热液喷口探测化学传感器的研制及应用*

海底热液喷口周围的水体具有显著的浊度和化学组分异常, 是寻找热液喷口的重要标志。文章提出了一种海底热液喷口的探测技术方法, 设计了低功耗化学传感器。该化学传感器可搭载在相关平台, 实时探测水体的Eh、H₂S、pH及CO₃^2-等电位值, 结合浊度异常, 可以推断热液喷口的位置。在西南印度洋中脊海试结果表明, 该化学传感器可有效探测由热液活动产生的水体异常, 是一种探测海底热液喷口的有效技术。     

热液喷口探测化学传感器的研制及应用

海底热液喷口周围的水体具有显著的浊度和化学组分异常,是寻找热液喷口的重要标志。文章提出了一种海底热液喷口的探测技术方法,设计了低功耗化学传感器。该化学传感器可搭载在相关平台,实时探测水体的Eh、H_2S、pH及CO_3~(2-)等电位值,结合浊度异常,可以推断热液喷口的位置。在西南印度洋中脊海试结果表明,该化学传感器可有效探测由热液活动产生的水体异常,是一种探测海底热液喷口的有效技术。     

离子色谱法测定海水中氯离子和硫酸根离子

氯离子和硫酸根离子是海水中重要的无机阴离子，在研究海洋生态变化、海洋循环作用过程与海洋全球气候变化等领域具有重要的指示意义。其测定方法较多，但缺少相应的测试方法。本文对测定海水中Cl^-，SO₄^2-的离子色谱方法进行了优化，选用IonPacAS14碳酸盐选择性离子色谱柱，以3.5 mmol/L Na₂CO₃+1 mmol/L NaHCO₃为流动相，可消除海水样品中碳酸盐及其他阴离子的干扰。该方法对Cl^-检出限为0.29 mg/L，线性相关系数r²=0.999 2，对SO₄^2-检出限为0.42 mg/L，线性相关系数r²=0.997 9。样品的加标回收率在95%~102%，Cl^-和SO₄^2-的相对标准偏差分别为1.92%和4.18%。该方法简便、迅速、灵敏、准确度高，可满足批量海水样品中Cl^-与SO₄^2-的准确测试。     

H2O/CO2污染对煤油燃料超声速燃烧影响数值研究

在纯净空气与H₂O/ CO₂污染空气来流对比试验结果基础上,采用数值计算方法和化学动力学方法,研究了H₂O和CO₂污染组分对煤油燃料超声速燃烧的影响,获得了试验手段难以得到的燃烧室流场参数和性能数据。完成了相应的煤油燃料超声速燃烧室二维数值计算,其中匹配了进口总温、总压、马赫数、氧气摩尔分数和工作当量油气比。将数值计算结果与相应试验测量值进行了对比分析,并结合燃烧室流场数据、性能参数分析了H₂O和CO₂污染的动力学影响、以及对燃烧室性能的影响。研究表明:(1)数值计算结果与实验测量值总体上吻合,两种手段均体现了纯净空气来流时不同煤油当量油气比的燃烧室性能,并反映了一致的“污染效应”影响趋势;(2) H₂O污染、H₂O+ CO₂污染的存在降低了煤油燃料超声速燃烧室性能,体现在燃烧诱导压升、燃烧效率、流向冲量增量的下降,而且随着污染组分含量的增加,燃烧室性能下降越加显著。      

氧掺杂碳气体扩散电极用于电催化产活性氧抗菌防污研究

过氧化氢(H₂O₂)等活性氧(ROS)物质因具有绿色高效的特点,在废水处理、杀菌消毒等领域受到研究者广泛关注。利用电催化生成H₂O₂是一种实时提供活性氧物质的有用方法。然而,目前报道的大多数高性能催化材料都是粉体形式,不便于在实际场景中的应用。因此,制备可直接应用的电极材料显得尤为重要。本研究利用喷涂-热解的制备方法,制备了高活性氧催化活性的氧化炭黑(O−CB)/多孔碳毡电极,通过聚四氟乙烯(PTFE)的修饰优化电极表面的氧气传质,成功制备氧掺杂碳气体扩散电极。研究结果表明,O−CB/PTFE-5 wt%电极具有最高的催化性能,其合成H₂O₂的速率达27.19 mg·L^-1(mg catalyst)^-1·cm^-1·h^-1。海洋典型污损微生物假单胞菌(Pseudomonas sp.)的抗菌实验表明,该电极电催化作用60 min产生的活性氧对Pseudomonas sp.的杀菌率可达到97.69%,作用120 min的杀菌率可达到99.99%。     

