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

Lars Olov Andersson 《Physics and Chemistry of Minerals》2008,35(9):505-520

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.  相似文献   

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

Robert M. Moore   《Marine Chemistry》2006,101(3-4):213-219

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.  相似文献   

Chlorine-36 in groundwater of the United States: empirical data     

Stanley N. Davis  Stephen Moysey  DeWayne L. Cecil  Marek Zreda 《Hydrogeology Journal》2003,11(2):217-227

Natural production of the radionuclide chlorine-36 (³⁶Cl) has provided a valuable tracer for groundwater studies. The nuclear industry, especially the testing of thermonuclear weapons, has also produced large amounts of ³⁶Cl that can be detected in many samples of groundwater. In order to be most useful in hydrologic studies, the natural production prior to 1952 should be distinguished from more recent artificial sources. The object of this study was to reconstruct the probable preanthropogenic levels of ³⁶Cl in groundwater in the United States. Although significant local variations exist, they are superimposed on a broad regional pattern of ³⁶Cl/Cl ratios in the United States. Owing to the influence of atmospherically transported ocean salt, natural ratios of ³⁶Cl/total Cl are lowest near the coast and increase to a maximum in the central Rocky Mountains of the United States. Electronic Publication  相似文献   

铅—试铁灵络合物吸附波及溴化十六烷基三甲基铵增敏效应的研究   总被引：1，自引：0，他引：1  

张淑云  何平 《岩矿测试》1997,16(4):313-315

在０３０ｍｏｌ／ＬＨＡｃ介质中，Ｐｂ（Ⅱ）与７＿碘＿８＿羟基喹啉＿５＿磺酸（试铁灵，Ｆｅｒｏｎ）的络合物于－０５４Ｖ（ｖｓ．ＳＣＥ）产生一尖锐的极谱波，加入溴化十六烷基三甲基铵（ＣＴＭＡＢ）显著增敏，可使极谱波增高约４倍。峰电流与Ｐｂ（Ⅱ）浓度在９６×１０－９～４８×１０－６ｍｏｌ／Ｌ呈良好的线性关系，检出限为４８×１０－９ｍｏｌ／Ｌ。用多种电化学方法研究了该极谱波的性质及电极反应机理表明，络合物组成比为ｎＰｂ（Ⅱ）∶ｎＦｅｒｏｎ＝１∶１，极谱波为吸附波，峰电流由中心离子Ｐｂ（Ⅱ）还原产生，电子转移数为２。试验了多种离子对峰电流的影响，拟定的方法用于矿样分析，结果与原结果相符。  相似文献   

Sulfide and iron control on mercury speciation in anoxic estuarine sediment slurries   总被引：2，自引：0，他引：2  

Seunghee Han  Anna Obraztsova  Patrizia Pretto  Dimitri D. Deheyn  Joris Gieskes  Bradley M. Tebo   《Marine Chemistry》2008,111(3-4):214-220

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.  相似文献   

臭氧及臭氧类高级氧化技术降解甲基对硫磷的效能          下载免费PDF全文

林存旺  许珊珊  项丰云  章小芳 《海洋开发与管理》2018,35(9):94-99

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。  相似文献   

锡－盐酸－溴化十四烷基三甲铵极谱催化波体系及其应用     

张文江  姚修仁 《岩矿测试》1995,(1)

在０．００２％溴化十四烷基三甲铵（ＴＴＭＡＢ）－２０％ＨＣＩ体系中，Ｓｎ有一灵敏的吸附波，峰电位在－０．４７Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ），线性范围２～１０００ｎｇ／ｍｌ。体系可用于岩石、土壤样品中微量Ｓｎ测定；机理研究表明，溴化一四烷基三甲铵通过诱导吸附ＳｎＣｌ提高测定的灵敏度。  相似文献   

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

R. Iannone  R. Koppmann  J. Rudolph 《Journal of Atmospheric Chemistry》2007,58(3):181-202

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.  相似文献   

Content Variations of Rubidium and Bromide in Sylvite Derived from Carnallite by Leaching of Magnesium Chloride     

CHENG Huaide  HAI Qingyu  ZHANG Xiying  FAN Qishun  MA Haizhou 《《地质学报》英文版》2014,88(Z1):298-300

正The relationship between sylvinite and carnallite is important in the potash mine body contained carnallite,especially sylvinite overlies carnallite,the reverse of a normal depositional sequence.Trace elements are more  相似文献   

Bromide as a conservative tracer for soil-water studies     

B. S. Levy  R. M. Chambers 《水文研究》1987,1(4):385-389

The assumption that potassium bromide is a conservative tracer for soil-water studies was tested in a series of batch sorption experiments. Sorption experiments were conducted on soil samples collected from the O, E, and A horizons of the Albemarle soil series near Charlottesville, VA. The experiments were conducted under conditions of differing bromide concentration and filter treatments. Bromide concentrations in soil-solution mixtures were measured through time using an Orion bromide-specific electrode. An analysis of variance of results showed no significant sorption of bromide through time under any concentration level or filter treatment (α = 0·01). No sorption of bromide between different soil horizons could be determined. This work clearly indicates that bromide is conservative under the conditions examined.  相似文献