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二甲基硫（ＤＭＳ）在大气化学和全球生物地球化学循环中起了重要作用,是影响气候变化的重要痕量气体。本文采用气提－冷阱捕集法处理海水样品,用带有火焰光度检测器的气相色谱仪分析。此方法的精密度为５．５％,回收率为８５％,最低检出限为５０ｐｇＳ（ＤＭＳ）。用此法实测了胶州湾及其附近海域表层海水的二甲基硫的含量 相似文献
2.
吹扫-捕集气相色谱法测定海水中挥发性卤代烃 总被引：6，自引：0，他引：6
挥发性卤代烃(VHC)是大气中的痕量气体,对臭氧层损耗和温室效应有重要作用。海洋是大气中VHC的主要自然排放源,开展海洋VHC的研究有助于了解海洋对大气VHC和全球变暖的贡献。本文建立了吹扫-捕集与气相色谱-微池电子捕获检测器联用技术(P-T-GC-(ECD)分析海水中6种VHC的方法,确定了吹扫-捕集条件和气相色谱分离条件。该方法的检测限在0.003~0.369 ng.L-1之间;相对标准偏差是1.83~3.97;加标回收率为98.1%~110.2%;相关系数在0.997 3~0.999 8之间。可准确地测定海水中6种VHC。 相似文献
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采用硼氢化纳还原法将海水中无机锡还原为挥发性锡化氢,氮为载气将锡化氢从反应器吹出,并于液氮冷阱中捕集,捕集后将锡化氢载入氢焰原子化器进行原子吸收测定。对该还原反应、氢化物转移、捕集及原子化实验条件进行了详细研究。实验结果表明:该法中可氢化元素As、Sb、Se等超过被测物浓度200倍时亦无明显干扰,检出限为0.0060μg/dm~3,对0.050μg/dm~3 Sn浓度的样品变异系数为±8％。标准曲线表明,在0—0.050μg/dm~3 Sn浓度范围内有理想的线性关系。对海水介质测定,该法所作校准曲线与蒸馏水介质具有相同的斜率,采用NaOH共沉淀预富集可提高灵敏度5—10倍,便于海水样品保存,总回收率95％以上。 相似文献
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运用电感耦合等离子体发射光谱法(Inductively Coupled Plasma-Optical Emission Spectrometry,ICP-OES)比较研究了干法灰化、湿法消解和微波消解3种前处理方法对海带样品中Se、Fe、Mn、Zn、Ca、Mg、P、As、Cd、Cr、Cu和Pb 12种元素含量测定的影响。结果表明,不同前处理方法对微量元素的测定结果会产生不同程度的影响。干法灰化对易挥发元素As等带来明显的负误差;湿法消解由于加入的消解液量大,对低含量的微量元素常带来较大的试剂空白;微波消解法相对于其他两种前处理方法适于样品的快速消解,具有操作简便、试剂用量少、操作误差小等优点,检测结果具备较高的准确度、精密度和回收率,对海带样品微波消解ICP-OES检测的相对标准偏差为0.29%~2.63%,加标回收率为87.3%~103.6%。微波消解是海带等海洋生物样品中微量元素测定较理想的前处理方法。 相似文献
5.
