海水中溶解有机磷的测定方法

磷和氮一样,都是海洋环境中的重要生源要素,其在水环境中的时空分布控制着海洋生态系统中的初级生产过程.在大洋或深海区,氮的供应相对不足常是初级生产的制约因素,但在浅海区,特别是河口和海湾,由于农业施肥、城市污水及大气干湿沉降等的作用,氮/磷比值常远高于Redfield比值,从而使磷成为初级生产的制约因素^[1-6].     

营养盐对中肋骨条藻和新用菱形藻生长及氮磷组成的影响

于１９９５年５月１９９６年３月一次２实验,研究了培养介质中营养盐含量变化对中肋骨条藻和新月菱形藻生长速率和藻体氮、磷含量的影响。根据Ｍｏｎｏｄ方程,磷酸盐影响中肋骨条藻和新月菱形藻生长速率的半饱和常数分别为０．５４μｍｏｌ／Ｌ和０．０５μｍｏｌ／Ｌ;硝酸盐影响两种藻生长速率的半饱和常数分别为４．０μｍｏｌ／Ｌ和１４．６μｍｏｌ／Ｌ,相比之下新月菱形藻更容易受到氮不足的限制。将Ｍｏｎｏｄ方程扩展得到     

营养盐对中肋骨条藻和新月菱形藻生长及氮磷组成的影响

：于１９９５年５月１９９６年３月通过一次培养实验,研究了培养介质中营养盐含量变化对中肋骨条藻和新月菱形藻生长速率和藻体氮、磷含量的影响。根据Ｍｏｎｏｄ方程,磷酸盐影响中肋骨条藻和新月菱形藻生长速率的半饱和常数分别为０．５４μｍｏｌ／Ｌ和０．５０μｍｏｌ／Ｌ;硝酸盐影响两种藻生长速率的半饱和常数分别为４．０μｍｏｌ／Ｌ和１４．６μｍｏｌ／Ｌ,相比之下新月菱形藻更容易受到氮不足的限制。将Ｍｏｎｏｄ方程扩展得到营养限制复合模式,限制程度可用限制作用系数定量化表示,代表氮或磷。培养介质中营养盐浓度是限制浮游植物生长的决定因素,其Ｎ／Ｐ比值则反映ＮＯ_３－Ｎ和ＰＯ_４－Ｐ何者起主要限制作用。藻体氮、磷含量随和有明显变化。当＜０．８０时较低,磷含量因贮存而明显升高;当＜０．８０时藻体磷含量下降,氮含量略有增加。藻体氮含量或＞０．８０时基本上为非限制状态。     

海洋中二甲基亚砜的来源、分布及迁移转化

二甲基亚砜(DMSO)是海水中的主要溶解态甲基硫化物,DMSO在二甲基硫(DMS)的生物地球化学循环中起着重要的作用。它能通过DMS的光化学氧化和细菌氧化生成,可作为DMS的1个汇,也可以通过生物直接合成或其它途径产生。DMSO同时又可以被酶、细菌、植物等还原为DMS,因此,DMSO又可充当DMS的1个源。DMSO除了能被还原为DMS外,还可能会被细菌氧化为SO42-,在氯过氧化物酶作用下被H2O2氧化为DMSO2等。海洋中DMSO的测定通常采用还原剂NaBH4将其还原为DMS后,再利用气相色谱进行测定。海水中DMSO的分布不均匀,高浓度区是那些温度较高,光照充足、浮游植物较多、生物活性较高的表层水或近岸水。     

海水中腐殖质对溶解态铁的络合及其影响因素

腐殖质(humic substances,简称HS)是地表普遍存在的天然有机物,对海洋中重要的微量营养元素-铁(Fe)的分布及生物地球化学循环具有重要的影响作用。本文对腐殖质的来源、分布及对海水中溶解态铁的迁移转化的影响做了总结,特别论述了其在河口及沿岸水域的行为。大量研究表明河口、沿岸及开放海水中溶解态铁分布的变化可以用腐殖质的浓度及其铁结合能力的变化来解释。腐殖质的络合作用不仅能够阻止溶解态铁(DFe)在河口、沿岸等水域被去除,而且能够通过洋流将DFe迁移至外海及大洋区域,此外还能增加铁的溶解度及对海水中浮游植物的生物可利用性,并且促进铁的氧化还原循环。研究还发现两者之间的络合强度受到盐度、pH等理化因素的影响。盐度是影响HS与DFe配合能力的重要影响因素,盐度增加,导致HS中可以与Fe配合的位点数量降低,配合总量呈现指数降低,而pH的增加可以增加HS与DFe的配合量。另外HS还能影响海水中DFe的氧化还原,并以此影响浮游植物对DFe的吸收利用。因此腐殖质对溶解态铁的有机络合作用是影响其海洋生物地球化学循环的一个重要参数,对进一步研究海水中腐殖质的浓度和分布具有重要的意义。     

