超声提取-离子色谱法测定铁矿石中水溶性氟氯溴及硝酸根

铁矿石样品经超声提取、离心机分离沉淀后,分别通过IC-RP柱、IC-Na柱及0.22μm微孔过滤膜过滤,25.00 mmol/L NaOH溶液作为淋洗液,利用AS-19型阴离子分离柱和ASRS 300-4 mm连续自动再生化学抑制器分离样品中氟、氯、溴和硝酸根多种水溶性阴离子和采集数据。经过IC-RP柱可吸附样品溶液中有机质,通过IC-Na柱可将溶液中重金属离子置换成Na+,使之与淋洗液的阳离子成分一致。对水溶性阴离子的提取效率进行实验,确定提取时间为30 min。在标准溶液及待测样品溶液中加入一定量相应的淋洗液,使溶液和淋洗液的电导值相匹配来消除水负峰的影响。F-、Cl-、Br-、NO3-的方法检出限分别为2.1、3.5、2.5、2.0μg/g,工作曲线的相关系数>0.999。用铁矿石标准样品GBW 07218a验证方法的准确度与精密度,测定值与标准值基本吻合,精密度(RSD,n=10)小于5%,加标回收率为96%～104%。用于实际样品的分析,测定值与离子选择电极法结果接近。方法线性范围宽,操作简单,快速高效,适用于实验室日常检测工作。     

土壤中氯的比色测定

本法采用碳酸钠-氧化锌混合试剂半熔后硫氰酸汞比色测定了土壤中微量的氯。实验并确定了各试剂的最佳加入量,方法相对标准偏差(RSD,n=12)为2%~9%。经国家标准物质验证,测定值与认定值基本符合。     

Retention of chloride in soil and cycling of organic matter‐bound chlorine

Chloride (Cl_inorg) is generally considered to be a hydrologically and chemically inert substance. Past research suggests that Cl_inorg participates in a complex biogeochemical cycle involving the formation of organically bound chlorine (Cl_org). The present study examines whether Cl_org cycling is sufficiently extensive as to influence the geochemical cycling of Cl_inorg. Undisturbed soil cores were collected in a coniferous forest soil in SE Sweden. The cores were stored in climate chambers for three months, irrigated with artificial rain, and the leachate was collected and analysed. The water balance of the lysimeters could be well described, and we found that 20–50% of the chlorine leached from the lysimeters was organically bound and that the amounts lost did not decrease with time. This strongly suggests that a substantial amount of Cl_org forms in topsoil, and that subsequent leaching to deeper layers causes a considerable withdrawal of Cl_inorg. The concentration of both organic carbon and Cl_org in the leachate was considerably higher than concentrations observed in the runoff in the actual catchment, suggesting that organic matter precipitates or is mineralized on its way through the soil. Copyright © 2005 John Wiley & Sons, Ltd.     

Measurement of IO radical concentrations in the marine boundary layer using a cavity ring-down spectrometer

An open-path cavity ring-down spectroscopy (CRDS) instrument for measurement of atmospheric iodine monoxide (IO) radicals has been tested in the laboratory and subsequently deployed in Roscoff on the north-west coast of France as part of the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) project in September 2006. In situ measurements are reported of local IO mixing ratios in the marine boundary layer. To obtain these mixing ratios, accurate absorption cross sections of IO are required at the selected wavelengths used for spectroscopic measurements. Absorption cross sections at the bandheads of the IO A²Π_3/2–X²Π_3/2 (3,0) and (2,0) vibronic bands were thus verified by a combination of spectral simulation methods, inter-comparison of prior determinations of cross-sections at high and low spectral resolution, and by measurement of rates of loss of IO by its self-reaction. The performance of the open-path CRDS instrument was tested by measuring concentrations of NO₂ in ambient air, both within and outside the laboratory, with results that were in excellent agreement with a previously validated continuous wave CRDS apparatus for NO₂ detection. During the RHaMBLe campaign, the open-path CRDS instrument was located within a few metres of the shoreline and operated at wavelengths close to 435 nm to detect the absorption of light by trace levels of IO. The IO mixing ratios were obtained on two days, peaked close to low tide, and were approximately 5–10 times higher than values calculated from column densities previously reported by long-path, differential optical absorption spectroscopy (DOAS) in coastal regions. The typical detection limit of the instrument was estimated to be 10 pptv of IO, with some fluctuation around this value depending on the conditions of wind and atmospheric aerosol particles, and the total accumulation time was 30 s for each data point. The observations of relatively high concentration of IO, compared to the values previously reported by DOAS, are consistent with the concurrent observations using a LIF (Laser induced Fluorescence) instrument (Whalley et al. in press). The first such measurements of localized IO by CRDS and LIF should contribute to an improved understanding of the chemistry of halogen compounds and the formation of iodine oxide aerosol particles in the marine boundary layer.     

