Vanadium and molybdenum concentrations in particulate from Palermo (Italy): analytical methods using voltammetry

The main purpose of this work was to develop a reliable method for the determination of vanadium (V) and molybdenum (Mo) in atmosphere particles or aerosols because they can not be readily measured using conventional techniques. For this research, 30 particulate samples were collected from five different stations located at Palermo, Italy. We used the catalytic adsorptive stripping voltammetry and differential pulsed voltammetry to measure V and Mo in atmospheric particulate, respectively. The represented method includes advantages of high sensitivity, high selectivity, simplicity, reproducibility, speed and low costs. The quantification limits for V and Mo are, respectively, 0.57 and 0.80 ng·m⁻³. The precision, expressed as relative standard deviation (RSD %), was about 2% for both metals. The mean recoveries of added V and Mo were about 99.5% and ranged from 97% to 101%. Vanadium concentrations in particulate samples collected in Palermo area ranged from 0.57 to 7.7 ng·m⁻³, while Mo concentrations were in the range 0.8–51 ng·m⁻³. In many cases the concentrations of two elements in the particulate samples fall below the detection limits. The mean concentrations for V and Mo in particulate samples, collected in Palermo area, were respectively 3.1 and 5.9 ng·m⁻³.     

The acidobasic and complexation properties of Humic acids

Complexation of Humic Acids (HA) of different origin, like Fluka, and especially those extracted from bohemian brown coal, with cadmium(II) and lead(II) was studied at pH 5.0 using differential pulse anodic stripping voltammetry. Conditions close to those present in the environment were chosen with 3‐ 10^‐4 moll^‐4 for HAs and 2. 10^‐8‐l . 10^‐5 moll^‐1 for Cd(II) and Pb(II). Stability constants evaluation was done assuming the electrode process is diffusion controlled and the complexes are labile. Obtained log K values were in the range 4.49–5.25 for Cd(II) and as expected the higher log K values 6.05–6.60 were found for Pb(II). There was no significant difference between complexation properties of HA extracted from bohemian brown coal and that of Fluka. The results obtained are in good agreement with the literature and those obtained by ISE in our laboratory.     

Comparison of zinc complexation properties of dissolved natural organic matter from different surface waters

The zinc binding characteristics of natural organic matter (NOM) from several representative surface waters were studied and compared. NOM samples were concentrated by reverse osmosis. The samples were treated in the laboratory to remove trace metals. Square wave anodic stripping voltammetry (SWASV) was used to study zinc complexing properties of those NOM samples at fixed pH, ionic strength, and dissolved organic carbon (DOC) concentrations. Experimental data were compared to the predictions from the Windermere Humic Aqueous Model (WHAM) Version VI. At the same pH, ionic strength, and temperature, the zinc titration curves for NOM samples from different surface water sources tested in our study almost overlapped each other, indicating similarity in zinc binding properties of the NOM. A discrete two-site model gave good fits to our experimental titration data. Non-linear fitting by FITEQL 4.0 shows that the conditional zinc binding constants at the same pH are similar for NOM from different sources, indicating that zinc complexation characteristics of the NOM used in our study do not depend on their origin and one set of binding parameters can be used to represent Zn-NOM complexation for NOM samples from those different surface water sources representing geographically diverse locations. In addition, the total ligand concentrations (L(1,T), L(2,T), and L(T)) of all NOM show no observable gradation with increasing pH (L(1,T)=2.06+/-0.80 mmol/g carbon; L(2,T)=0.12+/-0.04 mmol/g carbon; L(T)=2.18+/-0.78 mmol/g carbon), while the conditional binding constants of zinc by NOM (logK(ZnL)(c)) show a linear increase with increasing pH(logK(1)(c)(pH=6.0)=4.69+/-0.25; logK(1)(c)(pH=7.0)=4.94+/-0.10; logK(1)(c)(pH=8.0)=5.25+/-0.006; logK(2)(c)(pH=6.0)=6.29+/-0.13; logK(2)(c)(pH=7.0)=6.55+/-0.08; logK(2)(c)(pH=8.0)=6.86+/-0.023) with a slope of ca. 0.28, indicating the zinc-NOM complexes become more stable at higher pH. The WHAM VI predicted free zinc ion activities at high zinc concentrations agree with our experimental results at pH 6.0, 7.0, and 8.0. However, the zinc binding of these NOM samples is over estimated by WHAM VI at zinc concentrations below 10(-6) M at pH 8.0.     

