incubation experiments were conducted for 6 weeks with three acidic soils: Alfisol, Ultisol, and Oxisol. Three biochars were derived from chicken manure (CMB), pig manure (PMB), and peat moss (PB) at 400 °C and applied at 1 or 2% (wt/wt). The addition of the three biochars increased Olsen-P in the three acidic soils in the following order: CMB?>?PMB?>?PB. Application of 2% CMB increased Olsen-P contents by 2.41-, 7.4-, and 1.78-fold in the Ultisol, Oxisol, and Alfisol compared with controls, respectively. Moreover, CMB increased the soil pH, electrical conductivity (EC), cation exchange capacity (CEC), and alkaline phosphatase activity, but reduced exchangeable acidity, acid phosphatase activity, and the availability of heavy metals—more effectively than PMB and PB. Addition of CMB increased soil pH by 0.90, 0.90, and 0.92 units for the Alfisol, Ultisol, and Oxisol, respectively, correspondingly followed by 0.80, 0.84, and 0.87 units for PMB and 0.15, 0.28, and 0.25 for PM. Changes in EC, CEC, and exchangeable acidity followed the same order for the three soils: CMB?>?PMB?>?PB. The results suggested that the magnitude of changes in soil properties and Olsen-P contents depended on biochar type and application rate. Application of CMB increased nutrient availability and reduced the availability of heavy metals more than other amendments. Due to higher pH, EC, and CEC, and greater concentrations of carbon, nitrogen, and exchangeable calcium and potassium, incorporation of CMB should be a better cost-effective method to correct soil acidity and improve fertility and Olsen-P contents in Ultisols and Oxisols from tropical and subtropical regions of the world.     

Sorption and distribution of adsorbed metals in three soils of India

The mobility and bioavailability of heavy metals depends on the metal retention capacity of soil and also on the geochemical phases with which metals are associated. Laboratory batch experiments were carried out to study the sorption and distribution of Cd, Ni and Pb in 3 soils differing in their physicochemical properties from India: Oxyaquic Haplustalf (SL1), Typic Haplustalf (SL2) and Typic Haplustert (SL3). The heavy metal adsorption was studied by isotherms and the distribution coefficient (K_D) for each metal was obtained from the linear regressions of the concentration of metal remaining in equilibrium solution and the amount adsorbed. In general, the sorption capacity for all the metals decreased in the order: SL3>SL2>SL1. Among metals, the sorption capacity in all the soils decreased in the order: Pb>>Ni>Cd. Distribution of sorbed metals at various equilibrating concentrations was studied by sequential extraction. Results showed significant differences in the distribution of metals in these soils. At higher additions (such as 200 μM l⁻¹) most of the metals were extracted in their more mobile fractions, exchangeable and/or inorganic in contrast to their original partitioning in soils, where they were preferentially associated with the less mobile residual fraction. Largest percentages of metals extracted in the exchangeable fraction corresponded to those soil–metal systems with smaller K_D values, e.g. Cd, Ni and Pb in SL1 and Cd and Ni in SL2. In neutral and alkaline soils (SL2, pH=7.1, and SL3, pH=8.6) Pb was predominantly extracted from the inorganic fractions and this corresponded to higher K_D values for Pb in these soils. The predominance of metals associated with the exchangeable fraction together with low K_D values indicates higher mobility of metals retained in the acidic soil (SL1, pH=5.2) compared with the others.     

Distribution of Cd,Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40–80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.     

Release kinetics and distribution of boron in different fractions in some calcareous soils

The aim of this study was to evaluate the release kinetics, speciation, and fractionation of boron (B) in some calcareous soils of western Iran. Ten surface soil samples were incubated with 100 mg B kg^?1 for a week at field capacity moisture. After air drying of samples, the trend of B release was experimented using sequential extraction with 10 mM CaCl₂. B speciation in soil solution was calculated for the first and the last steps of extraction by the visual MINTEQ program. The distribution of B among five fractions including exchangeable (F1), specially adsorbed (F2), bound by Fe–Mn oxides (F3), organically bound (F4) and residual (F5), was determined in control and spiked soils. The results indicated that the release rates were initially rapid followed by a slower reaction and the main proportion of the added B was extracted by CaCl₂. The release kinetics of B was described well with Elovich, parabolic diffusion, power function, and first-order equations. The speciation results revealed that the uncharged boric acid (H₃BO ₃ ⁰ ) was the dominant species in soil solutions. In control soils, B concentration in different fractions decreased in the following order: F5 > F1 > F2 > F3 > F4. In spiked soils, however, the largest and the smallest fractions were exchangeable and residual, respectively. This implies that B transformation from soluble to less mobile and non-labile forms is not a rapid process and requires more than a week. The significant relationship observed between kinetic parameters of power and parabolic equations and organically bound B fraction and OM content indicated that organic matter played an important role in B adsorption and release in calcareous soils.     

Effects of key components of <Emphasis Type="Italic">S. triqueter</Emphasis> root exudates on fractions and bioavailability of pyrene–lead co-contaminated soils

The key components of S. triqueter root exudates involved 4-oxo-pentanoic acid, succinic acid, glutaric acid, phthalate acid, citric acid, vanillic acid, myristic acid, pentadecanoic acid, decanoic acid, 14-methyl-pentadecanoic acid, hexadecanoic acid, octadecanoic acid and oleic acid, and the content of the water-soluble organic acids (citric acid, succinic acid and glutaric acid) significantly increased in pyrene and lead co-contaminated rhizosphere soil. These three water-soluble organic acids including citric acid, succinic acid and glutaric acid were detected as the specific root exudates of S. triqueter under stress of pollutants for pyrene and lead, so they were chosen as the research objects, and they were added into the bioremediation systems of pyrene and lead co-contaminated wetland soils. Compared with the control, the treatments added the three organic acids always improved the quantity of the bioavailable fraction of pyrene and lead in wetland soils and greatly influenced other chemical states of pyrene and lead fractions in the test concentration range. Under the 50 g kg^?1 of organic acids concentration, the amount of the bioavailable fraction of pyrene and lead increased 41.0 and 872.7 % by citric acid, respectively. The enhancement of bioavailability of pyrene and lead in the wetland soil by adding organic acids generally decreased in the following order: citric acid > succinic acid > glutaric acid. Enhancing effects of organic acids on the bioavailability improvement of pyrene and lead is remarkable.     

