海水中溶解有机碳（DOC）的测定

本文论述了海水中溶解有机碳(DOC)的测定方法,对DOC的测定原理及氧化方法进行了讨论,并提出了妨碍海水中DOC测定准确度提高的因素,这对于建立高准确度和精密度的新分析方法具有重要的意义。     

Measurements of dissolved organic carbon (DOC) in sea water by high temperature combustion method

Dissolved organic carbon (DOC) is the largest organic carbon reservoir in sea water and plays an imporrant role in the marine carbon cycle and other biogeochemical processes in the ocean. Accurate and precise determinalion of the bOC concentration in sea water is thus a prerequisite for any interpretation of DOC biogeochemistry. A key factor in analytical quality control is an accurate determination of the blank. The assessment and distinction of DOC blanks are essential for the precise measurements of oceanic DOC. The total DOC blank includes instrument and water blanks in the high temperature catalytic oxidation (HTCO) method. DOC can be measured accurately using the HTCO method only when the instrument blank is correctly distinguished from the total DOC blank and corrected in the sample measurements. Low DOC blanks can be achieved by extensive conditioning of new catalysts and the whole instrument system, whereas instrument blanks can be quantified by subtracting the water blank from the total DOC blank. We have been able to produce low carbon nanopure water [≤2μmol/dm³(C)] and have a low instrumental blank [< 5-6 μmol/dm³(C)] when using the HTCO method. Results of concentrations and distributions of DOC in the Gulf of Mexico and the North Atlantic are oceanographically consistent. Results from DOC measurements on samples from the international DOC methods comparison program further confirmed our low values of both nenopure water and the instrument blank.     

A laser-based fluorometry system for investigations of seawater and porewater fluorescence

A highly sensitive laser-induced fluorescence (LIF) system has been developed to study the fluorescence of dissolved organic carbon (DOC) in the marine environment. The LIF detector has a detection limit of 10 attomoles (10 × 10⁻¹⁸ moles) of pterin and eliminates internal quenching in highly fluorescent samples such as anoxic porewaters encountered when using conventional fluorometry. LIF analysis is rapid, reproducible, and uses only 100 μl of a sample. This small size requirement permits fluorescence analyses of samples often available only in limited amounts, such as porewaters, hydrothermal vent waters, and rainwaters. In addition, the LIF detection system may greatly simplify extraction and separation procedures required to characterize the fluorescent components of DOC.     

Modeling the contribution of dissolved organic carbon to carbon sequestration during the last glacial maximum

Dissolved organic carbon (DOC) is a carbon reservoir that is as large as the atmospheric CO₂ pool, and its contribution to the global carbon cycle is gaining attention. As DOC is a dissolved tracer, its distribution can serve to trace the mixing of water masses and the pathways of ocean circulation. Published proxy and model reconstructions have revealed that, during the last glacial maximum (LGM), the pattern of deep ocean circulation differed from that of the modern ocean, whereby additional carbon is assumed to have been sequestered in stratified LGM deep water. The aim of this study is to explore the distribution of DOC and its production/removal rate during the LGM using the Grid ENabled Integrated Earth system model (GENIE). Modeled results reveal that increased salinity of bottom waters in the Southern Ocean is associated with stronger stratification and oxygen depletion. The stratified LGM deep ocean traps more nutrients, resulting in a decrease in the DOC reservoir size that, in turn, causes a negative feedback for carbon sequestration. This finding requires an increase in DOC lifetime to compensate for the negative feedback. The upper limit of DOC lifetime is assumed to be 20,000 years. Modeled results derive an increase (decrease) in DOC reservoir by 100 Pg C leading to an atmospheric CO₂ decrease (increase) of 9.1 ppm and a dissolved inorganic carbon δ¹³C increase (decrease) of 0.06‰. The DOC removal rate is estimated to be 39.5 Tg C year^–1 in the deep sea during the LGM. The contribution of DOC to the LGM carbon cycle elucidates potential carbon sink-increasing strategies.     