Effect of Fe-chelating complexes on a novel M2FC performance with ferric chloride and ferricyanide catholytes

As an effort to better utilize the microbial fuel cell (MFC) technology, we previously proposed an innovative MFC system named M2FC consisting of ferric-based MFC part and ferrous-based fuel cell (FC) part. In this reactor, ferric ion, the catholyte in the MFC part, was efficiently regenerated by the FC part with the generation of additional electricity. When both units were operated separately, the ferric-based MFC part produced approximately 1360 mW m⁻² of power density with FeCl₃ as catholyte and Fe-citrate as anolyte. The ferrous-based FC part with FeCl₃ as catholyte and Fe-EDTA as anolyte displayed the highest power density (1500 mW m⁻²), while that with ferricyanide as catholyte and Fe-noligand as anolyte had the lowest power density (380 mW m⁻²). The types of catholytes and chelating complexes as anolyte were found to play important roles in the reduction of ferric ions and oxidation of ferrous ion. Linear sweep voltammetry results supported that the cathode electrolytes were electrically active and these agreed well with the M2FC reactor performance. These results clearly showed that ligands played critical role in the efficiency and rate for recycling iron ion and thus the M2FC performance.     

Electrochemical treatment of aqueous wastes containing pyrogallol by BDD-anodic oxidation

In this work, the electrochemical oxidation of pyrogallol (1,2,3-trihydroxybenzene) on boron-doped diamond anodes has been studied. The voltammetric results showed that pyrogallol oxidation takes place in the same potential region as that of phenol where the supporting electrolyte is stable. Synthetic wastewaters containing pyrogallol have been treated in a bench-scale electrolysis plant. This plant operates in a discontinuous mode by recirculating the waste continuously through a single-chamber electrochemical flow cell. The complete mineralization of pyrogallol and the electro-generated pollutants is obtained in the electrolytic device. HPLC analyses show the formation of carboxylic acids as the main intermediates. The efficiency of the electrochemical process was found to depend mainly on the pollutant concentration present in the waste and on the applied current density. The high efficiency of this technology can be explained in terms of the direct electro-oxidation at the BDD surface and the oxidation carried out by hydroxyl radicals and other electro-generated oxidants.     

钛修饰电极的制备及电化学性能比较

通过电沉积法在钛网(Ti)上负载钯、钯镍双金属及聚吡咯(PPy)双金属,对比研究不同修饰对电极电化学催化活性的影响。循环伏安测试(CV)表明,在最佳制备条件下,Pd/Ti电极在-500 mV(以Hg/Hg₂SO₄为参比电极)左右获得氢吸附峰值为-59.47 mA;引入Ni制备双金属修饰电极(PdNi/Ti电极)获得氢吸附峰值为-64.40 mA,双金属修饰电极表现出较好的电催化性能;吡咯修饰后制得的Pd-Ni/PPy/Ti电极获得的氢吸附峰值最大,峰值为-80.14 mA,电催化性能更优。扫描电镜(SEM)分析了Ni和PPy的引入对电极表面形态的改变。利用原子发射光谱(AES)分析了电极表面Pd、Ni金属的负载量。实验表明,Ni与PPy的引入使Pd-Ni/PPy/Ti电极在大大减少钯负载量的情况下,仍具有很好的电催化性能,电化学脱氯潜能也很大。     

