Determination of Ionic to Colloid Form Ratio of Microcomponents in Fresh Water by Colloidal Chemical Extraction

Colloid forms of a series of microcomponents were studied in aqueous solutions by the colloidal chemical extraction method in combination with ICP MS. The potential of this combined method for determination of the total fraction of the colloid species and distribution of microcomponents of stable and radioactive elements throughout colloid forms at their natural abundance in potable water is examined.     

Removal of 2,4,6-trichlorophenol from a solution by humic acids repeatedly extracted from a peat soil

Humic acid (HA) is one of the major components of soil organic matter. It strongly affects the sorption behavior of organic and inorganic contaminants in soils. To obtain a better understanding of the interactions of contaminants with HA, a repeated extraction technique has been applied to a peat soil to obtain HA fractions with varying aliphaticity and aromaticity, which were subsequently correlated to the sorption properties of 2,4,6-trichlorophenol (TCP). HA fractions were extracted repeatedly using an alkaline solution and each HA fraction was separated into two portions with an air-drying or re-suspending (denoted as RSHAs) process. Solid-state (13)C NMR and elemental analysis demonstrated that the aromaticity and polarity of HAs decreased with extractions. Kinetic results indicated that air-dried HAs exhibited two-step first order sorption behavior with a rapid stage followed by a slower stage. The slower sorption is attributed to the diffusion of 2,4,6-TCP in the condensed aromatic domains of HAs. Conversely, sorption of 2,4,6-TCP on RSHAs was extremely rapid and could not be fitted with any kinetic model. For air-dried HAs the sorption capacity (K(oc)) was weakly correlated with the chemical compositions of HAs. However, a positive trend between K(oc) and aromaticity was observed for RSHAs. Compared with the results of air-dried HAs with their counterparts of RSHAs, it is therefore concluded that air-drying may alter the structure of HAs through artificially creating a more condensed domain in HAs. The structural alternation may result in an incorrect interpretation of the relationship between sorption capacity and chemical composition of HAs and a misjudgment of the transport behavior of 2,4,6-TCP in soils and sediments.     

Freshwater plankton as sorbent: Differences in the sorption properties of live and dead plankton

The distribution coefficients of a number of chemical elements between live and dead plankton and aquatic medium were determined experimentally. The sorption isotherms of macro- (Mg, Ca) and microelements (Sr, Ba, Mn, Fe, REE, Th, U) on plankton as biosorbent under the conditions when their level exceeds the natural background in water follow the Langmuir equation. The equation parameters for samples of live and dead plankton differ statistically significantly. In the sorption affinity level (logK_d [mL g^–1] ~3–5), freshwater plankton can be considered as effective biosorbent. Electron microscopic examination with local multielement analysis revealed abnormally high content of manganese in the form of adsorption colloid for Trachelomonas acanthostoma var. acanthostoma plankton alga in separate water samples taken from the cooling pond of the Beloyarsk NPP.     

Sorption properties of silicate materials based on Ca2SiO4 in humic acid solutions

The effect of humic acids (HA) in river water on the sorption properties of metallurgical slag (major component Ca₂SiO₄) was revealed in batch sorption experiments. Interaction of HA with sorbate cations in solution and with the sorbent surface affects the character of the sorption process found previously for dicalcium silicate. This interaction results in a decrease in the affinity of dicalcium silicate to multiple-charged cations [REE(III), U(VI), Th(IV)] in their sorption from river water by more than an order of magnitude. Possible chemical transformations responsible for a decrease in the sorption affinity of the silicate sorbent are discussed: complexation of HA with metal cations in the aqueous phase and competing reactions of the sorption of HA and calcium humate complexes on the surface of sorbent particles.     

Formation of a sol of mixed U(IV) · U(VI) hydroxide in aqueous solutions with pH 1.5–4

containing U(IV) polymer start to form. With an increase in pH from 1.5 to 4 or in temperature, the induction period becomes shorter. Under anaerobic conditions, the colloidal solution is stable for more than a month. Centrifugation at 8000 rpm (5500g) allows separation of the colloidal particles from the liquid phase. The colloid slowly dissolves in mineral acids saturated with argon or in a K₂CO₃ solution, whereas precipitates of individual freshly prepared U(IV) and U(VI) hydroxides dissolve rapidly. Short UV irradia-of a UO₂(ClO₄)₂ solution saturated with argon and containing ethanol (pH 2.5) results in the appearance of U(V) which then disproportionates, and U(IV) forms with U(VI) a black colloid similar to that arising on mixing U(IV) and U(VI) solutions.     