光谱法测定海水中溶解态无机氮的研究进展

溶解态无机氮（dissolved inorganic nitrogen, DIN）主要由亚硝酸盐-氮（NO^-₂-N）、硝酸盐-氮（NO^-₃-N）和铵氮（NH⁺₄-N）组成,它们在海洋的生物地球化学循环过程中起重要作用。但人类活动向海洋输入了大量无机氮,导致一系列环境问题。为了更好地开展海洋氮循环研究和环境污染管理,需对海水中的DIN进行测定。在众多分析方法中,光谱法因其通用性好、适用范围广、所需设备简单,成为测定海水DIN的首选。本文总结了近10年来基于光谱法测定海水DIN的研究进展,包括紫外分光光度法测定NO^-₃-N、萘乙二胺分光光度法测定NO^-₂-N和NO^-₃-N、次溴酸盐氧化-分光光度法测定NH⁺₄-N、靛酚蓝分光光度法测定NH⁺₄-N、酸碱指示剂-分光光度法测定NH⁺₄-N、荧光法和化学发光法测定DIN等,比较了各分析方法的特点,并展望了光谱法测定海水DIN的发展趋势。总的来说,在分析方法上,新试剂的使用以及一些新合成材料的出现,丰富了DIN的分析手段;在分析仪器上,以流动分析技术为基础的分析仪器在DIN的实验室及现场分析中得到了广泛应用。DIN的分析方法均朝着简单便捷、全自动化、分析速度快、精确度高、可适用范围广的方向发展。     

考洲洋牡蛎养殖海域海-气界面CO2交换通量的时空变化

根据2018年7月、11月和2019年1月、4月对广东考洲洋牡蛎养殖海域进行4个季节调查获得的pH、溶解无机碳(DIC)、水温、盐度、溶解氧(DO)及叶绿素a(Chla)等数据,估算该区域表层海水溶解无机碳体系各分量的浓度、初级生产力(P_P)、表层海水CO₂分压[p(CO₂)]和海-气界面CO₂交换通量(F_CO2),分析牡蛎养殖活动对养殖区碳循环的影响。结果表明:牡蛎养殖区表层海水中Chla、DIC、HCO₃^–和P_P显著低于非养殖区;养殖淡季表层海水中pH、DO、DIC、HCO₃^–、和CO₃^2–显著大于养殖旺季,养殖旺季的p(CO₂)和F_CO2显著大于养殖淡季。牡蛎养殖区表层海水夏季、秋季、冬季和春季的海-气界面CO₂交换通量F_CO2平均值分别是(42.04±9.56)、(276.14±52.55)、(–11.59±18.15)和(–13.02±6.71)mmol/(m²·d),冬季各站位F_CO2值离散度较大,其中位数是–10.73mmol/(m²·d)。在全年尺度,表层海水p(CO₂)及F_CO2与水温呈显著正相关,与盐度呈显著负相关。在非养殖区,浮游植物光合作用可能对影响表层海水p(CO₂)及F_CO2起主导作用。养殖牡蛎钙化、呼吸作用等生理因素释放的CO₂对表层海水p(CO₂)及F_CO2未产生显著影响。考洲洋养殖海域养殖旺季为CO₂的源,养殖淡季整体为CO₂的弱汇。     

