Detection of pollutants in water by raman spectroscopy

The possibility of monitoring pollutants in water by means of Raman spectroscopy is discussed with special reference to the CH-stretching vibration bands of possible impurities. From theoretical considerations the limits of detection were found to be in the range of 1 → 10 ppm. The perturbations due to fluorescence and turbidity in samples were investigated and methods for reducing their effects are discussed.     

Determination of nitrate ion in waste and treated waters by laser raman spectrometry

The determination of NO₃⁻ ion in pure and natural waters by laser Raman spectrometry has been examined. It is shown that in the case of pure water samples, the detection limit of NO₃⁻ is about 2 ppm, and that the analytical curve in 6–100 ppm can be fitted well enough to a straight line. In the case of waste and treated waters, the detection limit becomes about an order of magnitude higher than that in the case of pure water because of the strong luminescence of water samples. In this study, the reduction of this background has been pursued by various methods, and it is demonstrated that the addition of potassium iodide as a quencher makes the background markedly smaller. By this procedure, the sensitivity becomes comparable to that in the case of pure water samples. It is proved that under such circumstances, laser Raman spectrometry can be applied satisfactorily enough to the analysis of NO₃⁻ in actual waste and treated waters.     

Decomposition of diazinon in aqueous solution by ozonation

The decomposition of diazinon in aqueous solution by ozonation was studied under various solution pH values, gaseous ozone dosages, gaseous pressure, alkalinity levels and solution temperatures. Ozonation has been shown to be feasible for achieving nearly complete decomposition of diazinon within 1 h. The surface tension of aqueous solution was found to be affected by the dissolved diazinon and influenced the oxidation mechanism of diazinon by ozonation in aqueous solution. The gas–liquid reaction model was well used to describe the transfer and reaction behaviors of reacting species in the system. The quasi-global kinetics based on a simplified consecutive reaction scheme was developed to describe the temporal behavior of diazinon decomposition in aqueous solution by ozonation.     

Toxicity of 2,4-D acid to phytoplankton

The toxic effects of 2,4-D on Phaeodactylum tricornutum (Bohlin) and Dunaliella tertiolecta (Butcher), two species of phytoplankton well suited to bioassay studies and responsive to pollutants, were studied by monitoring changes in growth in terms of cell populations, chlorophyll fluorescence and the rate of ¹⁴CO₂ assimilation. Short term bioassays, batch and continuous cultures were studied. Pure 2,4-D acid appeared more toxic than the commercial amine form of the herbicide but this may have been due to small quantities of acetone present in the solvent. Concentrations of amine herbicide in excess of 100 mg l⁻¹ extended the duration of the lag phase and inhibited growth but smaller concentrations stimulated growth, the amine being consumed by phytoplankton in preference to nitrate. Continuous culture confirmed the ability of phytoplankton to adapt slowly to herbicide concentrations even as high as 500 mg l⁻¹. It is suggested that green algae adapt more rapidly to environmental change than do diatoms.     

Degradation of estrone in aqueous solution by photo-Fenton system

Photodegradation of estrone (E1) in aqueous solutions by UV-VIS/Fe(III)/H2O2 system (photo-Fenton system) was preliminarily investigated under a 250-W metal halide lamp (lambda > or = 313 nm). The influences such as initial pH value, initial concentration of Fe(III), H2O2 and E1 on degradation efficiency of E1 were discussed in detail. The results indicated that E1 could be decomposed efficiently in UV-VIS/Fe(III)/H2O2 system. After 160-min irradiation, the photodegradation efficiency of 18.5 micromol L(-1) E1 reached 98.4% in the solution containing 20.8 micromol L(-1) Fe(III), and 1664 micromol L(-1) H2O2 at initial pH value 3.0. The degradation efficiencies of E1 were dependent on initial pH value, Fe (III) concentration and H2O2 concentration. The degradation of four estrogens estrone (E1), estradiol (E2), 17alpha-ethynylestradiol (EE2) and diethylstibestrol (DES) in UV-VIS/Fe(III)/H2O2 system were also conducted. Under the conditions of pH 3.0, the E1 apparent kinetics equation -dC(E1)/dt=0.00093[H2O2]0.47[Fe(III)]0.63[E1]0.24 (r=0.9935, n=11) was obtained. The E1 mineralization efficiency was lower than degradation efficiency under the same conditions, which implied the mineralization occurred probably only at aromatic ring. There are several intermediate products produced during the course of E1 degradation. The comparison of the degradation efficiencies of E1, E2, EE2 and DES degradation in UV-VIS/Fe(III)/H2O2 system were also conducted, and the relative degradability among different estrogens were followed the sequence: DES>E2>EE2>E1.     

