Field investigation of dimethyl sulfur in the Bohai Sea and northern Yellow Sea by ion mobility spectrometry
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摘要: 渤海、黄海是高产二甲基硫（Dimethyl Sulfide, DMS）的大陆架海区。该海区DMS的现场调查研究有助于准确评估海洋DMS释放量及其对全球气候变化的负反馈作用。目前，无论是基于模型还是直接测量法的通量估算均以表层海水或低层大气DMS浓度为基础，因此，先进的检测技术对其通量估算的准确度具有决定性作用。气相色谱法、质谱法、化学发光法以及卫星遥感技术是现在常用的观测技术，而本文则基于苯辅助光电离离子迁移谱技术进一步提出了一种可在海域现场观测海水中DMS的方法。通过结合动态气提-Nafion管在线除水进样系统，消除环境水汽的干扰；在最优条件下，基于DMS两个产物离子峰，可以实现0.10～120 nmol/L之间DMS的定量分析，检测限低至0.065 nmol/L；然后将所建方法应用于2019年秋季渤海、北黄海海水中DMS的现场观测。结果表明，表层海水中DMS的浓度为0.080～0.96 nmol/L（平均值为（0.44±0.34）nmol/L），其海气通量为0.12～17.75 μmol/（m2·d）（平均值为（ 3.23±4.02）μmol/（m2·d））；通过结合实验室检测结果、环境因子和浮游植物群落结构讨论了海水样品低温储存条件下DMS的变化和影响因素，结果显示，营养盐成分及浮游植物群落结构是影响储存样品中DMS浓度显著增加的主要因素，进一步表明了现场观测方法的建立对海洋DMS释放量的准确评估具有重要意义。Abstract: The Bohai Sea and Yellow Sea are continental shelf areas with high production of dimethyl sulfide (DMS). Field investigation of DMS in this area is helpful to accurately assess its amount released from the ocean and its negative feedback on global climate change. Both model-based and direct measurement methods are based on DMS concentration in surface seawater and lower atmosphere, respectively, so advanced detection technology plays a decisive role in the accurate flux estimation. Gas chromatography, mass spectrometry, chemiluminescence and satellite remote sensing are commonly used observation techniques. At this paper, a method based on benzene-assisted photoionization positive ion mobility spectrometry (BAPI-PIMS) for in-situ observation of DMS in seawater is proposed. Combined with dynamic gas stripping and on-line water removal Nafion tube sampling system, the interference of environmental water vapor is eliminated. Under the optimal conditions, the linear range based on the two DMS product ions is 0.10−120 nmol/L, and the detection limit is as low as 0.065 nmol/L. Then the demonstrated method is applied to field detect DMS in the Bohai Sea and northern Yellow Sea, and the concentration of DMS in surface seawater ranged from 0.08 nmol/L to 0.96 nmol/L, while the air-sea exchange flux ranged from 0.12 μmol/(m2·d) to 17.75 μmol/(m2·d). Lastly, the difference between DMS detected on field and in lab and the main impact factors are discussed via the correlation analysis and canonical correspondence analysis, and results show that nutrients and phytoplankton community are the main factors during the seawater preservation, indicating the important significance of field observation method established currently for accurate evaluation of DMS release from the ocean.