稀土元素已越来越多地应用于示踪各类地球化学体系的物质来源与岩石矿物形成等演化过程。但在进行海水样品的稀土元素检测时,由于样品的高盐特征和稀土元素的痕量特征又使得分析具有相当的挑战性。本研究旨在从高盐的海水基质中有效分离并富集痕量的稀土元素,同时结合电感耦合等离子体质谱（Inductively Coupled Plasma Mass Spectrometry, ICP-MS）技术对海水中的稀土进行定量分析。通过对海水样品稀土元素的定量限分析、加标回收实验和梯度加标回收实验,验证了方法的准确性,评估方法的分离富集效率。通过共沉淀过程中的pH比较、氢氧化钠与氨水作为共沉淀剂的比较,确定了富集过程中共沉淀剂用量、种类等影响因素。通过稀土元素配分曲线的绘制与类似样品结果进行比对,以及标准海水的检测结果,验证了方法在实际样品中的可行性。本研究探索了共沉淀富集法在分离富集海水中稀土元素的实验条件,实现高盐背景下痕量稀土的准确定量,并将其用于近岸海水与孔隙水的实际检测。 相似文献
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于1983—1985年采集黄河口及邻海沉积物、海水及悬浮颗粒物样品,测定了底质总汞、海水总汞、溶解总汞、无机汞及悬浮颗粒物总汞。所测定的各种汞的形态均列于世界河口区最低的浓度水平。枯水期无机汞和海水总汞分布相对均匀。丰水期溶解总汞分布均匀,而无机汞、颗粒汞和海水总汞都显示出与盐度、颗粒物含量相似的梯度分布。显示了黄河迳流及所携带大量悬浮颗粒物的重要影响。黄河水的无机特征和海水相对高的有机物含量,使无机汞入海后部分转变成有机汞,同时海水与河水的颗粒汞出现明显差别。底质汞与中值粒径线性相关,颗粒汞与颗粒物含量双曲线相关。近河口区盐度、颗粒物含量及颗粒汞含量有明显分层现象。 相似文献
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从分离测定海水样品中稀土元素的经典工作开始，确定海水中稀土元素分布图便成为一个实际难题．由于稀土元素的浓度在pmolkg^-1范围，需要预富集或采用先进的分析仪器．作为预富集技术曾成功地运用过Fe(OH)3共沉淀法，离子交换色谱和溶剂萃取等方法．对稀土元素的测定， 相似文献
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汞的冷原子吸收测定具有简便快速、选择性好和灵敏度高等优点,因此,被广泛地用于海水中汞的分析.由于海水中汞的含量极微,一般认为是5—30毫微克/升[1,2],许多分析者常在原子吸收测定前先进行汞的预富集.各种汞的预富集步骤的共同缺点是:测定装置复杂,操作不便,样品用量大,分析时间长和易引进杂质.因此,研究海水中痕量汞的直接测定法是有现实意义的.近年来,汞的冷原子吸收测定的研究主要是改进测定方式和条件,以提高测定灵敏度.本文介绍了应用我组研制的冷原子吸收测汞仪所建立的海水中痕量汞的差示冷原子吸收测定法.用同样的测定方式和条件,差示法与非差示法比较,灵敏度提高了33倍,方法的检测限达0.1毫微克汞/100毫升. 相似文献
9.
测定了福建省泉州深沪湾海水、沉积物和生物体中的总汞含量,测定了沉积物、生物体中的甲基汞含量.海水总汞含量范围是1.16 ～7.29 ng/dm3,平均值为3.32 ng/dm3.沉积物中总汞含量为0.006～0.066 μg/g,甲基汞占总汞的比例为4.7％ ～38.6％,该比例与总汞含量呈负相关关系(r=-0.840,p＜0.05),这可能是因为总汞含量的升高使甲基汞合成反应受到抑制,导致反应速率降低甚至为负,即甲基汞的分解.生物体中总汞含量为0.037 ～0.353 μg/g(干重),甲基汞含量为1.01 ～42.50 ng/g(干重),甲基汞占总汞的比例为1.5％ ～40.4％.甲基汞含量与总汞含量显著相关(r =0.484,p＜0.10);总汞含量与甲基汞占总汞比例略有相关(r=-0.293,p＜0.10);甲基汞含量与其占总汞比例无相关性(r=0.061,p＞0.05).可以推测,生物体中的总汞和甲基汞都是外源性的,不同生物体甲基汞占总汞的比例变化很大.对深沪湾居民进行海产品摄入量评估,以美国EPA规定的甲基汞参考计量0.1 μg/(kg·d)为标准,计算得深沪湾周边居民每周食用3次(600g)湾内的海产品是安全的,不会产生汞中毒.未来还需要测定海水中甲基汞的含量,用以计算生物富集因子,表征不同生物对甲基汞的富集程度;通过测定鱼体中的δ13C、δ15N比值来确定不同鱼类的营养级,进而研究甲基汞的生物累积效应与营养级的关系. 相似文献
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11.
