生物硅的测定及其生物地球化学意义

生物硅（BSi）指用化学方法测定的沉积物中的无定形硅含量。生物硅的含量与水体中初级生产息息相关。硅藻、放射虫、海绵骨针和硅鞭毛虫产生的生物硅是地球化学和古海洋学研究的重要参数。重点讨论了目前生物硅测定方法中的化学提取法，评述了提取过程中存在的一些问题，并对BSi测定的生物地球化学意义进行了讨论。     

Geochemical processes controlling silica concentrations in groundwaters of the Salado River drainage basin, Argentina

Chemical analyses of dissolved silica in the shallow groundwater of the lower part of the Salado River drainage basin indicate that silica values averaged 60 ppm. The groundwaters are oversaturated in relation to quartz, Na-plagioclase, K-feldspar, and the weathering of quartz and aluminosilicates appear to have little control on silica concentrations in solution. Groundwater is undersaturated with respect to amorphous silica present in the loessic sediments, and these sediments are specially important in the control of the groundwater composition. The sources of amorphous silica are volcanic glass shards and biogenic silica derived from plant (silicophytoliths, diatom frustules) or animal remains (sponge spicules) also present in the Pampean loess. Silicophytoliths and diatoms have also been reported in A soil horizon samples. The dissolution of amorphous silica most likely controls the high dissolved silica concentrations in groundwater.     

Phosphorus Speciation and Sedimentary Fluxes in Hypersaline Sediments of the Guerrero Negro Salt Evaporation Area,Baja California Sur,Mexico

In the past several decades, the techniques used to discern the different sedimentary fractions of P have been refined. This has allowed for a better understanding of P burial of the different P fractions and diagenetic reactions and, ultimately, the constraining of P residence time in the oceans. P sequential extraction was performed on eight sediment cores (between 16 and 24 cm deep) collected along a salinity gradient from the Ojo de Liebre Lagoon and the salt evaporation saltern of Guerrero Negro, Baja California Sur, Mexico in order to determine, under purely diagenetic conditions (in the absence of anthropogenic activities and biogenic sediment reworking), the fractionation and flux of P to the sediments. The majority of P was found in the authigenic fraction (37 ± 5.4% to 53 ± 8.9%), with P associated to organic matter comprising the overall smallest percentage (0.25 ± 0.43% to 21 ± 6.0%) relative to total P. The average flux of total P to the sediments for all the sites was found to be (451 ± 127) × 10⁻⁴ mol m⁻² year⁻¹, up to several orders of magnitude greater than those found in other studies. It is concluded that P is most likely transformed from P associated to organic matter to the authigenic mineral phase and that P was retained in the sediments in its mineral form rather than in reactive forms. This particular study area has the ability to retain large quantities of P in the sediments.     

Dissolution kinetics of biogenic silica from the water column to the sediments

Stirred flow-through experiments were conducted for the first time with planktonic biogenic silica (BSi). We investigated the dissolution kinetics of uncleaned and chemically cleaned BSi collected in ocean surface water, sediment traps, and sediments from the Norwegian Sea, the Southern Ocean, and the Arabian Sea. The solubility at 2°C is rather constant (1000 to 1200 μM). The dissolution rates are, however, highly variable, declining with water depth, and phytoplankton reactivity is two to three orders of magnitude higher than pure siliceous oozes. The reactivity decrease correlates well with an increase in the integrated peak intensity ratios of Si-O-Si/Si-OH measured by Fourier transform infrared (FTIR) spectroscopy. The removal of organic or inorganic coatings enhance the reactivity by at least an order of magnitude. Atomic Al/Si ratios of 0.03 to 0.08 in sedimentary diatom frustules decrease significantly to 0.02 as a result of removal of inorganic coatings and detritals present. Near equilibrium, the dissolution rates exhibit a linear dependence on the degree of undersaturation. At higher degrees of undersaturation—that is, at low concentrations of dissolved silica—the dissolution rates of uncleaned samples define a nonlinear trend.The nonlinear kinetics imply that the dissolution of natural BSi is strongly accelerated in silica-depleted surface waters. The FTIR results suggest that internal condensation reactions reduce the amount of surface reaction sites and are partly responsible for the reactivity decrease with depth. The high content of Al in sedimentary BSi is likely caused by precipitation of dissolved silica with Al dissolved from minerals in sediment. Nonbiogenic silica as coatings or detritals are partly responsible for the solubility and reactivity decrease of BSi in sediments. One order of magnitude different rate constants measured in Norwegian Sea and Southern Ocean sediment trap material support the so-called opal paradox—that is, high BSi accumulation rates in sediments in spite of low BSi production rates in surface waters of the Southern Ocean.     