铵锌镉还原法测试硝酸盐氮、氧同位素方法研究

本研究利用铵锌镉还原法将海水、湖水和自来水水体中硝酸盐转化为N₂O气体测试氮、氧同位素, 结果表明当反应体系的pH值在6～8之间, NO₃^-还原为NO₂^-的转化率大于95%, NO₂^-还原为N₂O的转化率大于99%。配置5种丰度的硝酸盐氮、氧同位素标样, 将实验结果与理论值绘制校准曲线, 氮同位素校准曲线斜率为0.48, 相关性良好(R²=0.999 8), 5种丰度δ¹⁵N_N2O标准偏差在0.18‰～0.43‰之间(n=5);氧同位素校准曲线斜率为0.70, 相关性良好(R²=0.999 6), 5种丰度δ¹⁸O_N2O标准偏差在0.27‰～0.46‰之间(n=5)。铵锌镉还原法与镉柱还原法测定硝酸盐氮、氧同位素结果的精密度和准确度一致, 同时海水、湖水和自来水3种不同类型水样的硝酸盐氮、氧同位素测试数据满足实验要求, 而且在实验流程的简洁性和高效性方面更具优势。     

应用于龟山岛热液喷口探寻的散射光式水下浊度仪研制*

位于台湾岛东北部的龟山岛热液区属浅水型海底热液活动区,已探明有超过30处的热液喷口分布在约10—30m的水深范围内。通过机械封装、硬件电路以及配套软件的设计和加工,自制了散射光式水下浊度仪;2011年5月25—30日,使用该浊度仪,对龟山岛附近海域进行了拖航作业,在此次作业的东北方向发现一处新的热液喷口(24°50^′09^″N、121°58^′08^″E);海试结果表明,该水下浊度仪对于浊度较大海域有探测能力,对浊度较小海域的探测精度不高,还有待进一步改进。     

锑原位掺杂SiO2@PDA-Sb复合材料修饰电极用于海水中Zn离子检测

本研究提出了一种用于检测海水中锌离子（Zn²⁺）含量的电化学检测方法。该方法首先应用水热法合成SiO₂@PDA-Sb复合材料,然后将该复合材料修饰到玻碳电极上制备SiO₂@PDA-Sb-Nafion/GCE,利用差分脉冲阳极溶出伏安法（DPASV）对珠江口海水水样中Zn²⁺进行测定。研究结果表明,Zn²⁺在SiO₂@PDA-Sb-Nafion/GCE上具有较强的溶出峰。在最优条件下,SiO₂@PDA-Sb-Nafion/GCE对Zn²⁺浓度在1~1 000 nmol/L范围内可实现灵敏、准确的检测,Zn²⁺的检测出限为0.71 nmol/L。加标回收率实验显示Zn²⁺加标回收率为93.19%~100.12%,表明该方法可应用于现场海水样品Zn²⁺测定。本方法具有电极制作简单、稳定性和抗干扰性良好,能够提高现有测定方法的检测限和精确度,在现场海水检测痕量Zn²⁺具有较好的应用前景。     

基于多参数化学传感器的海底热液探测方法研究

基于热液及其羽状流的化学异常提出了一种海底热液的化学式探测方法。根据自行开发的Eh.Ag/Ag₂S和pH三种化学电极,设计了多参数化学传感器系统。通过海试证明多参数化学传感器可灵敏地检测出由热液异常引起的化学量变化,并在长达半年的多次使用中表现出其稳定性好、寿命长的特点。在东太平洋中脊(EPR)赤道区域和西南印度洋中脊(SWIR)的60条测线中,获得有效测线55条,其中在29条测线上发现明显或可能的热液异常。研究表明,应用多参数化学传感器探测进行海底热液化学异常,是一种有效的方法。     

Spatial distribution pattern of seafloor hydrothermal vents to the southeastern Kueishan Tao offshore Taiwan Island

