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The use of surface-enhanced Raman scattering (SERS) for detection of PAHs in the Gulf of Gdańsk (Baltic Sea)
2012
(Heinz-Detlef),
A field operable surface enhanced Raman scattering (SERS) sensor system was applied for the first time under real conditions for the detection of polycyclic aromatic hydrocarbons (PAHs) as markers for petroleum hydrocarbons in the Gulf of Gdańsk (Baltic Sea). At six stations, seawater samples were taken, and the sensor system was applied in situ simultaneously. These measurements were compared to the results of conventional GC/MS laboratory analysis of the PAH concentrations in the seawater samples. For a PAH concentration above 150ng(12PAH)l⁻¹, there was agreement between the SERS sensor and the GC/MS determinations. A standard addition experiment yielded a PAH concentration of 900ngl⁻¹ at the Gdańsk Harbor, which was of the same order as the GC/MS determinations of 12PAHs (200ng(12PAH)l⁻¹). The high SERS detection limit for seawater samples is explained by the competition for PAHs between the sensor membrane and particulate matter surfaces. Thus, the SERS sensor can be applied, e.g., as a non-quantitative alarm sensor for relatively high PAH concentrations in heavily polluted waters. The spectral unmixing procedure applied for Gdańsk Harbor water confirmed the presence of phenanthrene at the highest concentration ([Phe]=140ngl⁻¹) and of Chr (2.7ngl⁻¹), but it did not detect the other PAHs present in the Gdańsk Harbor water, as determined by GC/MS. When compared to the past literature and databases, the SERS spectra indicated the presence of a mixture of molecules consisting of carotenoids, n-alkanes, amines or fatty acids, and benzimidazoles at the coastal station ZN2. The spectra in the offshore direction indicated carboxylic acids. Interpretation of the farthest offshore in situ SERS measurements is difficult, principally due to the limited availability of reference spectra. The detection of the lower PAH concentrations commonly found in Baltic coastal water needs further research and development to obtain better sensitivity of the SERS sensor. However, the high analytical specificity of the SERS sensor also allows the detection of other chemical species that require the development of a SERS/Raman library for specific in situ spectral interpretation.
Afficher plus [+] Moins [-]Cu(II) Biosorption and Competitive Studies in Multi-ions Aqueous Systems by Arthrobacter sp. Sphe3 and Bacillus sphaericus Cells: Equillibrium and Thermodynamic Studies
2012
Aryal, Mahendra | Ziagova, Maria G. | Liakopoulou-Kyriakides, Maria
Arthrobacter sp. Sphe3 and Bacillus sphaericus cells were used for Cu(II) biosorption. The effect of contact time, biosorbent dose, equilibrium pH, temperature and the presence of other ions on the efficiency of the process were extensively studied. Optimum pH value and biomass concentration were determined at 5.0 and 1.0 g/l, whereas contact time was found to be 5 and 10 min for Arthrobacter sp. Sphe3 and Bacillus sphaericus biomass, respectively. Equilibrium data fitted very well to Freundlich model (R ²â=â0.996, nâ=â2.325, K fâ=â8.141) using Arthrobacter sp. Sphe3. In the case of B. sphaericus, a Langmuir adsorption model [R ²â=â0.996, Q ââââ=â51.54 mg-Cu(II)/g] showed to better describe the results. Potentiometric titration and Fourier transform infrared (FTIR) spectroscopy showed that amine, carboxyl and phosphate groups participate in Cu(II)-binding. The calculated thermodynamic parameters indicated the spontaneous and feasible nature of Cu(II) biosorption on both biosorbents. Selectivity of Cu(II) biosorption was examined in binary and multi-ions systems with various anions and cations which are commonly found in municipal and industrial wastewater. A specificity towards Cu(II) was observed in binary mixtures with Cl⁻, CO ₃ ⁻² , NO ₃ ⁻ , SO ₄ ⁻² , PO ₄ ⁻³ , Mg+² and Ca+², and As(V) with the maximum uptake capacity remaining constant even at high competitive ion’s concentrations of 200 mg/l. Desorption studies showed that Cu(II) could be completely desorbed from Cu(II)-loaded Arthrobacter strain Sphe3 and B. sphaericus biomass using 1.0 and 0.8 M HCl, respectively, and both bacterial species could be effectively reused up to five cycles, making their application in wastewater detoxification more attractive.
