湖北宜昌地区寒武系—下奥陶统的碳氧同位素记录

对宜昌地区寒武系和下奥陶统的碳酸盐碳、氧同位素进行测定,所得δ18O大 于－10‰且与δ13C不相关,表明研究区碳酸盐样品基本上保存了碳、氧同位素的初 始比值。δ18O在白云岩样品中呈现正漂移而在非白云岩样品中呈现负漂移,认为δ 18O反映海水古盐度变化,即δ18O随着古盐度升高而增大;δ13 C在缺氧沉积物中呈现负漂移,但负漂移的δ13C却不限于缺氧沉积物,推测δ13 C可能反映古海洋的初级生产力,即δ13C随着初级生产力的提高而降低。研究还指 出,由于Z值与δ13C密切正相关（相关系数为0.99）,综合运用δ18O和δ 13C的经典盐度公式不适用于研究区古盐度环境的重建。     

Preservation of organic matter and alteration of its carbon and nitrogen isotope composition during simulated and in situ early sedimentary diagenesis

The carbon and nitrogen isotope composition of organic matter has been widely used to trace biogeochemical processes in marine and lacustrine environments. In order to reconstruct past environmental changes from sedimentary organic matter, it is crucial to consider potential alteration of the primary isotopic signal by bacterial degradation in the water column and during early diagenesis in the sediments.In a series of oxic and anoxic incubation experiments, we examined the fate of organic matter and the alteration of its carbon and nitrogen isotopic composition during microbial degradation. The decomposition rates determined with a double-exponential decay model show that the more reactive fraction of organic matter degrades at similar rates under oxic and anoxic conditions. However, under oxic conditions the proportion of organic matter resistent to degradation is much lower than under anoxic conditions. Within three months of incubation the δ¹³C of bulk organic matter decreased by 1.6‰ with respect to the initial value. The depletion can be attributed to the selective preservation of ¹³C-depleted organic compounds. During anoxic decay, the δ¹⁵N values continuously decreased to about 3‰ below the initial value. The decrease probably results from bacterial growth adding ¹⁵N-depleted biomass to the residual material. In the oxic experiment, δ¹⁵N values increased by more then 3‰ before decreasing to a value indistinguishable from the initial isotopic composition. The dissimilarity between oxic and anoxic conditions may be attributed to differences in the type, timing and degree of microbial activity and preferential degradation. In agreement with the anoxic incubation experiments, sediments from eutrophic Lake Lugano are, on average, depleted in ¹³C (−1.5‰) and ¹⁵N (−1.2‰) with respect to sinking particulate organic matter collected during a long-term sediment trap study.     

Polyphosphates as a source of enhanced P fluxes in marine sediments overlain by anoxic waters: Evidence from <Superscript>31</Superscript>P NMR

Sedimentary phosphorus (P) composition was investigated in Effingham Inlet, a fjord located on the west coast of Vancouver Island in Barkley Sound. Solid-state ³¹P nuclear magnetic resonance (NMR) spectroscopy was applied to demineralized sediment samples from sites overlain by oxic and anoxic bottom waters. The two sites were similar in terms of key diagenetic parameters, including the mass accumulation rate, integrated sulfate reduction rate, and bulk sediment organic carbon content. In contrast, P benthic fluxes were much higher at the anoxic site. ³¹P NMR results show that P esters and phosphonates are the major organic P species present at the surface and at depth in sediments at both sites. Polyphosphates were only found in the surface sediment of the site overlain by oxic waters. The varying stability of polyphosphates in microorganisms under different redox conditions may, in part, explain their distribution as well as differences in P flux between the two sites.     

Early diagenesis of organic matter in recent Black Sea sediments: characterization and source assessment

The organic matter in 9 recent (not more than 250 years old) and ‘organic-rich’ sediments from the southern Black Sea shelf and upper slope have been characterized semi-quantitatively by Pyrolysis/Gas Chromatography/Mass Spectrometry (PY/GC/MS) and¹³C Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CPMAS-NMR) spectrometry. The organic matter of 7 of the studied sediments was found to be ligno-carbohydrate with a proteinaceous component, one sediment appeared to contain oxidized coal dust and one contained thiophenes in association with pyrite. The ligno component is derived from grasses and soft wood lignin. Material entrapped in an anoxic environment contained the highest proportions of carbohydrate and protein. All the samples had suffered diagenesis as is generally shown by the attachment of carboxyl groups and the removal of methoxyl groups. The evidence suggests that diagenesis occurred whilst the particles traversed the oxic water column.     

