Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) is utilized to molecularly characterize DOM as it is transported along a river to estuary to ocean transect of the lower Chesapeake Bay system. The ultrahigh resolving power (greater than 500,000) and mass accuracy of FTICR-MS allow for the resolution of the thousands of components in a single DOM sample, and can therefore elucidate the molecular-level changes that occur during DOM transformation from a terrestrial location to the marine environment. An important feature of FTICR-MS is that its sensitivity allows for direct analysis of low salinity samples without employing the traditional concentration approaches involving C₁₈ extraction or ultrafiltration. To evaluate the advantages of using direct analysis, a C₁₈ extract of riverine water is compared to its whole, unfractionated water, and it was determined that the C₁₈ extraction is selective in that it eliminates two major series of compounds. One group is aliphatic amines/amides that are not adsorbed to the C₁₈ disk because they exist as positive ions prior to extraction. The second group is tannin-like compounds with higher oxygen contents and a more polar quality that also allow them not to be adsorbed to the C₁₈ disk. This direct approach could not be used for brackish/saline waters, so the C₁₈ method is resorted to for those samples. Along the subject transect, a significant difference is observed in the molecular composition of DOM, as determined from assigned molecular formulas. The DOM tends to become more aliphatic and contain lower abundances of oxygen-rich molecules as one progresses from inshore to the offshore. A considerable amount of molecular formula overlap does exist between samples from sites along the transect. This can be explained as either the presence of refractory material that persists throughout the transect, due to its resistance to degradation, or that the assigned molecular formulas are the same but the chemical structures are different. ESI-FTICR-MS is a powerful technique for the investigation of DOM and has the ability to detect compositional variations along the river to ocean transect. Visualization tools such as two dimensional and three dimensional van Krevelen diagrams greatly assist in highlighting the shift from the more aromatic, terrestrial DOM to the more aliphatic, marine DOM.     

舟山海域陆源溶解有机质变化及其对近岸羽状流的响应

2007年夏季在东海舟山海域河口锋区开展了陆源溶解有机质的调查研究。测定了有色溶解有机质(CDOM)在激发波长370 nm/发射波长460 nm处的荧光强度和在λ=355 nm处的吸收系数,用于代表陆源CDOM浓度,并测定了荧光指数以指示CDOM来源。结果表明,CDOM的荧光值和紫外吸收系数之间呈显著正相关性,陆源CDOM浓度大体有向海方向降低的趋势,但是纵向上存在一些"突跃"现象。在舟山海域东北角不时观测到表层水体含有高浓度的CDOM,但变异性很大,推测可能该海区受到长江口羽状流的影响。在连续观测站发现陆源CDOM浓度在低平潮时往往比高平潮时要高。河海水在混合过程中CDOM浓度与盐度呈显著的线性负相关关系。在低盐度的悬沙锋区(S<24)CDOM浓度明显低于理论稀释值,而在较高盐度的羽状锋区,CDOM浓度接近于理论稀释值。在盐度为24~31范围内,大部分水样的荧光指数在1.50上下波动,表明其中CDOM来源以陆地来源为主;在较低盐度(S<24)的水样中荧光指数在1.70至1.90以上,表明CDOM以海洋来源为主,这与其陆源组分在高浊度的低盐度区存在显著的去除过程有关。研究表明,舟山海域水质存在着显著的变异性,与近岸羽状流密切相关,陆源溶解有机质的分布特征对此有较好的响应。     

Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS

Marine dissolved organic matter (DOM) was separated by reversed-phase (RP) liquid chromatography method and analyzed with fluorescence/absorption detection and Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The three key characteristics of the RP method are: (a) The C18-RP column chosen provides enhanced separation when the aqueous phase is 100% buffer-free water, and it does not degrade over time; (b) the water eluent adjusted to pH 7 significantly improves the resolution of water soluble compounds; (c) the initial flow maintained at low levels improves the separation of polar compounds. In samples, containing “fresh” DOM, specific peaks were detected, which were absent in “old” DOM samples. The combination with size exclusion chromatography (SEC) also demonstrated the relation between polarity and molecular size of DOM. FT-ICR-MS was applied to evaluate the quality of separation on a molecular scale demonstrating that physico-chemical characteristics of DOM can be related to molecular formulas. Sample extracts were separated into 4 preparative fractions, and a large suite of the identified molecular formulas only occurred in specific fractions. This is an important basis for the application of further analytical techniques in order to perform a more target-oriented analysis aiming at the determination of source and process biomarkers for DOM.     

