The ebb and flood of Silica: Quantifying dissolved and biogenic silica fluxes from a temperate salt marsh

Salt marshes are widely studied due to the broad range of ecosystem services they provide including serving as crucial wildlife habitat and as hotspots for biogeochemical cycling. Nutrients such as nitrogen (N), phosphorus (P), and carbon (C) are well studied in these systems. However, salt marshes may also be important environments for the cycling of another key nutrient, silica (Si). Found at the land–sea interface, these systems are silica replete with large stocks in plant biomass, sediments, and porewater, and therefore, have the potential to play a substantial role in the transformation and export of silica to coastal waters. In an effort to better understand this role, we measured the fluxes of dissolved (DSi) and biogenic (BSi) silica into and out of two tidal creeks in a temperate, North American (Rowley, Massachusetts, USA) salt marsh. One of the creeks has been fertilized from May to September for six years allowing us to examine the impacts of nutrient addition on silica dynamics within the marsh. High-resolution sampling in July 2010 showed no significant differences in Si concentrations between the fertilized and reference creeks with dissolved silica ranging from 0.5 to 108 μM and biogenic from 2.0 to 56 μM. Net fluxes indicated that the marsh is a point source of dissolved silica to the estuary in the summer with a net flux of approximately 169 mol h⁻¹, demonstrating that this system exports DSi on the same magnitude as some nearby, mid-sized rivers. If these findings hold true for all salt marshes, then these already valuable regions are contributing yet another ecosystem service that has been previously overlooked; by exporting DSi to coastal receiving waters, salt marshes are actively providing this important nutrient for coastal primary productivity.     

海洋硅藻硅质细胞壁结构的形成机理研究概述

硅藻具有形态各异、结构复杂、精美绝伦的硅质细胞壁,是海洋中进行生物硅化最主要的生物体。硅质细胞壁的形成同样是一个错综复杂的过程,它涉及硅藻细胞将硅酸从胞外转运到胞内;硅酸在细胞内的转移;在硅沉积囊泡(SDV)中的浓缩沉积;最后合成具种类特异性的细胞壁。重点介绍硅酸转运基因(SITs)的分子特征与作用机制;与生物硅化相关的三种蛋白即硅体蛋白(frus-tulins)、亲硅蛋白(silaffins)和侧壁蛋白(pleuralins)的结构与功能;硅质结构如何在硅沉积囊泡内最终形成的模式。     

Processes controlling solubility of biogenic silica and pore water build-up of silicic acid in marine sediments

Dissolution experiments in batch and flow-through reactors were combined with data on sediment composition and pore water silicic acid profiles to identify processes controlling the solubility of biogenic silica and the build-up of silicic acid in marine sediments. The variability of experimentally determined biogenic silica solubilities is due, in part, to variations in specific surface area and Al content of biosiliceous materials. Preferential dissolution of delicate skeletal structures and frustules with high surface areas leads to a progressive decrease of the specific surface area. This may cause a reduction of the solubility of deposited biosiliceous debris by 10–15%, relative to fresh planktonic assemblages. Dissolution of lithogenic (detrital) minerals in sediments releases dissolved aluminum to the pore waters. This aluminum becomes structurally incorporated into deposited biogenic silica, further decreasing its solubility. Compared to Al-free biogenic silica, the solubility of diatom frustules is lowered by as much as 25% when one out of every 70 Si atoms is substituted by an Al(III) ion.The build-up of silicic acid in pore waters of sediments with variable proportions of detrital matter and biogenic silica was simulated in batch experiments using kaolinite and basalt as model detrital constituents. The steady-state silicic acid concentrations measured in the experiments decreased with increasing detrital-to-opal ratios of the mixtures. This trend is similar to the observed inverse relationship between asymptotic pore water silicic acid concentrations and detrital-to-opal ratios in Southern Ocean sediments. Flow-through reactor experiments further showed that in detrital-rich sediments, precipitation of authigenic alumino-silicates may prevent the pore waters from reaching equilibrium with the dissolving biogenic silica. This agrees with data from Southern Ocean sediments where, at sites containing more than 30 wt.% detrital material, the pore waters remain undersaturated with respect to the experimentally determined in situ solubility of biogenic silica.The results of the study show that interactions between deposited biogenic silica and detrital material cause large variations in the asymptotic silicic acid concentration of marine sediments. The production of Al(III) by the dissolution of detrital minerals affects the build-up of silicic acid by reducing the apparent silica solubility and dissolution kinetics of biosiliceous materials, and by inducing precipitation of authigenic alumino-silicate minerals.     