Effects of humic acid on heavy metal uptake by herbaceous plants in soils simultaneously contaminated by petroleum hydrocarbons

The effects of humic acid (HA) on heavy metal uptake by herbaceous plants in soil simultaneously contaminated with heavy metals and petroleum hydrocarbons were investigated. The results showed that HA reduced readily soluble and exchangeable forms of heavy metals in the contaminated soil but increased their plant-available forms. Potential bioavailability and leachability factors became larger than 1 after adding HA to the soil, except for those of Ni, suggesting that more heavy metals could be potentially phytoavailable for plant uptake. Furthermore, HA increased the accumulation of Pb, Cu, Cd, and Ni in the shoots and roots of selected plants. The greatest increase in the accumulation of heavy metals was 264.7 % in the shoot of Festuca arundinacea, with the bioconcentration factor (BCF) increasing from 0.30 to 1.10. Humic acid also increased the BCFs of the roots of Brassica campestris for Ni and Pb. These results suggest that HA amendment could enhance plant uptake of heavy metals, while concurrently reducing heavy metal leachability and preventing subsurface contamination, even in soils simultaneously contaminated with petroleum hydrocarbons.     

氢化物发生-原子荧光光谱法测定土壤中水溶态和可交换态锑(Ⅲ)和锑(Ⅴ)

在0.10 mol/L酒石酸介质中,采用氢化物发生-原子荧光光谱法测定土壤中水溶态和可交换态Sb(Ⅲ)和Sb(Ⅴ)。以氢气发生器为氩-氢火焰提供氢气,明显降低了硼氢化钾浓度,改善了测定检出限。考察了酒石酸掩蔽Sb(Ⅴ)的量及共存干扰元素的允许量。方法检出限Sb(Ⅲ)为0.026 ng/L,总Sb为0.019 ng/L。加标回收试验表明,方法准确、可靠。     

Distribution and mobility of heavy metals in paddy soils of the Kočani Field in Macedonia

Contamination of soils with heavy metals is widespread and poses a long-term risk to ecosystem health. Abandoned and active mining sites contain residues from ore-processing operations that are characterised by high concentrations of heavy metals. The distribution and mobility characteristics of heavy metals (As, Cd, Cu, Pb, and Zn) in paddy soil samples from Kočani Field (Macedonia) using ICP-EAS and a sequential extraction procedure was evaluated. The results indicate that highly elevated concentrations of As, Cd, Cu, Pb, and Zn were detected in the paddy soil sample from location VII-2 in the vicinity of Zletovo mine and Zletovska river in the western part of Kočani Field, which drains the untreated acid mine waters and mine wastes from the active Zletovo mine. The degree of contamination based on index of geoaccumulation (I _geo) from strong to weak in the paddy soils samples is Pb > As > Cd > Zn > Cu. The mobility potential of heavy metals in all paddy soil samples increases in the order As < Cu < Pb < Zn < Cd. According to the results of the anthropogenic impact on the paddy soils, a further study on the heavy metal concentrations in rice and other edible crops, the remediation process of the paddy soils and a dietary study of the local population are needed.     

Effect of citric acid on phytoextraction and antioxidative defense in <Emphasis Type="Italic">Solanum nigrum</Emphasis> L. as a hyperaccumulator under Cd and Pb combined pollution

The impact of citric acid on the ability of Solanum nigrum L. to accumulate heavy metals and on its antioxidant enzyme activity were investigated to further elucidate the effect of chelation on the heavy metal uptake and antioxidative defense in plants under conditions of heavy metal pollution. In the presence of multiple metal contaminants (Cd and Pb), citric acid treatment can significantly enhance the Cd (10–30%) and Pb (10–20%) accumulation in S. nigrum when compared to non-citric acid-treated controls; with this enhanced accumulation, S. nigrum becomes a hyperaccumulator. However, citric acid treatment only slightly influences on the increase of S. nigrum biomass. Furthermore, the combined stress of Pb and Cd resulted in a decrease in S. nigrum photorespiration; the rate of carbon dioxide fixation was restored with the application of citric acid. In addition, the presence of Cd and Pb in the soil led to disturbances in the antioxidative responses of S. nigrum; endogenous superoxide dismutase activity was approximately 3–4 times higher in the leaves than in the roots, and guaiacol peroxidase activity in the leaves was only slightly affected. It was also observed that CA increased the malondialdehyde content and total acid soluble thiol content in the presence of elevated Cd and Pb concentrations in the soil. Moreover, the combined stress of Cd and Pb resulted in progressive decrease in total glutathione and significant increase in root phytochelatins as the heavy metal concentration increased. The application of citric acid improved the mechanisms of antioxidative response and phytoextraction in S. nigrum; this improvement resulted from an increase in the solubility of heavy metals in the soil, which alleviated the metal toxicity. Therefore, citric acid could be involved in the expression of specific proteins or defense-related enzymes.