The benthic silica cycle in the Northeast Atlantic: annual mass balance, seasonality, and importance of non-steady-state processes for the early diagenesis of biogenic opal in deep-sea sediments

Within the framework of the EU-funded BENGAL programme, the effects of seasonality on biogenic silica early diagenesis have been studied at the Porcupine Abyssal Plain (PAP), an abyssal locality located in the northeast Atlantic Ocean. Nine cruises were carried out between August 1996 and August 1998. Silicic acid (DSi) increased downward from 46.2 to 213 μM (mean of 27 profiles). Biogenic silica (BSi) decreased from ca. 2% near the sediment–water interface to <1% at depth. Benthic silicic acid fluxes as measured from benthic chambers were close to those estimated from non-linear DSi porewater gradients. Some 90% of the dissolution occurred within the top 5.5 cm of the sediment column, rather than at the sediment–water interface and the annual DSi efflux was close to 0.057 mol Si m⁻² yr⁻¹. Biogenic silica accumulation was close to 0.008 mol Si m⁻² yr⁻¹ and the annual opal delivery reconstructed from sedimentary fluxes, assuming steady state, was 0.065 mol Si m⁻² yr⁻¹. This is in good agreement with the mean annual opal flux determined from sediment trap samples, averaged over the last decade (0.062 mol Si m⁻² yr⁻¹). Thus ca. 12% of the opal flux delivered to the seafloor get preserved in the sediments. A simple comparison between the sedimentation rate and the dissolution rate in the uppermost 5.5 cm of the sediment column suggests that there should be no accumulation of opal in PAP sediments. However, by combining the BENGAL high sampling frequency with our experimental results on BSi dissolution, we conclude that non-steady state processes associated with the seasonal deposition of fresh biogenic particles may well play a fundamental role in the preservation of BSi in these sediments. This comes about though the way seasonal variability affects the quality of the biogenic matter reaching the seafloor. Hence it influences the intrinsic dissolution properties of the opal at the seafloor and also the part played by non-local mixing events by ensuring the rapid transport of BSi particles deep into the sediment to where saturation is reached.     

Coupling of benthic oxygen uptake and silica release: implications for estimating biogenic particle fluxes to the seafloor

A new approach to predict biogenic particle fluxes to the seafloor is presented, which is based on diffusive oxygen uptake and, in particular, opal fluxes to the seafloor. For this purpose, we used a recently published empirical equation coupling benthic silica to oxygen fluxes, and showing a clear negative correlation between Si and O₂ fluxes. Dissolution of biogenic silica mediated by aerobic microbial activity has been inferred at 24 sites along the African and South American continental margins. Based on the assumption that these findings hold essentially for the entire Southern Atlantic Ocean, we applied the silica to oxygen flux ratio to a basin-wide grid of diffusive oxygen uptake extracted from the literature. Assuming that the silica release across the sediment-water interface equals the particulate flux of biogenic opal to the seafloor, we estimated minimum opal rain rates. We combined these calculations with published relationships between aerobic organic carbon mineralization and dissolution rates of calcite above the hydrographical lysocline, thereby assessing the calcite rain rate and particulate organic carbon flux to the seafloor. The addition of the buried fraction completes our budget of biogenic particulate rain fluxes. The combination of such empirical equations provides a powerful and convenient tool which greatly facilitates future investigations of biogenic particle fluxes to the seafloor.     

A benthic Si mass balance on the Congo margin: Origin of the 4000 m DSi anomaly and implications for the transfer of Si from land to ocean

To elucidate the origin of the silicic acid (DSi) anomaly observed along the 4000 isobath on the Congo margin, we have established a benthic Si mass balance and performed direct measurements of biogenic silica (bSiO₂) dissolution in the deep waters and in the sediments. Results strongly suggest that the anomaly originates from the sediments; the intensity of DSi recycling is consistent with the degradation of organic matter, as observed from Si:O₂ ratios in the benthic fluxes compared to that ratio observed in the anomalies. Strong imbalances, observed in both the Si and C mass balances, suggest that the biogenic matter that degrades and dissolves in these sediments near 4000 m does not come from pelagic sedimentation. It is probably not coming also from the deep channel, because observations were similar in the deep channel vicinity (site D) and further south, far from its influence (site C). The composition of the sediments, with an Si:C ratio close to that observed on continental shelves, suggests that this matter is coming from downslope transport. A first estimate of the magnitude of this flux at global scale, close to 12 T mol Si yr⁻¹, suggests that it may be an important path for transferring Si from land to ocean.     

