一文了解化学电离质谱如何测量大气环境中OH自由基
p style=" text-indent: 2em " strong span style=" color: rgb(0, 112, 192) " span style=" line-height: 150% " 1. /span span style=" line-height: 150% font-family: 宋体 " 大气 /span span style=" line-height: 150% font-family: " times=" " new=" " · OH /span span style=" line-height: 150% font-family: 宋体 " 活性自由基的来源与作用 /span /span /strong /p p style=" margin-left: 24px text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " strong /strong /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 大气 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 、 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · HO sub 2 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 活性自由基是大气光化学反应的引发剂和催化剂,对于城市灰霾的形成和对流层中 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " O sub 3 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的平衡起关键作用,其浓度等级可作为衡量大气自身氧化水平的重要指标。 /span /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 其中 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基是大气化学中最活跃的氧化剂,能与大气中绝大多数组分发生化学反应。例如大气中的甲烷( /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CH sub 4 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " ),可以快速与 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基反应生成可溶解氧化物 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CH sub 2 /sub O /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 、 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CH sub 3 /sub COOH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 发生沉降,因此,虽然每年有 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 5.15× 10 sup 14 /sup g /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CH sub 4 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 排入地球大气层,但 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基可将其中的 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 4.45× 10 sup 14 /sup g /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 氧化,占 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CH sub 4 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 总量的 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 80% /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 以上,这使得 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CH sub 4 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 对全球温室效应的影响比排放量估算整整低了一个量级。从某种程度来看, /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基决定了这些组分在地球大气层中的寿命和浓度。不仅如此,酸雨、对流层臭氧平衡、城市光化学烟雾以及二次气溶胶形成等过程都有 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的参与。除此之外, /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 、 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " O sub 3 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 还可以与大气中的烯烃反应生成醛,后者再与 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基反应从而产生光化学烟雾中有毒且具有强烈刺激性的化合物过氧乙酰硝酸酯( /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " PANs /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " )。 /span /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 在低空对流层中, /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的主要来源有两个:一是 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " O sub 3 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 在 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 320 nm /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 光波条件下光解产生的 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " O( sup 1 /sup D) /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 与空气中水分子的反应,二是 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · HO sub 2 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 与氮氧化物以及臭氧的反应。但是, /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基的平均寿命通常为几秒甚至更短,它在对流层的最大浓度仅有 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 10 sup 6 /sup ~10 sup 7 /sup /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 个 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " /cm sup 3 /sup /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " ,且变化十分剧烈。 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 、 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · HO sub 2 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基在大气光化学反应和光化学烟雾形成过程中的作用如图 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 1.1 /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 所示。 /span /span /p p style=" text-align: center text-indent: 2em line-height: 1.75em " span style=" font-size: 16px line-height: 150% font-family: 微软雅黑 " /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 500px height: 385px " src=" https://img1.17img.cn/17img/images/202006/uepic/948b92d1-12cb-472e-a61b-c0944df80ea3.jpg" title=" 1.png" alt=" 1.png" width=" 500" height=" 385" border=" 0" vspace=" 0" / /p p style=" text-align: center text-indent: 2em line-height: 1.75em " span style=" text-indent: 2em font-family: 黑体 " 图 /span span style=" text-indent: 2em font-family: " times=" " new=" " 1.1& nbsp · OH /span span style=" text-indent: 2em font-family: 黑体 " 、 /span span style=" text-indent: 2em font-family: " times=" " new=" " · HO sub 2 /sub /span span style=" text-indent: 2em font-family: 黑体 " 在大气光化学反应和光化学烟雾形成过程中的作用 /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" color: rgb(0, 112, 192) " strong span style=" line-height: 150% " 2. /span span style=" line-height: 150% font-family: 宋体 " 常见大气活性自由基 /span span style=" line-height: 150% font-family: " times=" " new=" " · OH /span span style=" line-height: 150% font-family: 宋体 " 的检测手段 /span /strong /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 直到 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 20 /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 世纪 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 90 /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 年代,测量对流层大气中 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 浓度的技术才逐渐成熟。