基于空气介质的光学溶解氧传感器便捷校准方法研究

基于荧光猝灭原理的光学溶解氧传感器可获得海水溶解氧时空数据,被广泛应用于海洋环境长期监测,但因其在贮存期间和布放期间会发生"贮存漂移"和"测量漂移",需要进行校准.现有的实验室校准方法周期长、操作复杂.本文研究了光学溶解氧传感器在空气和水体两种不同介质中的响应特性,提出一种利用空气介质的光学溶解氧传感器现场校准方法,并...     

基于荧光猝灭溶解氧传感器的校准方法研究

溶解氧是海洋水质监测的常规关键参数,基于荧光猝灭原理研制的溶解氧传感器具有准确度高、稳定性好和可长期在线测量等优点,已经被广泛用于海水溶解氧浓度监测.针对传感器可能发生的数据漂移和显著偏差可能造成的准确度问题,本文设计了一套专门的校准装置和校准方法.通过严格控制校准水体的温度和溶解氧浓度,测量待校准传感器和参比传感器的...     

南黄海溶解氧的垂直分布特性

根据中韩黄海水循环动力学合作研究项目1996～1998年对南黄海全海域6个航次的现场调查资料,对南黄海溶解氧的断面分布和垂直分布特征及其季节变化规律进行了系统、全面地研究,并对更半年溶解氧垂直分布最大值的地理分布、强度及与温跃层和生物活动的关系等进行了进一步的探讨.     

Two-dimensional numerical simulation of vertical distributions of dissolved oxygen in Huanghai Sea

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东山湾海水盐度,温度和溶解氧的分布特征

1988年5月、8月、11月和1989年2月东山湾海水的盐度范围分别为20.81～33.89、30.43～34.24、26.76～30.59和30.27～31.57;水温范围分别为23.4～25.0、22.5～30.8、18.1～20.7和14.5～17.3℃;溶解氧体积分数分别为(4.12～4.91)×10~(-3)、(3.50～5.10)×10~(-3)、(5.21～6.68)×10~(-3)和(5.64～6.00)×10~(-3);氧饱和度分别为85.1%～104%、73.3%～116%、99.6%～124%和102%～104%。春、夏季东山湾受高盐外海水的影响明显,其中夏季可能还受到上升流的影响.秋季浮游植物大量生长和繁殖,成为溶解氧含量和氧饱和度的主要影响因素。     

南黄海溶解氧的平面分布及其季节变化

根据中韩“黄海水循环及物质通量合作研究”项目1996～1997年现场调查获得的资料,首次对南黄海整个海域溶解氧的平面分布特征及其季节变化规律进行了探讨.对一些主要海洋过程如黄海暖流、台湾暖流、沿岸流、长江冲淡水、黄海冷水团及浮游植物的光合作用等对南黄海溶解氧含量分布的影响进行了讨论.     

基于图相似性匹配的海水溶解氧辅助评价方法

海水溶解氧评价的正确性对于维护海洋生态系统的稳定性具有重要意义。海水溶解氧数据属于非线性时间序列,可视图方法(时间序列转化为图)是分析这类数据较有效的方法,但仍存在未同时考虑数据的时间演变特性以及变量间相互影响的问题。针对现存问题,本研究提出基于图相似性匹配的海水溶解氧辅助评价方法。首先,同时考虑海温、盐度对海水溶解氧的影响以及数据的不可逆性,提出溶氧温盐-转移概率(dissolved oxygen temperature salinity-transition probability, DOTS-TP)有向可视图方法,实现了多变量时间序列到单变量溶解氧图的转化;然后,在将墨西哥湾溶解氧图作为评价参照的基础上,综合利用图的多层次信息,提出子图节点全局(subtree node global, SNG)图相似性匹配方法,通过计算SNG评价指数实现对海水溶解氧的辅助评价。实验结果表明DOTS-TP有向可视图方法能更准确地表达海水溶解氧信息,SNG图相似性匹配方法适用于所有海水溶解氧数据,并能得出正确的辅助评价结果。     

长江口及邻近海域沉积物中四醚脂类的来源及其对底层溶解氧指示作用探究

甘油二烷基甘油四醚(glycerol dialkyl glycerol tetraethers,GDGTs)作为一种重要的膜脂化合物,广泛存在于海洋水体和沉积物中。基于GDGTs对温度的敏感性, TEX₈₆(Tetra Etherinde Xoftetraethers consisting of 86 carbons)指标被广泛用于海洋古温度重建。然而,研究表明GDGTs母源生物古菌也会受到环境中溶解氧(DO)变化的影响,进而影响其膜脂组成,但边缘海DO对GDGTs组成的影响仍不清楚。本文研究了夏季长江口及其邻近海域颗粒物与表层沉积物中GDGTs的含量与组成,探讨了表层沉积物中GDGTs的来源及其组成对底层DO的响应。结果表明,长江口及其邻近海域颗粒物GDGTs的含量随水深的增加而增加,同时表层沉积物中的GDGT-2/GDGT-3和GDGT-0/Cren比值均与底层颗粒物相近,表明沉积物中GDGTs主要来源于底层颗粒物的沉降输入。进一步对受陆源有机质输入影响较小的站位研究发现有机质来源BIT(Branched and Isoprenoid Tetractter)指...     