黄河下游营养盐浓度、入海通量月变化及“人造洪峰”的影响

于2009年至2011年在黄河下游采集溶解及颗粒态营养盐样品,分析了黄河下游各形态营养盐的浓度变化及营养盐入海通量,结果表明各形态氮的浓度多呈丰水期低、枯水期高,溶解无机氮是溶解态氮的主要存在形式;受黄河高悬浮颗粒物含量的影响,磷以颗粒态占绝对优势,而溶解态磷以溶解无机磷为主要存在形态;生物硅的含量平均约占硅酸盐与生物硅之和的20％,硅的浓度丰水期高于枯水期.颗粒态磷与生物硅的含量与悬浮颗粒物含量呈正相关.营养盐的组成具有高氮磷比、高硅磷比、低硅氮比的特点.近年来黄河下游溶解无机氮浓度显著升高而溶解无机磷变化不大,硅酸盐的浓度有所下降.黄河下游水沙通量、营养盐入海通量有明显的季节变化,丰水期占全年总入海通量的42％～84％.调水调沙期间,各营养盐的浓度和组成均有明显变化,氮的浓度、DIN/PO4-P下降,磷与硅的浓度、SiO3-Si/DIN、SiO3-Si/PO4-P升高,颗粒态营养盐的比例明显增加.短期内大量水沙及营养盐入海通量对黄河口及渤海生态系统产生重要影响.     

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.     

夏季珠江口及近岸海域悬浮颗粒物生物硅分析

2017年6月在珠江口及近岸海域61个站位采集了悬浮颗粒物生物硅(BSi,biogenic silica)和叶绿素a(Chl a)。利用RAGUENEAU et al(2005)提出的碱提取法测定了悬浮颗粒物生物硅,探讨不同环境条件下BSi浓度以及碱性提取液中岩源硅(LSi,lithogenic silica)的干扰程度。结果显示,Chl a质量浓度范围为0.06~8.64 μg·L^-1,悬浮颗粒物BSi浓度从低于检测限到14.3 μmol·L^-1,LSi浓度范围为0.00~9.56 μmol·L^-1;LSi/(LSi+BSi)比均值为0.38 mol·mol^-1。提取液中测得的Si/Al比均值为2.42 mol·mol^-1,与RAGUENEAU et al(2005)报道值接近。研究区域内的表层BSi反映了硅藻的生物量,与Chl a存在显著线性相关。LSi对BSi测量的干扰程度存在明显的空间差异,总体上近岸BSi和LSi高,LSi/(LSi+BSi)比低;外海BSi和LSi低,LSi/(LSi+BSi)比高;河口内BSi低,LSi高,LSi/(LSi+BSi)比高;上升流区BSi和LSi高,LSi/(LSi+BSi)比高;底层较表层具有更高的LSi和LSi/(LSi+BSi)比。最后,对常用的几种碱提取法在应用时存在的问题作了探讨。     

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.     

Problems with biogenic silica measurement in marginal seas

Surface sediment samples from the Bohai, Yellow Sea, and the Pacific were used to assess biogenic silica (BSi) content and to study uncertainties in BSi measurements. The contents of BSi in the Bohai and Yellow Sea are all less than 1%. The dissolution of BSi in sediments from the Bohai and Yellow Sea is very important to maintain high levels of silicate in the water column. The non-biogenic silica from clay minerals has an obvious effect on BSi of sediment samples in the Bohai and Yellow Sea with low BSi and high clay minerals. The solid to solution ratio was found to have a great influence on BSi measurement, which can induce uncertainties up to 75%. The effect of loss by sorption and centrifugation is negligible. Interlaboratory comparison of techniques for BSi measurement by the wet alkaline extraction technique of Mortlock and Froelich [Deep-Sea Res. 36 (1989) 1415-1426] with clay correction was suggested to give no significant differences. However, differences in sediment compositions and reagent to sample ratio may limit the application of the wet alkaline extraction method.     