英国 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " Leed /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 大学的 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " Heard /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 和 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " Pilling /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 教授在 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " Chem. Rev. /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 上撰写综述文章,全面评述了对流层中 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的各项测量技术,包括:化学电离质谱技术( /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CIMS /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " )、气体扩张激光诱导荧光技术( /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " FAGE /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " )、激光差分吸收光谱技术( /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " DOAS /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " )、 /span sup span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 14 /span /sup span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CO /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 示踪技术、水杨酸吸收技术以及自旋捕获技术。表 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 1.1 /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 给出了这几种测量方法的主要技术指标。 /span strong /strong /span /p p style=" text-indent: 2em line-height: 1.75em text-align: center " span style=" font-family: 微软雅黑 " span style=" font-family: 黑体 " 表 /span span style=" font-family: " times=" " new=" " 1.1& nbsp · OH /span span style=" font-family: 黑体 " 浓度测定的各种技术及指标 /span /span /p table border=" 1" cellspacing=" 0" cellpadding=" 0" style=" border-collapse: collapse border: none margin-left: 9px margin-right: 9px " align=" center" tbody tr style=" height:31px" class=" firstRow" td width=" 95" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 31" p style=" text-align:center" strong span style=" font-size:16px font-family:宋体" 测量技术 /span /strong strong /strong /p /td td width=" 42" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 31" p style=" text-align:center" strong span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" LOD( /span /strong strong span style=" font-size:16px font-family:宋体" 个 /span /strong strong span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" /cm sup 3 /sup ) /span /strong /p /td td width=" 12" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 31" p style=" text-align:center" strong span style=" font-size:16px font-family:宋体" 准确度 /span /strong strong /strong /p /td td width=" 59" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 31" p style=" text-align:center" strong span style=" font-size:16px font-family:宋体" 单次测量时间 /span /strong strong /strong /p /td td width=" 34" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 31" p style=" text-align:center" strong span style=" font-size:16px font-family:宋体" 机载 /span /strong strong /strong /p /td td width=" 130" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 31" p style=" text-align:center" strong span style=" font-size:16px font-family:宋体" 研究团队 /span /strong strong /strong /p /td /tr tr style=" height:23px" td width=" 81" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" CIMS /span /p /td td width=" 42" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 2 /span span style=" font-size:16px font-family:Symbol" span ´ /span /span span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 10 sup 5 /sup /span /p /td td width=" 12" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 20% /span /p /td td width=" 64" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 30 s /span /p /td td width=" 43" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" Y /span /p /td td width=" 121" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 3+3 /span /p /td /tr tr style=" height:23px" td width=" 81" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" FAGE /span /p /td td width=" 42" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 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font-size:16px font-family:Symbol" span ´ /span /span span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 10 sup 5 /sup /span /p /td td width=" 12" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 16% /span /p /td td width=" 64" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 300 s /span /p /td td width=" 43" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" Y /span /p /td td width=" 121" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 1 /span /p /td /tr tr style=" height:23px" td width=" 81" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:宋体" 自旋 /span span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" - /span span style=" font-size:16px font-family:宋体" 捕获法 /span /p /td td width=" 42" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 5 /span span style=" font-size:16px font-family:Symbol" span ´ /span /span span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 10 sup 5 /sup /span /p /td td width=" 12" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" & lt 30% /span /p /td td width=" 64" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 20 min /span /p /td td width=" 43" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" N /span /p /td td width=" 121" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 1 /span /p /td /tr tr style=" height:23px" td width=" 81" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:宋体" 水杨酸吸收法 /span /p /td td width=" 42" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 10 /span span style=" font-size:16px font-family:Symbol" span ´ /span /span span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 10 sup 5 /sup /span /p /td td width=" 12" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 30~50% /span /p /td td width=" 64" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 90 min /span /p /td td width=" 43" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" N /span /p /td td width=" 121" style=" border: 1px solid rgb(0, 0, 0) padding: 5px " height=" 23" p style=" text-align:center" span style=" font-size:16px font-family:& #39 Times New Roman& #39 ,serif" 2 /span /p /td /tr /tbody /table p style=" line-height: 1.75em text-indent: 2em " span style=" text-indent: 2em font-family: " times=" " new=" " span style=" line-height: 24px font-family: 宋体 " FAGE是一种在低压条件下测量大气活性自由基的激光诱导荧光技术( /span span style=" line-height: 24px font-family: " times=" " new=" " LIF /span span style=" line-height: 24px font-family: 宋体 " ),自其被提出以来,已经广泛应用于自由基的检测,成为测量大气自由基的有效方法之一。正常工作时, /span span style=" line-height: 24px font-family: " times=" " new=" " FAGE /span span style=" line-height: 24px font-family: 宋体 " 利用特定波长的激光束,使低能级的 /span span style=" line-height: 24px font-family: " times=" " new=" " · OH /span span style=" line-height: 24px font-family: 宋体 " 自由基发生跃迁,通过检测其从高能级回落过程中产生的荧光,从而实现对于 /span span style=" line-height: 24px font-family: " times=" " new=" " · OH /span span style=" line-height: 24px font-family: 宋体 " 自由基浓度的测量。 /span /span /p p style=" line-height: 1.75em text-indent: 2em " span style=" text-indent: 2em font-family: " times=" " new=" " DOAS /span span style=" text-indent: 2em font-family: 宋体 " 是利用空气中气体分子的窄带吸收特性及强度来鉴别气体成分、推演气体浓度的一种技术,其测量原理基于 /span span style=" text-indent: 2em font-family: " times=" " new=" " Beer-Lambert /span span style=" text-indent: 2em font-family: 宋体 " 定律: /span /p p style=" line-height: 1.75em text-indent: 2em " span style=" text-indent: 2em font-family: 宋体 " /span /p p style=" text-align: center" img style=" max-width:100% max-height:100% " src=" https://img1.17img.cn/17img/images/202006/uepic/766f80ed-bfa1-4612-b47e-bf2f50094303.jpg" title=" 化学式1.png" alt=" 化学式1.png" / span style=" text-indent: 0em font-family: 微软雅黑 " span style=" line-height: 150% font-family: " times=" " new=" " color:=" " E /span /span span style=" text-indent: 2em text-align: right font-family: 仿宋_GB2312 " & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 /span span style=" text-indent: 2em text-align: right font-family: 宋体 " ( /span span style=" text-indent: 2em text-align: right font-family: " times=" " new=" " 1.1 /span span style=" text-indent: 2em text-align: right font-family: 宋体 " ) /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" text-indent: 2em line-height: 24px font-family: 宋体 " 进而得到 /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-size: 16px font-family: 微软雅黑 " /span /p p style=" text-align: center" img style=" max-width:100% max-height:100% " src=" https://img1.17img.cn/17img/images/202006/uepic/98f4fc65-35a4-4751-a3df-6df88f1f708c.jpg" title=" 化学式2.png" alt=" 化学式2.png" / span style=" text-indent: 2em text-align: right font-family: " times=" " new=" " position:=" " top:=" " & nbsp /span span style=" text-indent: 2em text-align: right font-family: 仿宋_GB2312 " & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 /span span style=" text-indent: 2em text-align: right font-family: 宋体 " ( /span span style=" text-indent: 2em text-align: right font-family: " times=" " new=" " 1.2 /span span style=" text-indent: 2em text-align: right font-family: 宋体 " ) /span /p p span style=" text-indent: 2em text-align: right font-family: 宋体 " /span /p p style=" text-align: center" img style=" max-width:100% max-height:100% " src=" https://img1.17img.cn/17img/images/202006/uepic/7d7e75da-8bc5-47f5-982a-14f4e5ec72a8.jpg" title=" 微信截图_20200618164858.png" alt=" 微信截图_20200618164858.png" / /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " sup span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 14 /span /sup span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CO /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 示踪技术最早由华盛顿州立大学于 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 1979 /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 年报道,它是一种基于光稳态技术对 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基进行研究的方法,利用 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基对 /span sup span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 14 /span /sup span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CO /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的强氧化性,从而实现了对于 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基的高灵敏度检测。 /span /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 对于自旋捕获技术和水杨酸吸收技术,则由于其在检测中所需的时间均大于 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 20 min /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " ,从而不适合应用于 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基的连续在线检测。 /span /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CIMS /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 是一种利用 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的化学特性对其进行检测的技术,其原位测量 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的浓度是 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " Georgia Institute of Technology /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " Eisele /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 和 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " Tannar /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 在 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 1989 /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 年发明的。 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CIMS /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 对 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 进行测量的关键在于通过过量的 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " SO sub 2 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 将其滴定,从而把 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 全部转化为 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " H sub 2 /sub SO sub 4 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " ,再用 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " NO sub 3 /sub sup - /sup /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 离子通过化学电离方法把 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " H sub 2 /sub SO sub 4 /sub /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 电离为 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " HSO sub 4 /sub sup - /sup /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 离子,最终利用测量得到的 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " NO sub 3 /sub sup - /sup /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 与 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " HSO sub 4 /sub sup - /sup /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 离子的强度,完成对 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的检测。其基本原理如下: /span /span /p p style=" text-align: right text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " /span /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 200px height: 23px " src=" https://img1.17img.cn/17img/images/202006/uepic/5db3950c-6bb1-429f-a5dc-74721da12853.jpg" title=" 化学式3.png" alt=" 化学式3.png" width=" 200" height=" 23" border=" 0" vspace=" 0" / span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " & nbsp /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: 仿宋_GB2312 " & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ( /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " 1.3 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ) /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em " & nbsp /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 200px height: 26px " src=" https://img1.17img.cn/17img/images/202006/uepic/5fd7a534-5c7d-4f54-8c3a-b3664554a285.jpg" title=" 化学式4.png" alt=" 化学式4.png" width=" 200" height=" 26" border=" 0" vspace=" 0" / span style=" text-align: right text-indent: 2em line-height: 150% font-family: 仿宋_GB2312 " & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ( /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " 1.4 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ) /span /p p style=" text-align: right text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " position:=" " top:=" " /span /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 200px height: 22px " src=" https://img1.17img.cn/17img/images/202006/uepic/23d266a5-b30f-41b8-b389-5fe3b01adda6.jpg" title=" 化学式5.png" alt=" 化学式5.png" width=" 200" height=" 22" border=" 0" vspace=" 0" / span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " position:=" " top:=" " & nbsp /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: 仿宋_GB2312 " & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 ... /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ( /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " 1.5 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ) /span /p p style=" text-align: right