Decomposition of phorate in aqueous solution by photolytic ozonation

The degradation of phorate, a highly toxic organic phosphate pesticide, in aqueous solution by photolytic ozonation was studied under various experimental conditions. The rate constants of phorate decomposition and formation of various anions by photolytic ozonation were roughly independent of the solution's pH value. The initial step of the photolytic decomposition of phorate is considered to be the breakage and subsequent oxidation of the P=S double bond on the phorate molecule, followed by isomerization and consequent oxidation of various organic intermediates.     

Oxidation of bisphenol A by ozone in aqueous solution

Based on the literature data, an efficient removal of bisphenol A (BPA) during ozonation can be expected under water treatment conditions. However, up to now, the degradation products have not been identified. This has been the main point of this study. Aqueous solutions of BPA have been analyzed by LC-UV, LC-MS or MS/MS at different ozone doses. Under our experimental conditions, up to five major transformation products were evidenced. According to UV, MS and MS/MS spectra characteristics, chemical structures are consistent with catechol, orthoquinone, muconic acid derivatives of BPA, benzoquinone and 2-(4-hydroxyphenyl)-propan-2-ol. Moreover, three additional minor transformation products have been observed for which chemical structures have been tentatively proposed. In the case of major transformation products, the reaction pathway may involve an initial ozone reaction by electrophilic substitution or 1,3-dipolar cycloaddition. In the presence of ozone, these primary transformation products were shown to be unstable. Further transformation products, with smaller molecular weight and more polar character such as aliphatic acids or aldehydes, are then expected during ozonation. The identification of minor transformation products was more complex to assess. However, oligomeric structures have been evidenced, certainly arising from secondary reaction between various oxidation products of BPA. The formation of these latter products would not be favored under water treatment conditions.     

Chromatographic determination of pesticide 2,4-D in water bodies

New silica-based adsorbent with covalently immobilized groups of triton X-100 has been proposed for extraction and concentration of 2,4-dichlorophenoxyacetic acid (2,4-D) from water bodies. The recovery of this pesticide into adsorbent phase occurs in the form of its ionic associate with cationic surfactants (CSAS). It was shown that the application of cetyltrimethylammonium bromide made it possible to achieve the pesticide extraction ratio as high as 94%. Elution with acetonitrile allows us to achieve a 50-fold absolute concentration of 2,4-D making it possible to perform its determination by the high performance liquid chromatography method with ultraviolet detection, where the detection level is 0.07 mg/dm³ and the linearity range is from 0.09 to 0.20 mg/dm³.     

Degradation of MTBE in dilute aqueous solution by gamma radiolysis

The radiolytic degradation of methyl tert-butyl ether (MTBE) in air-equilibrated dilute solution was investigated. Complete degradation of MTBE can be achieved within 5 min of irradiation at 59.7 Gy/min. The observed first-order degradation rate constant, called dose constant, increased from 0.04 to 0.56 Gy(-1) as the concentration of MTBE decreased from 92500 to 19 microg/L. Tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were found to be the primary intermediates of the degradation reaction with yields of 47%, 11%, 6.4% and 9.1%, respectively. The degradation of MTBE or its intermediates was also found to depend on the concentrations of benzene and cupric ion. The study shows that the removal of MTBE can be significantly decreased with increasing concentration of benzene. Little affects were observed with the presence of cupric ions, while the degradation of TBF was apparently reduced. These results indicate that gamma radiolysis can be a potentially effective treatment for the removal of MTBE in contaminated water systems.     

无机盐对部分水解聚丙烯酰胺溶液黏度影响的实验与理论研究

采用实验与分子动力学模拟(MD)结合的方法研究无机盐对部分水解聚丙烯酰胺(HPAM)溶液黏度影响的规律及微观机制。结果表明:无机盐对溶液黏度影响较大,其中Ca Cl2和Mg Cl2对溶液降黏作用强于Na Cl,且当Ca Cl2和Mg Cl2浓度相同时Mg Cl2的降黏作用更加明显;当溶液中加入无机盐时,由于盐离子与聚合物中羧酸根基团的静电吸引,使其在聚合物周围形成阳离子层,从而减弱了聚合物分子链上羧酸根基团之间的排斥作用,导致分子链收缩,进而降低溶液的黏度;相比于Na+和Ca2+,Mg2+更易靠近HPAM分子链,对分子链构型及黏度的改变更加明显。     