渤海颗粒有机碳与生物硅的分布及来源

海洋碳、硅循环及其相关联的生物地球化学过程是全球环境变化的热点问题,也是海洋科学关心的重要领域。利用2012年5月和11月份对渤海海域的调查结果,对该海域颗粒有机碳和生物硅的分布特征及来源进行了讨论。主要结论为:渤海有机碳以溶解有机碳为主,具有春季高和秋季低的特征;由陆地来源和海洋自生的有机碳组成,且以海洋来源的有机碳为主。渤海生物硅分布具有明显的梯度特征,河流输入同样对其含量的影响较为突出。渤海沉积物中生物硅含量较高,明显高于中国东部陆架海。渤海表层沉积物中生物硅主要是海源的,依次由浮游藻类、植硅体和海绵骨针所构成,其中浮游藻类占62.9%,陆源植硅体占31.1%。渤海沉积物发现了来自于草本植物的植硅体,这说明了陆地产生的植硅体对海洋生物硅的贡献。     

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.     

Sedimentary Responses to an Abrupt Change of Biogenic Silica Flux by a Sediment Model for Long Timescale Simulations

A one-dimensional sediment model was developed by introducing the CIP-CSL2 scheme in the advection term. This enables us to represent fluctuations of the vertical profiles of 100 cm depth, which needs integrations on a longer timescale than 10 kyr, because this scheme avoids smoothing of the vertical profiles due to no numerical diffusion, instead of a commonly used forward scheme. Using the models with 10 and 100 cm depths (hereafter, called the 10 cm model and the 100 cm model, respectively) to predict the contents of biogenic silica and clay, we have evaluated the sedimentary responses to an abrupt change in the biogenic silica rain flux. When the rain flux of biogenic silica abruptly decreases, the 10 cm model underestimates the dissolution flux of biogenic silica compared with the 100 cm model. This is because only clay is supplied from the bottom boundary associated with excess dissolution and also because dissolution of biogenic silica below 10 cm depth is neglected by the 10 cm model. When we consider dissolved matter inputs from sediments to marine biogiochemical cycles, simulations by the 100 cm model would lead to more realistic responses in sediments.     

长江口邻近海域沉积物和间隙水中硅的研究

以2011年6月和8月在长江口邻近海域采集的沉积物和间隙水样品为研究对象,讨论了沉积物中生物硅（BSi）和间隙水中溶解硅（DSi）的分布情况和影响因素,并初步探讨了生物硅的循环和保存。结果表明,表层沉积物中BSi的含量较低,且均小于1%。柱状沉积物中BSi的含量范围为0.34%~0.52%。C3、D1站位柱状沉积物中BSi的记录主要是由早期成岩过程控制,33#站位的分布特征主要是由水动力等变化控制。沉积物间隙水中DSi的浓度范围为101.6~263.9 μmol/L,低于纯BSi的溶解度;间隙水的pH值越大,沉积物的含水率越低,还原性越强,间隙水中DSi的含量越高。3站位生物硅的埋藏效率均较高,表明长江口邻近海域是潜在的硅的汇。沉积通量的分布与沉积速率和埋藏效率的分布一致,均有近岸高于远海的趋势。     

Dissolution of silica accompanied by oxygen consumption in the bottom layer of Japan’s central Seto Inland Sea in summer

Distribution of silicic acid (Si(OH)₄) in bottom water was investigated in the central Seto Inland Sea under stratified conditions in summer. Water samples were collected at 10 stations on April 24 and 25 and July 7 and 8, 2012. In July, stratification progressed, and a cold water mass (dome) of <20 °C appeared. In response to the cold dome, low oxygen content was observed in the bottom layer of the eastern part of Hiuchi-Nada. In this water mass site, apparent oxygen utilization values calculated from dissolved oxygen (DO) concentrations increased, coinciding with increase of Si(OH)₄ concentrations from April to July. This suggests that increase of Si(OH)₄ [dissolution of biogenic silica (diatom frustules)] was accompanied by DO consumption due to degradation of organic matter such as plankton soft tissue. These findings suggest that a bacterial degradation of the organic matrix that covers diatom frustules could accelerate the dissolution of biogenic silica in bottom water under stratified conditions.     