Dissolved organic carbon and volatile fatty acids in marine sediment pore waters

The results of a study of the contribution of microbial metabolic products to total dissolved organic carbon (DOC) levels in coastal sediments are presented. The data indicate that acidic volatile compounds make up a substantial fraction of pore water DOC's in both oxic and anoxic pore waters of coastal marine sediments. Formic, acetic and butyric acids are the principal volatile species identified at levels exceeding 10 μM. Acid concentrations are up to five times higher in anoxic pore waters than in oxic waters. Volatile organic acids show promise as indicators of diagenetic processes in marine sediments and of the ecological succession of microorganisms, in particular.     

Effects of oxygen and redox oscillation on degradation of cell-associated lipids in surficial marine sediments

Degradation patterns of sedimentary algal lipids were tracked with time under variable redox treatments designed to mimic conditions in organic-rich, bioturbated deposits. Uniformly ¹³C-labeled algae were mixed with Long Island Sound surface muddy sediments and exposed to different redox regimes, including continuously oxic and anoxic, and oscillated oxic: anoxic conditions. Concentrations of several ¹³C-labeled algal fatty acids (16:1, 16:0 and 18:1), phytol and an alkene were measured serially. Results showed a large difference (∼10×) in first-order degradation rate constants of cell-associated lipids between continuously oxic and anoxic conditions. Exposure to oxic conditions increased the degradation of cell-associated lipids, and degradation rate constants were positive functions (linear or nonlinear) of the fraction of time sediments were oxic. Production of two new ¹³C-labeled compounds (iso-15:0 fatty acid and hexadecanol) further indicated that redox conditions and oxic: anoxic oscillations strongly affect microbial degradation of algal lipids and net synthesis of bacterial biomass. Production of ¹³C-labeled iso-15:0 fatty acid (a bacterial biomarker) was inversely proportional to the fraction of time sediments were oxic, rapidly decreasing after 10 days of incubation under oxic and frequently oscillated conditions. Turnover of bacterial biomass was faster under continuously or occasionally oxic conditions than under continuously anoxic conditions. ¹³C-labeled hexadecanol, an intermediate degradation product, accumulated under anoxic conditions but not under oxic or periodically oxic conditions. The frequency of oxic: anoxic oscillation clearly alters both the rate and pathways of lipid degradation in surficial sediments. Terminal degradation efficiency and lipid products from degradation of algal material depend on specific patterns of redox fluctuations.     

Iron reduction in the sediments of a hydrocarbon-contaminated aquifer

Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.     

沉积物成岩蚀变过程中的Mn、Cd和Mo元素活动特征:以ODP 1148站钻孔沉积物记录为例

通过对南海北部的ODP 1148站岩芯600 mcd以上(约30 Ma以来)的沉积物中自生富集Mn、Cd和Mo等过渡金属元素的含量变化的研究,并结合相关的化学组成结果,探讨了岩芯内部氧化-还原条件的变化以及相关元素的活动特征,反演了相应沉积时期的环境演变.结果显示,岩芯387 mcd以上,自生Mn富集明显,代表氧化的环境;387～485 mcd之间,自生Cd含量明显富集,Mn含量显著降低,代表少氧的环境;485 mcd以下,Mn和Cd含量极低,自生Mo明显富集,代表缺氧的环境.随氧化-还原条件的变化,Mo存在明显的向下迁移并在缺氧界面的缺氧一方达到最大值的趋势,而Cd在少氧环境形成的固相态则可能在缺氧环境下不稳定,溶解态的Cd有向上迁移的趋势,并且在少氧/缺氧界面的少氧一方富集.这些过渡金属元素记录的氧化-还原条件的变化,反映出ODP 1148站所在海区的沉积环境变化:早期有较丰富的陆源输入,表层海水生产力较高,随着南海不断扩张以及全球海平面上升,该海区表层海水生产力逐渐降低.     

Anthropogenic impacts recorded in the sediments of Lunawa, a small tropical estuary, Sri Lanka

The Lunawa Estuary has been selected as a model for studying the long-term diagnoss of tropical estuarine pollution and its impact on ecosystems. Surface and short-core sediments from the Lunawa Estuary were collected, and analyzed for total organic carbon (TOC), nitrogen, sulfur and hydrocarbon contents, hydrogen index and other related sediment properties. Water quality and surface sediment data indicate that the Lunawa Estuary is presently an anoxic water body. The upper part of the sediment cores, characterized by very high TOC values of more than 10%, and absence of bioturbation along with strong laminations indicate anoxic water since 1970 AD, determined by ¹⁴ C dating. However, before 1970 AD, lower TOC content and presence of bioturbation and homogenous sediments with animal traces suggest the presence of oxic bottom water and thus a much better physicochemical condition. The lower part of the cores may also suggest the influence of gradual global warming. Regular laminations in the upper portions of the cores probably resulted from monsoon pulses with material preserved under anoxic condition.     