The diffusion coefficient of dissolved silica revisited

The diffusion coefficient of dissolved silica was determined for two different salinities, 36 and 0, at temperatures ranging from 2 °C to 30 °C and at an average pH value of 8.1. Our results show limited influence of salinity and a variation by a factor of 2 to 3 of the silica diffusion coefficient within the temperature range considered in this study. The values obtained at 25 °C are in agreement with previous work carried out at room temperature for seawater and freshwater. The dependency on temperature and viscosity of the diffusion coefficient agrees well with the Einstein–Stokes equation. The composition of the solvent appears to be an important factor because it modifies the viscosity and allows for the complexation of the dissolved silica with less mobile ions, while its pH controls the dissolved silica speciation. In seawater, the higher viscosity and the presence of dissociated and polymeric species result in a decrease of the diffusion coefficient compared to freshwater systems.     

Effect of solid to solution ratio on biogenic silica determination in coastal sediments

The method of DeMaster (1981) for measuring biogenic silica (BSi) in marine sediments was modified. We found a considerable effect of the solid to solution (S/S) ratio on BSi determination in coastal sediments. The BSi contents determined by DeMaster’s method were overestimated due to the contribution of clay mineral-derived extractable Si at a low S/S ratio (<1 g l⁻¹), and incomplete recovery of BSi was observed due to incomplete extraction when using a high S/S ratio (>2 g l⁻¹). For BSi analysis of coastal sediment samples, the BSi content of representative samples must be measured using various S/S ratios to determine the appropriate S/S ratio in order to minimize the contribution of extractable Si derived from clay minerals and to obtain sufficiently efficient extraction with 1% Na₂CO₃ before actual sample measurement. One way to determine the appropriate S/S ratio is to use artificial sediment which has a theoretical Si and clay mineral content similar to the sediment sample composition. Using artificial sediment, the S/S ratio of 2 g l⁻¹ seems appropriate for measuring the BSi content of the coastal sediments investigated in this study, because 99.6% recovery can be achieved.     

渤海表层沉积物中的生物硅

采用0.1 mol/L HCl和1%Na2CO3两步连续提取法,对103个渤海表层沉积物样品的生物硅含量进行了分析,结果表明,渤海表层沉积物中生物硅含量范围为7.3~54.7 g/kg,均值31.5 g/kg,高于其他相关调查,原因可能是由于采用0.1 mol/L HCl提取过程中,破坏了生物硅表面的金属氧化膜。对沉积物生物硅含量的空间分布表征显示,莱州湾是沉积物生物硅的低值区、而渤海湾与辽东湾之间的河北沿岸海域是相对高值区,初步认为是陆源营养物质的输入与黄河泥沙长期不断输入干扰沉积环境的稳定性,造成了该海域表层沉积物生物硅分布差异。主成分分析显示,生物硅含量与沉积物黏粒含量、细粉砂、有机氮、有机碳的含量均呈极显著正相关(P0.01),进一步证实沉积物粒度特征和营养环境对生物硅积累的影响。     

烟台四十里湾表层沉积物中生物硅的研究

以烟台四十里湾作为研究区域,分析了16个站位表层沉积物中生物硅的含量,探讨沉积物中生物硅对内湾环境的指示作用.结果表明,污水排放区、垃圾倾倒区沉积物中生物硅含量较高(平均值分别为0.71％和0.78％),对应上层水体的富营养化;航道区生物硅含量很低(平均值0.37％),与航船扰动造成的低生产力状况符合.沉积物中生物硅含量较好地反映了上层水体的浮游植物状况,并与上层营养盐浓度具有很好的对应关系.研究表明,沉积环境能够明显影响沉积物中生物硅的沉积和保存.     