Contribution of Sponge Spicules to the Composition of Biogenic Silica in the Ligurian Sea

Abstract. The importance of sponge spicules in the turnover of biogenic silica (BSi) in the detritic bottoms of the Eastern Ligurian Riviera was evaluated by studying sediment cores and the detrital matter collected by a trap over a one year period.
This study made evident that: i) Sponge spicules represent the main component of the BSi both in the sediments and in the trapped matter; ii) A correlation exists between the sponge biomass present on the overhanging cliff and the amount of sponge spicules found in the sediment below; iii) Inside the sediments, a superficial layer (10 cm deep) characterized by intensive silica dissolution processes can be observed; and iv) The amount of spicules collected using the trap is not constant throughout the year, but shows a characteristic trend with low values in spring and summer and high values in autumn and winter.     

东海、黄海近代沉积物中生物硅含量的分布及其反演潜力

以东海、黄海2006年4月、10月航次采集的沉积物样品为研究对象,结合沉积物中生物硅(BSi)含量的空间分布特征进而讨论BSi的反演潜力。研究发现,调查海域表层沉积物中BSi的含量介于0.018%~2.516%,平均值为0.726%,柱状沉积物中BSi的含量波动较小,相对稳定。整体而言BSi含量与相应年代的浮游植物现存量变化的趋势相近。经一元线性分析发现BSi含量与硅藻生物量的相关性显著。为进一步证实由BSi含量反演古生产力的有效性和可信度,采用Tun-nicliffe等的方法探讨了BSi含量在沉积物中的稳定性,调查结果表明,近150 a来BSi几乎没有降解,能够稳定地保存于沉积物中。综上可以初步判断沉积物中BSi含量可作为古生产力指标来反演古生产力的潜力。     

The annual production of biogenic silica in the Antarctic Ocean

The total annual production of biogenic silica (BSi) of the Antarctic Ocean is estimated at about 50 tera (T = 10¹²) mol Si. This flux is calculated using available direct measurements of integrated silicic acid uptake rates, indirect estimates from field distribution of orthosilicic acid in austral winter compared with that in austral summer and/or after conversion of ^l4C primary production using appropriate Si/C mole ratios measured for the four Antarctic subsystems: the Polar Front Zone, the Permanently Open Ocean Zone, the Seasonal Ice Zone, and the continental shelves and coastal zones. We show that most of the total production of BSi occurs in the surface layers of the Permanently Open Ocean Zone and in the Seasonal Ice Zone, the contribution of the coastal areas being less relevant. Our results fit well with the previously described distributions of the net accumulation rates of opal in Antarctic abyssal and coastal sediments. The mean ratio of net opal accumulation at the sea-bed to the net production of BSi in the surface layer of the Antarctic Ocean is about 15%.     

Phosphorus regeneration vs. burial in sediments of the Arabian Sea

Solid-phase phosphorus (P) speciation and benthic phosphate fluxes have been determined in Arabian Sea sediments. Benthic phosphate fluxes are highest in the continental slope sediments, underlying bottom waters with low oxygen concentrations. Organic matter degradation and phosphate desorption from iron oxides do not produce sufficient phosphate to explain these high phosphate fluxes. The potentially high deposition of P associated with fish debris (P_fish) in the Arabian Sea, and a good correlation between benthic phosphate fluxes and P_fish accumulation rates suggest that benthic phosphate fluxes in these sediments are to a large extent governed by dissolution of biogenic apatite. Factors controlling dissolution and preservation of fish debris, therefore, may play an important role in the burial and regeneration of P in continental margin sediments. A sharp decrease of the reactive P accumulation rate with increasing water depth, in combination with rather constant primary productivity rates throughout the northern Arabian Sea, indicates that P burial in continental margin sediments located within the OMZ is more efficient than in deep basin sediments. The effectiveness of P burial is to a large extent regulated by P regeneration occurring in the water column and redeposition processes. Sedimentary phosphorus burial efficiencies, thus, should be interpreted with caution in terms of the environmental conditions.     

