非损伤微测Zn2+选择性微电极的研发及应用

非损伤微测技术(Non-invasive Micro-test Technology, NMT)是一种通过微电极实时测定进出活体材料离子和小分子流速的技术,已广泛应用于植物的生长发育和逆境胁迫等研究领域中。目前该技术专用的重金属微电极种类非常少,因此其在重金属胁迫研究中的应用也受到了限制。本文在前期工作的基础上开发了一种基于非损伤微测技术的Zn²⁺选择性微电极,首次实现了活体条件下植物根际Zn²⁺离子流的实时、动态检测。研发的微电极在去离子水中对Zn²⁺的线性响应范围为10–6～10^–1 mol/L,能斯特斜率为30.2mV/decade(浓度每增加或减少10倍电位值的变化),响应时间t_95%≤1s,正常工作pH范围为3.5～7.0;在简易模拟土壤溶液(0.1mmol/L Ca(NO₃)₂、0.1 mmol/L KNO₃、0.1 mmol/L Mg(NO₃)₂和1 mm...     

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.     

黑麦草生长及根系形态对土壤Cd，Pb与石油污染的响应

[目的] 研究不同污染条件下黑麦草生理指标的动态变化,为植物修复污染土壤提供初步理论基础。[方法] 通过室内试验模拟不同类型的土壤污染。设置4个处理,未污染土壤+黑麦草（SH）、重金属污染土壤（500 mg/kg Pb²⁺和50 mg/kg Cd²⁺）+黑麦草（SGH）、石油污染土壤（1 000 mg/kg石油）+黑麦草（SPH）、石油和重金属复合污染土壤（500 mg/kg Pb²⁺,50 mg/kg Cd²⁺和1 000 mg/kg石油）+黑麦草（SPGH）,采用WINRHIZO根系分析系统测量根系形态指标,用分光光度计测量叶片色素指标,研究不同类型土壤污染对黑麦草生长的影响。[结果] 3种不同类型的污染土壤均不同程度地刺激了黑麦草根系的生长。与未污染处理相比,在20 d时,石油重金属复合处理下的黑麦草根系的根长、根表面积、根体积、根直径分别增加了88.10%,148.60%,221.90%,32.20%。与未污染相比,随着培养时间的增加各污染处理的地下生物量呈现出先增加后减少的趋势,地上生物量均低于未污染处理,且在第10,40,80 d时,复合污染处理的地上生物量最小,较未污染处理分别降低了34.68%,45.42%,58.05%。80 d时,重金属污染处理、石油污染处理和石油重金属复合污染处理的黑麦草叶绿素含量显著低于未污染处理,分别降低了26.84%,44.82%和47.02%。[结论] 不同污染物都可以促进黑麦草根系形态发育,降低黑麦草的生物量及色素含量;石油重金属复合处理对黑麦草的生长影响最大,石油污染处理次之。基于不同污染物对黑麦草根系形态及生长影响的差异,在今后植物修复土壤污染过程中,可添加一些生长调节物质来缓解污染对植物的毒害作用,提高植物生物量及增强相关生理功能,提升污染土壤修复效果。     

Stable Incorporation of Co2+ into Ferrite Structure at Ambient Temperature: Effect of Operational Parameters