钱塘江河口溶解硅的变化与影响研究

根据2013年~2014年四个季度的调查资料,结合历史数据并采用数理分析与经验模型计算相结合的方法,分析讨论了钱塘江河口溶解硅的分布、年代际变化和潜在影响。结果表明,研究区域受到河流冲淡水和东海海水混合的双重影响,溶解硅的分布与浓度呈现出明显的梯度变化与季节规律,其浓度在秋季最高,夏季次之,春季与冬季较低。近些年来溶解硅的浓度呈降低趋势,较历史水平降低了12%~25%,硅氮比也有大幅度的降低,比值自1.25降低到0.52。钱塘江河口溶解硅浓度降低主要是由于东海低溶解硅浓度海水的稀释造成的,而浮游植物量对溶解硅浓度影响有限。另外,河口叶绿素a含量与历史数据相比也存在明显降低,浮游植物细胞总量和种数都有显著下降;硅藻种类减少了近70%,并出现了绿藻、蓝藻和甲藻等非硅藻类生物,造成这几方面变化的原因很可大程度上与营养盐结构和浓度的变化有关。     

Biological controls on dissolution of diatom frustules during their descent to the deep ocean: Lessons learned from controlled laboratory experiments

The majority of opal produced by diatoms dissolves during their sedimentation to the seafloor, but spatial and temporal variability of dissolution rates are large. Controlled laboratory experiments using live phytoplankton or phyto-detritus may help identify the different processes, including those that are biologically mediated or physico-chemically driven, that impact the dissolution of frustules and the aforementioned variability. Results of eight bSiO₂ dissolution experiments, seven of which were conducted at low temperatures (<6 °C) are presented within the context of earlier similar studies, and different phases of dissolution dynamics characterized. TEP concentration, aggregation and the physiological status of the diatoms determined the period during which diatoms may maintain the protective membrane that surrounds their frustule and effectively reduces or completely inhibits (lag period) dissolution for some time. Once diatoms loose the capability to maintain their protective membrane, bacterial activity compromises it. Physico-chemical dissolution, which depends on frustule structure and abiotic environmental conditions, begins once the protective membrane is damaged. The ability of diatoms to maintain their membrane, the bacterial composition and activity governing its degradation, and the physico-chemical dissolution dynamics of exposed frustules are all impacted by temperature. In our experiments instantaneous dissolution rates were not dependant on bSiO₂ concentration at low temperatures, although such a relationship was observed under otherwise identical conditions at 15 °C, implying that biotic factors rather than physico-chemical processes initially dominated dissolution at polar temperatures. Since inhibition of bSiO₂ dissolution at low temperatures was inhibited to a greater extent than organic matter degradation, we postulate that it was not reduced bacterial activity but the enhanced ability of diatoms to maintain their membrane and thus withstand microbial attack that caused the low initial dissolution rates at <6 °C. In situ, interactions between the different biotic and abiotic processes impacting dissolution combined with differences in sinking velocity of diatom aggregates and grazing effects could easily explain high spatial and temporal variability in the accumulation of diatoms on the seafloor. Simple calculations based on our experimental results suggest that Fragilariopsis kerguelensis, for example, would be appreciably more likely to reach the seafloor than Chaetoceros debilis if both grow at low growth rates, e.g. under growth limiting conditions. However, dissolution behavior of Chaetoceros debilis during sedimentation may differ under conditions where this species forms large blooms.     

Vertical and seasonal differences in biogenic silica dissolution in natural seawater in Suruga Bay, Japan: Effects of temperature and organic matter

Vertical and seasonal characteristics of biogenic silica (BSi) dissolution in seawater were investigated by multiple dissolution experiments using seawater collected from surface and mesopelagic layers in Suruga Bay during the period 2002–2004. The dissolution rate coefficients calculated based on temporal changes of BSi concentration varied with the season of sample collection. They ranged from 0.023–0.057 day^− 1 for surface samples and 0.0018–0.0025 day^− 1 for mesopelagic samples for temperatures approaching in situ conditions. Experiments at various temperatures confirmed that BSi dissolution depends on temperature in natural seawater. Dissolution rate coefficient (day^− 1) of BSi correlated significantly with temperature (°C), and Q₁₀ was 2.6. Addition of bioavailable organic matter to low-bioactivity seawater enhanced the protease activity and abundance of bacteria, and increased BSi dissolution rate by a factor of 1.4–2.0. There is clear evidence that BSi dissolution is accelerated by bacterial activity and potentially limited by bioavailable organic matter in natural seawater. Dissolution rates and total decreases of BSi concentration were lower during experiments using mesopelagic samples than in those using surface samples. This suggests that dissolution of BSi varies with depth and that BSi in the mesopelagic water is more resistant to the dissolution than that in the surface water. This lower dissolution rate was caused by lower temperature and lower bacterial activity due to less bioavailable organic matter in mesopelagic water. Our results provide a mechanistic understanding of variations in silica cycling within the seasonally and vertically differing marine environment.     