Elemental and spectroscopic characterization of humic-acid-like compounds during composting of olive mill by-products

Humic acids (HAs) were isolated at different stages of composting from two piles of solid olive mill residues (SOR) treated for the first 30 days with tap water (pile C1) or olive mill wastewater (pile C2), for a total composting period of 9 months. The HA fractions were characterized by elemental analysis, UV-visible, Fourier transform infrared and fluorescence spectroscopy in order to monitor humification process and the maturity of the composts. As composting proceeded, the elemental composition of the humic acids showed a decrease in C and H content, and in the C/N ratio, and an increase in N and O contents and in the C/H and O/C ratios. These changes could be attributed to a loss of aliphatic groups and to an increase of aromatic character, polycondensation and degree of oxidation of the HAs. Spectroscopic data agree and support these results, suggesting that the chemical and structural features of the HAs of both composts tend to reach those typical of native soil HAs, that is compounds with a high degree of humification and a high molecular weight and complexity. Therefore, both composting processes seem suitable to produce well-humified organic matter, with important benefits for their use in soil amendment. No differences appeared between the two treatments concerning the humic character of the two final composts.     

Comparison of adsorption capacity of young brown coals and humic acids prepared from different coal mines in Anatolia

Binding of Zn2+ and Cd2+ cations to relatively young brown coals YBC (lignite), humic acids (HAs) and commercial humic acid (CHA) were studied in aqueous media at pH 2.7-6 by polarographic method. This study was conducted to evaluate the removal of heavy metals in an aquatic system without prior treatment. The general principles of cation binding to YBC and humic materials are discussed. Sorption of heavy metal ions (Zn2+ and Cd2+) on samples of YBCs from three areas (Ilgin, Beysehir, and Ermenek) in the vicinity of the city of Konya in Anatolia (Turkey) were compared with sorption of these metal ions on HAs, prepared from these YBCs. The ability of both types of sorbent to remove metals from aqueous solutions was studied as a function of pH and concentration of initial metal solutions. Sorption depends strongly on pH, the origin of the YBC and on the nature of the metal ion. Whereas, for YBCs the main ligand groups seem to be carboxylate ions, this is not the case for the HA polymers, prepared from three YBCs, which differ substantially from properties of commercial samples of "HA". The process is very efficient especially in the case of low concentrations of pollutants in water, where common methods are either economically unfavorable or technically complicated. Of the two metal ions examined, Cd2+ was found to form the most stable HA complexes, followed by Zn. Effective removal of metals was demonstrated at pH-values of 5-5.7. The adsorption isotherm was measured at 25 degrees C, using adsorptive solutions at the optimum pH-value to determine the adsorption capacity. An important aspect of the proposed method was that the removal was performed on several metals at a pH-range in which a given metal undergoes an adsorption process making the method useful for wastewater treatment.     

Sorption behavior of strontium ions in humic acid solutions

As shown by distribution, thermodynamic modeling, and dispersion analysis methods, the ability of freshly precipitated humic acid to take up Sr(II) ions is influenced by energy heterogeneity of its sorption sites, characteristic of both natural and synthetic samples. It is manifested in that the distribution coefficient K _d exceeds 1.9 × 10⁴ mL g^–1 at Sr(II) concentrations in solutions lower than 20 μg L^–1 but is equal to 1.9 × 10³ mL g^–1 at Sr(II) concentrations higher than 1 mg L^–1. In solutions with ultralow Sr(II) concentrations, humic acids exhibit high affinity for the humate complex Sr(HA) and do not interact with the complex Sr(HA)₂.     