A preliminary methods comparison for measurement of dissolved organic nitrogen in seawater

Routine determination of dissolved organic nitrogen (DON) is performed in numerous laboratories around the world using one of three families of methods: UV oxidation (UV), persulfate oxidation (PO), or high temperature combustion (HTC). Essentially all routine methods measure total dissolved nitrogen (TDN) and calculate DON by subtracting the dissolved inorganic nitrogen (DIN). While there is currently no strong suggestion that any of these methods is inadequate, there are continuing suspicions of slight inaccuracy by UV methods.This is a report of a broad community methods comparison where 29 sets (7 UV, 13 PO, and 9 HTC) of TDN analyses were performed on five samples with varying TDN and DIN concentrations. Analyses were done in a “blind” procedure with results sent to the first author. With editing out one set of extreme outliers (representing 5 out of 145 ampoules analyzed), the community comparability for analyzing the TDN samples was in the 8–28% range (coefficient of variation representing one standard deviation for the five individual samples by 28 analyses). When DIN concentrations were subtracted uniformly (single DIN value for each sample), the comparability was obviously worse (19–46% cv). This comparison represents a larger and more diverse set of analyses, but the overall comparability is only marginally better than that of the Seattle workshop of a decade ago. Grouping methods, little difference was seen other than inconclusive evidence that the UV methods gave TDN values for several of the samples higher than HTC methods. Since there was much scatter for each of the groups of methods and for all analyses when grouped, it is thought that more uniformity in procedures is probably needed. An important unplanned observation is that variability in DIN analyses (used in determining the final analyte in most UV and PO methods) is essentially as large as the variability in the TDN analyses.This exercise should not be viewed as a qualification exercise for the analysts, but should instead be considered a broad preliminary test of the comparison of the families of methods being used in various laboratories around the world. Based on many independent analyses here, none of the routinely used methods appears to be grossly inaccurate, thus, most routine TDN analyses being reported in the literature are apparently accurate. However, it is not reassuring that the ability of the international community to determine DON in deep oceanic waters continues to be poor. It is suggested that as an outgrowth of this paper, analysts using UV and PO methods experiment and look more carefully at the completeness of DIN conversion to the final analyte and also at the accuracy of their analysis of the final analyte. HTC methods appear to be relatively easy and convenient and have potential for routine adoption. Several of the authors of this paper are currently working together on an interlaboratory comparison on HTC methodology.     

Measurement of dissolved oxygen using optodes in a FerryBox system

Optode sensors can provide detailed information on concentrations of dissolved oxygen, which in turn may be used to quantify variations in net primary productivity. Throughout 2005 and 2006 the performance of commercially available oxygen optodes was examined, one in each year. The optode was part of an autonomous measurement system (FerryBox) on a ferry operating between Portsmouth (UK) and Bilbao (Spain). On crossings during which water samples were collected manually, the optode outputs were compared to measurements of dissolved oxygen made by Winkler titrations. The optodes maintained good stability with no evidence of instrumental drift during the course of a year. Over the observed concentration range (230–330 mM m⁻³) the optode data were approximately 2% low in both years. By fitting the optode data to the Winkler data the median difference between the optode and Winkler measurements is reduced to less than 1 mM m⁻³ (0.3%) in both years. The most appropriate calibration factor for 2005 was corrected O₂ = Optode O₂ × 1.018 and for 2006 the corresponding equation is corrected O₂ = Optode O₂ × 0.884 + 36.8. The standard deviation (95%) of the difference between the individual Winkler measurements was 5 mM m⁻³ and 3 mM m⁻³ in 2005 and 2006 respectively.Calculation of the oxygen saturation anomaly is required for calculation of the air sea exchange of oxygen and net biological production. This calculation requires the use of both salinity and temperature data. Salinity is measured to better than 0.1 so the corresponding error in anomaly is less than 0.2 mM m⁻³. Distortion of the temperature data is present due to warming of the water pumped to the optode. In winter this warming at the optode may be as great as 0.4 °C. The difference in the pumped water temperature can be corrected for by reference to other measurements of sea surface temperature reducing the error to less than 1 mM m⁻³.     