The behaviour of dissolved silica during the mixing of river and sea waters in Tokyo Bay

The behaviour of dissolved silica was studied in Tokyo Bay during six surveys in 1979 and 1980. The data from late spring and mid-summer samples showed concave mixing curves of silica versus salinity, whereas for the winter samples a simple conservative dillution curve was obtained. Plots of particulate silicon to particulate aluminium showed that even for winter samples as well as summer ones there were some processes removing silica from solution. The processes could not be adequately explained by adsorption onto suspended solids. The data are indicative of uptake by diatoms as the principal removal mechanism. Most of the diatom skeletons settled to the bottom where dissolution was rapid. The silica-salinity curves in this study thus demonstrate an apparent removal process for dissolved silica. This is because during summer the displacement rate of biogenic silica from a unit water column to the bottom as fecal pellets or by sinking is greater than the supply rate of dissolved silica by the action of diffusion and mixing of bottom water enriched with dissolved silica whereas in winter these rates are reasonably balanced.     

3种海洋硅藻不同培养阶段挥发性成分的比较分析

本文应用顶空固相微萃取气相色谱-质谱联用技术,对威氏海链藻Thalassiosira weissflogii、小新月菱形藻Nitzschia closterium、角毛藻Chaetoceros calcitrons 3种硅藻的挥发性成分进行分析。结果表明,在3种硅藻的培养过程中,其挥发性成分除了壬醛及醇类呈现先增后降的趋势外,大多数不饱和醛类的含量在不断增加,烷烯烃类物质在不断减少,而乙酸乙酯、2-甲基-2-丙酸甲酯这类酯类化合物在角毛藻衰败期会显著富集。通过对代表性饵料硅藻的挥发性成分进行研究,可为海水养殖过程中微藻投喂种类、投喂时机的选择提供理论依据,并为海洋硅藻的进一步开发奠定基础。     

近海污染物对海洋浮游植物生长及生化组成影响的比较研究

威氏海链藻(Thalassiosira weissflogii)属沿海中心硅藻纲,是海洋硅藻的模式种之一。实验探讨氮营养盐(硝酸盐,N,c(N)分别为8.0,16.0,32.0,64.0μmol/L)、石油烃(0号柴油分散液,WAFs,c(WAFs)分别为0,0.1,0.5,1.0,5.0 mg/L)、抗生素(土霉素,c(OTC)分别为,0,1.0,3.0,5.0,10.0 mg/L)等3类近海常见污染物对威氏海链藻细胞生长及生化组成的影响。结果表明,3类近海常见污染物对藻生长(即藻细胞密度)、叶绿素a合成、蛋白质生成、藻细胞抗氧化能力(即超氧化物歧化酶活性)、脂质过氧化(即丙二醛含量)的影响程度分别为WAFsNOTC、NOTCWAFs、NWAFsOTC、WAFsNOTC、OTCNWAFs;影响程度的差异,揭示了近海各污染物的毒性作用机制及靶位不同。     

培养基对海藻真菌PT2菌株的生长及活性代谢产物合成的影响

本文采用PD、GPY、YES、SYE、GPM5种不同培养基培养海藻真菌菌株PT2，并对其在不同培养基中的生长情况、代谢产物的形成及抗肿瘤活性进行分析，旨在了解不同培养基对菌株生长和活性物质合成的影响．结果显示，PT2菌株在不同培养基上的培养特征及生长速率有所不同，液体培养基发酵液抽提物的抗肿瘤活性也有较大差别，其中SYE发酵液抽提物活性最强，对KB、Raji和Hela 3种肿瘤细胞的IC50分别为7．6μg／cm^3、2．4μg／cm^3和3．3μg／cm^3．采用HPLC法对不同抽提物进行分析，发现它们之间的组成成分有显著差异．本文的实验结果表明，不同培养基对该菌株的生长及活性代谢产物的合成具有显著的影响。     