Possibilities of using composite track membranes with nitride coating for fractionation of microelements in natural water

A plasma chemical procedure was developed for preparing composite track membranes with a conducting coating of titanium nitride particles having a complex hierarchic structure. Owing to oxynitride deposition on the surface of a poly(ethylene terephthalate) track membane, the membrane channels become asymmetrical and the membrane strength is enhanced. The pore opening size in composite membranes can be varied in a wide range by varying the synthesis parameters. The possibilities of directly using composite track membranes for electron-microscopic imaging of the form and composition of nonconducting mineral and biological substances and for qualitative and quantitative size fractionation of microelements in natural water by ultrafiltration were demonstrated by the example of a series of macro- (C, Al, Si, Mg, Fe, P) and microelements (Sr, U, Th).     

Dissolution of monazite in humic solutions

Physicochemical analysis shows that prolonged contact (15 days) of monazite powder with solutions containing humic acids (HA) of various acidities leads to an increase by 1–2 orders of magnitude in the dissolution of heavy p, d, and f elements present in monazite. The concentration of the dissolved elements depends on the initial content of HA in solution and on pH. These factors should be taken into account when using inorganic phosphates as matrices for long-term storage of radioactive and toxic elements.     

Influence of inorganic soil components and humic substances on the mechanochemical removal of pentachlorophenol

The influence of the presence of humic acids of different origin on the catalytic transformation of pentachlorophenol (PCP) by two metal oxides, ferrihydrite and birnessite, using mechanochemical contact was studied. The mechanochemical dry contact with light grinding of PCP and birnessite was more effective than that observed in the presence of ferrihydrite (approximately 70 and 40% of PCP removal after 20 days, respectively). The removal of PCP by birnessite and ferrihydrite was significantly enhanced in the presence of humic acid (HA). The different origin of humic acids (agricultural, forest and commercial) showed a slight influence on the overall reaction. The commercial HA, when mixed with birnessite, was more effective in reducing PCP concentration compared to the others two HAs investigated. The transformation process in the presence of birnessite with and without HA was accompanied by the release of four chlorides per molecule of PCP transformed.     

海洋沉积物DNA提取前的简易脱腐方法研究

针对海洋沉积环境样品DNA提取中的腐殖酸去除难题,采取先脱除腐殖酸再提取DNA的策略,进行了海洋沉积物DNA提取前的简易脱腐方法研究.依据腐殖酸的理化性质, 遴选出由Tris-HCl、EDTA、Na4P2O7、NaCl、PVP、Triton X-100及脱脂奶粉组成脱腐缓冲液,有效地脱除了腐殖酸.之后采用温和的溶菌酶-蛋白酶K-SDS直接裂解法,获取了大片段(分子量21kb以上)可进行rpoB 基因PCR扩增的海洋沉积物DNA,为海洋沉积环境分子生态学研究与海洋生物活性物质开发奠定了基础.     

Interaction of pesticides with humic compounds and their metal complexes

The interaction of pesticides with humic compounds (humic and fulvic acids) and with their metal complexes was studied potentiometrically and radiometrically, using the pesticides Aldicarb and Methomyl, and the herbicide Ametryne. The metal humate or fulvate complexes were prepared by precipitation of the complexes using Co²⁺, Zn²⁺, or Sr²⁺. The results indicated that Aldicarb, Methomyl, and Ametryne form stable complexes with humic acid (HA) and fulvic acid (FA). The complexation strength increases in the order Aldicarb ≤ Methomyl < Ametryne. The complexes of Aldicarb and Methomyl with HA and FA are stronger than the metal humate/fulvate complexes with Co²⁺, Zn²⁺, and Sr²⁺, and these pesticides displace the metal ions. Ametryne adds to the metal humate/fulvate by physical adsorption or ligand exchange. The complexation of Aldicarb and Methomyl with humic compounds causes the release of radionuclides (⁶⁰Co, ⁶⁵Zn, ⁹⁰Sr) from the soil organic matter to the solution. The pH exerts a decisive effect on the complexation of the pesticides with humic compounds. Published in Russian in Radiokhimiya, 2006, Vol. 48, No. 4, pp. 377–383. The text was submitted by the authors in English.     