Geochemical-focusing of manganese in lake sediments — An indicator of deep-water oxygen conditions

The lateral distributions of Mn concentrations in the sediments of two Swiss lakes under varying oxygen conditions have been determined. The comparison of Mn distribution patterns with oxygen in the deep-water provides strong evidence for a geochemical-focusing effect, which is driven by the redox cycle of manganese. Conditions essential for this process to occur are anoxic sediments in contact with oxic deep-water. Average sedimentary manganese concentrations determined for different water-depth ranges are directly proportional to the area of shallower sediments. This result indicates that geochemical-focusing of manganese in lake sediments is a promising proxy indicator for the reconstruction of oxygen conditions during deposition.     

沉积物-水界面的生物地球化学作用

沉积物－水界面是天然水体在物理、化学和生物特征等方面差异性最显著和负责水体和沉积物之间物质输送和交换的重要边界环境。对沉积物－水界面生物地球化学的定义、研究方法和它在水体微量物质循环中所起的作用、物质迁移方式、典型氧化还原敏感性元素转化反应（Ｃ、Ｏ、Ｎ）、界面扩散通量和表面扩散亚层的意义和估算等进行了讨论。      

Pyritization of iron and trace metals in anoxic fjord sediments (Nordåsvannet fjord,western Norway)

The accumulation and storage of trace metals in coastal sediments is an environmental concern. It is, therefore, important to understand better how these metals are bound or released under different redox conditions. This study of Fe and trace metal fixation under continuously anoxic conditions in the bottom sediments and the lower water column of the Nordåsvannet fjord in western Norway contributes further to such understanding. It allows investigation of both an end member redox state and one important mechanism of Fe and trace metal accumulation in sediments, the pyritization of Fe and trace metals. Pyrite formation occurs both in the water column and in the sediments of the Nordåsvannet fjord and favours the fixing of Fe and trace metals in the bottom sediments of the fjord. Thus, these sediments act as a continuous sink for Fe and trace metals. The DOP, and the degrees of trace metal pyritization for Mo, Ni and Cr correlate with organic matter content. While it is generally thought that Fe is the factor limiting pyrite formation in anoxic environments, this study found that degrees of pyritization of Fe (DOP) are clearly below 100%, and the availability of metabolizable organic matter is limiting pyrite formation. This is an important finding, because it indicates that increased supply of organic and mineral matter by higher runoff from land would further enhance the fixation of these metals in the fjord sediments, as would higher organic matter availability from increased productivity due to higher nutrient supply. The metals stored in the bottom sediments could be released into the biogeochemical cycle if redox conditions were to change from anoxic to suboxic or oxic. The fjord would then become a source rather than a sink for these metals.     

沉积物－水界面的生物地球化学作用

沉积物－水界面是天然水体在物理、化学和生物特征等方面差异性最显著和负责水体和沉积物之间物质输送和交换的重要边界环境。对沉积物－水界面生物地球化学的定义、研究方法和它在水体微量物质循环中所起的作用、物质迁移方式、典型氧化还原敏感性元素转化反应（Ｃ、Ｏ、Ｎ）、界面扩散通量和表面扩散亚层的意义和估算等进行了讨论。     

