EPR investigation of the methyl radical,the hydrogen atom and carbon oxide radicals in Maxixe-type beryl

The EPR spectra of Maxixe-type beryl contain a large number of overlapping signals. The angular dependence of the 1:3:3:1 signal typical for the CH₃ radical shows that this radical is located at the center of the channel cavity with its symmetry axis parallel to the crystal c-axis and is rotating around this axis. Its EPR spectrum is axially symmetric with g _// = 2.00263, g _⊥ = 2.00249 and A_// = 2.288 mT, A_⊥ = 2.256 mT. These anisotropies have the opposite signs of those found for surface-adsorbed methyl radicals. Hydrogen atoms are located at position 2a at the center of the beryl cavity and the EPR parameters of the narrow doublet signal are A ₀ = 1,407 MHz and g = 2.00230. Another doublet signal, which is broader and has axial symmetry with g _// = 2.00265, g _⊥ = 2.00625 and A_// = 0.895 mT, A_⊥ = 0.885 mT, could come from a HCO₃ radical. One narrow and easily saturated signal with g _// = 2.00227 and g _⊥ = 2.00386 is interpreted to arise from a carbon monoxide radical in the beryl channel, oriented with its axis parallel to the crystal c-axis. Additional weak doublet lines, which have similar g values as the carbon monoxide radical, are created by nearby hydrogens. A powder spectrum with g _// = 2.0017 and g _⊥ = 2.0004 appears upon UV irradiation of the single crystal and is easily saturated. This spectrum is interpreted to arise from a carbon dioxide radical, which rotates around its symmetry axis.     

Methyl halide production and loss rates in sea water from field incubation experiments

Experiments were conducted in the field to determine the non-chemical loss rate of methyl iodide in seawater and to examine production rates of methyl halides. The loss rate of added C13 labelled methyl iodide, present at concentrations similar to those found in seawater, corrected for chemical loss due to reaction with Cl⁻ varied from < 1 to 18% day^− 1, with a mean value of 7%. This rate of loss is much lower than that which was proposed by Bell et al. [Bell, N., Hsu, L., Jacob, D. J., Schultz, M. G., Blake, D. R., Butler, J. H., King, D. B., Lobert, J. M., Maier-Reimer, E., 2002. Methyl iodide: Atmospheric budget and use as a tracer of marine convection in global models, Journal of Geophysical Research-Atmospheres 107(D17), 4340-4351.] to account for the large discrepancies between observed and predicted mid-latitude concentrations of CH₃I based on their global photochemical source model. The suitability of several types of container for seawater incubations was studied and only quartz tubes appeared to be free of experimental artifact. Collapsible polyvinyl fluoride containers showed major production of methyl halides on irradiation with simulated sunlight. Polyethylene containers caused spurious production of methyl iodide at lower rates.     

催化光度法测定痕量锇

在０５ｍｏｌ／Ｌ的Ｈ２ＳＯ４介质中，Ａｓ（Ⅲ）存在下，Ｏｓ（Ⅷ）催化ＫＣｌＯ３氧化邻苯二酚紫褪色反应。反应受温度、反应时间影响，冷却及加入抗坏血酸可终止反应。据此，建立了一个测定痕量Ｏｓ（Ⅷ）的新方法。方法的灵敏度为２５７×１０－１０ｇ／ＬＯｓ（Ⅷ），测定范围为０～００９１μｇ／Ｌ，用地质管理样中锇的测定验证，结果与原结果相符     

