海水pCO2流通式光度测定方法研究

将膜分离技术与流动注射分析相结合 ,采用聚四氟乙烯疏水性微孔膜 ,使样品流与接受液流进行物理分离。通过测定含有显色剂的接受液流吸光度的变化来测定 p CO2 ,初步建立海水中p CO2 流通式光度测定方法。该方法的相对标准偏差小于 1.2 %,与气相色谱法相比 ,无显著性差异。整个实验仅需 11min,样品用量不到 10 m L,操作简便、快速。     

夏季东海西部表层海水中的pCO2及海-气界面通量

根据2001年夏季长江口及东海西部海域表层海水pCO     

海水pCO2测定中喷淋-鼓泡式平衡器与层流式平衡器互校

在全球变化研究中，海气交换平衡器是海水中二氧化碳分压(pCO2)直接测定的关键。作者在Inoue,H.(1987)的喷淋式平衡器和Goyet,C.(1991)的鼓泡式平衡器的基础上设计了新的喷淋-鼓泡式平衡器，并与层流式平衡器(Cooper,D.J.etal.1998)进行了互校(气相色谱法现场测定)。经显著性检验，两种平衡器之间无显著性差异。结果表明，新的喷淋-鼓泡式平衡器能很好地用于海水中pCO2的测定。     

渤海主要温室气体与海水pCO2环境特征

通过对渤海主要温室气体及海水二氧化碳分压的调查与研究,分析了渤海区底层大气二氧化碳(CO2)、甲烷(CH4)和二氧化碳分压(pCO2)的时空分布特征;渤海大气CH4含量春、夏、秋、冬季均值分别为2085、1974、2056和2060×10-9nl/L,各季节高值区均出现在黄河口邻近海域;黄河口邻近海域大气较高浓度的甲烷可能是渤海沿岸城市夏季出现高值的重要原因;渤海区大气二氧化碳浓度在2006年-2009年呈增高的趋势,2009年9月渤海中、北部海水pCO2在285～617μatm之间变化,渤海中部海水pCO2明显低于辽东湾内海水pCO2,研究区CO2海气通量-5.9～13.4mmol.m-2.d-1在之间,人类活动以显著影响到渤海的碳汇能力。     

基于浮标观测的春季青岛近岸海水pCO2变化及海-气CO2通量研究

利用海-气界面浮标观测得到的高频数据,分析了春季青岛近岸海域海表二氧化碳分压(pCO₂)的变化规律及驱动因素,并对海-气CO₂通量进行了估算。观测期间该海域由大气的碳汇转变为碳源,主要是由海表pCO₂的不断增长所致。对海表pCO₂控制因素进行分析,发现温度升高是pCO₂增长的主要驱动因素,生物过程起到一定的抑制作用。海表pCO₂呈现出日变化特征,温度和生物因素对海表pCO₂日变化的作用均与太阳辐射相关,但两者的作用相反。此外,分析发现浮标的不同采样频率会对海-气CO₂通量估算产生影响,缩短采样间隔能有效降低海-气CO₂通量估算的偏差,提高估算的准确性。     

夏季东海西部表层海水中的pCO_2及海-气界面通量

根据 2 0 0 1年夏季长江口及东海西部海域表层海水pCO2 的实测数据 ,结合水文、化学和生物等要素的同步观测资料 ,对该海域pCO2 分布和变化的重要影响因素进行了探讨。结果表明 ,长江冲淡水是造成东海西部海域表层海水pCO2 分布不均匀的主要原因。利用Wan ninkhof( 1 992 )提出的通量模式计算 ,长江口口门附近海域和浙江近岸海域为CO2 的源区 ,1 2 3°E以东的调查海域表现为大气CO2 的汇 ,尤其是以 1 2 3°E ,32°N为中心 ,存在着一个极强的大气CO2 汇区。就整个东海西部海域而言 ,夏季可从大气净吸收 1 5 3× 1 0 4 tC。     