Partitioning of heavy metals in surface Black Sea sediments

Bulk heavy metal (Fe, Mn, Co, Cr, Ni, Cu, Zn and Pb) distributions and their chemical partitioning, together with TOC and carbonate data, were studied in oxic to anoxic surface sediments (0–2 cm) obtained at 18 stations throughout the Black Sea. TOC and carbonate contents, and available hydrographic data, indicate biogenic organic matter produced in shallower waters is transported and buried in the deeper waters of the Black Sea. Bulk metal concentrations measured in the sediments can be related to their geochemical cycles and the geology of the surrounding Black Sea region. Somewhat high Cr and Ni contents in the sediments are interpreted to reflect, in part, the weathering of basic-ultrabasic rocks on the Turkish mainland. Maximum carbonate-free levels of Mn (4347 ppm), Ni (355 ppm) and Co (64 ppm) obtained for sediment from the shallow-water station (102 m) probably result from redox cycling at the socalled ‘Mn pump zone’ where scavenging-precipitation processes of Mn prevail. Chemical partitioning of the heavy metals revealed that Cu, Cr and Fe seem to be significantly bound to the detrital phases whereas carbonate phases tend to hold considerable amounts of Mn and Pb. The sequential extraction procedures used in this study also show that the metals Fe, Co, Ni, Cu, Zn and Pb associated with the ‘oxidizable phases’ are in far greater concentrations than the occurrences of these metals with detrital and carbonate phases. These results are in good agreement with the recent studies on suspended matter and thermodynamic calculations which have revealed that organic compounds and sulfides are the major metal carriers in the anoxic Black Sea basin, whereas Fe-Mn oxyhydroxides can also be important phases of other metals, especially at oxic sites. This study shows that, if used with a suitable combination of the various sequential extraction techniques, metal partitioning can provide important information on the varying geological sources and modes of occurrence and distribution of heavy metals in sediments, as well as, on the physical and chemical conditions prevailing in an anoxic marine environment.     

A study of oxic/anoxic effects on degradation of sterols at the simulated sediment–water interface of coastal sediments

Laboratory incubation experiments were conducted to determine the behavior of sterols at the sediment–water interface in oxic and anoxic sediments. Both plankton and 4- -cholesterol were used as tracers. Cholesterol was rapidly degraded at the sediment–water interface: 55% of -cholesterol was lost from sediments under anoxic conditions and 78% under oxic conditions over three and one-half months. About 3% of initially-added free radiolabel was incorporated into a bound pool that was released only by saponification of solvent-extracted sediment. Less than 1% of initially-added radiolabel remained in pore waters after three and one-half months. Rate constants for degradation of cholesterol in oxic and anoxic surficial sediments were estimated by tracking variations in radioactivity and sterol concentration as a function of time. We discuss our results in terms of factors affecting sterol degradation in coastal marine sediments, including molecular structure, sediment matrix effect, and redox conditions.     

Rare earth elements in pore waters of marine sediments

The rare earth elements (REEs) were measured in pore waters of the upper ∼25 cm of sediment from one site off Peru and three sites on the California margin. The pore water REE concentrations are higher than sea water and show systematic down core variations in both concentration and normalized pattern. From these analyses and from comparison to other chemical species measured (dissolved Fe, Mn, Ba, oxygen, nitrate, phosphate), it is suggested that pore water REEs can be grouped into three categories: those that are from an Fe-source, those that are from a POC-source, and cerium oxide. REEs from the Fe-source appear where anoxia is reached; they have a distinctive “middle-REE (MREE) enriched” pattern. The concentrations in this source are so elevated that they dominate REE trends in the Fe-oxide reduction zone. The net result of flux from the POC-source is relative enrichment of heavy-REEs (HREEs) over light-REEs (LREEs), reflecting remineralizing POC and complexation with DOC. A common “linear” REE pattern, seen in both oxic and anoxic sediments, is associated with this POC-source, as well as a “HREE enriched” pattern that is seen in surficial sediments at the Peru site. Overall, the pore water results indicate that Mn-oxides are not an important carrier of REEs in the oceans.A REE biogeochemical model is presented which attempts to reconcile REE behavior in the water and sediment columns of the oceans. The model proposes that POC, Fe-oxide and Ce-oxide sources can explain the REE concentration profiles and relative abundance patterns in environments ranging from oxic sea water to anoxic pore water. The model is also consistent with our observation that the “Ce-anomaly” of pore water does not exceed unity under any redox condition.     

Organic matter and lipids in sediments of Lake Bled (NW Slovenia): Source and effect of anoxic and oxic depositional regimes

Sources of organic matter (OM) and lipids were assessed and factors affecting OM degradation were studied for two sediment cores representing distinct depositional regimes (i.e., the oscillating oxic to suboxic/anoxic western basin and oxic Zaka Bay) for eutrophic Lake Bled, NW Slovenia. Lower surface organic carbon (OC) concentration was determined in the western basin than for Zaka Bay sediments (5.1 vs. 5.4 wt% dry sediment, respectively), but one order of magnitude greater total lipid concentration was observed in the former. Also, there was a higher proportion of autochthonous OM in the western basin (77% vs. 66%) on the basis of atomic C/N ratios. Lipid-based origin assessment suggested a similar contribution of autochthonous OM in the western basin (64–77%), but a lower one in Zaka Bay (<50%). It seems that redox potential is the main factor governing OM degradation in the western basin. In contrast, a contribution from more refractory terrestrial OM, via the surface inflow in Zaka Bay, and higher sedimentation rates may surpass redox effects in Zaka Bay. Overall, oxygen may play a more important role in degradation of the more labile pool (i.e., lipids) than bulk OM. Higher apparent degradation rate constants (k′) for lipids also suggested a greater lability than for OC, while respective k′ values were higher in the oxic than anoxic environment.     