text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " /span /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 200px height: 21px " src=" https://img1.17img.cn/17img/images/202006/uepic/8bde4373-fe29-4b3a-8810-266a5776b2ec.jpg" title=" 化学式6.png" alt=" 化学式6.png" width=" 200" height=" 21" border=" 0" vspace=" 0" / span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " & nbsp /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: 仿宋_GB2312 " & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ( /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " 1.6 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ) /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 进而可以得到 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 的计算公式: /span /span /p p style=" text-align: right text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " /span /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 200px height: 44px " src=" https://img1.17img.cn/17img/images/202006/uepic/1d1e9059-1c2a-4c7e-a908-8c34733ab6b9.jpg" title=" 化学式7.png" alt=" 化学式7.png" width=" 200" height=" 44" border=" 0" vspace=" 0" / span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " & nbsp /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: 仿宋_GB2312 " & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 & #8230 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ( /span span style=" text-align: right text-indent: 2em line-height: 150% font-family: " times=" " new=" " 1.7 /span span style=" font-family: 微软雅黑 text-align: right text-indent: 2em line-height: 150% " ) /span /p p style=" text-indent: 2em " span style=" color: rgb(0, 112, 192) " strong span style=" line-height: 150% " 3. /span span style=" line-height: 150% font-family: 宋体 " 自主研发化学电离质谱测量 /span span style=" line-height: 150% font-family: " times=" " new=" " · OH /span /strong /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 中科院大连化物所李海洋研究员带领的“快速分离与检测”课题组( /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 102 /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 组)基于质谱检测核心技术,致力于发展用于在线、现场、原位快速分析的质谱新仪器和新方法,聚焦于化工生产、环境监测和临床医学精确诊断对高端在线质谱的迫切需求,注重技术创新,以“做有用的仪器”为至高追求,先后攻克了新型软电离源、高分辨质量分析器等在线质谱多项关键技术,并于 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 2017 /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 年与金铠仪器(大连)有限公司共同建立质谱发展事业部,携手推动高端质谱技术的发展。近年来,团队先后获得在线质谱仪从设计、生产到应用全链条认证,成功搭建了台式质谱仪、便携式质谱仪、毒品现场鉴别离子阱质谱仪等多个系列产品线,并实现了定型产品“高灵敏光电离飞行时间质谱仪”出口美国、团队成功入选辽宁省兴辽英才计划“高水平创新创业团队”等多项创举。 /span /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " /span /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 455px height: 600px " src=" https://img1.17img.cn/17img/images/202006/uepic/65377ae1-b7f4-4dc3-9cd4-fe11db074f89.jpg" title=" f962b4b3bb4bb46555334acec7d0997_副本.png" alt=" f962b4b3bb4bb46555334acec7d0997_副本.png" width=" 455" height=" 600" border=" 0" vspace=" 0" / /p p style=" text-indent: 2em line-height: 1.75em " span style=" text-indent: 2em line-height: 150% font-family: 宋体 " 针对大气活性自由基 /span span style=" text-indent: 2em line-height: 150% font-family: " times=" " new=" " · OH /span span style=" text-indent: 2em line-height: 150% font-family: 宋体 " 的检测难题,质谱发展事业部科研工作者基于垂直加速和双场加速聚焦技术,完全自主研发了一台大气压负离子直线式 /span span style=" text-indent: 2em line-height: 150% font-family: " times=" " new=" " TOFMS /span span style=" text-indent: 2em line-height: 150% font-family: 宋体 " 用于大气活性自由基 /span span style=" text-indent: 2em line-height: 150% font-family: " times=" " new=" " · OH /span span style=" text-indent: 2em line-height: 150% font-family: 宋体 " 在线监测,其结构示意图如图 /span span style=" text-indent: 2em line-height: 150% font-family: " times=" " new=" " 1.2 /span span style=" text-indent: 2em line-height: 150% font-family: 宋体 " 所示。 /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 14px font-family: 黑体 " /span /span /p p style=" text-align: center" img style=" max-width:100% max-height:100% " src=" https://img1.17img.cn/17img/images/202006/uepic/99cdf405-749e-4743-989c-4cc3c7893cf3.jpg" title=" 88.jpg" alt=" 88.jpg" / /p p style=" text-indent: 2em line-height: 1.75em text-align: center " span style=" text-align: center text-indent: 32px font-size: 14px font-family: 黑体 " 图 /span span style=" text-align: center text-indent: 32px font-size: 14px font-family: " times=" " new=" " 1.2& nbsp & nbsp /span span style=" text-align: center text-indent: 32px font-size: 14px font-family: 黑体 " 自行研制的大气压负离子直线式 /span span style=" text-align: center text-indent: 32px font-size: 14px font-family: " times=" " new=" " TOFMS /span span style=" text-align: center text-indent: 32px font-size: 14px font-family: 黑体 " 的结构示意图 /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" text-indent: 2em font-family: 宋体 " 基于 /span span style=" text-indent: 2em font-family: " times=" " new=" " CIMS /span span style=" text-indent: 2em font-family: 宋体 " 技术的基本原理,针对大气活性自由基浓度低、寿命短等自身特点,利用 /span sup style=" font-family: 微软雅黑 text-indent: 2em " span style=" font-size: 16px font-family: " times=" " new=" " 63 /span /sup span style=" text-indent: 2em font-family: " times=" " new=" " Ni /span span style=" text-indent: 2em font-family: 宋体 " 放射源作为电离源,采用自由基转化反应管、试剂离子产生管与化学电离反应区相互平行同轴设计的结构,对自由基进行测量。