浮游植物是海洋生态系统中的主要初级生产者，构建海洋食物网、生物泵和元素循环（包括碳循环、氮循环和硅循环等）的基石。因此，海洋生态系统中的元素循环和能量流动均与浮游植物的生长和代谢息息相关。海洋碳循环是全球碳循环的关键环节，也是全球生态系统中生物地化循环的重要组成部分。尽管浮游植物在海洋碳循环中起着至关重要的作用，但是直接测定浮游植物的初级生产力和碳生物量依旧受到传统技术和方法的限制。本文详细介绍了有关浮游植物初级生产力和碳生物量检测的各种技术和方法，列举了其各自的优缺点。目前，测定海洋浮游植物初级生产力的主要方法有黑白瓶法、遥感估算法、碳同位素测定、快速重复率荧光法；测定海洋浮游植物碳生物量的主要方法有细胞体积转换法、流式细胞术、电子探针X射线显微分析、分位数回归模型估算法。通过对比分析发现碳同位素与快速重复率荧光法相结合可以更高效测定出初级生产力，而最具优势与应用前景的碳生物量检测方法是基于分位数回归模型估算法。其中，基于分位数回归模型估算法具有拟合异常值、测定结果准确等优势，能够实现现场浮游植物群落以及各个功能群碳生物量的估算，并能够与卫星遥感技术手段相结合，可以应用于大尺度和长时间序列的海洋浮游植物碳生物量估算。通过本文的综述，一方面为海洋浮游植物初级生产力和碳含量的研究提供一个基本和系统的认识，另一方面为深入研究浮游植物在海洋碳循环以及全球碳循环中的作用提供参考。 相似文献
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氟喹诺酮类(FQs)药物是一种广泛使用的人工合成类抗生素,存在于水体、沉积物等各种环境介质中,并在水生生物体内得到富集,对人类健康和全球生态系统的可持续发展有重要的影响。环境中FQs残留的分析检测是了解其环境生物地球化学行为和潜在生态环境风险的基础,本文系统总结了近几年海洋水体、沉积物和生物体样品中FQs的残留特征、样品前处理与检测技术,在此基础上,前瞻分析了海洋环境中FQs残留分析检测技术的发展趋势。分析表明,FQs的分离富集和测定必须充分考虑FQs的物理化学性质和样品成分的复杂性。海水样品准备应注意过滤膜的选择和pH的调节;沉积物和生物体的样品准备应考虑水分、萃取溶剂、基质效应和pH的影响,并使用超声萃取。固相萃取、QuEChERS萃取、磁性固相萃取是分离富集FQs较常用的方法,吸附剂、淋洗溶液和洗脱溶液的选择和优化是提高样品回收率的关键。FQs的检测大多通过液质联用或液相色谱结合荧光检测器进行,其中色谱柱的选择、离子对试剂的添加和进样pH值的调整都是优化的关键因素。研究指出海洋领域FQs在线自动SPE技术的开发以及新型萃取吸附剂的研制应在未来研究中被重点关注。 相似文献
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辽河口区域丰富的生物多样性在生物地球化学循环和维持生态系统功能等方面发挥着极其重要的作用。研究辽河口表层沉积物中参与常见地球化学循环的功能基因及其关键影响因子,对揭示和预测辽河口沉积物微生物的功能代谢潜力和受环境变化的影响具有重要意义。应用功能基因芯片(GeoChip 4.0)技术开展微生物功能基因多样性研究。结果表明:在6个沉积物样品中,检测到各类型功能基因48742个,反映了9个微生物介导的关键生物过程。其中,碳循环相关功能基因最多,其次是氮循环和硫循环,而磷循环相关功能基因较少。各站位生物过程相关的功能基因数量和荧光信号值整体呈由远海到近海上升的趋势,即河相区的微生物功能基因较海相区与混合区普遍丰富。碳循环中参与碳固定的基因荧光信号值最高。氮循环中反硝化功能基因荧光信号值最高。总磷与硝酸盐是影响微生物功能基因多样性分布格局的重要因素。该研究有助于了解环境变化对辽河口沉积物生态系统结构和功能的影响,为研究辽河口表层沉积物微生物介导的生物地球化学循环提供科学依据。 相似文献
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Mercury evasional fluxes from the sea surface into the atmosphere play an important role in the Hg biogeochemical cycle, especially in the Mediterranean basin, which is characterized by the presence of large cinnabar deposits, intense solar radiation and high temperatures for many months of the year. Since the available experimental methodologies to measure mercury flux can be used only in good weather conditions, at present it is necessary to make use of exchange models that require the knowledge of the dissolved gaseous mercury (DGM) concentration in seawater. In this paper, the main factors affecting DGM levels are discussed considering the determination of the DGM daily behaviour in different meteo-marine and weather conditions at coastal and offshore locations of the Mediterranean basin. A fully automatic device for continuous analyses of DGM concentration with a high time resolution was used. Results show that the daily trend of DGM concentration tracks that of the solar radiation intensity, often mapping the movement of the clouds. DGM levels can be decreased by the presence of high winds that increase mercury evasion from the water surface, as well as by the mixing of the surface water layer. The presence of high levels of dissolved organic matter favours the photo-induced reduction of mercury as observed by the measurements performed in a lagoon water. 相似文献
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P.C. Tavares A. Kelly R. Maia R.J. Lopes R. Serrão Santos M.E. Pereira A.C. Duarte R.W. Furness 《Estuarine, Coastal and Shelf Science》2008