Speciation and determination of ultra trace amounts of chromium by solidified floating organic drop microextraction (SFODME) and graphite furnace atomic absorption spectrometry

Solidified floating organic drop microextraction (SFODME) method in combination with graphite furnace atomic absorption spectrometry (GFAAS) has been used for the determination of chromium species in water and urine samples. 1-undecanol containing 2-thenoyltrifluoroacetone (TTA) was used as a selective chelating agent for the extraction of Cr(III). The total Cr was determined after the reduction of Cr(VI) to Cr(III) with hydroxylamine. The concentration of Cr(VI) was determined from the difference between the concentration of total chromium and the Cr(III). Several variables such as the sample pH, concentration of TTA, salt concentration, extraction time and the sample volume were investigated in detail. Under the optimum conditions, the limit of detection of the proposed method was 0.006 μg l(-1) for Cr(III) and the relative standard deviation for six replicate determinations at 0.1 μg l(-1) Cr(III) was 5.1%. The proposed method was successfully applied for the determination of chromium species in tap water, well water, mineral water, and urine samples.     

Nanoscale size dependence in the conjugation of amyloid beta and ovalbumin proteins on the surface of gold colloidal particles

Absorption spectroscopy was utilized to investigate the conjugation of amyloid β protein solution (Aβ(1-40)) and chicken egg albumin (ovalbumin) with various sizes of gold colloidal nanoparticles for various pHs, ranging from pH?2 to pH?10. The pH value that indicates the colour change, pH(o), exhibited colloidal size dependence for both Aβ(1-40) and ovalbumin coated particles. In particular, Aβ(1-40) coated gold colloidal particles exhibited non-continuous size dependence peaking at 40 and 80?nm, implying that their corresponding cage-like structures provide efficient net charge cancellation at these core sizes. Remarkably, only the pH(o) value for ovalbumin coated 80?nm gold colloid was pH>7, and a specific cage-like structure is speculated to have a positive net charge facing outward when ovalbumin self-assembles over this particular gold colloid. The previously reported reversible colour change between pH 4 and 10 took place only with Aβ(1-40) coated 20?nm gold colloids; this was also explored with ovalbumin coated gold colloids. Interestingly, gold colloidal nanoparticles showed a quasi-reversible colour change when they were coated with ovalbumin for all test sizes. The ovalbumin coated gold colloid was found to maintain reversible properties longer than Aβ(1-40) coated gold colloid.     

碳纳米管吸附腐植酸的动力学、热力学及机理研究

针对天然水中腐植酸(HA)类溶解性有机物去除问题, 采用多壁碳纳米管为吸附剂, 在不同的pH值、吸附剂量、初始HA浓度下进行吸附动力学实验, 用准二级速率方程拟合了动力学数据, 其线性相关度在0.99以上, 拟合得到的平衡吸附量为27mg/g,与实验结果(25.5 mg/g)基本一致. 在25~50℃下进行了碳纳米管吸附腐植酸的等温吸附实验, 以Langmuir模型拟合的平衡吸附量为29.7mg/g, 与实验结果相近. 用Clapeyron-Clausius与Gibbs- Helmholtz方程计算的自由能(Δ G)、焓(Δ H)、熵(Δ S)皆为负值, 说明碳纳米管对腐植酸的吸附为放热熵减过程. 碳纳米管的表面、管间隙、管内腔及管束之间形成的束聚孔为其有效吸附点位, 腐植酸与碳纳米管间的π-π作用也是吸附的主要原因之一.     

不同模拟体液对硼硅酸盐生物活性玻璃基骨水泥矿化性能的影响

硼硅酸盐生物活性玻璃基(Borosilicate bioactive glass-based, BBG)骨水泥由于其优异的生物活性和生物降解性, 在治疗骨质疏松性骨折以及骨肿瘤、骨创伤、骨髓炎等疾病方面具有重要的应用前景, 受到人们的广泛关注。为进一步了解氨基酸对其植入生物体内后的矿化影响, 本研究在常规的SBF溶液中添加了不同种类及浓度的氨基酸物质, 重点研究对植入体表面形貌的影响。同时为在矿化过程中同步形成白磷钙矿(Whitlockite, WH)和羟基磷灰石(hydroxyapatite, HA), 调整了SBF溶液的温度以及酸碱度和Mg²⁺浓度, 研究了不同SBF溶液中BBG骨水泥表面形成的矿化产物。研究结果表明, 不同的氨基酸及浓度的变化对矿化产物的影响有较大差异, 天冬氨酸和赖氨酸的浓度变化影响矿物的长径比, 而甘氨酸对矿物形貌的影响较小。将硼硅酸盐生物活性玻璃压片放置在70 ℃下的高Mg²⁺浓度的酸性(pH=3.5)SBF溶液中浸泡一定时间后, 能够获得HA/WH的复相矿物。     

