Controls on the age of vascular plant biomarkers in Black Sea sediments

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated.Here we show compound-specific radiocarbon (¹⁴C) ages of terrigenous biomarkers and bulk ¹⁴C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. ¹⁴C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C₂₉₊₃₁ alkanes and n-C₂₈₊₃₀ fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C₂₉₊₃₁ alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C₂₉₊₃₁ alkanes show contributions from petrogenic sources, n-C₂₈₊₃₀ fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C₂₈ and n-C₃₀ fatty acids appear clearly much less influenced by autochthonous sources than n-C₂₄ and n-C₂₆ fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.     

苏北潮滩湿地不同生态带碳、氮、磷分布特征*

通过对比苏北潮滩湿地不同生态带的表层以及柱状沉积物中总有机碳、总氮、总磷和有机磷含量,并结合不同植被不同植株部位中碳、氮、磷的含量变化,分析了潮滩沉积物中碳、氮、磷的垂向和水平分布特征与规律,探讨了不同生态带以及潮滩植被对碳、氮、磷等生源要素的富集作用。对比分析结果表明:苏北潮滩湿地各生态带对不同的测量指标有着不同的富集作用,互花米草滩的总有机碳、总氮和有机磷含量要远大于其他几个生态带,光滩沉积物中总磷的含量最高; 粒度效应是控制互花米草前缘地带以及互花米草滩沉积物中有机碳和氮分布的一个重要因素,盐蒿和芦苇滩中有机碳和氮的分布更多的是受粒度之外的其他因素影响; 不同生态带表层沉积物中的C/N比值分布,大致可反映其有机物来源的差异,而不同生态带中柱状沉积物中的C/N比值相对接近,很难根据C/N比值大小来对不同生态带中的有机物来源进行判断,这可能是埋藏在柱状沉积物中的有机物更多的受到了早期成岩作用造成的。植被对潮滩湿地中碳、氮、磷的分布有着重要影响,3种物质在互花米草、盐蒿和芦苇中的含量差别不是很大,因此潮滩植被对沉积物中上述3种物质的贡献差别主要是由不同植被的生物量和其所处环境的沉积动力差异造成的。     

Organic carbon isotope ratios (δ13C) of Arctic Amerasian Continental shelf sediments

Organic matter origins are inferred from carbon isotope ratios ('¹³C) in recent continental shelf sediments and major rivers from 465 locations from the north Bering-Chukchi-East Siberian-Beaufort Sea, Arctic Amerasia. Generally, there is a cross-shelf increase in '¹³C, which is due to progressive increased contribution seaward of marine-derived organic carbon to surface sediments. This conclusion is supported by the correlations between sediment '¹³C, OC/N, and '¹⁵N. The sources of total organic carbon (TOC) to the Amerasian margin sediments are primarily from marine water-column phytoplankton and terrigenous C₃ plants constituted of tundra taiga and angiosperms. In contrast to more temperate regions, the source of TOC from terrigenous C₄ and CAM plants to the study area is probably insignificant because these plants do not exist in the northern high latitudes. The input of carbon to the northern Alaskan shelf sediments from nearshore kelp community (Laminaria solidungula) is generally insignificant as indicated by the absence of high sediment '¹³C values (-16.5 to -13.6‰) which are typical of the macrophytes. Our study suggests that the isotopic composition of sediment TOC has potential application in reconstructing temporal changes in delivery and accumulation of organic matter resulting from glacial-interglacial changes in sea level and environments. Furthermore, recycling and advection of the extensive deposits of terrestrially derived organic matter from land, or the wide Amerasian margin, could be a mechanism for elevating total CO₂ and pCO₂ in the Arctic Basin halocline.     

Elucidation of different forms of organic carbon in marine sediments from the Atlantic coast of Spain using thermal analysis coupled to isotope ratio and quadrupole mass spectrometry

Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO₂) and m/z 18 (H₂O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ¹³C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.     

Vertical Profiles of Major Organic Geochemical Constituents and Extracellular Enzymatic Activities in Sandy Sediments of Aransas and Copano Bays, TX

Vertical distribution patterns of organic geochemical constituents and the enzymes aminopeptidase and β-glucosidase provide insights about the nature and reactivity of sediment organic matter in the sandy sediments of two shallow “South Texas” estuaries. Sediment total organic carbon (TOC) δ¹³C values indicated that the organic matter (OM) was derived more from a mixture of seagrass and phytoplankton than from terrigenous OM. Down-core amounts of TOC and total nitrogen (TN) were <0.2% of dry weight, respectively. Enzyme activities were highest near surface and ranged from 25 to 1 μM/h for aminopeptidase as compared to 5 to 0.2 μM/h for glucosidase. In Aransas Bay, aminopeptidase activity correlated with sediment TN content (r _s = 0.30) and β-glucosidase with TOC content (r _s = 0.27). In Copano Bay, aminopeptidase correlated with TOC, TN, and carbohydrate content (r _s = 0.89, 0.90, and 0.83, respectively). Variations of glucosidase activity also related positively to TOC, TN, and total carbohydrate content (r _s = 0.68, 0.77, and 0.48, respectively). Overall, enzyme activities in these low OM, sandy sediments resembled those for other benthic marine environments.     