Removal of heavy metals (HM) from industrial wastewater is of primary environmental importance. The seeded ambient temperature ferrite process, in which heavy metals are removed from solution by their incorporation into a magnetite structure, is an attractive alternative for both complete metals separation and generation of stable magnetic sludge. Despite its potential, the effects of various operational parameters on the composition and stability of the final product are not fully understood to-date. The current paper addresses the combined effect of selected operational parameters on Co²⁺ incorporation efficiency. Co²⁺, which is used in many industries (e.g., plating, alloys manufacturing, catalytic converters, and paint pigments) and hence may pose a significant environment risk, was shown previously to be incorporated successfully into ferrite structures. Co²⁺-bearing ferrites were synthesized from Fe(II) solutions at ambient temperature (20 and 30°C), applying slow oxidation, pH 10.5, 20 g (as Fe) l^?1 ferrite seed, and different Fe²⁺ to Co²⁺ influent ratios. Pure magnetite was used as an initial seed, which was gradually exchanged, as the reaction proceeded, by the Co²⁺-bearing ferrite generated within the reactor (until full exchange at steady state). Under all conditions investigated >99% of the Co²⁺ was removed from solution (yielding Co²⁺ levels below 20 μg/l in the effluent) while the generated precipitates were composed predominately of magnetite/ferrite (based on XRD analysis). Favorable results in terms of Co²⁺ incorporation efficiency and sludge stability were obtained when the following operational conditions were applied: 1:10 Co²⁺:Fe²⁺ molar influent ratio, 30°C, 1,500 mgFe²⁺ l^?1 metal intermediate concentration, and 16 h aging period (pH 10.5).     

重金属和pH值对类芦种子萌发的影响

类芦(Neyraudia reynaudiana)是一种具有极强耐干旱、贫瘠、高温等逆境的多年生禾草植物,是南方水蚀荒漠化地区、采矿采石厂及各类边坡植被自然恢复中的先锋植物。为探索在各类矿区及受重金属污染的地区采用类芦进行生态修复的可行性,通过室内发芽试验,对类芦种子在Hg2+,Cr6+,Cd2+,Pb2+,Zn2+,Cu2+等6种重金属离子胁迫及不同pH值条件下的萌发能力进行了研究。结果表明,类芦种子在pH值为5.0~9.0的范围内具有良好的萌发能力;6种重金属离子随着处理浓度的升高,对类芦种子的抑制作用逐渐加强,且出现显著抑制作用的最低浓度顺序为:Cd2+Cu2+Hg2+,Zn2+,Cr6+Pb2+;6种重金属对类芦种子活力指数出现显著影响的浓度均较显著影响发芽率、发芽势和发芽指数3个指标的浓度低,说明类芦幼苗生长比种子萌发对6种重金属更加敏感。     

The Remobilization of Metals from Iron Oxides and Sediments by Metal-EDTA Complexes

Synthetic chelating agents such as EDTA form strong complexes with heavy metals and therefore have the potential to remobilize metals from sediments and aquifers. In natural waters EDTA is present almost exclusively in the form of metal-complexes. Therefore, remobilization of metals is always a metal-metal-EDTA exchange reaction. We have investigated, to our knowledge for the first time, the remobilization of metals from the surface of synthetic iron oxides and from a river sediment by different metal-EDTA complexes. The metals are exchanged as follows:MeEDTA_dissolved + Me^ast _adsorbed Me^astEDTA_dissolved + Me_adsorbed The order of the remobilization rate of Zn²⁺ from goethite is CaEDTA > Fe(III)EDTA, reflecting the slow exchange reaction of Fe(III)EDTA. For the remobilization of Pb²⁺ from goethite, the rate was found to be Fe(III)EDTA > CaEDTA > ZnEDTA. Here, Fe(III)EDTA has surprisingly the fastest exchange rate. Only very limited remobilization of Pb²⁺ is possible from hydrous ferric oxide at pH 8 due to the very strong adsorption of Pb²⁺. The order of remobilization of Zn²⁺ from a natural river sediment was found to be CaEDTA > CuEDTA > Fe(III)EDTA. The remobilization rate of Zn²⁺ with Fe(III)EDTA is only 12% of the rate with CaEDTA, illustrating the importance of EDTA speciation for assessing remobilization.     

Sorption of polycyclic aromatic hydrocarbons to soils enhanced by heavy metals: perspective of molecular interactions

Purpose

Combined pollution by polycyclic aromatic hydrocarbons (PAHs) and heavy metals are commonly found in industrial soils. This study aims to investigate the effect of the coexistence of heavy metals on the sorption of PAHs to soils. We focused specifically on the relationship of the sorption capacity with the estimation of the binding energy between PAHs and heavy metals.