海水观赏水族缸中不同挂膜法对氮转化的影响

为了构建生态平衡的海水水族缸闭合循环系统，笔者设置了4种海水水族缸挂膜实验缸，缸内分别加入虾肉（腐尸法）、虾肉和硝化细菌（综合法）、硝化细菌（生物制剂法）、自然海水（对照空白缸），定期测定缸内三态氮的含量，通过三态氮含量的变化来判断缸内生物膜的成熟程度．腐尸法和综合法在15d后就能达到氨氮含量稳定，但硝酸盐含量较高；硝化细菌法氨氮含量达到稳定需要28d，而空白对照缸氨氮达到稳定需要35d．在生物膜挂膜后，加入观赏鱼进行实验，发现硝化细菌法和自然海水法所构建的水族缸氨氮含量变化较小，而腐尸法处理的水族缸易引起藻类大量出现．     

海洋中生源活性气体的来源与迁移转化

海洋生源活性气体主要包括二甲基硫（DMS）、甲烷（CH₄）、氧化亚氮（N₂O）、一氧化碳（CO）、挥发性卤代烃（VHCs）和非甲烷烃（NMHCs）等。它们通过海-气交换进入大气,不仅在全球碳、氮和硫循环中发挥关键作用,而且会直接或间接地对环境和气候变化产生重要影响。海洋释放的活性气体一类属于温室效应气体（CH₄、N₂O、VHCs和CO等）,另一类会在大气中发生化学反应,控制着大气氧化平衡和臭氧浓度（VHCs和NMHCs）。而DMS属于负温室效应气体,其在大气中被快速氧化形成硫酸盐气溶胶,进而对云的形成和辐射强迫产生重要影响。本文综述了国内外海洋生源活性气体的研究现状,着重介绍了DMS、CH₄和N₂O的来源、迁移转化、海-气通量及其影响机制,并指明了该领域存在的科学问题及今后的研究方向。     

光照和盐度对海水介质中磷化氢转化的影响

通过室内模拟实验,研究了光照和盐度对海水介质中磷化氢转化的影响。结果表明,不同光照条件下磷化氢转化率有明显差异,按对磷化氢转化促进作用由大到小排列依次为：UVC〉UVB〉日光〉UVA〉避光条件,单位辐照强度的UVC比UVB更能促进磷化氢的转化。在实验体系中加入臭氧、过碳酸钠的实验进一步验证自由基反应对磷化氢转化有促进作...     

黄海南部海域不同类群微型浮游原生生物生长对亚洲沙尘和磷添加的响应

海洋原生生物是微食物环的重要组成部分,在海洋生态系统的物质循环和食物传递中发挥着不可替代的作用;亚洲沙尘颗粒经长距离输运后沉降入黄海,会对海洋生态系统产生显著影响。本研究在黄海南部海域进行了现场模拟培养实验,分析了不同浓度沙尘和P添加对不同粒径、异养类型浮游原生生物生长速率的影响。结果表明,在培养早期,P和沙尘的添加都会促进各营养类型浮游原生生物的生长,特别是对10~20μm自养型生长速率的促进作用最为显著,其在高、低浓度P和高、低浓度沙尘添加组的生长速率分别为1.39、0.96、0.69和0.47 d-1,分别是对照组的5.35、3.69倍和2.65、1.81倍(P<0.05),表明研究海区为P潜在限制海区,沙尘对原生生物的促进作用可能和P的溶出有关;沙尘对异养型和兼养型原生生物早期是抑制作用。在培养后期,沙尘添加对各类群原生生物的生长以促进作用为主,对2~5μm异养型的促进作用最为显著,其在高、低浓度沙尘组的生长速率分别为0.84和0.40 d-1,显著高于对照组的-0.46 d-1(P<0.05)。沙尘沉降早期对大粒径自养型原生生物生长的促进作用会加速富营养海区赤潮的发生,但对异养型的抑制作用会削弱海区物质循环和食物传递的效率;沙沉降对不同粒径和营养类型浮游原生生物生长的影响会改变黄海南部海区微型食物网的结构,影响原生生物在该海区物质转化和食物产出中的生态功能,研究结果可为深入探讨沙沉降对海洋生态系统的作用机制和生态效应提供科学参考。     