Wet-oxidation and automated colorimetry for simultaneous determination of organic carbon, nitrogen and phosphorus dissolved in seawater

We developed a simple and reliable method which allows simultaneous determination of organic forms of carbon (DOC), nitrogen (DON) and phosphorus (DOP) dissolved in seawater. Conversion of dissolved organic matter (DOM) to inorganic products (carbon dioxide, nitrate+nitrite and soluble reactive phosphate) is performed by a persulfate wet-oxidation in low alkaline condition. After oxidation, the concentration of the inorganic products dissolved in the sample was measured automatically by colorimetry using a 3-channel Technicon AutoAnalyzer system. A number of pure organic compounds were tested in the concentration range encountered in coastal and open ocean, indicating a high efficiency of the digestion procedure. The recovery range is similar to that obtained by other wet-oxidation procedures and by high-temperature catalytic oxidation techniques. Direct comparisons with usual methods used for separate determination of DOC, DON and DOP indicated a high efficiency of the procedure. Reproducibility tests demonstrated a very good precision (around 5%) for lagoonal and coastal waters, while precision was sometimes around 10–25% in oligotrophic oceanic waters, especially for DOP where values approached limits of detection for measuring phosphate. This method is highly suitable for routine analysis and especially appropriate for shipboard work.     

Polymer dynamics of DOC networks and gel formation in seawater

The ocean plays a major role in global biogeochemical carbon cycling; it holds an important reservoir of reduced organic carbon, mostly in the form of dissolved organic carbon (DOC), and processes about one-half of the total primary production of the planet. Dissolved molecules present between living and assimilable size extremes (∼1000 nm^-1 nm), constitute the most abundant form of remnant biochemicals in the ocean, outweighing the total living biomass by a factor of roughly 200. Because DOC is the fundamental substrate for marine microorganisms, and is primarily composed by small refractory biopolymers, this prompted the idea that the ocean might function as a huge repository of recalcitrant carbon. The missing link that elucidates this paradox and explains how the rich and vast stock of DOC becomes available to bacteria was the discovery that DOC throughout the water column remains in reversible assembly/dispersion equilibrium forming porous microscopic gels (Chin et al., Nature 391, 568-572, 1998). This abiotic DOC-POM shunt yields a microgel pool containing ∼70 gigatons of carbon forming discrete patches of high nutrient concentration that can be readily colonized by microorganisms. The presence of this huge gel mass in seawater extending far into the dark ocean has ramifications that might well scale nonlinearly through the microbial loop to the World Ocean and global climate system and it is fundamentally changing how oceanographers think about processes linking the microbial loop and biological pump to the rest of the biosphere and the geosphere. Even if a small fraction of DOC remains self-assembled, marine scientists will have to revise the rationale of established aquatic paradigms ranging from trace metal chelation, size–reactivity relationships, the microbial loop, the biological pump, colloid pumping, and humification. A ubiquitous, reversible DOC assembly/dispersion process implies a dynamic “patchiness” spanning from the molecular to the micron scale, where the assignment of static bulk features including dimension, concentration, functionalities and vertical fluxes can be open to question. This brief revision illustrates two case studies that show how simple methods and principles of polymer networks theory can be used to advance the understanding of one of the most intriguing and significant processes taking place in the ocean. Namely, the kinetics and thermodynamics of: (a) Ca-driven DOC self-assembly, and (b) hydrophobic bond-driven self assembly of DOC by amphiphilic exopolymers released by marine bacteria.     

南沙渚碧礁生态系有机碳的分布及周日变化特征

1999 年 4 月对我国南沙群岛渚碧礁海水中溶解有机碳的分布及礁坪区颗粒有机碳 (POC) 和溶解有机碳 (DOC) 的周日变化特征进行了观测。结果表明,渚碧礁表层海水 DOC 变化范围为 1.43~3.62 mg/L,平均为 2.16 mg/L,含量分布大致表现为礁坪区>潟湖>礁外。潟湖 DOC 的垂直分布大致表现为表层高于底层,可能与表层浮游植物的光合作用有关。礁坪区 POC 及 DOC 都呈现显著的周日变化特征,POC 呈现夜晚高,白天低的特点,浮游植物的昼夜垂直移动可能是产生该现象的主要原因。DOC 的周日变化则主要受浮游动物昼夜垂直移动及细菌等生物活动的影响。     