Materials and methods

The sorption of typical PAHs (naphthalene, phenanthrene, and pyrene) to soils coexisting with heavy metals (Cu(II), Pb(II), and Cr(III)) was characterized in batch sorption experiments. The binding energy between PAHs and heavy metals in aqueous solution was estimated by quantum mechanical (QM) method using density functional theory (DFT) at the M06-2x/def2svp level of theory.

Results and discussion

Sorption capacity and nonlinearity of the PAHs to the soils were enhanced by the coexisting heavy metals. The extent of increment was positively associated with the hydrophobicity of the PAHs and the electronegativity and radius of the metal cations: Cr(III)?>?Pb(II)?>?Cu(II). The cation-π interaction was revealed as an important noncovalent binding force. There was a high correlation between the binding energies of the PAHs and K _f ′ (K _f adjusted after normalizing the equilibrium concentration (C _e) by the aqueous solubility (C _s)) (R ²?>?0.906), indicating the significant role of the cation-π interactions to the improved PAH sorption to soils.

Conclusions

In the presence of heavy metals, the sorption capacities of naphthalene, phenanthrene, and pyrene to soils were enhanced by 21.1–107 %. The improved sorption capacity was largely contributed from the potent interactions between PAHs and heavy metals.

     

砖红壤及其矿物表面对重金属离子的专性吸附研究

本文对Ｃｕ＾２＋、Ｚｎ＾２＋、Ｃｏ＾２＋、Ｎｉ＾２＋和Ｃｄ＾２＋在砖红壤、针铁矿、无定形氧化铝和高岭石表面上的专性吸附进行的研究结果表明：ＰＨ是影响重金属离子吸附过程的最重要因素，而表面带电性质对吸附过程的影响不大。砖红壤表面的吸附顺序是Ｃｕ＾２＋〉Ｚｎ＾２＋〉Ｃｏ＾２＋〉Ｎｉ＾２＋≥Ｃｄ＾２＋；针铁矿表面的吸附顺序是Ｃｕ＾２＋〉Ｚｎ＾２＋〉Ｃｄ＾２＋〉Ｎｉ＾２＋〉Ｃｏ＾２＋；而无定形氧化铝和高岭     

Estimating Sorption Affinities of Heavy Metals on Humic Acid and Silica using a Constant Capacitance Model

The adsorption of heavy metals [cadmium (Cd ²⁺), cobalt (Co²⁺), nickel (Ni²⁺), zinc (Zn²⁺), and lead (Pb)] and calcium (Ca²⁺) on humic acid and silica were investigated to understand the adsorptive selectivities of heavy metals on the constituents of soil. The experiments for the adsorption of Cd and Pb were carried out in a 0.1 mol L^?1 (M) sodium nitrate (NaNO₃) background solution, whereas those for the other metals were done in a 0.1 M sodium chloride (NaCl) solution. The adsorptive affinities of the metal ions on the humic acid and silica were ranked by the intrinsic surface complexation constants [K _m ¹(int)] that were calculated approximately from the adsorptive data using a constant capacitance model. The log [K _m ¹(int)] values of the metals were in the order Zn²⁺(?2.29) > Cd²⁺(?2.41) > Co²⁺(?2.74) > Ni²⁺(?2.92) ?> Ca²⁺ (?3.33) for the humic acid and Zn²⁺(?4.23) > Cd²⁺(?4.49) > Ni²⁺(?4.51) ? Co²⁺ (?5.99) > Ca²⁺(?6.37) for silica.     