基于连续流同位素质谱的地下水无机物氯稳定同位素测试方法及影响因素研究

氯稳定同位素作为示踪剂,能指示水体演化和探索地质环境变化,在地球科学领域具有广泛的应用前景.连续流同位素质谱法(CF-IRMS)具有样品用量少和灵敏度高的优点,被广泛应用于氯等稳定同位素的测试.氯甲烷作为一种易挥发的气体,在反应过程及测试管路中容易逸出,造成样品损失.如何减少反应及测试过程中氯甲烷的流失,实现氯甲烷的分...     

胶州湾海水中一氧化碳光致生成影响因素的研究

海水中的一氧化碳(CO)主要由溶解有色有机物(CDOM)光降解产生,且CO的光致生成量受到环境因素的影响。采集了胶州湾及其河口表层水样,通过实验室模拟实验开展了不同的环境条件(辐射强度、光照时间、温度、pH和盐度)以及水体中CDOM的来源对CO光致生成的影响研究。结果表明胶州湾海水中CO的光致生成速率随辐射强度的增强、水温的升高和水体pH的增大而增大;随着光照时间的延长、水体盐度的增大而逐渐减小;不同来源的CDOM对水体中CO的光致生成速率产生了不同的影响。     

A Case Study of CO<Subscript>2</Subscript>, CO and Particles Content Evolution in the Suburban Atmospheric Boundary Layer Using a 2-μm Doppler DIAL,a 1-μm Backscatter Lidar and an Array of In-situ Sensors

A network of remote and in-situ sensors was deployed in a Paris suburb in order to evaluate the mesoscale evolution of the daily cycle of CO₂ and related tracers in the atmospheric boundary layer (ABL) and its relation to ABL dynamics and nearby natural and anthropogenic sources and sinks. A 2-μm heterodyne Doppler differential absorption lidar, which combines measurements of, (1) structure of the atmosphere, (2) radial velocity, and (3) CO₂ differential absorption was a particularly unique element of the observational array. We analyse the differences in the diurnal cycle of CO, CO₂, lidar reflectivity (a proxy for aerosol content) and H₂O using the lidar, airborne measurements in the free troposphere and ground-based measurements made at two sites located few kilometres apart. We demonstrate that vertical mixing dominates the early morning drawdown of CO and aerosol content trapped in the former nocturnal layer but not the H₂O and CO₂ mixing ratio variations. Surface fluxes, vertical mixing and advection all contribute to the ABL CO₂ mixing ratio decrease during the morning transition, with the relative importance depending on the rate and timing of ABL rise. We also show evidence that when the ABL is stable, small-scale (0.1-km vertical and 1-km horizontal) gradients of CO₂ and CO are large. The results illustrate the complexity of inferring surface fluxes of CO₂ from atmospheric budgets in the stable boundary layer.     

海洋混凝土结构表面自由氯离子含量时变规律及对其寿命影响

表面氯离子含量(C_s)是研究海洋环境条件下混凝土结构耐久性和服役寿命的氯离子扩散方程的边界条件,是海洋混凝土结构耐久性分析和定量设计的重要参数。依据国内外大量自然暴露试验与工程实测数据,通过采用Excel、Origin等数据分析软件进行数据统计和回归分析,确定了海洋混凝土结构表面自由氯离子含量(C_(sf))与表面总氯离子含量(C_(st))之间的相互关系,探讨了海洋混凝土结构的C_(sf)时变规律,建立了C_(sf)与暴露时间之间的关系表达式及其取值范围,并运用可靠度理论和修正氯离子扩散理论分析了C_(sf)时变性对海洋混凝土结构寿命的影响。结果表明:C_(sf)与C_(st)线性相关,且C_(sf)随着暴露时间的延长呈指数或者幂函数的增长关系;采用不同的C_(sf)时变性规律,对海洋混凝土结构寿命具有重大的影响。     

温度与侵蚀对沥青混凝土冻融疲劳寿命的影响

为了提高盐渍土地区沥青路面的疲劳性能, 对SBS改性沥青混凝土进行了清水与饱和氯盐溶液的冻融劈裂疲劳试验, 研究了温度与氯盐侵蚀共同作用下, 沥青混凝土冻融疲劳寿命衰减规律. 结果表明: 温度与氯盐侵蚀是影响沥青混凝土冻融疲劳寿命的重要因素. 当冻融次数相同时, 沥青混凝土冻融疲劳寿命随冻融温度降低而不断减小; 当冻融温度相同时, 其冻融疲劳寿命随冻融次数增加而不断减小. 饱和氯盐溶液中沥青混凝土冻融疲劳寿命明显低于清水条件, 说明氯盐能够加速沥青混凝土冻融疲劳寿命衰减, 冻融温度越低, 盐冻破坏越严重. 通过对试验数据回归分析可知, 沥青混凝土冻融疲劳寿命与冻融循环次数之间具有较好的相关性, 可以利用两者之间的指数函数关系来预测沥青混凝土冻融疲劳寿命.