臭氧及臭氧类高级氧化技术降解甲基对硫磷的效能

文章研究了臭氧及臭氧类高级氧化技术(AOPs-O3)在不同pH条件下降解甲基对硫磷(MP)的效能。结果表明,在pH 3~10的条件下(反应过程控制pH),单独臭氧化5min即可完全降解MP,但不同pH下化学耗氧量(COD)和有机磷的释放率差异明显。在pH为3.3,7.5和9.4的条件下单独臭氧30min后COD的去除率分别为55.17%,89.64%和93.10%,有机磷的释放率分别为16.33%,95.00%和99.99%。考虑酸性条件下可以规避碳酸盐的负面影响(特别是高浓度废水),利用O3/H2O2/Ti(IV)在pH 3.3条件下处理MP溶液,COD去除率和有机磷释放率分别达到89.64%和81.57%。相对法计算求得MP与O3和羟基自由基(·OH)的速率常数分别为31.98L·(mol·s)-1和7.488×109 L·(mol·s)-1。活性污泥法的测试结果表明,MP经O3/Ti(IV)/H2O2(pH=3.3)和O3(pH=9.4)可提升含MP废水的可生化性,但与培养液体系相比仍具有一定的毒性。     

A technique for atmospheric measurements of stable carbon isotope ratios of isoprene,methacrolein, and methyl vinyl ketone

A technique was developed to measure stable carbon isotope ratios (¹³C/¹²C) of light volatile organic compounds (VOCs) such as isoprene, methacrolein (MACR) and methyl vinyl ketone (MVK) using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). An automated sampling and cryofocussing system allowed for the extraction of VOCs from air samples of up to 140 L of air collected over 3 h, and the subsequent ¹³C/¹²C analysis of the VOCs by GCC-IRMS. Chromatography using selective transfer between two columns was used to improve the separation for selected compounds, increasing peak resolution and attaining less noisy baselines. Still, some target compounds could not be completely separated from co-eluting peaks. To reduce the bias of isotope ratio determinations, which can result from incomplete peak resolution, a peak-fitting procedure has been developed. In cases of overlapping peaks or substantial baseline drift, this peak fitting allows more accurate determination of isotope ratios than conventional integration schemes. Comparisons between off-line IRMS measurements and a peak-evaluation procedure using a prepared VOC gas-phase standard show that isotope ratios derived from large (>1 ng of carbon per peak) and well-resolved peaks have a reproducibility of ±0.3‰. With smaller masses in the range of 0.1–1 ng of carbon, reproducibility decreased to ±(0.5–0.8)‰. For a 140 L sample of air, such small masses of carbon correspond to mixing ratios in the low pptV range. The developed measurement technique was applied to a small set of ambient air samples taken during hot, sunny periods from late May to early August, 2005, at Forschungszentrum Jülich, Germany, a semi-rural area. The range of δ¹³C values determined for isoprene, benzene, and toluene are consistent with those reported in the literature. GCC-IRMS results of δ¹³C for ambient samples of isoprene, MACR, and MVK, measured at mixing ratios of 15–280 pptV, are presented and discussed.     

Sulfide and iron control on mercury speciation in anoxic estuarine sediment slurries

In order to understand the role of sulfate and Fe(III) reduction processes in the net production of monomethylmercury (MMHg), we amended anoxic sediment slurries collected from the Venice Lagoon, Italy, with inorganic Hg and either potential electron acceptors or metabolic byproducts of sulfate and Fe(III) reduction processes, gradually changing their concentrations. Addition of sulfide (final concentration: 0.2–6.3 mM) resulted in an exponential decrease in the sulfate reduction rate and MMHg concentration with increasing concentrations of sulfide. Based on this result, we argue that the concentration of dissolved sulfide is a critical factor controlling the sulfate reduction rate, and in turn, the net MMHg production at steady state. Addition of either Fe(II) (added concentration: 0–6.1 mM) or Fe(III) (added concentration: 0–3.5 mM) resulted in similar trends in the MMHg concentration, an increase with low levels of Fe additions and a subsequent decrease with high levels of Fe additions. The limited availability of dissolved Hg, associated with sulfide removal by precipitation of FeS, appears to inhibit the net MMHg production in high levels of Fe additions. There was a noticeable reduction in the net MMHg production in Fe(III)-amended slurries as compared to Fe(II)-amended ones, which could be caused by a decrease in the sulfate reduction rate. This agrees with the results of Hg methylation assays using the enrichment cultures of anaerobic bacteria: whereas the enrichment cultures of sulfate reducers showed significant production of MMHg (4.6% of amended Hg), those of Fe(III), Mn(IV), and nitrate reducers showed no production of MMHg. It appears that enhanced Fe(III)-reduction activities suppress the formation of MMHg in high sulfate estuarine sediments.     