南极普里兹湾及其邻近海域溶解有机碳的分布

中国南极科学考察第16航次期间(1999年11月～2000年4月),在南极普里兹湾及邻近海域的不同站位与水深采集海水样品用于溶解有机碳测定,通过高温催化氧化法完成样品的分析.结果表明,在调查期间,南极普里兹湾及其邻近海域各测站上层水体(0～100m)溶解有机碳浓度的变化范围为14.3～181.1μmol/dm3,平均为52.5μmol/dm3,该变化幅度比Ross海、太平洋等海域的相应值略大.溶解有机碳垂直分布的特征是0大于25大于50大于100m,即随深度的增加溶解有机碳浓度逐渐减小,与生物活动在垂直方向上的强弱变化相关.根据200m以深水柱溶解有机碳的垂直分布,可确定研究海域难降解溶解有机碳的浓度为40.4μmol/dm3,与其他研究所报道的数值(～42μmol/dm3)相近.上层水体(0～100m)过剩溶解有机碳的空间分布显示,64°S以北海域溶解有机碳过剩较多,而64°S以南海域则过剩溶解有机碳较少.溶解有机碳浓度与分布特征显示,普里兹湾及其邻近海域溶解有机碳浓度与南大洋其他海域相当,具有低溶解有机碳的一般特征.溶解有机碳浓度的空间分布呈现由西南向东北方向逐渐增加的趋势,这可能与南极陆架夏季上层水的北向扩展有关.生物活动及水体运动是研究海域溶解有机碳分布的主要影响因素.     

Dynamics of DOC of euphotic layer in the Taiwan Strait——Diurnal variation of large range

ThisstudywassupportedbytheStateEducationalCommittee(SEC)ofChina.INTRODUCTIONThedissolvedorganiccarbon(DOC),ordissolvedorganicmatter(DOM),isoneofthemostimPortantorganiccarbonreservoiroftheworld,whichmayaffectthecontentofCO2intheatmospherewithatime-scaleof1OOO~1OOOOyears(Hedges,1992).Theratesofproduction,degradationortransPortationofDOCareseveralmaindynamicalparametersofDOCintheeu-photiclayer.Inthispaper,wefocusonthediurnalvariationsofDOCinordertoestimatetheseparameters.METso…     

Review and suggestions for estimating particulate organic carbon and dissolved organic carbon inventories in the ocean using remote sensing data

Dissolved organic carbon（DOC） and particulate organic carbon（POC） are basic variables for the ocean carbon cycle.Knowledge of the distribution and inventory of these variables is important for a better estimation and understanding of the global carbon cycle.Owing to its considerable advantages in spatial and temporal coverage,remote sensing data provide estimates of DOC and POC inventories,which are able to give a synthetic view for the distribution and transportation of carbon pools.To estimate organic carbon inventories using remote sensing involves integration of the surface concentration and vertical profile models,and the development of these models is critical to the accuracy of estimates.Hence,the distribution and control factors of DOC and POC in the ocean first are briefly summarized,and then studies of DOC and POC inventories and flux estimations are reviewed,most of which are based on field data and few of which consider the vertical distributions of POC or DOC.There is some research on the estimation of POC inventory by remote sensing,mainly in the open ocean,in which three kinds of vertical profile models have been proposed：the uniform,exponential decay,and Gauss models.However,research on remote-sensing estimation of the DOC inventory remains lacking.A synthetic review of approaches used to estimate the organic carbon inventories is offered and the future development of methods is discussed for such estimates using remote sensing data in coastal waters.     

燃烧氧化-非色散红外吸收法测定海水中溶解有机碳

采用燃烧氧化-非色散红外吸收法测定了海水中的溶解有机碳.结果表明,标准曲线的线性较好,精密度较高,方法检出限为0.024 mg/L;所测海水样DOC质量浓度的最高值为3.95 mg·L-1,最小值为1.47 mg·L-1;采样点距离海岸越远,DOC质量浓度越低.海水样品置于4 ℃下冷藏保存,滴加饱和HgCl2溶液的水样,其保存效果要好于不加饱和HgCl2溶液的水样,且在55 d内,其DOC质量浓度基本上没有发生变化.     

Seasonal Investigations of Dissolved Organic Carbon Dynamics in the Tamar Estuary, U.K.