近海海洋酸化对痕量元素在沉积物-海水界面处生物地球化学特性的影响研究

痕量元素在海洋环境中不仅能够密切参与物质循环,显著调控生命代谢,有些情况下还会对浮游及底栖生物产生抑制和毒害,是海洋系统中具有重要生物地球化学作用的“双刃剑”。工业革命以来,海洋不断吸收大气CO₂使得海水pH和碳酸根浓度持续下降,在全球范围内都出现了海洋酸化的现象。海洋酸化作为新的环境胁迫打破了痕量元素在沉积物-间隙水-上覆水中既有的平衡态势,导致痕量元素在海洋环境中的生物地球化学特性变得更加复杂和不确定。本文从痕量元素在沉积物-海水体系中的赋存形态与交换过程入手,探讨了海洋酸化条件下痕量元素在沉积物-海水体系中的扩散迁移与再平衡行为,分析了由此产生的生物毒性效应和生物可用性影响。最后,对海洋酸化与多种环境条件、多种污染物联合作用所导致的与痕量元素相关的生态效应研究进行了展望,以期为未来海洋酸化与痕量元素协同研究提供有意义的科学参考。     

The fluorescence of dissolved organic matter in seawater

A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO₃⁻, PO₄³⁻) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.     

Luminescence quenching of dissolved organic matter in seawater

To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κ_q, for these quenchers were found to decrease in the order MV²⁺ (κ_q 10¹⁰M⁻¹s⁻¹) > I⁻ (κ_q 2 × 10⁹ M⁻¹ s⁻¹) >CH₂CHCONH₂ (κ_q 2 × 10⁸ M⁻¹ s⁻¹) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.     

Metaproteomic characterization of dissolved organic matter in coastal seawater

We performed a comprehensive metaproteomic analysis of the dissolved organic matter (DOM) in Japanese coastal waters using liquid chromatography–tandem mass spectrometry and demonstrated that these proteomes were characterized by proteins with various functions, including metabolic enzymes, membranes, and photosynthetic proteins. The protein sources included cyanobacteria, heterotrophic bacteria, and eukaryotic phytoplankton. Most of the components were similar among samples and also similar to pelagic components. We also observed differences in the compositions of the microbial communities of origin among the different dissolved protein samples and differences in the relative abundance of specific dissolved protein types (e.g., cytoskeletal proteins), possibly indicating potential dynamics in the coastal DOM pool.     

Binding of monomeric organic compounds to marcomolecular dissolved organic matter in seawater

Several monomeric organic compounds, including amino acids, sugars, and fatty acids, were found to bind abiologically to dissolved macromolecular materials in particle-free seawater at natural substrate concentrations. The binding primarily occurred in ocean surface waters, at rates slower than in situ biological utilization rates of most of the compounds. Seasonal patterns of binding in Gulf of Maine waters may have been related to seasonal variations in macroalgal exudation of polyphenolic materials. Enhanced reactivity of relatively hydrophobic monomers implicated hydrophobic effects as potentially important in marine organic condensations. The resultant condensates showed high particle reactivity, consistent with low concentrations of dissolved condensed materials in seawater.     