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图 1 动态气提-Nafion管在线除水苯辅助光电离离子迁移谱（Nafion-BAPI-PIMS）检测平台（a）及2019年秋季渤海、北黄海海域调查站位（b）
Fig. 1 Schematic of gas stripping-Nafion tube benzene-assisted photoionization positive ion mobility spectrometry (Nafion-BAPI-PIMS) (a) and locations of the sampling stations in the Bohai Sea and northern Yellow Sea in autumn 2019 (b)
图 2 5 mL人工海水中DMS（浓度：10 nmol/L ）样品的离子迁移谱图（a）和连续鼓泡进样检测5 mL人工海水样品（DMS浓度：10 nmol/L）得到的产物离子峰的监测曲线（b）
Fig. 2 Ion mobility spectra of DMS (concentration: 10 nmol/L) in 5 mL artificial seawater (a) and monitoring curves of corresponding DMS product ion peaks’ intensity versus analysis time for 5 mL artificial seawater sample with 10 nmol/L DMS detected through continuous bubble stripping (b)
图 3 鼓泡气流速（a）和海水进样体积（b）对Nafion管在线除水BAPI-PIMS检测5 mL人工海水样品（DMS浓度为10 nmol/L）的影响
Fig. 3 The effect of bubbling gas flow rate (a) and seawater sampling volume (b) on the detection of 5 mL artificial seawater with 10 nmol/L DMS by Nafion-BAPI-PIMS
图 4 2019年秋季渤海、北黄海海域现场观测获得的表层海水中DMS的浓度及其海−气通量分布
Fig. 4 Distribution of DMS detected on field in the surface seawater and its air-sea exchange flux of the Bohai Sea and the northern Yellow Sea during autumn 2019
图 5 2019年秋季渤海、北黄海海水DMS的现场观测值和实验室检测值及两者比例的变化曲线
Fig. 5 The variations of DMS concentration detected on field and in laboratory, and their ratio in the Bohai Sea and the northern Yellow Sea during autumn 2019
图 6 DMS的现场观测值、实验室检测值及两者的比值与浮游植物群落结构（前15种优势种群）和环境因子间的典范对应分析
2019年秋季浮游植物的前15种优势种如下：b1. 具槽帕拉藻Paralia sulcate; b2. 蜂腰双壁藻Diploneis bombus; b3. 菱形藻Nitzschia spp.; b4. 柔弱伪菱形藻Pseudonitzschia delicatissima; c. 小等刺硅鞭藻Dictyocha fibula; b5. 曲舟藻Pleurosigma spp.; b6. 斯氏几内亚藻Guinardia striata; b7. 海链藻Thalassiosira spp.; b8. 圆筛藻Coscinodiscus spp.; b9. 格氏圆筛藻Coscinodiscus granii; b10. 细弱圆筛藻Coscinodiscus subtilis; b11. 膜状谬氏藻Meuniera membranacea; b12. 舟形藻Navicula spp.; b13. 洛氏菱形藻Nitzschia lorenziana; b14. 羽纹藻Pinnularia spp.；其中b1−b14为硅藻门优势物种，c为金藻门优势物种
Fig. 6 Canonical correspondence analysis of DMS concentration detected on field and in laboratory, their ratio, phytoplankton community (top 15 dominant phytoplankton species) and environmental factors
Top 15 dominant phytoplankton species during autumn 2019: b1. Paralia sulcate; b2. Diploneis bombus; b3. Nitzschia spp.; b4. Pseudonitzschia delicatissima; c. Dictyocha fibula; b5. Pleurosigma spp.; b6. Guinardia striata; b7. Thalassiosira spp.; b8. Coscinodiscus spp.; b9. Coscinodiscus granii; b10. Coscinodiscus subtilis; b11. Meuniera membranacea; b12. Navicula spp.; b13. Nitzschia lorenziana; b14. Pinnularia spp.; among them, b1−b14 are the dominant diatom and c is the dominant chrysophyta
表 1 人工海水中DMS的定量分析结果
Tab. 1 Quantitation results for DMS samples prepared with artificial seawater
参数 动态响应曲线 R2值 线性范围/(nmol·L−1) 检测限 (信噪比为3, 单位：nmol/L) DMS 1 强度 y=61.46x+7.63 0.9983 0.10～10.00 0.065 面积 y=2 628.34x+126.60 0.9971 0.10～20.00 0.067 DMS 2 强度 y=15.46x−49.46 0.9923 10.00～80.00 − 面积 y=608.78x−2423.34 0.9961 5.00～120.00 − 注：DMS 1代表DMS产物离子单体峰；DMS 2代表DMS产物离子二聚体峰；−代表无数据。 
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表 2 2019年秋季渤海、北黄海海水中DMS浓度的现场观测值（DMSF）、实验室检测值（DMSL）及两者比值与环境因子的相关性分析
Tab. 2 Correlation analysis of DMS concentration detected in field (DMSF) and lab (DMSL) and environmental factors in the Bohai Sea and the northern Yellow Sea during autumn 2019
DMSF DMSL DMSL∶DMSF DMSL 0.206 1 0.677** DMSF 1 0.206 −0.536* DMSL∶DMSF −0.536* 0.677** 1 Chl a浓度 0.082 −0.116 −0.139 ${{\rm{PO}}_4^{3-} }$浓度 −0.808** −0.187 0.486* TIN浓度 −0.832** −0.147 0.453* ${{\rm{SiO} }_3^{2-}}$浓度 −0.852** −0.191 0.449* 温度 0.356 −0.221 −0.308 盐度 0.056 0.190 0.052 注：* 在0.05级别（双尾）相关性显著；** 在0.01级别（双尾）相关性显著；TIN代表总无机氮。
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