A high temperature catalytic oxidation (HTCO) technique was used to measure dissolved organic carbon (DOC) during seasonal surveys of the Tamar Estuary, U.K. At the time of the programme, the field of DOC analysis had been plagued by numerous analytical difficulties. However, using thorough calibration of the analytical systems and the systematic analysis of an internal reference material, a valuable estuarine DOC data set was produced. The range of DOC concentrations observed (478–110 μM C) is consistent with the published data for riverine and coastal sea waters respectively. The Tamar Estuary is a freshwater DOC-dominated system, with strong correlation between lateral DOC distribution and salinity. However, mixing behaviour was not strictly conservative. During tidal cycle studies at a fixed station, DOC concentrations appeared to be uncoupled from salinity, and were inversely related to turbidity. It is concluded that tidally-induced resuspension of bottom sediments provided the dominant control mechanism for DOC concentration. The Tamar Estuary shows contrasting behaviour to the larger, more heavily impacted, Severn Estuary. Hence it is likely that the behaviour of DOC in estuaries cannot be classified as typical per se, but is a function of the natural and anthropogenic characteristics of the catchment and hydrology.     

鼠尾藻(Sargassum thunbergii)固碳能力对流速的响应

流动的海水可以为海藻的生长提供所需的营养物质,对其生长和繁殖起到了非常重要的作用,而当前的生理生态学模拟实验,大多忽略了这一重要的环境因子.大型海藻虽然被认为是第4类"蓝碳",但关于其固碳能力的研究较少.本研究设计了一种可以调节流速的大型海藻固碳能力测量系统,既可以测量大型海藻的净光合速率、呼吸速率和对无机氮、无机磷的...     

Zooplankton vertical migration and the active transport of dissolved organic and inorganic carbon in the Sargasso Sea

The least known component of the “biological pump” is the active transport of carbon and nutrients by diel vertical migration of zooplankton. We measured CO₂ respiration and dissolved organic carbon (DOC) excretion by individual species of common vertically migrating zooplankton at the US JGOFS Bermuda Atlantic Time-series Study (BATS) station. The inclusion of DOC excretion in this study builds on published research on active transport by respiration of inorganic carbon and allows a direct assessment of the role of zooplankton in the production of dissolved organic matter used in midwater microbial processes. On average, excretion of DOC makes up 24% (range=5–42%) of the total C metabolized (excreted+respired) and could represent a significant augmentation to the vertical flux that has already been documented for respiratory CO₂ flux by migrant zooplankton. Migratory fluxes were compared to other transport processes at BATS. Estimates of combined active transport of CO₂ and DOC by migrators at BATS averaged 7.8% and reached 38.6% of mean sinking POC flux at 150 m, and reached 71.4% of mean sinking POC flux at 300 m. DOC export by migrator excretion averaged 1.9% and reached 13.3% of annual DOC export by physical mixing at this site. During most of the year when deep mixing does not occur, diel migration by zooplankton could provide a supply of DOC to the deeper layers that is available for use by the microbial community. A carbon budget comparing migrant zooplankton transport to the balance of fluxes in the 300–600 m depth strata at BATS shows on average that the total migrant flux supplies 37% of the organic carbon remineralized in this layer, and that migrant DOC flux is more than 3 times the DOC flux gradient by diapycnal mixing. New estimates of active transport of both organic and inorganic carbon by migrants may help resolve observed imbalances in the C budget at BATS, but the magnitude is highly dependent on the biomass of the migrating community.     

溶解有机碳在混合水中的行为研究

研究溶解有机碳(DOC)在海水和黄河水所组成的混合水中的迁移转化行为,结果表明,海水和已过滤黄河水混合时,DOC呈近似的保守性;海水与未过滤的黄河水混合时,DOC呈明显的非保守性。通过研究沉积物对DOC的解吸过程,发现沉积物在盐水中能解吸出DOC,随着盐度的增大,其解吸量也迅速增大。因此可以认为,DOC在河口区的非保守行为是DOC的絮凝和颗粒物的解吸共同作用的结果。     

长江口区海水中溶解有机碳和颗粒有机碳的分布及变化的研究

长江每年有上千万吨有机物质注入河口邻近海域，影响着这一海域独特的生态环境。 本文根据1985年8月至1986年5月专业调查资料,论述了长江口邻近海域溶解有机碳(DOC)和颗粒有机碳(POC)的分布及变化，并从有机物质的变化推测三峡工程对河口海生态系的影响。     