Composition of rare earth elements in settling particles collected in the highly productive North Pacific Ocean and Bering Sea: Implications for siliceous-matter dissolution kinetics and formation of two REE-enriched phases

Settling particles were sampled monthly for 1 year using an automated time-series sediment trap positioned at similar depths at two sites of high diatomaceous productivity in the North Pacific Ocean and Bering Sea. The particles were analyzed for rare earth elements (REEs) by inductively coupled plasma mass spectrometry (ICP-MS) with and without chemical treatment of the bulk samples to isolate siliceous fractions. The REE composition of the bulk samples is explained largely by the contribution of two distinct components: (i) carbonate with a higher REE concentration, a negative Ce anomaly and lighter REE (LREE) enrichment; (ii) opal with a lower REE concentration, a weaker negative Ce anomaly and heavier REE (HREE) enrichment.The siliceous fractions of settling particles are characterized by high Si/Al ratios (30-190), reflecting high diatom productivity at the studied sites. The La/Al ratio of the siliceous fraction is close to that of the upper crust, but the Lu/Al and Lu/La ratios are significantly higher than those of the upper crust or airborne particles, indicating the presence of excess HREEs in the siliceous fraction. Diatoms are believed to be important carriers of HREEs.The Ce anomaly, Eu anomaly, slope of the REE pattern, and ΣREE of the siliceous fraction vary exponentially with decreasing total mass flux. They can be well-reproduced according to the differential dissolution kinetics of elements in the order of Ce < lighter REEs (LREEs) < Eu = heavier REEs (HREEs) < Si from settling particles, where the dissolution rate is critically reduced through particle aggregation. This order is consistent with the vertical distribution of dissolved REEs and Si in oceans. The differential dissolution kinetics leads to HREE enrichment of the original diatoms and REE enrichment of dissolved diatoms. The Lu/Si ratio of the siliceous fraction of settling particles recovered from some of the highest diatom fluxes is identical to that of the two elements dissolved in deep seawater, providing further evidence for the dissolution of siliceous matter in deep water.     

Advection and removal of Pb and stable Pb isotopes in the oceans: a general circulation model study

Natural Pb-isotope variability in the oceans encodes information about the sources of continental material to the oceans, about ocean circulation, and about Pb removal. In order to use this information, we must understand the natural cycle of Pb in the oceans, which is overprinted by large anthropogenic input. In this study we use ²¹⁰Pb, which has not been significantly anthropogenically perturbed, to investigate oceanic Pb. GEOSECS ²²⁶Ra and model-derived atmospheric fluxes of ²¹⁰Pb are used to input ²¹⁰Pb into an ocean general circulation model. Irreversible scavenging of this ²¹⁰Pb onto settling biogenic particles and at the seafloor are tuned so that the model replicates the observed pattern of ²¹⁰Pb in the oceans. The best-fit model run provides a map of the variability of residence time for Pb. The global average residence time of Pb in this model is 48 yr, but there is over an order of magnitude variation between areas of high and low productivity. This is expected to enhance provinciality of Pb isotope ratios in the oceans. Because stable Pb isotopes are expected to behave in seawater in a similar fashion to ²¹⁰Pb, the pattern of removal of ²¹⁰Pb derived by the model can be used to investigate the behavior of stable Pb isotopes. We use a simplified input of Pb consisting of five point sources representing major rivers and a disseminated dust input. Although this simplified input scheme does not allow precise reconstruction of Pb concentration and isotopes in the oceans, it allows us to answer some first-order questions about the behavior of Pb as an ocean tracer. With a total Pb input of 6.3 × 10⁷ mol/yr (Chow T. J. and Patterson C. C., “The occurrence and significance of Pb isotopes in pelagic sediments,” Geochim. Cosmochim. Acta26, 263-308, 1962), the model predicts natural seawater Pb concentrations averaging 2.2 pmol/kg. Even in the absence of anthropogenic input, the model ocean exhibits a near-surface maximum in Pb concentration. And the model suggests natural Pb concentrations in the Northern Hemisphere an order of magnitude higher than in the Southern Hemisphere. A point source of Pb is suggested to dominate the seawater Pb inventory close to the source but is reduced to typically less than 10% of the inventory by the time that Pb is advected out of the originating ocean. This length scale of advection for Pb isotope signals confirms their potential as tracers of ocean circulation. Assuming an 8% dissolution of dust, their input to the open ocean are seen to be a significant portion of Pb inventory throughout the oceans and make up >50% of the Pb inventory in the model’s Southern Ocean. Finally, a preliminary investigation of the response of Pb-isotope distributions to changes in boundary conditions between glacial and interglacial times illustrates that significant variation in the Pb isotopes are expected in some regions, even for reasonably small changes in climate conditions.     