Molecularly imprinted polymers for selective extraction of crystal violet from natural seawater coupled with high-performance liquid chromatographic determination

Molecularly imprinted polymers(MIPs) were prepared by the bulk polymerization using crystal violet as the template molecule, and the methacrylic acid and ethylene glycol dimetheacrylate as functional monomer and cross-linker, respectively. Systematic investigations of synthetic conditions were conducted. The surface morphology and recognition mechanism of the obtained polymers were studied using scanning electron microscope and spectrophotometric analysis. MIPs showed high affinity to template molecule and were successfully applied as special solid-phase extraction sorbent for selective extraction of crystal violet from natural seawater. An off-line molecularly imprinted solid-phase extraction(MISPE) method followed by high-performance liquid chromatography with diodearray detection for the analysis of crystal violet was also established. MISPE columns have good recoveries for crystal violet standard solutions and good linearity was obtained over the concentration range of 0-200 μg L-1(R2 0.99). Finally, two natural seawater samples were investigated. The recoveries of spiked seawater on the MISPE columns were from 44.47% to 62.34%, the relative standard deviation(n=3) being in the range of 2.89%-5.96%.     

掺杂锡的纳米二氧化钛的合成、表征及光催化性能

以Ti(OC4H9)4和SnCl4.5H2O为原料,乙醇为溶剂,离子液体1-丁基-3-甲基四氟硼酸咪唑盐([Bmim][BF4])为表面活性剂,12%的氨水为沉淀剂,采用共沉淀法合成了不同形态的掺杂锡的二氧化钛。利用X-射线粉末衍射仪(XRD)、场发射扫描电镜(FESEM)、同步热分析仪(TG-DSC)、紫外—可见吸收光谱仪(UV-Vis)、比表面积孔隙度分析仪(BET)和能量色散X射线光谱仪(EDS)表征所合成材料的结构、形貌、热稳定性、光学性能、比表面积。Sn掺杂后各样品在紫外和可见光区的吸收能力均有不同程度地增强。与未掺杂TiO2的吸收带边相比,Sn掺杂TiO2的吸收带边分别红移了约35 nm,从而提高了光催化降解甲基橙的活性。为了评估产品的光催化性能,进行了掺杂锡的纳米二氧化钛对甲基橙的光催化降解实验,实验结果表明在2 mL离子液体中合成掺杂锡为7%的纳米二氧化钛对甲基橙的光降解具有最好的催化作用。光照90 min对甲基橙的降解率就达到了97%以上,大幅度提高了TiO2的可见光催化活性,这是因为有效抑制了光生电子和空穴的复合,也明显降低了TiO2的禁带宽度。     

海洋细菌脂肪酸的气相色谱分析

以副溶血性弧菌VP-X-3为试验对象,利用气相色谱技术分析了其细胞脂肪酸的组成和含量,以色谱峰的数量、色谱峰高及脂肪酸含量作为评价指标,探讨了不同的皂化和甲酯化条件对细菌细胞脂肪酸测定结果的影响。结果表明:皂化和甲酯化条件都对细胞脂肪酸的组成和含量产生一定的影响。较低温度皂化处理利于增加色谱峰数量和色谱峰高。甲酯化温度过高容易破坏脂肪酸,尤其是长链脂肪酸和不饱和脂肪酸的结构。高温甲酯化条件下,时间越长,甲酯化效果越差。试验得到较为理想的气相色谱前处理条件:2 mol/L NaOH-甲醇溶液2 mL,70℃水浴10 min;10%(V/V)H2SO4-甲醇溶液2 mL,70℃水浴15 min。此条件下的色谱峰的数量多达29种,色谱峰高明显高于其他处理条件下的峰高。