Pseudo-nitzschia spp. (Bacillariophyceae) and dissolved organic matter (DOM) dynamics in the Ebro Delta (Alfacs Bay, NW Mediterranean Sea)

Samples were collected during one annual cycle (April 2007–March 2008) at Alfacs Bay (NW Mediterranean Sea) central station in order to assess the influence of organic nutrients in the growth of the microalgae assemblage, with special reference to Pseudo-nitzschia spp. This potentially toxic diatom forms natural and recurrent blooms in the study area. To assess further the relationship between Pseudo-nitzschia spp. and nutrients an enrichment experiment with high molecular weight dissolved organic matter (HMWDOM) was performed with field samples obtained during a Pseudo-nitzschia spp. bloom. HMWDOM was extracted from water collected at Alfacs Bay. Five bioassays were prepared: N + P (seawater with addition of nitrate and phosphate), DOM (addition of HMWDOM), (−N + P) + DOM (nitrogen deficient, with addition of phosphate and HMWDOM), (N + P) + DOM (addition of nitrate, phosphate and HMWDOM), seawater control (without added nutrients), and B + DOM (control of bacteria, without microalgae). The experiment was run in batch mode over 4 days. Results from the field study revealed that the concentrations of organic nutrients mostly surpassed the inorganic pool. Pseudo-nitzschia spp. was the most frequent and abundant taxa of the microalgae community. The micro-planktonic assemblage was arranged according to a seasonal factor (ANOSIM and cluster analysis). DON, nitrate and silicate were the most important abiotic parameters contributing to the dissimilarities between seasons (SIMPER analysis) and thereby potentially influencing the seasonal distribution of microalgae in the representative station. In the experimental investigation, Pseudo-nitzschia cells increased by the end of the experiment in the DOM bioassay but no respective increase was observed for chlorophyll a. This could point to an acquisition of nutrients through the DOM fraction that would conjointly reduce the need of chlorophyll a. The data obtained suggest that organic nutrients may exert an important role in the development of microalgae, including Pseudo-nitzschia spp., in the selected location.     

Chromophoric dissolved organic matter and dissolved organic carbon in Chesapeake Bay

Chromophoric dissolved organic matter (CDOM) is the light absorbing fraction of dissolved organic carbon (DOC). The optical properties of CDOM potentially permit remote sensing of DOC and CDOM, and correction for CDOM absorption is essential for remote sensing of chlorophyll a (chl a) in coastal and estuarine waters. To provide data for this purpose, we report the distributions of CDOM, DOC, and chl a from seven cruises in Chesapeake Bay in 1994–1997. We observed non-conservative distributions of chl a and DOC in half of the cruises, indicating net accumulations within the estuary; however, there were no net accumulations or losses of CDOM, measured as absorption at 355 nm or as fluorescence. Freshwater end member CDOM absorption varied from 2.2 to 4.1 m⁻¹. Coastal end member CDOM absorption was considerably lower, ranging over 0.4–1.1 m⁻¹. The fluorescence/absorption ratio was similar to those reported elsewhere for estuarine and coastal waters; however, in the lower salinity/high CDOM region of the Bay, the relationship was not constant, suggestive of the mixing of two or more CDOM sources. Chl a was not correlated with the absorption for most of the cruises nor for the data set as a whole; however, CDOM and DOC were significantly correlated, with two groups evident in the data. The first group had high CDOM concentrations per unit DOC and corresponded to the conservative DOC values observed in the transects. The second group had lower CDOM concentrations per unit DOC and corresponded to the non-conservative DOC values associated with net DOC accumulation near the chl a maximum on the salinity gradient. This indicates the production of non-chromophoric DOC in the region of the chl a maximum of Chesapeake Bay. In terms of remote sensing, these data show that (1) the retrieval of the absorption coefficient of CDOM from fluorescence measurements in the Bay must consider the variability of the fluorescence/absorption relationship, and (2) estimates of DOC acquired from CDOM absorption will underestimate DOC in regions with recent, net accumulations of DOC.     

The role of various dissolved organic matter forms on chlorpyrifos bioavailability to the estuarine bivalve Mercenaria mercenaria