北黄海夏季pCO2分布及海-气CO2通量

基于在2006年夏季北黄海收集的的高分辨率的表层CO2分压(pCO2)数据,结合水文和生物地球化学同步观测参数,探讨了夏季北黄海pCO2空间分布的控制因素。结果表明,夏季北黄海与大多数中低纬度陆架海类似,由于水温较高,表层pCO2较高(平均值为(463±41)μatm),整个海域相对大气CO2过饱和。表层pCO2分布具有明显的区域差异,辽南和鲁北近岸海域pCO2明显高于中部区域,辽南近岸的高pCO2主要与河流输入和水产养殖引起的生物好氧呼吸有关,而鲁北沿岸的高pCO2主要与烟台近岸的底层冷水涌升及由混合引起的高碳酸盐含量的黄河泥沙的再悬浮有关;在海区中部大部分水域,pCO2与温度之间有较好的相关性,说明温度是这一区域pCO2分布较为重要的控制因子。另外,采用Wannikhof的海-气气体交换系数估计了北黄海夏季海-气CO2通量,结果表明整个北黄海是大气CO2的源,平均释放速率为(4.00±0.57)mmol.m-2.d-1,高于南黄海夏季海-气CO2通量。     

2011年3月胶州湾表层海水pCO2及海-气界面通量

依据2011年3月4日对胶州湾走航连续实测所得pCO2数据,结合水文、化学和生物等要素的同步实测资料,对胶州湾海域pCO2分布及其影响因素进行了初步探讨,并估算了3月海-气CO2通量。结果表明:3月胶州湾表层海水pCO2实测值在191～332μatm之间,平均值为278μatm,海-气CO2通量在-22.76～-7.13mmol·m-2·d-1,平均值为-14.2mmol·m-2·d-1,这一时期胶州湾从大气吸收约1.59×103t C,表现为大气CO2的强汇。生物活动是影响这一时期表层海水pCO2分布的主要原因。     

长江口淡水端淡、盐水混合表层pCO2的急剧变化及其影响机制

根据2004年5月长江口淡水端淡、盐水混合初期表层水二氧化碳分压(pCO2)的实测数据,结合水文、化学和生物等要素的同步观测资料,对pCO2的变化及其影响因素进行了研究。研究结果表明:在长江口淡水端盐度0~15的淡、盐水混合初期,表层水pCO2由3 500μatm左右大幅度下降至约1 000μatm。生源要素的补充使生物活动的急剧增加是pCO2以对数形式大幅度降低的主要原因,这一性质显著体现的拐点为(S<0.6,50<浊度<110)这一范围。同时由于生物活动和物理混合作用的分别控制,使得长江口淡水端淡、盐水混合初期表层水碱度与盐度呈二次抛物线关系,拐点处的盐度约为0.6。     

黄河口总碱度保守与非保守行为探讨

为了阐明黄河口TAlk（总碱度）的行为特征及主要影响因素,根据2004年4月黄河口TAlk实测数据,结合其它化学要素的同步观测资料对其进行了初步探讨.研究结果表明： 黄河口水体在S〈24的区域范围内TAlk呈现出非保守行为,其中 S〈5时TAlk非保守表现为净TAlk的“亏损”, 即水体TAlk低于理论混合TAlk,是由于水体中DIC的沉淀作用引起;在盐度为8～24之间,TAlk非保守表现为净TAlk的“增加”,即水体TAlk高于理论混合TAlk,主要是由于水体中颗粒碳酸盐溶解引起;水体中的CO2参与了颗粒碳酸盐的溶解,并且很可能是影响水体中碳酸盐溶解的主要因素.     