Investigations of the diffusion activities both within and outside the seafloor hydrothermal vents, as well as related mineral genesis, have been one of the key focuses of ocean biogeochemistry studies. Many hydrothermal vents are distributed close to the southern Okinawa Trough on the less-than-30-m deep shallow seafloor off Kueishan Tao, northeast of Taiwan Island. Investigations of temperature, pH and Eh at four depths of hydrothermal plume were carried out near Kueishan Tao at the white(24.83°N, 121.96°E) and yellow(24.83°N, 121.96°E) vents. An 87 h of temperature time series observation-undertaken near the white vent showed that tide is the main factor affecting the background environment. Based on the observed data, 3-dimensional sliced diffusion fields were obtained and analyzed. It was concluded that the plume diffused mainly from north to south due to ebb tide. The yellow vent's plume could effect as far as the white vent surface. From the temperature diffusion field, the vortices of the plume were observed. The Eh negative abnormality was a better indicator to search for hydrothermal plumes and locate hydrothermal vents than high temperature and low pH abnormalities.     

Small Scale Field Study of an Ocean CO<Subscript>2</Subscript> Plume

We have carried out a small-scale (∼20 l) CO₂ sequestration experiment off northern California (684 m depth, ∼5°C, background ocean pH ∼7.7) designed as an initial investigation of the effects of physical forcing of the fluid, and the problem of sensing the formation of a low pH plume. The buoyant CO₂ was contained in a square frame 1.2 m high, exposing 0.21 m² to ocean flow. Two pH electrodes attached to the frame recorded the signal; a second frame placed 1.9 m south of the CO₂ pool was also equipped with two recording pH electrodes. An additional pH electrode was held in the ROV robotic arm to probe the fluid interface. Local water velocities of up to 40 cm sec⁻¹ were encountered, creating significant eddies within the CO₂ box, and forcing wavelets at the fluid interface. This resulted in rapid CO₂ dissolution, with all CO₂ being depleted in a little more than 2 days. The pH record from the sensor closest (∼10 cm) to the CO₂ showed many spikes of low pH water, the extreme value being ∼5.9. The sensor 1 m immediately below this showed no detectable response. The electrodes placed 1.9 m distant from the source also recorded very small perturbations. The results provide important clues for the design of future experiments for CO₂ disposal and biogeochemical impact studies. These include the need for dealing with the slow CO₂ hydration kinetics, better understanding of the fluid dynamics of the CO₂-water interface, and non-point source release designs to provide more constant, controlled local CO₂ enrichments within the experimental area. This revised version was published online in July 2006 with corrections to the Cover Date.     

Use of voltammetric solid-state (micro)electrodes for studying biogeochemical processes: Laboratory measurements to real time measurements with an in situ electrochemical analyzer (ISEA)

Solid-state voltammetric (micro)electrodes have been used in a variety of environments to study biogeochemical processes. Here we show the wealth of information that has been obtained in the study of sediments, microbial mats, cultures and the water column including hydrothermal vents. Voltammetric analyzers have been developed to function with operator guidance and in unattended mode for temporal studies with an in situ electrochemical analyzer (ISEA). The electrodes can detect the presence (or absence) of a host of redox species and trace metals simultaneously. The multi-species capacity of the voltammetric electrode can be used to examine complex heterogeneous environments such as the root zone of salt marsh sediments. The data obtained with these systems clearly show that O₂ and Mn²⁺ profiles in marine sedimentary porewaters and in microbial biofilms on metal surfaces rarely overlap indicating that O₂ is not a direct oxidant for Mn²⁺. This lack of overlap was suggested originally by Joris Gieskes' group. In waters emanating from hydrothermal vents, Fe²⁺, H₂S and soluble molecular FeS clusters (FeS_aq) are detected indicating that the reactants for the pyrite formation reaction are H₂S and soluble molecular FeS clusters. Using the ISEA with electrodes at fixed positions, data collected continuously over three days near a Riftia pachyptila tubeworm field generally show that O₂ and H₂S anti-correlate and that H₂S and temperature generally correlate. Unlike sedimentary environments, the data clearly show that Riftia live in areas where both O₂ and H₂S co-exist so that its endosymbiont bacteria can perform chemosynthesis. However, physical mixing of diffuse flow vent waters with oceanic bottom waters above or to the side of the tubeworm field can dampen these correlations or even reverse them. Voltammetry is a powerful technique because it provides chemical speciation data (e.g.; oxidation state and different elemental compounds/ions) as well as quantitative data. Because (micro)organisms occupy environmental niches due to the system's chemistry, it is necessary to know chemical speciation. Voltammetric methods allow us to study how chemistry drives biology and how biology can affect chemistry for its own benefit.     