Effect of persulfate on the oxidation of benzotriazole and humic acid by e-beam irradiation

These days, the use of persulfate in advanced oxidation processes (AOPs) has gained more attention as an emerging clean and efficient technology to degrade the organic pollutants. The objective of this study was to investigate the effect of the addition of persulfate on the oxidation of benzotriazole (BT) and humic acids (HAs) by irradiation. The degradation of BT (3.7 μM) was followed under the influence of persulfate addition (200-500 μM) in combination with a fixed radiation dose (15 Gy) in the absence and presence of HA (5 and 20mg/L) in deionized water. The main results obtained in this study on the degradation of BT in the presence of HA showed a different effect of S(2)O(8)(2-) addition during irradiation, depending on whether HA are oxidized or not-oxidized. (1) An inhibitory effect of S(2)O(8)(2-) was observed in the presence of non-oxidized HA. (2) The removal of BT was generally more important during irradiation in the presence of S(2)O(8)(2-) when HA is pre-oxidized. This could be explained by the different structures of humic acids. These differences of structures of HA were identified by physico-chemical parameters such as the absorbance in the UV (254 nm), the fluorescence and the SUVA measurement.     

Effect of short-term natural weathering on MSWI and wood waste bottom ash leaching behaviour

Short term natural weathering was applied on municipal solid waste (MSW) and wood waste incinerator bottom ash (BA). The materials were analysed at different steps of treatment and characterized for chemical and mineralogical composition. Both short and long term leaching behaviour of main elements and heavy metals were investigated as well. Lead, zinc and copper were the main heavy metals to be released. After 12 weeks of treatment the concentration of leached zinc decreased. Lead concentration was not found to be influenced by pH and decreased only for the biomass samples. Weathering did not have beneficial effects on copper leaching, which was well described by complexation processes with DOC. The findings from the experimental campaign indicated that weathering reactions improved the mineral stability of the analysed materials but, in contrast with previous works, the treatment was not sufficient to guarantee pH stability and to comply with leaching law limits.     

Coupling of HDPE/hydroxyapatite composites by silane-based methodologies

Several coupling treatments based on silane chemicals were investigated for the development of high density (HDPE)/hydroxyapatite (HA) composites. Two HA powders, sintered HA (HAs) and non sintered HA (HAns), were studied in combination with five silanes, namely y-methacryloxy propyltrimethoxy silane (MEMO), 3-(2-aminoethyl)aminopropyltrimethoxy silane (DAMO), vinyltrimethoxy silane (VTMO), 3-aminopropyltriethoxy silane (AMEO) and trimethoxypropyl silane (PTMO). The HA particles were treated by a dipping in method or by spraying with silane solutions. After drying, the treated powders were compounded with HDPE or HDPE with acrylic acid and/or organic peroxide and subsequently compression molded. The tensile test specimens obtained from the molded plates were tensile tested and their fracture surfaces were observed by scanning electron microscopy (SEM). For the sintered HA (HAs) composites, the most effective coupling treatments concerning stiffness are those based on MEMO and AMEO. The low influence of these coupling procedures on strength is believed to be associated to the low volume fraction and the relatively smooth surface of the used HA particles. For the non-sintered HA (HAns) composites, it was possible to improve significantly both the stiffness and the strength. Amino silanes demonstrated to be highly efficient concerning strength enhancement. The higher effectiveness of the coupling treatments for HAns filled composites is attributed to their higher particle surface area, smaller particle size distribution and expected higher chemical reactivity. For both cases, the improvement in mechanical performance after the coupling treatment is consistent with the enhancement in interfacial adhesion observed by SEM.