冲绳海槽中段西陆坡下缘天然气水合物存在的可能性分析

海洋中的天然气水合物主要发育在有机质供应充分、沉积速率快、热流值较高、水深大于300m的大陆斜坡和活动边缘的增生楔发育区;沉积物类型主要以泥质砂岩、砂质泥岩和浊积岩为主。似海底反射层(BSR)和极性反转是识别天然气水合物层的关键标志。冲绳海槽中段西陆坡下缘水深大于1000m;沉积物类型主要为粉砂质泥和泥质粉砂,在部分层位见浊积层。与东海陆架相比,西陆坡下缘的有机质含量、沉积速率的热流值都较高,其范围分别为0.75%～1.25%、10～40cm/ka和70～437mw/m2;单道地震剖面具有明显的似海底反射层(BSR)和极性反转特征,因此,推断冲绳海槽中段西陆坡下缘可能存在天然气水合物层。     

Nature and reactions of dissolved organic matter in the interstitial waters of marine sediments

Two organic rich sediments, an oxic muddy sand and a silty mud containing sulphate reducing and methane producing metabolic zones, were sampled from Loch Duich, a fjord type estuary in the N.W. coast of Scotland. Dissolved organic carbon (DOC), as measured by dry combustion and UV absorption, remained constant (8.3–15.8 mg C/l) with depth in the oxic pore waters at a concentration at least twice that of the overlying seawater. DOC in the anoxic pore waters increased linearly with depth from 13.6 at the surface to 55.9–70.5 mg C/l at 80cm. Most of the DOC was present in the high molecular weight (HMW) fraction as separated by ultrafiltration; the low molecular weight (LMW) fraction remained constant (10.0 mg C/l) in both oxic and anoxic pore waters. Spectroscopic data showed the ‘humic’ fraction of the HMW dissolved organic matter was mainly fulvic acid, a small proportion (approx 1%) of humic acid, and a third fraction, possibly melanoidins, which increased relative to fulvic acid with depth. These data confirm the pathway of humification (NissenBaum et al, 1971; nissenbaum and Kaplan, 1972) where HMW organic matter accumulates in pore waters as condensation products of LMW organic substances.     

The sedimentary expression of oceanic anoxic event 1b in the North Atlantic

The Aptian/Albian oceanic anoxic event 1b contains the record of several perturbations in the global carbon cycle and multiple black shale levels, particularly in the Western Tethys. The local lithological expression of an oceanic anoxic event depends on palaeogeographical and depositional setting as well as on regional palaeoclimate. Marine sediments at a particular location may therefore be more or less organic‐rich (or not at all) and they may consist of different lithologies. In most studies, however, much of the lithological variability associated with oceanic anoxic events is left unaccounted for and, thus, the exact processes leading to the enrichment of organic matter in these marine sediments and their subsequent preservation in the geological record are unknown. This study focuses on the local sedimentary processes behind the deposition of organic‐rich sediments at Deep Sea Drilling Project Site 545 and Ocean Drilling Program Sites 1049 and 1276 in the North Atlantic during oceanic anoxic event 1b. Although specifically dealing with the sediments deposited during this particular event at these localities, it is expected that the same processes were responsible for determining the exact sedimentary products at localities in similar settings, as well as during other similar events in the Mesozoic. Here, it is shown that the deposition of organic‐rich sediments during oceanic anoxic event 1b was a consequence of the enhanced productivity favoured by upwelling and by riverine nutrient input, or aeolian fertilization of the euphotic zone depending on geographical location. Slope instability processes resulted in the transfer of part of these organic‐rich sediments from the shelf to deep sea depocentres as mud‐laden organic‐rich turbidites, especially in the northern North Atlantic. The so‐called ‘black shales’ are much more varied than their name implies. The end product of sedimentation during an oceanic anoxic event at a particular location is commonly the result of several equifinal processes acting on a local scale rather than the direct result of basinal or even global mechanisms.