水稻耐低锌基因型的生长发育和若干生理特性研究

在不同Zn2+活度（pZn2+9.7,pZn2+11.0和pZn2+＞11.5）的溶液培养条件下,研究了水稻耐低锌基因型的生长发育和若干生理特性。结果表明:水稻锌营养存在明显的基因型差异,降低锌离子活度会增加地下部于物质的积累,当Zn2+活度从pZn2+9.7下降到pZn2+11.0时,耐低锌品种的地上部干重虽下降,但因地下部干重显著增加,故总干重相近;锌敏感品种则地上部干重显著下降,而地下部干重增加不明显,总干重显著下降。当严重缺锌（pZn2+＞11.5）时,所有基因型水稻的干重构极显著地下降,但锌敏感品种比耐低锌品种下降得更多。降低Zn2+活度使水稻秧苗的出叶速度减慢,在极度缺锌条件下,敏感品种只能生长到3.5叶,而耐低锌品种能生长到4.5叶左右。对叶绿素和根系氧化力的测定结果表明,轻度缺锌或缺锌初期会使叶绿素含量上升和根系氧化力下降,但严重缺锌时,则使叶绿素含量显著降低,而使根系氧化力明显增加。锌敏感品种比耐缺锌品种的变化更为明显。锌离子活度对秧苗的含水量也有明显的影响。因此,耐低锌基因型在低Zn2+活度条件通过保持较低的根氧化作用,促进根系生长以维持地上部新叶生长,达到低锌适应稳态。     

羟基磷灰石对铅锌矿区土壤吸附Zn2+、Cd2+的影响

为探究羟基磷灰石(HAP)对矿区土壤重金属的固化效果,采用吸附试验,研究施加HAP的铅锌矿区土壤对Cd~(2+)、Zn~(2+)的动力学吸附和等温吸附效果。结果表明:土壤对Cd~(2+)、Zn~(2+)的吸附量随Cd~(2+)、Zn~(2+)初始浓度的增加而增加;在酸性条件下,其吸附量随pH上升而上升;准二级动力学方程能很好地描述两者的吸附过程,土壤吸附能力随HAP的添加量增大而增强;在Zn—Cd共存体系中,当初始浓度为20mg/L时,土壤对Zn~(2+)、Cd~(2+)的吸附无明显差异,2种金属离子竞争力度小,随着初始浓度上升,竞争明显,对Zn~(2+)的最大吸附量能达到单一体系中的79%～87%,而Cd~(2+)的最大吸附量只有单一体系中的57%～72%,Zn~(2+)的竞争力优于Cd~(2+),Zn~(2+)对Cd~(2+)吸附产生严重的抑制。综上可知,HAP能提高矿区土壤的吸附性能,在Zn、Cd污染土壤中,更能提升土壤对Zn~(2+)的吸附固持能力。     

Phytoremediation Potential of Vetiver Grass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis>) for Treatment of Metal-Contaminated Water

Phytoremediation using vetiver grass (Vetiveria zizanioides) has been regarded as an effective technique for removing contaminants in polluted water. This study was conducted to assess the removal efficiency of heavy metals (Cu, Fe, Mn, Pb, Zn) using vetiver grass (VG) at different root lengths and densities and to determine metals uptake rate by plant parts (root and shoot) between treatments (low and high concentration). Removal efficiency for heavy metals in water by VG is ranked in the order of Fe>Pb>Cu>Mn>Zn. Results showed that VG was effective in removing all the heavy metals, but removals greatly depend on root length, plant density and metal concentration. Longer root length and higher density showed greater removals of heavy metals due to increased surface area for metal absorption by plant roots. Results also demonstrated significant difference of heavy metals uptake in plant parts at different concentrations indicating that root has high tolerance towards elevated concentration of heavy metals. However, the effects were less significant in plant shoot suggesting that metals uptake were generally higher in root than in shoot. The findings have shown potential of VG in phytoremediation for heavy metals removal in water thus providing significant implication for treatment of metal-contaminated water.     