Carbon inputs and distribution in estuaries of turbid rivers: the Yang Tze and Yellow rivers (China)

Particulate and dissolved organic and inorganic carbon concentrations were measured in the Yang Tze (Changjiang) and Huanghe (Yellow) river estuaries, during two different seasons. During the winter, the organic matter in the suspended load of both estuarine systems was dominantly of terrestrial origin, while in the summer, there were significant contributions from aquatic production. In these turbid rivers, there is a strong positive correlation between the concentrations of total suspended matter and particulate organic carbon, probably because biological production is inhibited when turbidity exceeds a certain limit. Dissolved organic carbon (DOC) does not exhibit a conservative behavior in these estuarine systems. High dissolved organic carbon values in bottom water samples suggest remobilization of DOC from near-surface, bottom sediments. Dissolved inorganic carbon concentrations were very high in the Huanghe River, and the trend in the calculated saturation indices for calcite suggests precipitation of carbonate in this estuarine system. There is no such evidence for carbonate precipitation in the Yang Tze River.     

Dynamics of dissolved organic carbon in the northwestern Indian Ocean

We report here the non-conservative behaviour of DOC in the northwestern Indian Ocean by studying this parameter together with other carbon and nitrogen components. This contrasts with earlier reports of conservative behaviour. Concentrations of DOC, 3–4 times higher than those reported earlier, were found to decrease northward from the equator. Total carbon dioxide (TCO₂) increases in proportion of the oxygen utilized, thus revealing the dominant biological role in the carbon turnover. The CO₂ added through dissolution of biogenic debris is found to decrease southward, in general. Decomposition of organic material contributes at least 64% to the CO₂ addition that increases southward, the rest being from dissolution of skeletal material. Evidence is provided for the utilization of oxygen and nitrate for DOC oxidative decomposition. Accumulation of DOC without its complete oxidation to CO₂ could be the main reason for the TCO₂ decrease in southern Arabian Sea. Relationships of DOC with nitrification and denitrification processes show that the microbial population plays a major role in regulating the DOC contents in the seawater of this region. Consumption/decomposition by denitrifying bacteria and other micro-organisms responsible for nitrogen cycling in the sea are found to be intimately related to the DOC dynamics and are responsible for decreased DOC concentrations in the north. DOC accumulation in the southern Arabian Sea seems to facilitate bacterio-particulate aggregate formation and consequent nitrification, which results in excess nitrate. Application of a one-dimensional advection-diffusion model to the present data set provides evidence for the non-conservative nature of DOC in the Arabian Sea.     

Accumulation and Export of Dissolved Organic Carbon in Surface Waters of Subtropical and Tropical Pacific Ocean

Dissolved organic carbon (DOC) concentrations in surface waters of the Pacific Ocean during October–November, 1995, were determined using a high-temperature combustion method. The DOC in the surface mixed-layer was approximately homogeneous with a concentration between 55 and 89 μmol C l⁻¹. This homogeneity indicates that there is a strong control of the vertical distribution of DOC by mixing processes. The DOC concentrations in the mixed-layer in the subtropical region were up to 27 μmol C l⁻¹ higher than in the tropical region. This difference reflects the subtropical accumulation and the tropical export of DOC. There is a significant positive correlation between DOC and chlorophyll a concentrations in the mixed-layer of the North Pacific subtropical region, suggesting that phytoplankton is the primary source of DOC accumulated in this region. Calculations using simple box models suggest that DOC export in the tropical region (0–50 m depth, 10°N-10°S, along 160°W) occurs primarily by poleward advection at a rate of 0.5–3 mmol C m⁻²day⁻¹. A comparison with estimates of the export rate of particulate organic carbon published in previous studies leads us to conclude that DOC export may contribute less to the carbon budget in the tropical region than has recently been supposed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO₂ evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1–5 μmol of carbon and has an associated blank of 0.1–0.2 μmol of carbon.Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO₂ as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3.. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The δ¹³C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC.The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average δ¹³C = −12.4.). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and δ¹³C of pore-water DOC was nearly 8. lighter at 1.5–2.0-cm depth than in the mat surface layer (0–0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and δ¹³C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.