Marine biogeochemistries of Be and Al: A study based on cosmogenic10Be, Be and Al in marine calcite, aragonite, and opal

The geochemical behaviors of Be and Al in ocean waters have been successfully studied in recent years using natural, cosmogenic, radioactive¹⁰Be and²⁶Al as tracers. The present day dissolved concentrations and distribution of the stable and radioactive isotopes of Be and Al in ocean waters have revealed their short residence times and appreciable effects of exchange fluxes at the coastal and ocean-sediment interfaces. It follows that concentrations of these particle-active elements must have varied in the past with temporal changes in climate, biological productivity and aeolian flux of continental detritus to the oceans. We therefore investigated the feasibility of extending the measurements of Be and Al isotope concentrations in marine systems to the 10³–10⁶ y BP time scale. We report here the discovery of significant amounts of intrinsic Be and Al in marine foraminiferal calcite and coral aragonite, and of Al in opal (radiolarians) and aragonite (coral), which makes it possible to determine¹⁰Be/Be and²⁶Al/Al in oceans in the past. We also report measured¹⁰Be/⁹Be in foraminiferal calcite in Pacific Ocean cores, which reveal that the concentrations and ratios of the stable and cosmogenic isotopes of Be and Al have varied significantly in the past 30 ky. The implications of these results are discussed.     

The occurrence and significance of biogenic opal in the regolith

Biogenic opal produced by vascular plants, diatoms, and siliceous sponges have been found in soils and terrestrial sediments of all continents except Antarctica since the middle of the 19th century. The opal particles range in size from fine silt to fine sand. Almost all soils contain detectable opal up to levels of 2–3%, and a significant number contain values in excess of 5%. Even higher values have been found from soils and sediments of all continents in a wide range of soil types. The most important factor is poor soil drainage and seasonal to permanent water logging. This encourages the proliferation of silica producing organisms. Such conditions have been found in the soils and aquatic sediments of the monsoonal tropics, tropical rain forests, temperate forests, tropical savanna, tropical islands, semi-arid grasslands and savanna, and temperate woodland and grassland. The presence of a volcanic substrate also appears favourable in some cases, but is not necessary. Biogenic opal preferentially collects in the A horizon of soils and, to a lesser extent, in the B horizon. This preferential distribution facilitates identification of palaeosols in stacked soil sequences. Biogenic opal is also a component of windblown dust, even in arid environments. Biogenic opal is significant to regolith processes in a number of ways. Firstly, as in the case in marine environments, it is likely to be important in silica cycling and storage because of its greater lability compared to quartz. Secondly, dissolution and reprecipitation of opal A as opal CT or micro-quartz may play a role in cementation and silicification of regolith to form silica hardpans and silcrete. Thirdly, the organisms that form biogenic opal can have considerable palaeoenvironmental significance and be valuable in reconstructing regolith evolution. Finally, some forms of biogenic silica, in particular sponge spicules, can present a health hazard. Their high abundance in some soils and sediments needs to be considered when assessing the health implications of airborne dust.     