不同土地利用方式土壤对铜、镉离子的吸附解吸特征

采用一次平衡法对Cu²⁺、Cd²⁺在城市及城郊农田、林地、草地3种土地利用方式土壤中的吸附解吸过程进行比较研究, 结果表明: Cu²⁺、Cd²⁺在3种土地利用方式土壤中的吸附量均随平衡液浓度的增加而增大, Cu²⁺、Cd²⁺在农田土壤上的吸附量均高于林地和草地土壤。分别用Langmuir和Freunlich两种等温吸附方程对吸附过程进行拟合, 3种土壤对Cu²⁺的吸附过程运用Langmuir方程拟合效果好, 而对Cd²⁺的吸附过程运用Freunlich方程拟合效果更好。Cu²⁺在3种土壤的解吸量大小顺序为农田>林地>草地, Cd²⁺在3种土壤的解吸量大小顺序为农田>草地>林地。两种离子在3种土壤中的动态吸附是个快速反应的过程, 随时间延长, 吸附反应趋于平衡。运用双常数函数方程和Elovich方程能较好地拟合重金属在土壤上的吸附动力学过程。Cu²⁺、Cd²⁺的吸附与土壤黏粒含量、有机质含量、CEC和pH均有关。     

中国东部太湖地区酸性水稻土团聚体上铜的专性和非专性吸附动力学研究

The Taihu Lake region in East China has become prone to soil acidification, which changes heavy metals such as copper(Cu) in soil into water-soluble species and increases the mobility and contamination risks of heavy metals in the biological environment. In this study, the kinetics of Cu2+sorption by the bulk soil and the aggregate size fractions of an acidic paddy soil collected from the Taihu Lake region, the effects of temperature on Cu2+sorption, and the p H changes of the solution were investigated by static sorption and magnetic stirring. The aggregate size fractions were prepared by low-energy ultrasonic dispersing and freeze-drying. The total sorption amounts of the bulk soil and the aggregate size fractions for Cu2+followed a descending order of clay > coarse sand > bulk soil > silt> sand, corresponding to those of organic matter content, free iron oxide content, free aluminum oxide content, and cation exchange capacity. The kinetic sorption curves of Cu2+by the bulk soil and the aggregates, which were divided into two stages(rapid and slow sequentially), were well fitted by the first-order equation, the diffusion equation, and the Elovich equation, showing significant correlations(P < 0.05). Specific and non-specific sorption dominated in the fast and slow stages, respectively, and the former was predominant throughout the sorption process. The specific sorption accelerated and the non-specific sorption decelerated with rising temperature. The p H of the solution decreased significantly during the specific sorption and remained unchanged or increased slightly during the non-specific sorption. When the specific sorption terminated, the p H of the solution was minimized nearly simultaneously.The sorption progress of Cu2+by the bulk soil significantly preceded that by the aggregates. Therefore, heavy metal contamination may be another factor reducing soil p H and metal sorption forms should be taken into consideration in studies of mitigating soil heavy metal pollution or determining environmental capacity of heavy metal in soil.     

Two-stage Batch Adsorber Design: A Time-Dependent Langmuir Model for Adsorption of Pb2+ and Cd2+ onto Modified Kaolinite Clay

The kinetics of the adsorption of Pb²⁺ and Cd²⁺ by sodium tetraborate (NTB)-modified kaolinite clay adsorbent was studied. A one-stage and two-stage optimization of equilibrium data were carried out using the Langmuir and time-dependent Langmuir models, respectively. Increasing temperature was found to increase the pseudo-second order kinetic rate constant and kinetic data for Pb²⁺ adsorption were found to fit well with the pseudo-second order kinetic model (PSOM) while that for Cd²⁺ were found to show very good fit to the modified pseudo-first order kinetic model (MPFOM). Binary solutions of Pb²⁺ and Cd²⁺ reduced the adsorption capacity of the modified adsorbent for either metal ion with increased initial sorption rate due to competition of metal ions for available adsorption sites. The use of NTB-modified kaolinite clay adsorbent reduces by approximately 72.2% and 96.3% the amount of kaolinite clay needed to adsorb Pb²⁺ and Cd²⁺ from wastewater solutions. From the two-stage batch adsorber design study, the minimum operating time to determine a specified amount of Pb²⁺ and Cd²⁺ removal was developed. The two-stage batch adsorption process predicted less than half the minimum contact time to reach equilibrium in the one-stage process for the adsorption of Pb²⁺ and Cd²⁺ by NTB-modified kaolinite clay adsorbent and requires 0.05 times the mass of the adsorbent for the single-stage batch adsorption at the same operating conditions.     