Numerical hindcasting of sea surface pCO2 at Weathership Station Papa

A one-dimensional model of temperature, salinity, nutrients, oxygen, carbon, and argon chemistry is used to hindcast the annual cycle of sea surface pCO₂ at weathership Station Papa in the subarctic Pacific (50°N, 145°W), based on recent biological and chemical measurements made in conjunction with the SUPER program. Heat fluxes are calculated from the meteorological time series data from the Canadian weathership program. The Price, Weller and Pinkle (1986) model is used for predicting mixed layer dynamics. The rate of new production in the model is based on sediment trap data (Welschmeyer, personal communication) and a comparison of model oxygen and argon concentrations with the recent data of Emerson, Quay, Stump, Wilbur and Knox (1991). The balances of nutrients and oxygen in the permanent halocline require isopycnal ventilation on a time frame of approximately 10 years; this estimate is consistent with estimate of Van Scoy, Fine and Ostlund (1991) based in tritium data from Geosecs and Long Lines programs. The model results are compared with the 5 year time series data presented by Wong and Chang (1990). The model appears to capture the mean sea surface pCO₂ and the magnitude and timing of the seasonal cycle. The data, howeber, contain much greater high frequency variation than the model results, which we believe is caused by patchiness in the horizontal distribution of NO₃. The model pCO₂ sensitivity to the chemistry of the upwelling water and the rate of biological new production are presented.Although the model simulation of pCO₂ is satisfactory, this study illustrates the limitations of modelling the chemistry of the upper ocean in one dimension. The slow currents and horizontally homogeneous sea surface in the subarctic Pacific make Papa one of the best available candidates for modelling in 1-D. In spite of this, a 1-D formulation is inadequate to address the chemistry of the halocline (a crucial lower boundary condition to the mixed layer) and does not constrain the transport of the nutrients by wind-driven currents in the mixed layer. We conclude that further progress in modelling the upper ocean nutrient and carbon cycles will requires simulation in three dimensions.     

Influence of giant kelp beds (Macrocystis pyrifera) on diel cycles of pCO2 and DIC in the Sub-Antarctic coastal area

The partial pressure of CO₂ (pCO₂) and dissolved inorganic carbon (DIC) were monitored in shallow coastal waters located inside and outside giant kelp beds (Macrocystis pyrifera) located in the Kerguelen Archipelago (Southern Ocean). Photosynthesis and respiration by microplankton and kelp lead to marked pCO₂ and DIC diel cycles. Daily variations of pCO₂ and DIC are significant in the spring and summer, but absent in the winter, reflecting the seasonal cycle of biological activity in the kelp beds. If the kelp beds seem to favour the onset of phytoplankton blooms, most of the primary production inside the kelp beds is due to the kelp itself. The primary production of Macrocystis kelp beds in the Sub-Antarctic high-nutrient, low-chlorophyll (HNLC) waters off the Kerguelen Archipelago is elevated and closely linked to light availability. This production is significant from October to March and reaches its climax in December at the solar radiation maximum.     

On the CO2O2 system in the Northeastern Pacific

The TCO₂, O₂, TA and δ¹³C data of the 1969 Geosecs Intercalibration Cruise was analyzed and found to be consistent with a vertical mixing model which assumes that each point along a vertical profile is a mixture of the upper and lower boundaries. Calculated regression coefficients are in agreement with the model of Redfield et al. (1963) and with the assumption that TA variation is due to carbonate reaction. Oxygen consumption and TCO₂ production decrease exponentially with depth and approximately 80% of ΔCO₂ can be accounted for, on average, by O₂ consumption. The remaining 20% are probably due to carbonate solution which seems to take place at depths below 2,500 m. The present study suggests that the isotopic composition (δ¹³C) of the carbon source, required to account for most of the oxygen consumed, may be heavier than the value of −23%. assigned to dissolved organic carbon and particulate organic carbon.     

Accurate measurement of O2, N2, and Ar gases in water and the solubility of N2

The degree of atmospheric saturation for O₂, Ar, and N₂ gases in water can be determined to accuracies of ±0.1–0.3% using mass spectrometry to determine the gas ratios and Winkler titrations for oxygen analysis. We describe methods used to obtain this level of accuracy and precision. Oxygen accuracy of ±0.1% can be obtained by careful attention to standardization using KIO₃ standards that have been corrected for impurities. Accurate O₂/Ar and O₂/N₂ gas ratios (±0.1–0.2%) are obtainable by measuring the mass ratios against the atmosphere if the effect of different gas concentrations on the performance of the mass spectrometer are taken into account. Oxygen and argon saturation values have been determined previously to accuracies of less than or equal to ±0.1%, but published estimates of the saturation value for nitrogen differ by more than 1%. We have redetermined the N₂ saturation value at 19°C and zero salinity to be 0.92% greater than the results reported in the work of Weiss (1970).     