海洋Nd同位素演化及古洋流循环示踪研究

海洋Nd同位素演化已经成为示踪陆源风化输入和洋流循环改变的最重要的手段之一,得到了越来越多的应用,并取得了许多重要的成果。海水的Nd同位素组成主要受陆源输入物质控制,热液输入几乎可以忽略。由于Nd在海洋中的停留时间(约500～1000a)略小于海水的平均混合时间(约1500a),且各洋盆有不同的Nd同位素风化输入,因此现代各大洋海水具有不同的Nd同位素组成。在陆源输入稳定的情况下,可以利用海水的Nd同位素组成和演化来示踪水体的混合或洋流循环的改变。目前主要依靠对海洋中水成铁锰结壳、海洋钙质有孔虫壳体、磷酸质鱼骨头或鱼牙齿化石以及沉积物中铁锰氧化物组分等的研究来恢复和反演古海水的Nd同位素组成和演化。4种分析材料各有其优缺点。其中,通过对水成铁锰结壳的Nd同位素分析,基本建立了各大洋新生代以来的主要洋流的Nd同位素组成的长尺度演化。通过有孔虫壳体、鱼化石碎片和沉积物中Fe-Mn氧化物组分可以进行高时间分辨率的古海水Nd同位素演化示踪。利用海水Nd同位素演化可以示踪古洋流通道的开启或闭合,以及获得水体交换的直接信息,为研究构造运动与气候变化之间的关系提供指示。同时,将海水Nd同位素演化与气候变化的指标结合起来,可以用于示踪各种气候条件下洋流循环的改变,将洋流循环的改变与气候变化联系起来,研究两者之间的成因关系。对表层水体的Nd同位素组成的研究则可以示踪不同气候条件下大陆陆源风化输入的改变。     

Silica Gel as a Surrogate for Biogenic Silica in Batch Dissolution Experiments at pH 9.2: Further Testing of the Shrinking Object Model and a Novel Approach to the Dissolution of a Population of Particles

Recently, the increase in dissolved concentration in the batch dissolution of various salts or sucrose has been successfully modelled with three equations, one a cubic in time. However, from three separate earlier investigations with ocean sediments and phytoplankton frustules, there is residual suspicion that biogenic silica does not follow this behaviour. This paper shows that the Shrinking Object Model applies to the dissolution of sieved silica gel particles, as well as to a sample of unsieved, freeze-dried frustules of Odentella sp. Silica gel, being readily available in quantities that can be sieved, is a useful surrogate for biogenic silica in allowing problems of experimental design to be overcome. The dissolutions covered three possible analytic integrations that arise from the model: an exponential for approach to saturation with excess solid silica; the approach to near saturation with either a slight excess or deficiency of silica; dissolution at high under-saturation. Good agreement was found between experimental results and mathematical modelling. The paper provides template calculations by which future raw results can be parameterized. Nevertheless, the reasons for non-linear kinetics reported in earlier work have not been identified, and so controversy over non-linear dissolution kinetics is enhanced. Stirring regime was found to be important with silica gel dissolution, and so biogenic silica dissolution is therefore likely to be ‘transport limited’ at low stirring rate. Accordingly, all archived and future data should be scrutinized for stirring effects before being applied to the oceanic environment. A rigorous test for determining whether a substance’s dissolution deviates from the model is recommended as a preliminary to any future dissolutions, whether in batch or with the chemo-stat. A fixed amount of frustule sample is added to a series of buffered mixtures containing increasing background silicic acid concentrations. Absence of any problem is marked by a linear plot between the increase in silicic concentration accruing over a fixed reaction period and that of the background silicic acid. A novel mathematical proof is provided to justify the test’s use. The reasons for the earlier deviations from expected behaviour of, for example, oceanic sediments, are discussed. Lastly, the paper provides a novel approach to the dissolution of a population of particles of mixed sizes which will probably find ready future application in oceanography.     