KINETICS OF ION EXCHANGE IN SOIL ORGANIC MATTER. IV. ADSORPTION AND DESORPTION OF Pb2+, Cu2+, Cd2+, Zn2+ AND Ca2+ BY PEAT

The equilibria as well as the rates of adsorption and desorption of the ions Pb²⁺, Cu²⁺, Cd²⁺, Zn²⁺, and Ca²⁺ by soil organic matter were determined in batch experiments as a function of the amount of metal ions added to an aqueous suspension of HCl-washed peat. Simultaneous determination of the metal ions and hydrogen ions in the solution by atomic absorption spectrophotometry and pH-measurements showed that the adsorption of one divalent metal ion by peat was coupled with the release of two hydrogen ions. Since this equivalent ion-exchange process causes a corresponding increase of the electric conductivity of the solution, the rates of the adsorption and desorption processes were determined by an immersed conductivity electrode. The distribution coefficients show that the selective order for the metal adsorption by peat is Pb²⁺ > Cu²⁺ > Cd²⁺≌ Zn²⁺ > Ca²⁺ in the pH range of 3·5 to 4·5. The slope of -2, as observed in a double logarithmic plot of the distribution coefficients versus the total solution concentration confirms the equivalence of the ion-exchange process of divalent metal ions for monovalent H₃O⁺ -ions in peat. The absolute rates of adsorption, as well as the rates for the fractional attainment of the equilibrium, increase with increasing amounts of metal ions added. This behaviour is also observed for the subsequent desorption of the metal ions by H₃O⁺-ions. At a given amount of metal ions added, the absolute rates of adsorption decrease in the order Pb²⁺ > Cu²⁺ > Cd²⁺ > Zn²⁺ > Ca²⁺, while the rates for the fractional attainment of the equilibrium decrease in the order Ca²⁺ > Zn²⁺≌ Cd²⁺ > Pb²⁺ > Cu²⁺. The half times for adsorption and desorption were in the range of 5 to 15 sec.     

Using humic products as amendments to restore Zn and Pb polluted soil: a case study using rapid screening phytotest endpoint

Purpose

Heavy metal contamination is a priority issue affecting millions of hectares of soil throughout the world. One of the most promising, environmentally friendly, and cost-effective approaches to restore polluted soils could be applying organic amendments. We investigated the remediation potential of three types of humic products with regard to their effect on the bioavailability of Pb and Zn, content of nutrients, and the ability to mitigate acute phytotoxicity in contaminated soil.

Materials and methods

Spodosol samples were spiked with Pb (550 mg kg^?1) and Zn (880 mg kg^?1). Then, two different commercial humic products (from peat and lignosulfonate) and natural humic acids (from brown oxidized coal) were added in two doses to reach an equal content of carbon: a 10% increment and a 30% increment of the initial total organic carbon in the soil. After 30 days, the content of metals and nutrients (S, K, Na, Ca, Mn, P) was determined by the sequential extraction (i?H₂O, ii?NH₄COOH pH 4.8, iii–CH₃COOH). The effect of humic products on heavy metals bioavailability was evaluated using the calculated partition indexes. Seed germination and root elongation of Sinapis alba were also determined. Chemical and biochemical variables were aggregated by the principal component analysis.

