生物和环境样品中痕量溴碘的小体积交换分离与测定

针对微克量级卤素的分离问题,研究了不同形态卤素在７１７阴离子交换柱上的吸附特点。通过离子交换柱的改进和分离条件的选择,实现了卤素与基体以及卤素之间的有效分离。洗脱体积小,盐份浓度低,经水样、土壤和生物样品分析考查,方法可行。     

DOAS Zenith Sky Observations: 1. BrO Measurements over Bremen (53°N) 1993–1994

Observations of stratospheric BrO over Bremen (53°N) are reported for winter and early spring periods of 1993 and 1993/94. The BrO was observed by ground-based near-UV absorption spectroscopy of sunlight scattered in the zenith. Differential slant column densities for solar zenith angles 90°/80° in the range of9× 10¹³ (detection limit) to 4.5×10¹⁴ molecules/cm² having a high day-to-day variability were found. For the majority of the measurements no significant difference was observed between the morning and evening behaviour of BrO. Exceptions are the morning measurements from the winter of 1992/93 where an accelerated production of BrO was observed. We believe the latter best to be explained by the early morning rapid photolysis of elevated amounts of photo-labile Br-reservoirs formed during the night. The largest differential slant column densities of BrO were measured in December 1993 when the temperatures at 30 hPa dropped below 205 K. This might be an indication of heterogeneous conversion of bromine compounds on sulfate and other aerosols.     

Kinetic investigation of the OH + CH3Br reaction between 248 and 390 K

The rate parameters for the reaction of the OH radical with CH₃Br have been measured using the discharge flow-electron paramagnetic resonance method. The result isk ₁=(1.86±0.48)×10^–12 exp[–(1230±150)/T] cm³ molecule^–1 s^–1. This value is compared to earlier data and is found to be in excellent agreement with the most recent results, which greatly increases the accuracy of the ozone depletion potential of CH₃Br which can be derived from these kinetic data.     

电感耦合等离子体质谱法同时测定地质样品中痕量碘溴硒砷的研究Ⅰ．不同介质及不同阴离子形态对测定信号的影响

研究了半熔-电感耦合等离子体质谱法（ICP-MS）同时测定地质样品中痕量碘、溴、硒和砷等非金属元素的可行性。重点研究了不同介质中碘以及溴、砷、硒不同形态对测定信号的影响。比较并讨论了在纯水溶液、0.07mol/LNH     

薄膜吸附制样-波长色散X射线荧光光谱法测定卤水中的溴

溴主要以离子形式分布在地壳水圈的溴化物型卤水、卤化物硫酸盐型卤水中,目前应用波长色散X射线荧光光谱(WDXRF)测定卤水中的溴,主要采用粉末载体压片法前处理待检样品,制样工作量大,制样均匀性和制样过程中的污染都会影响准确度,方法实用性不强。本文借助薄膜吸附前处理卤水样品,通过优化筛选薄膜材料及卤水取样量,确定移取50μL卤水样品滴于Ф=40 mm的3#层析滤纸的圆心位置,自然晾干后高压压平来前处理待检样品,采用人工配制标准样品校正溴的标准曲线,用WDXRF测定溴的含量。钾钠钙镁氯和硫酸根等共存离子的影响可以忽略,方法检出限(3σ)为0.95 mg/L,精密度(RSD,n=11)不大于0.8%,加标回收率为99.4%~101.2%。本方法操作简便,不需要使用化学试剂,解决了现行卤水中溴的分析方法流程复杂、分析成本高的问题。     

High resolution spectral features of a series of aromatic hydrocarbons and BrO: Potential interferences in atmospheric OH-measurements

Naphthalene (C₁₀H₈), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy.Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section was determined.The strongest naphthalene line at 308.002 nm is close to the Q ₁(2) OH line, but about a factor of 200 weaker (=(65.2±15.3)×10^-20 cm²/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration.BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q ₁(2) and Q ₁(3) OH lines.     

气态膜法海水提溴影响因素的研究

以聚偏氟乙烯 (PVDF)为材料 ,采用中空纤维气态膜法对影响海水及增浓后海水 (卤水 )提溴的因素进行了探讨。通过分析确定原料液 (含溴海水和卤水 )的温度 T、流速μ、浓度 c以及膜外侧的真空度为影响提溴收率 η、传质系数 k和通量 J的优选因素 ,对此 4因素进行 L16 (44)正交实验。实验结果极差分析表明 :温度是收率和传质系数的首要影响因素 ,而通量的首要影响因素是浓度。在本实验条件下 ,η,k和 J均达最佳时各因素水平分别为 :温度 48℃ ,真空度 60 0 mm Hg,流速 7.81cm/ s,浓度 190× 10 - 6。     

南极大陆沿岸地面臭氧损耗事件的研究

利用南极大陆沿岸中山站2008-2013年的地面臭氧连续观测数据和相关资料,对地面臭氧损耗事件（ODE）进行研究。结果显示,春季南极中山站常发生臭氧损耗事件。在该事件发生期间,气象要素有明显的突变过程,包括气温明显下降,风向由偏东风转变为偏北风,风速随之下降。来自海冰区的偏北风增多,风速很小,使臭氧浓度维持在较低水平。地面臭氧损耗事件主要与南极沿岸海冰区的活性溴（BrO）浓度有关。春季南极大陆沿岸海冰冻融过程中形成的冰间水道和冰间湖,在低温的作用下会再次冻结,形成薄冰和霜花。卫星资料能够观测到薄冰区释放的活化海盐溴高浓度区,活性溴与臭氧发生化学反应形成地面臭氧损耗事件。臭氧损耗现象是在未受到人为影响的自然状态下发生的,与中高纬度地区光化学反应导致臭氧消耗有所不同。      

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。     

Gas BenchⅡ-IRMS测定地下水中溴同位素新技术

建立了利用GasBenchⅡ联用同位素比值质谱仪（GasBench Ⅱ-IRMS）用于测定地下水中溴稳定同位素的方法。基于溴比氯更容易被重铬酸钾氧化的性质,将Br-氧化成Br2,而氯残留在原溶液中,从而把溴与氯分离开;再利用AgNO3将溴以AgBr的形式沉淀下来,然后将AgBr转化成CH。Br进行溴稳定同位素质谱测定。反应中,CHsI用量为20μL,AgBr用量为0．5mg。本测试流程需溴4～10mg,质谱测试时问由1．5h缩短为800s,测试精度优于±0．1‰（2σ）。该方法可以用于地下水中溴同位素测定,在水文地质研究中具有广阔的应用前景。