相变存储材料Ge1Sb2Te4和Ge2Sb2Te5薄膜的结构和电学特性研究

采用射频磁控溅射方法制备了两种用于相变存储器的Ge₁Sb₂Te₄和Ge₂Sb₂Te₅相变薄膜材料,对其结构、电学输运性质和恒温下电阻随时间的变化关系进行了比较和分析.X射线衍射(XRD)和原子力显微镜(AFM)的结果表明:随着退火温度的升高,Ge₁Sb₂Te₄薄膜逐步晶化,由非晶态转变为多晶态,表面出现均匀的、     

生物固氮速率测定中15N2同位素示踪剂的引入

生物固氮作用是一个重要的海洋新氮来源,在海洋生物地球化学循环中扮演着不可替代的角色。基于稳定同位素（15N₂）示踪吸收法,是目前直接测定海洋生物固氮速率最有效的手段。其中,高效、洁净地将15N₂引入海水培养体系,并准确定量培养体系底物的同位素示踪水平,是同位素示踪吸收法准确获取固氮速率的关键。本研究针对15N₂同位素示踪剂引入这一关键环节进行了探讨,确认改进气泡法是将15N₂引入海水培养体系的首选操作。在对培养体系造成的较小扰动的情况下,可将培养体系氮气底物的15N原子丰度提升至10%以上,相对于另一种导入同位素示踪剂的手段——预溶解海水法,改进气泡法将培养瓶中氮气底物的15N原子丰度提升了近200%。此外,改进气泡法还具有最小化痕量金属沾污、操作简便等优点。将改进气泡法结合与稳定同位素比值质谱测定结合,是准确测定水体生物固氮速率的推荐方法。     

High-resolution measurement of Southern Ocean CO2 and O2/Ar by membrane inlet mass spectrometry

This paper evaluates the simultaneous measurement of dissolved gases (CO₂ and O₂/Ar ratios) by membrane inlet mass spectrometry (MIMS) along the 180° meridian in the Southern Ocean. The calibration of pCO₂ measurements by MIMS is reported for the first time using two independent methods of temperature correction. Multiple calibrations and method comparison exercises conducted in the Southern Ocean between New Zealand and the Ross Sea showed that the MIMS method provides pCO₂ measurements that are consistent with those obtained by standard techniques (i.e. headspace equilibrator equipped with a Li–Cor NDIR analyser). The overall MIMS accuracy compared to Li–Cor measurements was 0.8 μatm. The O₂/Ar ratio measurements were calibrated with air-equilibrated seawater standards stored at constant temperature (0 ± 1 °C). The reproducibility of the O₂/Ar standards was better than 0.07% during the 9 days of transect between New Zealand and the Ross Sea.The high frequency, real-time measurements of dissolved gases with MIMS revealed significant small-scale heterogeneity in the distribution of pCO₂ and biologically-induced O₂ supersaturation (ΔO₂/Ar). North of 65°S several prominent thermal fronts influenced CO₂ concentrations, with biological factors also contributing to local variability. In contrast, the spatial variation of pCO₂ in the Ross Sea gyre was almost entirely attributed to the biological utilization of CO_2, with only small temperature effects. This high productivity region showed a strong inverse relationship between pCO₂ and biologically-induced O₂ disequilibria (r² = 0.93). The daily sea air CO₂ flux ranged from − 0.2 mmol/m² in the Northern Sub-Antarctic Front to − 6.4 mmol/m² on the Ross Sea shelves where the maximum CO₂ influx reached values up to − 13.9 mmol/m². This suggests that the Southern Ocean water (south of 58°S) acts as a seasonal sink for atmospheric CO₂ at the time of our field study.