Marine proteomics: generation of sequence tags for dissolved proteins in seawater using tandem mass spectrometry

Dissolved proteins in seawater samples from the Gulf of Mexico were concentrated using tangential flow ultrafiltration and methanol/chloroform/water precipitation. Following concentration and purification, two different separation methods were employed. In one method, intact proteins were separated by SDS–PAGE and digested enzymatically in-gel. In the second method, the peptides resulting from a solution proteolytic digest of the whole protein pellet mixture were separated by capillary HPLC. In both methods, the final chromatographic separation was coupled on-line with a mass spectrometer using an electrospray interface, and peptide CID spectra were collected using tandem mass spectrometry (MS). De novo sequencing of the peptide tandem mass spectra generated short amino acid sequences (peptide tags) that were used to search databases for protein class and source information. Trends of conserved sequences for two specific classes of proteins were observed: membrane/envelope proteins and enzymes. Similarity searching of peptide tags produced identification of conserved sequences from several protein homologues originating from many different species, including: long chain fatty acyl CoA synthetase, anthranilate synthase, ribulose bisphosphate carboxylase, and luminal binding protein. These results provide new insight into the sources and production mechanisms for dissolved organic matter (DOM), as there is direct evidence for dissolved proteins other than the bacterial outer membrane proteins reported by Tanoue et al. Furthermore, the data presented herein support the idea that physical protection and selective preservation are not mutually exclusive survival mechanisms, but rather these two models are dependent upon one another for explaining the survival of refractory dissolved proteins in seawater.     

长江口邻近海域溶解氧的时空分布及影响因素研究

基于2018年早春和夏季长江口邻近海域的调查数据,分析溶解氧(DO)的时空分布,并讨论其影响因素.结果表明,夏季DO浓度变化范围为1.58～9.37 mg/L,浮游生物光合作用产生的DO是夏季表层水体过饱和的主要因素;夏季调查海域受台湾暖流北上引起海水层化加强,同时水体富营养化导致表层生物大量繁殖所引起有机碎屑的沉降和...     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

A method to measure the isotopic (C) composition of dissolved organic carbon using a high temperature combustion instrument

The stable isotopes of dissolved organic carbon (DOC) are a powerful tool for distinguishing sources and inputs of organic matter in aquatic systems. While several methods exist to perform these analyses, no labs routinely utilize a high temperature combustion (HTC) instrument. Advantages of HTC instruments include rapid analysis, small sample volumes and minimal sample preparation, making them the favored devices for most routine oceanic DOC concentration measurements. We developed a stable carbon DOC method based around an HTC system. This method has the benefit of a simple setup, requiring neither vacuum nor high pressures. The main drawback of the method is a significant blank, requiring careful accounting of all blank sources for accurate isotopic and concentration values. We present here a series of experiments to determine the magnitude, source and isotopic composition of the HTC blank. Over time, the blank is very stable at  20 ng of carbon with a δ¹³C of − 18.1‰ vs. VPDB. The similarity of the isotopic composition of the blank and seawater samples makes corrections relatively minor. The precision of the method was determined by oxidizing organic standards with a wide isotopic and concentration range (− 9‰ to − 39‰; 18 μM to 124 μM). Analysis of seawater samples demonstrates the accuracy for low concentration, high salinity samples. The overall error on the measurement is approximately ± 0.8‰.     

秋季东海溶解态和颗粒态氨基酸的分布与组成*

本文对2012年秋季中国东海31个站位的海水样品中溶解态氨基酸（THAA）和颗粒态氨基酸（PAA）的分布与组成进行了研究。结果表明：表层海水中溶解游离氨基酸(DFAA)的平均浓度为0.12±0.04 μmol/L (0.06~0.19 μmol/L),溶解结合氨基酸(DCAA)的平均浓度为0.61±0.51 μmol/L (0.15~1.79 μmol/L),PAA的平均浓度为0.11±0.06 μmol/L (0.02~0.27 μmol/L)。THAA的水平分布特点大致为近岸高、远岸低;PAA的水平分布特点是近岸海域向远海海域分布呈现逐渐减小的趋势。THAA的垂直分布特点是由表层向底层逐渐降低。DCAA、PAA与Chl-a有很好的相关性,而DFAA与Chl-a的相关性不明显。东海表层海水中THAA的主要组分是天门冬氨酸、谷氨酸、丝氨酸、甘氨酸、苏氨酸及丙氨酸,PAA的主要组分是天门冬氨酸、谷氨酸、丝氨酸、甘氨酸、丙氨酸及亮氨酸。在表层海水中氨基酸是作为一个整体而对海洋生物地球化学过程产生影响的。     

山东半岛东部近海海水溶解氧时空变化

山东半岛沿岸海域陆海相互作用强烈,有着复杂水动力环境的同时也是我国重要的渔业资源区和水产养殖区,针对其DO时空变化特征及影响机制的研究具有重要意义.本文基于2015—2017年期间的监测数据,研究了山东半岛东部近海海水溶解氧的时空变化特征,并结合实测的温度、盐度、pH数据探究其影响机制.结果表明:表、底层溶解氧的空间分...     