Results and discussion

Humic products reduced the amount of bioavailable fractions of Pb and Zn in soils. The partition index, which quantitatively describes bioavailable fractions of the Zn and Pb in the soil, was 28–49% lower than in the spiked (Pb+Zn) control. The inhibition of root elongation and seed germination of mustard by Zn and Pb was significantly mitigated by humic products; in the soil test, the root length and seed germination were up to 36–87% higher than those of the Pb+Zn control and did not differ from those in the non-amended treatments. This effect may have been associated with the structural differences (H/C and O/C ratio) and content of nutrients (Na and K) in humic products.

Conclusions

Commercial humic products used in poor multi-contaminated soils can maintain plant growth by improving nutrient status due to heavy metals immobilization and can be a promising approach to remediate the soil contaminated with heavy metals at extremely high concentrations.

     

Comparison of the <Emphasis Type="Italic">Rhodotorula mucilaginosa</Emphasis> Biofilm and Planktonic Culture on Heavy Metal Susceptibility and Removal Potential

This study compares the effect of heavy metals (Hg²⁺, Cu²⁺, and Pb²⁺) on the Rhodotorula mucilaginosa and Saccharomyces boulardii biofilm and planktonic cells. A MBEC^TM-HTP assay was used to test the levels of tolerance to heavy metals. The minimum inhibitory concentration (MICp) and minimum lethal concentration (MLCp) of the R. mucilaginosa and S. boulardii planktonic cells were determined, as well as minimum biofilm eradication concentration (MBEC). Metal removal efficiency was determined by batch biosorption assay. Previous studies had focused on heavy metal tolerance and removal efficiency of planktonic cells from Rhodotorula species only. Hence, our study presents and compares results for metal tolerance and removal efficiency of the R. mucilaginosa planktonic cells and biofilm. Biofilm tolerance was higher than the planktonic cells. The R. mucilaginosa planktonic cells showed the tolerance in the presence of Hg²⁺ (MICp 0.08 mM), Cu²⁺ (MICp 6.40 mM), and Pb²⁺ (MICp 3.51 mM), while the S. boulardii planktonic cells only tolerated Pb²⁺ (MICp 0.43 mM). The R. mucilaginosa biofilm showed the highest tolerance in the presence of Hg²⁺ (MBEC >0.31 mM), Cu²⁺(MBEC >12.81 mM), Pb²⁺ (MBEC >7.12 mM), and obtained results were confirmed by fluorescence microscopy. S. boulardii did not show potential in biofilm formation. The R. mucilaginosa biofilm exhibited better efficiency in removal of all tested metals than the planktonic cells. Metal removal efficiency was in the range from 4.79–10.25% for planktonic cells and 91.71–95.39% for biofilm.     

Infrared spectra of Cu2+ Pb2+ and Ca2+ complexes of soil humic substances

An infrared spectroscopic investigation of the complexes of Cu²⁺, Pb²⁺, and Ca²⁺ with humic and fulvic acids demonstrated the participation of OH and CO groups in addition to COOH in the binding of heavy-metal cations. The degree to which metal-carboxylate linkages are ionic or covalent cannot be accurately determined from the positions of antisymmetric and symmetric carboxylate stretching vibrations due to interference from covalent bonding with other groups. The apparent order of the reaction of three divalent cations with humic and fulvic acids was Cu²⁺ > Pb²⁺ > Ca²⁺.     

Effects of combinations of heavy metals on hill activity of Azolla pinnata

The effects of combinations of Hg, As, Ph, Cu, Cd, and Cr on Hill activity of Azolla pinnata R.Br. were studied. All of the combinations of heavy metals decreased Hill activity of chloroplasts over control values. The effects were most pronounced with the treatments of (Hg + As + Pb + Cu + Cd + Cr), followed by (Hg + As + Pb + Cu + Cd). The degree of inhibition of Hill activity in the species by combinations of heavy metals is less due to antagonistic effects (when 2 or 3 metals in combinations), and is much higher due to synergism (when 4 or more metals in combinations) than that by individual heavy metals tested. The harmful effects of the individual metals were, in general, found by the treatments in the order: Cd > Hg > Cu > As > Pb > Cr.