A nitrate and silicate budget in the equatorial Pacific Ocean: a coupled physical–biological model study

A coupled physical–biological model was developed to simulate the low-silicate, high-nitrate, and low-chlorophyll (LSHNLC) conditions in the equatorial Pacific Ocean and used to compute a detailed budget in the Wyrtki box (5°N–5°S, 180–90°W) for the major sources and cycling of nitrogen and silicon in the equatorial Pacific. With the incorporation of biogenic silicon dissolution, NH₄ regeneration from organic nitrogen and nitrification of ammonia in the model, we show that silicon recycling in the upper ocean is less efficient than nitrogen. As the major source of nutrients to the equatorial Pacific, the Equatorial Undercurrent provides slightly less Si(OH)₄ than NO₃ to the upwelling zone, which is defined as 2.5°N–2.5°S. As a result, the equatorial upwelling supplies less Si(OH)₄ than NO₃ into the euphotic zone in the Wyrtki box, having a Si/N supply ratio of about 0.85 (2.5 vs. 2.96 mmolm⁻² day⁻¹). More Si(OH)₄ than NO₃ is taken up with a Si/N ratio of 1.17 (2.72 vs. 2.33 mmolm⁻² day⁻¹) within the euphotic zone. The difference between upwelling supply and biological uptake is balanced by nutrient regeneration and horizontal advection. Excluding regeneration, the net silicate and nitrate uptakes are nearly equal (1.76 vs. 1.84 mmolm⁻² day⁻¹). However, biogenic silica export production is slightly higher than organic nitrogen (1.74 vs. 1.59 mmolm⁻² day⁻¹) following a 1.1 Si/N ratio. In the central equatorial Pacific, low silicate concentrations limit diatom growth; therefore non-diatom new production accounts for most of the new production. Higher silicate supply in the east maintains elevated diatom growth rates and new production associated with diatoms dominate upwelling zone. In contrast, the new production associated with small phytoplankton is nearly constant or decreases eastward along the equator. The total new production has a higher rate in the east than in the west, following the pattern of surface silicate. This suggests that silicate regulates the diatom production, total new production, and thereby carbon cycle in this area. The modeled mean primary production is 48.4 mmolCm⁻² day⁻¹, representing the lower end of direct field measurements, while new production is 15.0 mmolCm⁻² day⁻¹, which compares well with previous estimates.     

东海典型港湾表层沉积物中主要生源要素分布及污染状况分析

分别于2016年11月、2018年4月、2016年7月、2014年11月采集了福建东山湾、福宁湾、浙江象山港以及江苏大丰港52个表层沉积物样品,分析了表层沉积物中总有机碳(TOC)、总氮(TN)、总磷(TP)、生物硅(BSi)、有机质(OM)及含水率(MC)的含量。TOC、TN、TP、BSi、OM及MC含量分别为:0.35%～1.52%,0.08%～0.32%,0.020%～0.074%,0.28%～1.89%,1.86%～9.53%,19.55%～52.55%。福宁湾TN和BSi含量较高,东山湾TP含量较高,而象山港TOC含量较高。从元素之间的摩尔比来看,本研究中各港湾沉积物中的TOC均主要来自浮游植物等水生生物,而TOC的分解和再生速率应远高于BSi的溶解速率。根据主要生源要素污染评价标准,东山湾海域污染较严重,TN、TP、TOC均达到Ⅱ级污染标准。福宁湾及象山港TN、TOC均为Ⅱ级污染。而大丰湾海域总体污染较轻,只有TN超过Ⅱ级标准。