Ammonia removal from aqueous solution by membrane distillation

Environmental regulation, increased pressure on water resources and rising cost for wastewater discharges make wastewater treatment for recycling an essential investment for many industries. Ammonia is a major pollutant in many industrial and agricultural wastewaters, and its elimination is essential for wastewater to be reused or meeting local discharge standards. In this study, the removal of ammonia from dilute aqueous solution has been investigated using sweep gas and vacuum membrane distillation (SGMD and VMD). Factors that affect the separation process such as feed and air flow rates, vacuum degree and feed temperature have been investigated. Overall, mass transfer coefficients (K_ov) were calculated, and the results indicated that K_ov for VMD is higher than that for SGMD under similar operation. Overall, ammonia mass transfer coefficient up to 12.06 × 10^?5 and 5.63 × 10^?5 m/s can be achieved for VMD and SGMD, respectively. The ammonia removal efficiency was enhanced by increasing sweep gas flow rate or by decreasing downstream pressure.     

Ozonation of pyrene in aqueous solution

The reaction of pyrene with ozone was studied in aqueous solution at low (10–200 μg l⁻¹) substrate concentration and with ozone concentrations (5 mg l⁻¹) approximating to those used in potable water treatment. Degree of reaction and the formation of polyaromatic/aromatic reaction products were assessed using a technique of solvent extraction and derivatisation with gas chromatographic (GC), gas chromatographic-mass spectrometric (GC-MS), high performance liquid chromatographic (HPLC) and u.v. spectrometric analysis of extracts. A freeze drying/derivatisation technique with GC and GC-MS analysis was employed for the isolation/identification of short chain polar aliphatic reaction products. Substantial destruction of pyrene was recorded within 1 min of reaction with ozone. Polyaromatic/aromatic compounds did not persist; reaction products are likely to be short chain polar aliphatic compounds. Products of this type were isolated but not identified in the study.     

Photocatalytic degradation of 2,4-dinitrophenol (DNP) by multi-walled carbon nanotubes (MWCNTs)/TiO2 composite in aqueous solution under solar irradiation

Nanosized multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite and neat TiO₂ photocatalysts were synthesized by sol-gel technique using tetrabutyl titanate as a precursor. The as prepared photocatalysts were characterized using XRD, SEM, FTIR and UV-vis spectra. The samples were evaluated for their photocatalytic activity towards the degradation of 2,4-dinitrophenol (DNP) under solar irradiation. The results indicated that the addition of an appropriate amount of MWCNTs could remarkably improve the photocatalytic activity of TiO₂. An optimal MWCNTs:TiO₂ ratio of 0.05% (w/w) was found to achieve the maximum rate of DNP degradation. The effects of pH, irradiation time, catalyst concentration, DNP concentration, etc. on the photocatalytic activity were studied and the results obtained were fitted to the Langmuir-Hinshelwood model to study the degradation kinetics. The optimal conditions were an initial DNP concentration of 38.8 mg/L at pH 6.0 with catalyst concentration of 8 g/L under solar irradiation for 150 min with good recyclisation of catalyst. The degree of photocatalytic degradation of DNP increased with an increase in temperature. The MWCNTs/TiO₂ composite was found to be very effective in the decolorization and COD reduction of real wastewater from DNP manufacturing. Thus, this study showed the feasible and potential use of MWCNTs/TiO₂ composite in degradation of various toxic organic contaminants and industrial effluents.     

Kinetics and mechanisms of polyethyleneglycol fragmentation by ozone in aqueous solution

The oxidative fragmentation of Polyethyleneglycol by ozone is investigated by means of batch and semibatch ozonation experiments in the pH range 4.0–9.0. Chemical mechanisms and reaction kinetics of the ozonation processes are determined by also exploiting chemical information from experiments on Diethyleneglycol and Ethyleneglycol ozonation. A kinetic model is proposed capable of describing the fragmentation process due to the direct polymer oxidation by ozone.     