如图 /span span style=" text-indent: 2em font-family: " times=" " new=" " 1.3 /span span style=" text-indent: 2em font-family: 宋体 " 所示为同轴式自由基进样系统及电离源的反应原理图与结构设计图。 /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" text-indent: 2em font-family: 宋体 " /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 600px height: 614px " src=" https://img1.17img.cn/17img/images/202006/uepic/0e654476-5bf0-4572-bc19-9a0e78fb151e.jpg" title=" 99.jpg" alt=" 99.jpg" width=" 600" height=" 614" border=" 0" vspace=" 0" / /p p style=" text-indent: 2em line-height: 1.75em text-align: center " span style=" text-align: center text-indent: 2em font-family: 黑体 " 图 /span span style=" text-align: center text-indent: 2em font-family: " times=" " new=" " 1.3& nbsp /span span style=" text-align: center text-indent: 2em font-family: 黑体 " 同轴式 /span span style=" text-align: center text-indent: 2em font-family: " times=" " new=" " · OH /span span style=" text-align: center text-indent: 2em font-family: 黑体 " 自由基进样系统及电离源的反应原理图 /span /p p style=" margin: 10px 0px text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px font-family: 宋体 " 基于上述 /span span style=" font-size: 16px font-family: " times=" " new=" " CIMS /span span style=" font-size: 16px font-family: 宋体 " 检测方法,科研人员于 /span span style=" font-size: 16px font-family: " times=" " new=" " 2018 /span span style=" font-size: 16px font-family: 宋体 " 年 /span span style=" font-size: 16px font-family: " times=" " new=" " 4 /span span style=" font-size: 16px font-family: 宋体 " 月 /span span style=" font-size: 16px font-family: " times=" " new=" " 30 /span span style=" font-size: 16px font-family: 宋体 " 日对大连市沙河口区中山路 /span span style=" font-size: 16px font-family: " times=" " new=" " 457 /span span style=" font-size: 16px font-family: 宋体 " 号生物楼楼顶平台环境空气中 /span span style=" font-size: 16px font-family: " times=" " new=" " · OH /span span style=" font-size: 16px font-family: 宋体 " 自由基进行了连续在线监测,时间范围为 /span span style=" font-size: 16px font-family: " times=" " new=" " 6:00 ~18:00 /span span style=" font-size: 16px font-family: 宋体 " 。测试过程中每张质谱图采集 /span span style=" font-size: 16px font-family: " times=" " new=" " 5 s /span span style=" font-size: 16px font-family: 宋体 " ,经过计算,得到环境空气中 /span span style=" font-size: 16px font-family: " times=" " new=" " OH /span span style=" font-size: 16px font-family: 宋体 " 自由基浓度在一天内随时间的变化趋势如图 /span span style=" font-size: 16px font-family: " times=" " new=" " 1.4 /span span style=" font-size: 16px font-family: 宋体 " 所示,所得监测结果与相关文献报道规律保持一致,且分析速度更具优势,展现了所发展 /span span style=" font-size: 16px font-family: " times=" " new=" " CIMS /span span style=" font-size: 16px font-family: 宋体 " 的巨大应用潜力。 /span /span /p p style=" margin: 10px 0px text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px font-family: 宋体 " /span /span /p p style=" text-align: center" img style=" max-width: 100% max-height: 100% width: 600px height: 449px " src=" https://img1.17img.cn/17img/images/202006/uepic/fb123cb4-f106-42c3-8e9e-13bd104b1612.jpg" title=" 10101.png" alt=" 10101.png" width=" 600" height=" 449" border=" 0" vspace=" 0" / /p p style=" margin: 10px 0px text-indent: 2em line-height: 1.75em text-align: center " span style=" font-family: 微软雅黑 text-align: center text-indent: 2em " 图 /span span style=" text-align: center text-indent: 2em font-family: " times=" " new=" " 1.4& nbsp /span span style=" font-family: 微软雅黑 text-align: center text-indent: 2em " 环境空气中 /span span style=" text-align: center text-indent: 2em font-family: " times=" " new=" " · OH /span span style=" font-family: 微软雅黑 text-align: center text-indent: 2em " 自由基浓度在一天内随时间的变化 /span /p p style=" margin: 10px 0px text-indent: 2em line-height: 1.75em " span style=" color: rgb(0, 112, 192) " strong style=" font-family: 微软雅黑 text-indent: 2em " span style=" line-height: 150% font-family: 宋体 " 4.结语 /span /strong /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 由中科院大连化物所“快速分离与检测”课题组与金铠仪器(大连)有限公司共建的质谱发展事业部,采用 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " CIMS /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 技术设计研制了一套基于 /span sup span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " 63 /span /sup span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " Ni /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 放射源的大气压化学电离源及进样系统,利用自行研制的大气压负离子 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " TOFMS /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 实现了对于大气中的超痕量 /span span style=" font-size: 16px line-height: 150% font-family: " times=" " new=" " · OH /span span style=" font-size: 16px line-height: 150% font-family: 宋体 " 自由基的原位、实时、在线、连续测量,展现了其在大气环境领域的巨大应用前景。 /span /span /p p style=" text-indent: 2em line-height: 1.75em " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " br/ /span /span /p p style=" text-indent: 2em line-height: 1.75em text-align: right " span style=" font-family: 微软雅黑 " span style=" font-size: 16px line-height: 150% font-family: 宋体 " 供稿来源:金铠仪器(大连)有限公司 /span /span /p p br/ /p