REE geochemistry of fine-grained sediments from major rivers around the Yellow Sea

To investigate the distribution pattern and controlling factors of rare earth elements (REEs) in riverine sediments, river mouth sediments were collected at five geographically different rivers around the Yellow Sea. Two- (1 M HCl leached and residual fractions) and five-step sequential extraction schemes (the SEDEX method) were applied to size-separated sediments < 20 µm. For the total REE composition, patterns normalized relative to the upper continental crust (UCC) showed light REE (LREE) and middle (MREE) enrichments in the Korean river sediments and MREE enrichment in the Chinese river sediments. LREE and MREE enrichments in 1 M HCl leached fractions played a major role in the distribution patterns of the total compositions in all the river sediments. About half of LREE enrichment in Korean river sediments was explained by the residual fraction. Comparison of the REE composition with major elements (Al, Fe, Ca, P) in each fraction of the SEDEX scheme revealed that MREE enrichment could be explained by reactive iron minerals, including goethite and hematite, although REE/Fe ratios showed different trends among the rivers due to different major REE-host iron minerals. After extracting reactive irons, authigenic phosphate, and carbonate, the sequential 1 M HCl fraction indicated that LREE enrichment in Korean river sediments may have originated from clay minerals, such as chlorite. These observations suggest that LREE enrichment may be a good tracer, while MREE enrichment should be used cautiously considering diagenetic modification, when using the REE composition to identify the sources of terrestrial materials.     

Influence of hydrodynamic regime on the mineral composition of deep-sea sediments

The composition of sand-silt and pelite fractions of deep-sea sediments deposited under different hydrodynamic conditions was studied. Assemblages of clastic, clayey, biogenic, and authigenic minerals formed under the influence of surface and bottom currents were traced. It is shown that biogenic opal, fine-dispersed celestobarite, and authigenic protosyngenetic ferromanganese micronodules, which are composed of only manganese phases, represent indicators of cyclonic gyres characterized by enhanced bioproductivity. Collophane (bone detritus), phillipsite, palagonite, and large celestobarite crystals prevail in mineral assemblages below the anticyclonic gyres, whereas ore micronodules are depleted in manganese. Surface and bottom currents control the distribution of clastic (terrigenous edaphogenic, terrestrial-volcanogenic) and clay minerals, as well as biogenic opal in the form of Ethmodiscus frustules in sediments. Edaphogenic mineral assemblages represent the reliable indicators of bottom currents.     

Diagenesis of diatomite from the Kolubara Coal Basin,Baroševac,Serbia

Diatomite associated with the Kolubara Coal Basin was studied to better understand early stage silica diagenesis of shallow water deposits. The Kolubara Basin consists of Neogene siliciclastic rocks, diatomite, marlstone and rare carbonates. Palaeozoic metamorphic and Mesozoic sedimentary and igneous basement rocks are transgressively overlain by Upper Miocene sandstone, siltstone, shale and mudstone. This Upper Miocene section is transgressively overlain by the Pontian section, which contains diatomite and coal beds. White and grey diatomite forms beds 0.7-2.2 m thick that are continuous over an area of about 2 km². Siliceous rocks vary in composition from diatomite (81-89 per cent SiO₂) to diatom-bearing shale (58-60 per cent SiO₂). Siliceous deposits are laminated in places, with the laminae defined by variations in clay minerals, organic matter and diatoms. Diatomite shows only incipient diagenesis characterized by the fragmentation of diatom frustules, the minor to moderate corrosion of frustules and the formation of minor amounts of opal-A' (X-ray amorphous inorganic opal) cement. The low degree of diagenesis results from the young age of the deposits, low burial temperatures and possibly also from the presence of abundant organic matter and the dissolution of kaolinite. The presence of only weak diagenesis is also reflected by the characteristically poor consolidation of the rocks and low rank of the associated coal.     

The behavior of arsenic and antimony at Pezinok mining site,southwestern part of the Slovak Republic