长江口及杭州湾邻近海域夏季表层海水中的溶解无机碳

根据2004年8月在长江口、杭州湾附近海域获得的调查资料对表层水中Ph值、总碱度和溶解无机碳的分布特征及其与环境参数的关系进行了研究,并由此得到了溶解无机碳的组成情况.结果表明,HCO3-、CO23-;和CO2(T)占溶解无机碳浓度百分比分别为80.33%～97.75%、0.61%～19.42%和0.25%～2.34%,平均值分别为(93.28±3.68)%、(5.58±4.03)%和(1.14±0.43)%.水文、浮游植物等对各参数的分布具有重要影响,但对不同参数的影响程度不同.     

GEOCHEMICAL CHARACTERISTICS OF ARSENIC IN SEDIMENTS FROM BOHAI GULF

This paper deals with the geochemical characteristics of arsenic in sediments from Bohai Gulf. The arsenic in seawater, surface sediments and cores is determined. Also measured are other physical and chemical parameters, such as Ni, Fe, C, pH and Eh in sediments. The values of As range from 0.6 to 4.5 ppb in seawater, from 10.0 to 20.9 ppm in surface sediments and from 6.8 to 22.8 ppm in cores.The contents of As from south are higher than those from north. However the As in sediments is the element not affected by pollution.The adsorption and codeposition of Ferric oxide colloid are the major form of transference of As from seawater to sediments in Bohai Gulf.The valence state of As in sediments is HAsO42-     

Gas flux and carbonate occurrence at a shallow seep of thermogenic natural gas

The Coal Oil Point seep field located offshore Santa Barbara, CA, consists of dozens of named seeps, including a peripheral ～200 m² area known as Brian Seep, located in 10 m water depth. A single comprehensive survey of gas flux at Brian Seep yielded a methane release rate of ～450 moles of CH₄ per day, originating from 68 persistent gas vents and 23 intermittent vents, with gas flux among persistent vents displaying a log normal frequency distribution. A subsequent series of 33 repeat surveys conducted over a period of 6 months tracked eight persistent vents, and revealed substantial temporal variability in gas venting, with flux from each individual vent varying by more than a factor of 4. During wintertime surveys sediment was largely absent from the site, and carbonate concretions were exposed at the seafloor. The presence of the carbonates was unexpected, as the thermogenic seep gas contains 6.7% CO₂, which should act to dissolve carbonates. The average δ¹³C of the carbonates was ?29.2?±?2.8‰ VPDB, compared to a range of ?1.0 to +7.8‰ for CO₂ in the seep gas, indicating that CO₂ from the seep gas is quantitatively not as important as ¹³C-depleted bicarbonate derived from methane oxidation. Methane, with a δ¹³C of approximately ?43‰, is oxidized and the resulting inorganic carbon precipitates as high-magnesium calcite and other carbonate minerals. This finding is supported by ¹³C-depleted biomarkers typically associated with anaerobic methanotrophic archaea and their bacterial syntrophic partners in the carbonates (lipid biomarker δ¹³C ranged from ?84 to ?25‰). The inconsistency in δ¹³C between the carbonates and the seeping CO₂ was resolved by discovering pockets of gas trapped near the base of the sediment column with δ¹³C-CO₂ values ranging from ?26.9 to ?11.6‰. A mechanism of carbonate formation is proposed in which carbonates form near the sediment–bedrock interface during times of sufficient sediment coverage, in which anaerobic oxidation of methane is favored. Precipitation occurs at a sufficient distance from active venting for the molecular and isotopic composition of seep gas to be masked by the generation of carbonate alkalinity from anaerobic methane oxidation.