海洋微藻的无菌化处理及对其生长特性和生化组成的影响

利用常用抗生素(氨苄青霉素、链霉素、氯霉素和卡那霉素)对4株海洋微藻(1株金藻和3株小球藻)进行了无菌化处理,并对这4株微藻在带菌和无菌培养时的生长特征和生化组成进行了比较。结果表明:中高浓度(≥100 mg/dm3)的单种抗生素或抗生素组合可抑制微藻的生长,个别低浓度(50 mg/dm3)的抗生素或抗生素组合可促进微藻的生长;氨苄青霉素、链霉素和卡那霉素各200 mg/dm3联合使用处理球等鞭金藻,氯霉素100, 50, 50 mg/dm3单独使用分别处理小球藻C95, CV和C146,可获得这4株微藻的无菌藻系;无菌培养的4株海洋微藻的稳定期持续时间由除菌前的4~5 d延长到15~20 d,藻液悬浮性增强,藻细胞不易老化;除菌后微藻的主要生化成分发生明显变化,球等鞭金藻的叶绿素A、叶黄素和总脂含量显著增加,小球藻C95和CV的总蛋白含量显著增加,3株小球藻的脂肪酸组成如EPA, PUFA等的含量发生显著变化。     

不同海洋微藻对石油污染的响应差异

微藻对油污染物的不同响应,势必造成其群落种类组成和结构的变化,进一步影响海洋生态系统的变迁。由于油污染对于浮游植物的影响具有污染源及生物响应的多样性、多维度性和复杂性,产生影响的时效长但可显示度低等特点,造成该研究领域的极大限制。作者以石油标准品20-3和3种石油化学品(双酚、对苯二甲酸、对二甲苯)作为油污染源,利用多孔板高通量检测方法及大数据处理分析软件Simca-P,对中国沿海常见单种微型藻类的种群消长受油污染影响进行了研究。以石油标准品20-3为油污染源,分析了31株微藻增殖对不同油标浓度的不同响应;利用Simca-P软件对3种不同浓度的石油化学品对4种典型微藻(柔弱角刺藻(Chaetoceros debilis)、球等鞭金藻(Isochrysis galbana)、东海原甲藻(Prorocentrum donghaiense)、剧毒卡罗藻(Karlodinum veneficum))增殖的影响进行了比较分析。研究结果显示:不同种类微藻因油污种类及其浓度不同,其响应存在显著差异。利用多孔板以及微藻的吸光特征,可以高通量快速筛查不同微藻对不同油污及其不同浓度的响应差异,并利用计算机软件对大数据的分析能力,挖掘和比较不同微藻与不同油污之间的相互关系,从而就油污染对微藻影响这种多维度复杂关系进行研究。     

铅离子对海洋浮游植物生长影响的研究

采用一次培养实验方法,研究了Pb^2 对8种常见海洋浮游植物生长的影响。在Logistic生长模型的基础上,结合Lorentz方程和GaussAmp方程,引入Pb^2 浓度项,建立新的方程来描述Pb^2 存在条件下海洋浮游植物的生长过程,并且通过对实验数据的非线性拟合,验证该方程是合理的。实验拟合结果表明,高浓度Pb^2 (c(Pb^2 )≥2500μg／L)对浮游植物的生长普遍有抑制作用,而较低浓度Pb^2 (c(Pb^2 )≤100μg／L)则易促进赤潮异弯藻(Heterosigma akashiuo Hada)、旋链角毛藻(Chaetoceros curvisetus Cleve)、三角褐指藻(Pheodactylum tricormutum Bohlin)、中肋骨条藻(Skeletonema costatum (Greville) Cleve)、青岛大扁藻(Platymonas helgolanidica Kylin var tsingtaoensis)、亚心型扁藻(Platymonas subcordiformis)的生长,它们最佳的促进生长浓度分别为：1991、2523、101、1488、627、509μg／L,但对于海洋原甲藻(Prorocentrum micans Ehrenberg)、裸甲藻(Gymnodinium sp．)的生长没有明显的影响。应用该方程在一定程度上不仅可以根据浮游植物的生长情况．推测相应海区的Pb^2 污染物浓度;而且也可以预测不同浓度Pb^2 条件下,相应海区的海洋浮游植物的生长情况。