Arsenic and antimony contamination is found at the Pezinok mining site in the southwest of the Slovak Republic. Investigation of this site included sampling and analysis of water, mineralogical analyses, sequential extraction, in addition to flow and geochemical modeling. The highest dissolved arsenic concentrations correspond to mine tailings (up to 90,000 μg/L) and the arsenic is present predominately as As(V). The primary source of the arsenic is the dissolution of arsenopyrite. Concentration of antimony reaches 7,500 μg/L and its primary source is the dissolution of stibnite. Pore water in mine tailings is well-buffered by the dissolution of carbonates (pH values between 6.6 and 7.0) and arsenopyrite grains are surrounded by reaction rims composed of ferric iron minerals. Based on sequential extraction results, most solid phase arsenic is in the reducible fraction (i.e. ferric oxyhydroxides), sulfidic fraction, and residual fraction. Distribution of antimony in the solid phase is similar, but contents are lower. The principal attenuation mechanism for As(V) is adsorption to ferric oxide and hydroxides, but the adsorption seems to be limited by the competition with Sb(V) produced by the oxidation of stibnite for adsorption sites. Water in mine tailings is at equilibrium with gypsum and calcite, but far from equilibrium with any arsenic and antimony minerals. The concentrations of arsenic and antimony in the surrounding aquifer are much lower, with maximum values of 215 and 426 μg/L, respectively. Arsenic and antimony are transported by ground water flow towards the Blatina Creek, but their loading from ground water to the creek is much lower compared with the input from the mine adits. In the Blatina Creek, arsenic and antimony are attenuated by dilution and by adsorption on ferric iron minerals in stream sediments with resulting respective concentrations of 93 and 45 μg/L at the site boundary south of mine tailing ponds.     

Analysis of natural diatom communities reveals novel insights into the diversity of long chain polyamine (LCPA) structures involved in silica precipitation

The intricately nanopatterned siliceous frustules of diatoms are formed under the control of template organic molecules, some of which are tightly incorporated into the frustule during formation. Long chain polyamines (LCPAs) attract dissolved silicic acid species, enhance silica precipitation and play a role in frustule nanopattern formation. LCPAs thus play a central biogeochemical role, linking the cycling of organic matter with the cycling of silicic acid in the photic zone of the upper ocean. Their distribution and molecular diversity in the environment are as yet unknown. We used high performance liquid chromatography electrospray ionization–mass spectrometry (HPLC–ESI–MSⁿ) to investigate the distribution and molecular diversity of aliphatic LCPAs extracted from the frustules of diatoms in mixed marine plankton communities collected within the euphotic zone of the northeastern Pacific coast, Bering Sea, and Puget Sound estuary. An astonishing variety of over 100 natural LCPAS with complex distribution patterns was found in each sample. Structural variation included degree of methylation, overall chain length, presence of secondary amine functionalities, incorporation of quaternary ammonium and occurrence of sulfonated derivatives. Putrescine-based LCPAs with various degrees of methylation and N-methyl propylamine repeat units were ubiquitous. Although some LCPA species overlapped between samples, there were regional differences in composition and structural characteristics. The structural variety of LCPAs employed by diatoms to produce their nanopatterned silicified exoskeleton could inform biomimetic studies of silica precipitation.     

Diagenetic Ge-Si fractionation in continental margin environments: further evidence for a nonopal Ge sink

We present data for dissolved germanic and silicic acids from several settings: sediment pore water profiles collected from the Peru-Chile continental margin, fluxes measured with in situ benthic flux chambers and shipboard whole-core incubations, and water column profiles from the California continental margin. Collectively, these data show that Ge and Si are fractionated in these continental margin sedimentary environments during diagenesis with ∼50% of the Ge released by opal dissolution being sequestered within the sediments. The areal extent of this diagenetic fractionation covers station depths from ∼100 m to >1000 m. Sediments from these sites typically have high pore water Fe²⁺ present in the upper ∼2 cm. At sites with low Fe²⁺ concentrations in the upper pore waters, the Ge:Si benthic regeneration ratio indicates little or no fractionation during diatom dissolution. Consistent with the sedimentary fractionation, water column dissolved Ge:Si ratios along the continental margin are on average lower (0.66 μmol/mol) than the global average ratio (0.72 μmol/mol, Mortlock and Froelich, 1996). This lower “average” ratio is driven by two distinct ΔGe:ΔSi data trends having similar slopes but different intercepts. Data from the upper ∼150 m has a Ge:Si slope of 0.74 ± 0.04 μmol/mol (2σ) and an intercept of 0.5 ± 0.4; whereas below ∼550 m the slope is 0.70 ± 0.06 μmol/mol, but the intercept is −5.0 ± 8.0. Assuming that the sediments sampled here are representative of all reducing marine environments, an assumption requiring further testing, our calculations indicate that sequestration of Ge into a nonopal phase throughout the global ocean in the depth range 0.2-1 km is sufficient to balance the Ge budget. Thus, we tentatively conclude that sequestering of Ge in reducing continental margin sediments is the “missing” Ge sink.     

