Potential of capillary electrophoresis mass spectrometry for the characterization and monitoring of amine-derivatized naphthenic acids from oil sands process-affected water

Capillary electrophoresis coupled to mass spectrometry(CE–MS) was used for the analysis of naphthenic acid fraction compounds(NAFCs) of oil sands process-affected water(OSPW). A standard mixture of amine-derivatized naphthenic acids is injected directly onto the CE column and analyzed by CE–MS in less than 15 min. Time of flight MS analysis(TOFMS), optimized for high molecular weight ions, showed NAFCs between 250 and 800 m/z. With a quadrupole mass analyzer, only low-molecular weight NAFCs(between 100 and 450 m/z) are visible under our experimental conditions. Derivatization of NAFCs consisted of two-step amidation reactions mediated by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide(EDC), or mediated by a mixture of EDC and N-hydroxysuccinimide, in dimethyl sulfoxide, dichloromethane or ethyl acetate. The optimum background electrolyte composition was determined to be 30%(V/V) methanol in water and 2%(V/V) formic acid. NAFCs extracted from OSPW in the Athabasca oil sands region were used to demonstrate the feasibility of CE–MS for the analysis of NAFCs in environmental samples, showing that the labeled naphthenic acids are in the mass range of 350 to 1500 m/z.     

Organic matter and amino acid concentrations in surface sediments of Vembanad Lake – a tropical estuary, west coast of India

The surface sediments of Vembanad Lake, a tropical estuary on the west coast of India, were analyzed for carbon (TC, TOC, TIC), nitrogen (TN), amino acids and two amino sugars. C/N ratios for the surface sediments vary from 1.0–21.8, indicating terrestrial sources of organic matter. Various biogeochemical indicators based on amino acids such as Asp/β-ala and Glu/γ-aba ratios revealed that the organic matter in the 5- to 10-cm surface sediments was fresh and had not undergone extensive degradation. However, the Gluam/Galam ratio for surface sediments of Vembanad Lake varies from 0.4–2.1, indicating the dominance of bacterial biomass in the sediments. Organic matter in the sediments was found to be highly reactive, with a reactivity index ranging from 2.4–7.4, suggesting rapid remineralization. Electronic Publication     

红球菌PR-1菌株破乳性能研究

利用乳化剂Span 80配制出一种稳定的煤油-水乳浊液作为模型乳浊液,进而从大港油田废水中筛选出1株破乳能力较强的红球菌PR-1.该菌株培养液在55℃下8h可以使模型乳浊液完全破乳,且在实验条件下比化学破乳剂DGF-01具有更强的破乳活性.研究发现,乳浊液的破乳为线性增长过程,冻融和高压灭菌对其破乳能力没有影响,菌体细胞是破乳的主要活性成分,经超声波破碎及有机溶剂处理后其破乳活性显著降低.菌体表面有很强的疏水性,其对烃的粘附率为84%,碳链长度范围在C₂₇～C₅₄的枝菌酸类物质是保持菌体细胞完整性和疏水性的关键,其对细胞的破乳活性也至关重要.PR-1菌株发酵液用于原油乳状液的破乳具有操作方便,破乳率高,应用面广,无毒无害等优点,且能完全脱出J9-19原油乳状液中的水,因此可作为原油乳状液或油田采出水的破乳剂.     

Multivariate curve resolution of multidimensional excitation-emission quenching matrices of a Laurentian soil fulvic acid

Fluorescence excitation–emission matrices (EEM) of aqueous solutions of Laurentian soil fulvic acid (LFA) at three concentrations (50, 75 and 100 mg/l) were obtained at two pH values (pH = 4.0 and 6.0) and as function of the Cu(II) ion concentration. The presence of Cu(II) ion provokes quenching of the intrinsic LFA fluorescence due to complex formation. Multivariate curve resolution (MCR-ALS) was used to successfully decompose single EEM into excitation and emission spectra for the detected components. Moreover, multidimensional (up to six dimensions) data matrices were generated by adding EEM collected as function of the LFA and Cu(II) concentrations and pH. MCR-ALS was able to resolve the excitation and emission spectra from these multidimensional data matrices given further information about the spectral variation profiles induced by the experimental factors. Conditional stability constants (log K_LFACu) were calculated from the quenching profiles observed as function of the Cu(II) concentration, as well as, their trends as function of pH and LFA concentration were obtained – average (and standard deviation) of log K_LFACu = 4.6 ± 0.2. This EEM/MCR-ALS methodology constitutes a new tool for the study of natural organic matter under varying experimental conditions that characterize natural environmental systems.     

Effect of low molecular weight organic acids on adsorption and desorption of fluoride on variable charge soils

The effect of four low molecular weight organic acids on F⁻ adsorption by two variable charge soils was investigated using a batch method. The organic acids reduced F⁻ adsorption through competition by the acids with F⁻ for sorption sites. Oxalic and malonic acids, both of which have simpler chemical structures, were more effective than citric or malic acid. The effect of organic acids on F⁻ adsorption was more prominent at higher pH values and with larger amounts of the organic acids. The desorption study showed that the organic acids enhanced the desorption of F⁻ adsorbed by the soils. In the control and malic acid systems, desorption increased sharply with decreasing pH, while in the oxalic acid system, desorption rose slightly with decreasing pH. Desorption also increased with increasing amount of organic acid added. There are two possible mechanisms for the effect of the organic acids on F⁻ adsorption and desorption: (1)␣competition of the organic acids with F⁻ for adsorption sites and (2) dissolution of the adsorbents, especially dissolution of soil Al.     

有机酸强化Fe(Ⅲ)还原介导的Shewanella oneidensis MR-1降解磺胺甲噁唑

在实验室条件下,研究了Shewanella oneidensis MR-1对磺胺甲噁唑（Sulfamethoxazole,SMX）的降解特性以及低分子有机酸强化Fe（Ⅲ）还原介导的S.oneidensis MR-1对SMX的降解.结果表明,S.oneidensis MR-1对不同浓度SMX的降解能力与体系中的有机酸和Fe（Ⅲ）密切相关.低浓度SMX对其生长影响不大,高浓度时细菌生长则受到抑制,进而抑制SMX的降解率.当低分子有机酸单独加入体系后,S.oneidensis MR-1对SMX的最大降解率为58.5%;Fe（Ⅲ）单独加入体系后,S.oneidensis MR-1对SMX的最大降解率为67.6%.此外,当柠檬酸和Fe（OH）₃同时加入体系后,S.oneidensis MR-1对SMX生物降解和铁还原作用促进效果最显著,培养5 d后SMX降解率为90.3%.最后,采用液相色谱-质谱联用仪（LC-MS）对SMX的降解中间产物进行了分析,推测SMX的可能降解途径是由S-N键断裂引起的.本研究以期为地下水污染场地修复提供理论依据.