Argo浮标观测溶解氧数据的原理与质量控制

Argo剖面浮标已成为海洋溶解氧观测数据的主要来源,截至2018年7月已在全球范围内获取了超过13万条溶解氧剖面,然而目前其数据的质量控制仍然存在不足。本文首先介绍了Argo浮标上携带的溶解氧传感器的测量原理、主要误差来源以及两种校正方法:气候态校正法与空气测量校正法,并提出了目前在溶解氧传感器数据质量控制研究亟需解决的技术问题,包括:①由于传感器伸出水面的高度不够,一些浮标并不能有效测量空气氧含量,因为无法进行空气测量校正方法;②Argo观测的溶解氧数据库中目前存在一些异常测量剖面没有得到有效剔除,影响校正系数的计算;③使用平均值确定校正系数的方法容易受到异常剖面的干扰。     

Vertical and horizontal distribution of fluorescent dissolved organic matter in the Southern Ocean

The vertical and horizontal distribution of fluorescent dissolved organic matter (FDOM), determined by fluorescence intensity at 320 nm excitation and 420 nm emission, were clarified in nine stations on two transects at the Southern Ocean, including a subtropical, subantarctic, polar frontal and Antarctic zone. All vertical profiles of fluorescence intensity showed that levels were lowest in the surface waters, increased with increasing the depth in mid-depth waters ( 2000 m), and then stayed within a relatively narrow range from there to the bottom. Such vertical profiles of FDOM were similar to those of nutrients, but were adverse to dissolved oxygen. In water columns below the temperature-minimum subsurface water (dichothermal waters) in the Antarctic zone and below the winter mixed layer in the other zones, we determined the relationships of fluorescence intensity to concentrations of nutrients and apparent oxygen utilization (AOU) over the entire area of the present study, and found significant linear correlations between the levels of fluorescence intensity and nutrient concentrations (r =  0.70 and 0.71 for phosphate and nitrate + nitrite, respectively) and AOU (r = 0.91). From the strong correlation coefficient between fluorescence intensity and AOU, we concluded that FDOM in the Southern Ocean is formed in situ via the biological oxidation of organic matter. The regeneration of the nutrients/consumption of the oxygen/formation of FDOM was active in mid-depth waters. However, the correlations between fluorescence intensities and nutrients and AOU were different in the mid-depth water masses, Subantarctic Mode Water (SAMW), and Antarctic Intermediate Water (AAIW), indicating that the sources of organic matter responsible for FDOM formation were different. A considerable amount of FDOM in the SAMW is thought to be produced by the remineralization of DOM in addition to sinking particulate organic matter, while DOM is less responsible for FDOM formation in the AAIW.     

长江口溶解氧赤潮预报简易模式

在海洋浮游生物中,有很多单细胞微小生物,由于异常地急剧繁殖,并高度密集在一起,从而引起海水变色的现象,称谓“赤潮”.目前,普遍认为赤潮的发生与海水中磷、氮等营养盐、铁、锰等微量元素以及某些有机化合物的大量增加有关[l];另外,还与水体的停滞和气象条件密切联系[2,3].赤潮的发生意味着生态平衡的破坏.     

南沙群岛海域溶解氧垂直分布最大值的季节特征

根据“八五”、“九五”国家科技专项南沙群岛海域综合科学考察的现场调查资料,对南沙群岛海域溶解氧垂直分布最大值现象的分布特征、季节变化规律作了较为全面的分析和研究,同时比较了东海、黄海海域春、夏季溶解氧垂直分布出现的最大值现象及其特征.研究结果表明南沙群岛海域溶解氧垂直分布的最大值现象与我国东海、黄海海域的溶解氧垂直分布最大值现象无论在地理分布、深度、强度、季节性变化还是存在条件的特征化方面,均有着较大的差别.反映影响南沙群岛海域溶解氧垂直分布最大值形成的原因,均与东海、黄海海域溶解氧垂直分布最大值形成的原因有所不同