Afficher plus [+] Moins [-]Adsorption of Cu²⁺ on Amine-Functionalized Mesoporous Silica Brackets
2012
Hu, Zhihui | Zhang, Xiaodan | Zhang, Donghui | Wang, Ji-xiao
A directly amine-functionalized mesoporous silica (AMS) was prepared via an anionic surfactant-mediated synthesis method and used as adsorbents for deep removal of Cu ions from aqueous solution at room temperature. The synthesized AMS had been characterized by X-ray diffraction, nitrogen physisorption measurement, and thermogravimetric analysis. The amine groups prefer to position to the surface of AMS material due to the SN ∼ I mechanism. Copper adsorption process had been studied from both kinetic and equilibrium points of view for AMS material. Experiments proved that the aqueous Cu adsorption rates were fast and adsorption capacity was about 53.3 mg/g.
Afficher plus [+] Moins [-]Adsorptive Removal of Pentachlorophenol by Anthracophyllum discolor in a Fixed-Bed Column Reactor
2012
Rubilar, Olga | Tortella, Gonzalo R. | Cuevas, Raphael | Cea, Mara | Rodriguez-Couto, Susana | Diez, María Cristina
This study investigates pentachlorophenol (PCP) adsorption by the white-rot fungus Anthracophyllum discolor in a fixed-bed column reactor. PCP adsorption at different concentrations (20, 30, and 50 mg L−1) and pH values (5.0, 5.5, and 6.0) was determined and modeled using the Thomas model. Fourier transform infrared spectroscopy (FTIR) was used to identify functional groups of biomass that may participate in the interaction of PCP. The biosorption capacity of A. discolor was pH-dependent, and the PCP adsorbed increased with the decrease in the pH solution. Acid pH values of the influent gave an increase in saturation time in all PCP concentrations. By contrast, the increase in PCP concentration caused that the binding sites were filled quickly, resulting in a decrease in saturation time. The Thomas model was found suitable for describing the entire dynamic of the column with respect to the PCP concentration and pH of the solution. FTIR results showed that amines, carboxylates, alkanes, and C–O groups might participate in the PCP adsorption on the biomass surface. It was concluded that A. discolor biomass was a good adsorbent for PCP removal from influent with mainly acidic pH.
Afficher plus [+] Moins [-]Carbon Dioxide Capture with Amine-Grafted Activated Carbon
2012
Houshmand, Amirhossein | Daud, Wan Mohd Ashri Wan | Lee, Min-Gyu | Shafeeyan, Mohammad Saleh
There are several possible methods by which amine groups can be grafted on the surface of activated carbon (AC) to improve their capacity for CO2 adsorption. Ethylenediamine and diethylenetriamine were selected as amino compounds for anchoring on the surface of an oxidized AC. Oxidation of AC was carried out by concentrated nitric acid. For each amino compound, two “in-solvent” and “solvent-free” methods with a number of grafting times were studied. Nitrogen adsorption–desorption at 77 K and proximate and ultimate analysis were used to determine physical and chemical characteristics of the samples. Temperature-programmed (TP) CO2 adsorption test from 30°C to 120°C were performed to investigate the effect of modification on CO2 capture. The modification clearly had a negative effect on the textural characteristics of the samples, so the samples showed a less CO2 uptake at lower temperatures. However, the decrease of capture capacity with increasing temperature is to somewhat softer for amine-grafted samples, so that they have a capacity comparable to the parent sample or even more than that at elevated temperatures. This property may give the new adsorbents this opportunity to be used at flue gas temperature with a higher efficiency. CO2 capture capacity per unit surface area of all the amine-modified samples, however, was significantly improved, compared to the parent sample presenting a great influence of amino groups on the CO2 capture capacity. Moreover, the used amine compounds and grafting methods were compared in terms of adsorbent characteristics and CO2 uptake curves. Cyclic adsorption–desorption tests showed a satisfactory regeneration for the modified samples.
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