Causes of variation in mobilization of mercury into Black-winged Stilt Himantopus himantopus chicks were studied through analysis of stable isotope ratios of carbon and nitrogen. Blood and breast feathers were collected from chicks in coastal saltpans during successive breeding seasons. Detritus samples and potential prey (macroinvertebrates) were also collected. Total mercury concentrations and stable isotope signatures were measured using atomic absorption spectroscopy and isotope ratio mass spectrometry respectively. Mercury levels in Chironomidae, Corixidae and Hydrophilidae correlated with mercury levels in chick feathers. Differences of δ15N signatures between macroinvertebrate groups indicated that they belong to different trophic levels. δ15N signatures of invertebrates correlated with mercury levels in invertebrates and chicks, but not with δ15N signatures in chicks. Between-group and between-site differences of δ15N signatures and mercury levels in invertebrates suggested that they contribute differently to mercury mobilization into chicks, and their relative contribution depends on prey availability in each site. Inter-site differences in the biomagnification factor reinforced that idea. δ13C signatures in invertebrates marked a larger range of carbon sources than just detritus. Variation of water inflow regime and prey availability may cause between-group and between-site differences of δ13C signatures in prey. Discrepancies between feather and blood for δ13C signatures in Praias-Sado and Vaia suggested that temporal variation of prey availability may be the main factor affecting mercury mobilization into chicks in both those cases, since their water inflow regimes are the same. The lowest levels of δ13C signatures in Vau suggested that water inflow regime may be the main factor in this case, since no discrepancy existed in δ13C signatures between blood and feather. 相似文献
16.
Arsenic(As) and mercury(Hg) are pollutants presented in marine environment. A process of atomic fluorescence spectrometry was proposed for the simultaneous determination of As and Hg in marine sediment samples(n =38) collected from the Changjiang River Estuary and adjacent East China Sea. The proposed method used an optimized pretreatment procedure in an aqua regia–H_2 O digestion system. Recoveries of As and Hg increased to97% and 98%, respectively, with suitable precisions(2.7%–4.1%) under optimized process conditions. As and Hg were widely presented in these samples, with the ranges of content values were 2.39–8.77 μg/g for As and48.03–410.8 ng/g for Hg. Results indicate that anthropogenic factors strongly influence the abundances of As and Hg in investigated samples. The preliminary environmental risk assessment was investigated using the I_(geo)accumulation index(I_(geo)) and anthropogenic contribution rate(M). Findings reveal that Hg demonstrates a strong ecological risk(with average values of 1.3 and 72% for I_(geo) and M, respectively) in the sediments from the Changjiang River Estuary and adjacent East China Sea. Therefore, Hg should be considered in future investigations. 相似文献
17.