Dissolved organic matter (DOM) is comprised of a myriad of macromolecules with specific physical and chemical properties that may influence the bioavailability of hydrophobic pesticides to animals. This study was conducted to assess the role of various forms of DOM on the uptake and bioconcentration of the organophosphate insecticide chlorpyrifos (CHPY) to the bivalve Mercenaria mercenaria. Bivalves were exposed to DOM-free seawater (30 per thousand) or to seawater containing a single form of DOM. DOM forms included two filtrate fractions of natural salt-marsh sediment DOM (DOM-(<0.45 mum) and DOM-(<3 kDa)); natural purified humic (HA) and fulvic (FA) acids; and water soluble cyclic oligosaccharides alpha and beta cyclodextrins (CD-alpha and CD-beta). In (14)C-CHPY uptake and elimination experiments, juvenile bivalves were exposed to uniformly-labeled (14)C-CHPY and collected at time intervals during 48 h. The remaining bivalves were transferred to (14)C-CHPY-free elimination chambers with bivalve collection at time intervals over 144 h. Total uptake of (14)C-CHPY by bivalves in DOM-free seawater was >40% greater than in bivalves exposed to (14)C-CHPY in the presence of most DOM forms. These results are consistent with much faster (14)C-CHPY uptake rates estimated using a simple two parameter model. After the elimination period, bivalves exposed to DOM-free seawater had (14)C-CHPY body residue concentrations between 25% and 86% greater than bivalves in the presence of DOM forms. Experiments with larger bivalves showed that pulse-chase exposures with a 1.5 h exposure period to (14)C-CHPY was not long enough to detect differences in (14)C-CHPY tissue accumulation efficiencies across treatments. Our findings suggest that natural forms of DOM, at environmentally realistic organic carbon concentrations, reduced pesticide uptake and bioconcentration, consistent with much lower uptake rates relative to bivalves exposed to (14)C-CHPY in the absence of DOM. Interestingly, at the tested organic carbon concentrations CD-alpha and CD-beta did not reduce (14)C-CHPY bioconcentration in M. mercenaria.     

A simple guideline to apply excitation-emission matrix spectroscopy (EEMs) for the characterization of dissolved organic matter (DOM) in anoxic marine sediments

Marine sediments represent a major carbon reservoir on Earth. Dissolved organic matter(DOM) in pore waters accumulates products and intermediates of carbon cycling in sediments. The application of excitation-emission matrix spectroscopy(EEMs) in the analysis of subseafloor DOM samples is largely unexplored due to the redoxsensitive matrix of anoxic pore water. Therefore, this study aims to investigate the interference caused by the matrix on EEMs and propose a guideline to prepare pore water sam...     

溶解有机物的光降解及其对浮游细菌和浮游植物的影响

作为海洋中最大的动态有机碳储库,溶解有机物的光降解(主要是紫外波段)对生源要素的生物地球化学循环以及海洋生态系统的结构和功能具有重要的影响。本文探讨了影响溶解有机物光降解的环境因素、其光化学过程和产物,并重点阐述了溶解有机物的光降解对浮游细菌和浮游植物的影响。溶解有机物的来源和成分复杂,其光降解在不同海区有不同的生态效应,为了能更准确地把握其生态效应,需要更全面和深入的研究。     

Photochemical production of ammonium and transformation of dissolved organic matter in the Baltic Sea

The release of ammonium from the photochemical degradation of dissolved organic matter (DOM) has been proposed by earlier studies as a potentially important remineralisation pathway for refractory organic nitrogen. In this study the photochemical production of ammonium from Baltic Sea DOM was assessed in the laboratory. Filtered samples from the Bothnian Bay, the Gulf of Finland and the Arkona Sea were exposed to UVA light at environmentally relevant levels, and the developments in ammonium concentrations, light absorption, fluorescence and molecular size distribution were followed. The exposures resulted in a decrease in DOM absorption and loss of the larger sized fraction of DOM. Analysis of the fluorescence properties of DOM using parallel factor analysis (PARAFAC) identified 6 independent components. Five components decreased in intensity as a result of the UVA exposures. One component was produced as a result of the exposures and represents labile photoproducts derived from terrestrial DOM. The characteristics of DOM in samples from the Bothnian Bay and Gulf of Finland were similar and dominated by terrestrially derived material. The DOM from the Arkona Sea was more autochthonous in character. Photoammonification differed depending on the composition of DOM. Calculated photoammonification rates in surface waters varied between 121 and 382 μmol NH₄⁺ L^− 1 d^− 1. Estimated areal daily production rates ranged between 37 and 237 μmol NH₄⁺ m^− 2 d^− 1, which are comparable to atmospheric deposition rates and suggest that photochemical remineralisation of organic nitrogen may be a significant source of bioavailable nitrogen to surface waters during summer months with high irradiance and low inorganic nitrogen concentrations.