Varve-counting by the annual pattern of diatoms accumulated in the sediment of Big Watab Lake, Minnesota, AD 1837–1990

The goal of this study was to develop a method for extracting quantitative annual records of diatoms and other microfossils from sediments that are resistant to existing varve-counting methods because of their variable, complex, or indistinct laminations. Very linely laminated organic sediments from a deep diamictic lake in central Minnesota, USA were collected by freeze-core, dehydrated by solvent exchange, embedded with epoxy, and petrographically thin-sectioned. Diatom frustules and pollen grains were counted in contiguous 400 pm microscope fields-of-view and used to construct a sediment chronology. The concentration of diatoms in the sediment was cyclic and lowest in sediment deposited during summer. The concentration of pollen in the sediment was also cyclic and sediment deposited during the summer contained the highest concentrations of pollen and the highest percentages of ragweed ( Ambrosia spp.) pollen. The sediment chronology that was produced accurately records the onset of regional (c. 1850) and watershed ( c . 1880) development, a historic tornadic storm complex (1894), and individual drought years (1932, 1934 & 1935) within the 1930's drought.     

A critical analysis of processes governing the nutrient profiles in the ocean

We have theoretically considered the problem of interpretation of nutrient profiles in the upper ocean (100–2000m). We compare the experimental depth profiles of nonconservative tracers, both stable and radioactive, with solutions of one-dimensional steady state transport equations of increasing complexity including situations not encountered in the real oceans. Apart from gaining insight into the nutrient transport processes, this analysis is useful in offering a way to obtain operational estimates of depth dependent/independent eddy diffusivity and dissolution fluxes in the ocean. These parameters are essential for estimating new production, total production and burial of carbon in the sediments.     

红枫湖、百花湖沉积物中磷的存在形态研究

湖泊沉积物中磷存在形态,是理解湖泊系统中磷的生物地球化学循环的重要方面,对研究湖泊富营养化等环境问题具有重要意义。本次工作中,采用连续提取化学分析技术,对红枫－百花尖沉积物中磷的存在形态及其剖面变化进行了研究,磷的存在形态包括：吸附态磷（Ｌｏｓｅｌｙ ｓｏｒｂｅｄＰ）、铁结合态磷（Ｆｅ－ｂｏｕｎｄ Ｐ）、钙结合态磷（Ｃａ－ｂｏｕｎｄ Ｐ）、矿物晶格中结合力强的残留态磷（Ｄｅｔｒｉａｌ－Ｐ）和有机态     

Determining Biogenic Silica in Marine Samples by Tracking Silicate and Aluminium Concentrations in Alkaline Leaching Solutions

This study introduces an alkaline leaching technique for the simultaneous analysis of biogenic silica and aluminium in sediments. Measuring aluminium facilitates the discrimination between silica from the biogenic (BSiO₂) and the non-biogenic fraction, because it originates almost solely from the lithogenic phase. The method was tested using fine-grained silicagel, standard clay minerals, artificial sediments, and natural samples ranging from fresh diatoms to aged sediment from different depositional settings. To determine the BSiO₂ content, four different models each describing the dissolution curves, but of increasing complexity, were applied and for each different type of sample the optimum model was selected on the basis of F-test statistics. For mixtures of silicagel and clay minerals, the contribution of Si from the dissolution of clay was negligible compared to Si originating from silicagel. For natural samples with high clay content, complex dissolution curves were observed and single-phase first order dissolution was the exception. This deviation from `ideal' behavior could only be recognized because of high-resolution sampling, especially in the first 20 minutes of the experiment. For most of the samples, the distinction between the biogenic silica fraction and the silica originating from dissolution of clays could be made on the basis of the Si/Al ratios and reactivity constants of the dissolving phases calculated with the models. Clay minerals typically dissolve slowly at a Si/Al ratio close to 1–2, depending on the type of clay mineral. In contrast, biogenic silica displays a wide range of reactivities and Si/Al ratios. Fresh biogenic silica from the water column usually has a high reactivity and a low Al content. Aged biogenic silica from the sediments has a lower reactivity, but Si/Al ratios as low as 5 were found. The method as described here therefore presents an accurate method to analyze biogenic silica in marine sediments with a relatively high clay mineral content.