溶出伏安法快速测定水中砷的研究

利用阳极溶出伏安法实现水体中砷含量的现场快速分析。方法检出限为0.007 mg／L,测定范围为0.03 mg／L～0.14 mg／L。该法可由单标法测定和标准添加法测定。采用单标测定,对国家标准物质的分析误差在20％以内,加标回收率在94.0％～126.2％之间;采用标添测定,对国家标准物质的分析误差在5％以内,加标回收率在93.5％～104.8％之间。对浓度为0.01、0.02、0.05、0.10 mg／L的统一样品进行测定, RSD在7.0％～18.7％之间。特别是浓度在0.05 mg／L以上时,RSD在10％以内,完全满足应急状态下As项目Ⅲ类水分析要求。完全满足应急状态下现场分析的要求。     

Behaviour and Quantification Studies of Terbacil and Lenacil in Environmental Samples Using Cyclic and Adsorptive Stripping Voltammetry at Hanging Mercury Drop Electrode

The cyclic voltammograms of terbacil and lenacil at the hanging mercury drop electrode showed a single well defined four electron irreversible peak in universal buffer of pH 4.0 for both compounds. The peak potentials were shifted to more negative values on the increase of pH of the medium, implying the involvement of protons in the electrode reaction and that the proton transfer reaction precedes the proper electrode process. The four electron single peak may be attributed to the simultaneous reduction of carbonyl groups present in 2 and 4 in pyrimidine ring of terbacil and lenacil to the corresponding hydroxy derivative. Based on the interfacial adsorptive character of the terbacil and lenacil onto the mercury electrode surface, a simple sensitive and low cost differential pulse adsorptive stripping voltammetric procedure was optimized for the analysis of terbacil and lenacil. The optimal operational conditions of the proposed procedure were accumulation potential E _acc = −0.4 V, accumulation time t _acc = 80 s, scan rate = 40 mV s⁻¹, pulse amplitude = 25 mV using a universal buffer pH 4.0 as a supporting electrolyte. The linear concentration range was found to be 1.5 × 10⁻⁵ to 1.2 × 10⁻⁹ mol/l and 1.5 × 10⁻⁵ to 2.5 × 10⁻⁸ mol/l with the lower detection limit of 1.22 × 10⁻⁹ and 2.0 × 10⁻⁸ mol/l. The correlation coefficient and relative standard deviation values are found to be 0.942, 0.996, 1.64% and 1.23%, respectively, for 10 replicants. The procedure was successfully applied for determination of terbacil and lenacil in formulations, mixed formulations, environmental samples such as fruit samples and spiked water samples.     

土壤中二价铁离子的伏安法测定

利用二价铁离子的联吡啶络合物,示差脉冲伏安法测定土壤中的二价铁离子．结果表明:二价铁离子的浓度与铁联吡啶络合物的峰电流在１．６×１０－６－９．８×１０－６ｍｏｌ·ｌ－１和９．８×１０－６－６．６× １０－５ｍｏｌ·ｌ－１浓度范围内成正比,检测下限为４．１× １０－７ｍｏｌ·ｌ－１,相对标准偏差为０．８４%(ｎ＝６)．在该方法中,联吡啶的浓度对二价铁离子联吡啶络合物的峰电位、峰电流及半峰宽度有影响,而测定体系的ｐＨ值和支持电解质的浓度对二价铁离子联吡啶络合物的峰电位、峰电流及半峰宽度影响较小．     

脉冲伏安法测定乳品废水中的Cd(Ⅱ)和Pb(Ⅱ)离子

采用差分脉冲伏安法在CH3COOH-CH3COONa底液中测定乳品工业废水中的Cd2 和Pb2 等金属离子,并讨论了支持电解质、pH值的影响及部分离子的干扰等.在pH值为3-4范围内,铅的出峰电位为-0.36V.在正确是的条件下,对乳品废水中铅和镉的回收率分别为94%-106.5%和97%-103.5%.