分别于1989年，1992年，1991年8月，1991年5月对大辽河口、鸭绿江口、滦河口、东村河口水体中总汞进行了取样和分析，其中又对大辽河口和东村河口进行了溶解态汞的分析。大辽河口和东村河口溶解态汞的含量分别为85～460ng/L和180～500ng/L，平均值分别为210和324ng/L；总汞含量分别为95～550和400～1000ng/L，平均值分别为310和640ng/L。大辽河河流段和河口段溶解态汞和颗粒态汞是主要存在形式。河口溶解态汞和颗粒态汞随氯度变化趋势相似。东村河口溶解态汞约占50%。鸭绿江口和滦河口总汞含量分别为30～2500和3700～6700ng/L，平均值分别为700和5700ng/L。鸭绿江口总汞随氯度变化趋势与随浊度变化趋势一致。而在滦河口总汞含量随两者变化趋势则不同。还讨论了滦河口、东村河口、鸭绿江口和大辽河口汞的污染程度。 相似文献
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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。 相似文献
19.
Bias errors, resulting from inaccurate boundary and forcing conditions, incorrect model parameterization, etc. are a common problem in environmental models including biogeochemical ocean models. While it is important to correct bias errors wherever possible, it is unlikely that any environmental model will ever be entirely free of such errors. Hence, methods for bias reduction are necessary. A widely used technique for online bias reduction is nudging, where simulated fields are continuously forced toward observations or a climatology. Nudging is robust and easy to implement, but suppresses high-frequency variability and introduces artificial phase shifts. As a solution to this problem Thompson et al. (2006) introduced frequency dependent nudging where nudging occurs only in prescribed frequency bands, typically centered on the mean and the annual cycle. They showed this method to be effective for eddy resolving ocean circulation models. Here we add a stability term to the previous form of frequency dependent nudging which makes the method more robust for non-linear biological models. Then we assess the utility of frequency dependent nudging for biological models by first applying the method to a simple predator–prey model and then to a 1D ocean biogeochemical model. In both cases we only nudge in two frequency bands centered on the mean and the annual cycle, and then assess how well the variability in higher frequency bands is recovered. We evaluate the effectiveness of frequency dependent nudging in comparison to conventional nudging and find significant improvements with the former. 相似文献
20.
A.Yu Lein 《Marine Chemistry》1985,16(3):249-257
Dissimilatory sulphate reduction is the main biogeochemical reaction responsible for the cycle of sulphur and its isotopic composition in modern oceanic sediments. The maximal intensity of this process, measured with the help of radioactive isotopes, is typical of sediments in the peripheral regions of the ocean to a depth of 1000 m and makes up 10–60 μg S/kg wet silt/day.The minimal enrichment with 32S of the buried, reduced sulphur and the maximal accumulation of heavy isotopes in sulphate sulphur of pore waters are observed under conditions of the most intensive biogeochemical processes. Further away from continents the intensity of bacterial sulphate reduction diminishes to a fraction of 1 μg S/kg wet silt/day, the reduced sulphur becomes enriched in 32S (up to ? 50.0‰), and the isotope composition of sulphate sulphur in pore waters approximates that in oceanic water and the solid phases of sediments.The amount of reduced sulphur in the total sulphur buried in modern sediments of the Pacific Ocean is twice the amount of sulphate sulphur. The δ34S value of the total sulphur buried and removed from the cycle makes up ? 17.9‰. This value is comparable to that of the average isotope composition of total sulphur in clay rocks of the lithosphere. 相似文献