Photodegradation of the antibiotics nitroimidazoles in aqueous solution by ultraviolet radiation

The objective of this study was to analyze the efficacy of ultraviolet (UV) radiation in the direct photodegradation of nitroimidazoles. For this purpose, i) a kinetic study was performed, determining the quantum yield of the process; and ii) the influence of the different operational variables was analyzed (initial concentration of antibiotic, pH, presence of natural organic matter compounds, and chemical composition of water), and the time course of total organic carbon (TOC) concentration and toxicity during nitroimidazole photodegradation was studied. The very low quantum yields obtained for the four nitroimidazoles are responsible for the low efficacy of the quantum process during direct photon absorption in nitroimidazole phototransformation. The R₂₅₄ values obtained show that the dose habitually used for water disinfection is not sufficient to remove this type of pharmaceutical; therefore, higher doses of UV irradiation or longer exposure times are required for their removal. The time course of TOC and toxicity during direct photodegradation (in both ultrapure and real water) shows that oxidation by-products are not oxidized to CO₂ to the desired extent, generating oxidation by-products that are more toxic than the initial product. The concentration of nitroimidazoles has a major effect on their photodegradation rate. The study of the influence of pH on the values of parameters ? (molar absorption coefficient) and k′_E (photodegradation rate constant) showed no general trend in the behavior of nitroimidazoles as a function of the solution pH. The components of natural organic matter, gallic acid (GAL), tannic acid (TAN) and humic acid (HUM), may act as promoters and/or inhibitors of OH· radicals via photoproduction of H₂O₂. The effect of GAL on the metronidazole (MNZ) degradation rate markedly differed from that of TAN or HUM, with a higher rate at low GAL concentrations. Differences in MNZ degradation rate among waters with different chemical composition are not very marked, although the rate is slightly lower in wastewaters, mainly due to the UV radiation filter effect of this type of water.     

Heavy-metal removal from aqueous solution by fungus Mucor rouxii

Biosorption of lead, cadmium, nickel and zinc by live and dead Mucor rouxii biomass treated with NaOH was studied over a range of pH. In the case of dead biomass, low pH resulted in a decrease in the biosorption capacity. At pH 3.0 or less, the inhibition of biosorption of metal ions took place. At pH 4.0 or higher, the biosorption of metal ions increased sharply. Ho's pseudo-second-order model described the biosorption kinetics better than the Lagergren model. Live biomass had high biosorption capacity, i.e. 35.69, 11.09, 8.46 and 7.75 mg/g at pH 5.0 for Pb(2+), Ni(2+), Cd(2+) and Zn(2+), respectively. The dead biomass adsorbed metal ions in the order of Pb(2+), Zn(2+), Cd(2+) and Ni(2+), with the biosorption capability of 25.22, 16.62, 8.36 and 6.34 mg/g at pH 5.0, respectively. At pH 6.0, the capacity of the dead biomass increased to 53.75, 53.85, 20.31 and 20.49 mg/g, respectively. For bi- or multi-metal ion adsorption, biosorption capacity of individual metal ion was reduced in the presence of other metal ions, but the total biosorption capacity increased, indicating the capability of M. rouxii biomass in adsorbing multi-metal ions. In addition, M. rouxii biomasses cultured with different media exhibited the same level of capacity to bind metal ions. Metal ions adsorbed by the biomass could be eluted effectively with HNO(3), while distilled water demonstrated negligible metal elution capability. Regeneration of the biomass with NaOH regained or enhanced the biosorption capacity even after five cycles of adsorption-elution-regeneration.     

液液萃取/高效液相色谱法测定水中灭草松和2,4-滴

采用液液萃取/高效液相色谱法(HPLC)测定地表水和生活饮用水中的灭草松和2,4-滴。测定范围为0.01～10 mg/L,相关系数分别为R=1.000 0、0.999 9,检出限均为0.000 05mg/L,回收率分别为89%～107%和86%～106%,RSD分别为1.2%～2.3%和2.5%～3.1%,满足地表水和生活饮用水的检测要求。     

Sonochemical decomposition of dibenzothiophene in aqueous solution

Dibenzothiophene is decomposed rapidly by sonication in aqueous solution. Decomposition of dibenzothiophene follows a first-order reaction kinetics. The rate constant was found to increase with increasing ultrasonic energy intensity, temperature, and pH and decrease with increasing initial dibenzothiophene concentration. The activation energy was 12.6 kJ/mol in the temperature range of 15–50°C, suggesting a diffusion-controlled reaction. Hydroxydibenzothiophenes and dihydroxydibenzothiophenes were identified as reaction intermediates. It is proposed that dibenzothiophene is oxidized by OH radical to hydroxy-dibenzothiophenes and then to dihydroxy-dibenzothiophenes. Kinetic analysis suggests that approximately 72% of the dibenzothiophene decomposition occurred via OH radical addition. A pathway and a kinetic model for the sonochemical decomposition of dibenzothiophene in aqueous solution are proposed.