六极杆碰撞池-电感耦合等离子体质谱法测定海洋沉积物中的钒和铬

采用带六极杆碰撞池技术(CCT)的电感耦合等离子体质谱(ICP-MS)测定了海洋沉积物中的钒和铬。在六极杆碰撞池中引入He/NH3(99/1)混合气,有效地减轻了多原子离子(ClO+,ClN+,ClOH+,ClNH+等)对钒、铬测定的干扰,降低了方法的检出限。对He/NH3混合气的流量及ICP-MS的测定条件进行了最佳化选择。方法对钒和铬的检出限(3σ)分别为0.035μg·g-1和0.083μg·g-1(稀释因子1000),12份样品测定的相对标准偏差均小于5%。方法经海洋沉积物国家一级标准物质验证,测定值与标准推荐值吻合。     

高压密闭消解-电感耦合等离子体光谱和质谱联合测定海洋地质样品中52种元素

An improved analytical method to determine the content of 52 major, minor and trace elements in marine geological samples, using a HF-HCl-HNO_3 acid system with a high-pressure closed digestion method(HPCD), is studied by an inductively coupled plasma optical emission spectrometry(ICP-OES) and an inductively coupled plasma mass spectrometry(ICP-MS). The operating parameters of the instruments are optimized, and the optimal analytical parameters are determined. The influences of optical spectrum and mass spectrum interferences, digestion methods and acid systems on the analytical results are investigated. The optimal spectral lines and isotopes are chosen, and internal standard element of rhodium is selected to compensate for matrix effects and analytical signals drifting. Compared with the methods of an electric heating plate digestion and a microwave digestion, a high-pressure closed digestion method is optimized with less acid, complete digestion,less damage for digestion process. The marine geological samples are dissolved completely by a HF-HCl-HNO_3 system, the relative error(RE) for the analytical results are all less than 6.0%. The method detection limits are 2–40μg/g by the ICP-OES, and 6–80 ng/g by ICP-MS. The methods are used to determine the marine sediment reference materials(GBW07309, GBW07311, GBW07313), rock reference materials(GBW07103, GBW07104,GBW07105), and cobalt-rich crust reference materials(GBW07337, GBW07338, GBW07339), the obtained analytical results are in agreement with the certified values, and both of the relative standard deviation(RSD) and the relative error(RE) are less than 6.0%. The analytical method meets the requirements for determining 52 elements contents of bulk marine geological samples.     

Relative molar mass distributions of chromophoric colloidal organic matter in coastal seawater determined by Flow Field-Flow Fractionation with UV absorbance and fluorescence detection

A new method for the characterization of chromophoric colloidal organic matter in seawater has been applied to samples from the Baltic Sea, Kattegatt and Skagerrak seas. Size fractionation of the sample by Flow Field-Flow Fractionation and measurement of the fluorescent and UV absorbing properties of the individual size fractions result in a relative molar mass distribution (RMM) of the optical properties. The RMM distributions have been used to estimate number and weight average relative molar masses, and polydispersity indices. At least two sources of coloured organic matter were identified from the ratio of fluorescence to UV: the Baltic surface water and the Skagerrak deep water. The dominating processes were mixing and dilution, but processes such as photo bleaching of fluorescence are also believed to be important. The RMM distribution derived from UV detection (1150–1300 Dalton) increased with increasing salinity while that derived for fluorescence (1500–1250 Dalton) decreased with increasing salinity. The specific UV absorbance taken as a proxy of the aromaticity of the chromophoric organic material showed decreasing trend with both increasing salinity and increasing UV derived weight average relative molar mass. Increasing polydispersity of the colloidal material was also observed as a function of salinity.