Composition of organic matter in subducted and unsubducted sediments off the Nicoya peninsula, Costa Rica (ODP Leg 170, Sites 1039 and 1040)

Investigation of sediment samples from Sites 1039 and 1040 (ODP Leg 170) drilled off the Nicoya peninsula (Costa Rica) by organic geochemical and organic petrological methods has revealed that subduction has only little influence on the composition of the sedimentary organic matter. Organic carbon contents reached 1.5% in the Pleistocene samples but Miocene and Pliocene sediments had an average organic carbon content of less than 0.5%. Organic carbon/sulfur ratios are generally below 2.8, reflecting an intense sulfate reduction in the uppermost sediments which was enhanced by sulfate supply both from sea water and deeper strata. Microscopical examinations indicate that the organic matter is mainly derived from marine sources. A small amount of terrigenous organic matter is, however, present as well according to n-alkane and fatty acid distributions. The alkenone unsaturation index U₃₇^k′ shows only a slight decrease during the Miocene and Pliocene, and stronger variations in the Pleistocene, probably indicating more stable sea surface temperatures during the Miocene and Pliocene. Variations in the Pleistocene can possibly be related to glacial/interglacial changes.     

Organic matter enrichment in the first member of the Xiagou formation of the lower Cretaceous in the Jiuquan Basin,China

The sources and enrichment of organic matter in a sediment core in the first member of the Xiagou Formation (K₁g¹) from the Chang 2-2 borehole of the Jiuquan Basin, NW China, have been examined using Rock–Eval, maceral, carbon isotopes and biomarker data. This data indicates that highly variable organic matter sources and preservation conditions in response to climate change. TOC content, HI, and δ¹³C value were strongly correlated with the abundance of gammacerane, woody organic matter content, steranes/hopanes ratio, and C₂₉ sterane content. This correlation demonstrates the importance that the control of the salinity of the depositional environment and organic matter sources can have upon the enrichment, type, and carbon isotopic composition of organic matter. In the Jiuquan Basin’s relatively high temperature and arid climate, high salinity lakes with high primary productivity of algae, planktons, and bacteria, and good organic matter preservation conditions (anoxic bottom water) resulted in the enrichment of isotopically-light algae-bacterial organic matter. In the Jiuquan Basin’s regions with a relatively low temperature and wet climate, fresh lakes with low primary productivity of algae, planktons, and bacteria received significant terrigenous high plants input, resulting in the deposition of a low abundance of isotopically heavier terrestrial organic matter.     

Sediment Organic Carbon in Todos Santos Bay, Baja California, Mexico

Sediment grain size and organic carbon (OC) data collected over the past 50 years, together with δ¹³C values of OC in recently collected samples, were analyzed to improve understanding of sediment OC distribution and abundance in Todos Santos Bay. Sediments in the submarine canyon at the mouth of the bay and in quiet-water locations along the shore are fine grained, high in OC, and have generally low δ¹³C values; sediments in high-energy environments are low in OC and have high δ¹³C values. A bivariate isotopic mixing model indicates that none of the sediments contain >50% terrigenous OC (average ~30%), and that the terrigenous OC content of the sediments is a small proportion of the OC content of local soils. Sediment OC composition is apparently controlled by energy-related sorting and deposition, oxidation of much of the original terrigenous OC, and replacement of some terrigenous OC by marine OC.     

泰国湾百年来有机碳埋藏记录及环境响应

受热带季风气候和周边陆源输入的影响,低纬泰国湾海—陆相互作用强烈,是研究海洋沉积有机碳与陆源输入、海洋初级生产力等气候环境变化响应关系的理想区域.通过对泰国湾泥质区T43柱样中总有机碳(TOC)、总氮(TN)、稳定碳同位素(δ13C)以及粒度等指标的分析,基于210Pb建立的高分辨年代地层框架,重建了该区百年来有机碳的...     

Sources of fine-sized organic matter in North Atlantic Heinrich Layers: δC and δN tracers

Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ¹³C, δ¹⁵N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ¹³C = −22.8 ± 1.0‰; δ¹⁵N = 5.5 ± 0.6‰). δ¹³C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ¹⁵N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL₁, HL₂, HL₄, and HL₅), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ¹³C (down to −28‰) and δ¹⁵N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL₁, HL₂, and with lesser extent for HL₄. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL₅, only the δ¹³C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL₅ to HL₁ (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ¹³C, increasing OC/TN and decreasing δ¹⁵N values.     

Organofacies and paleoenvironment of the Oligocene Maikop series of Angeharan (eastern Azerbaijan)

The Maikop Formation, deposited in eastern Azerbaijan during Oligocene and Early Miocene times, contains prolific source rocks with primarily Type II organic matter. Paleontological analyses of dinoflagellate cysts revealed a Lower to Upper Oligocene age for the investigated succession near Angeharan. A major contribution of aquatic organisms (diatoms, green algae, dinoflagellates, chrysophyte algae) and minor inputs from macrophytes and land plants to organic matter accumulation is indicated by n-alkane distribution patterns, composition of steroids and δ¹³C of hydrocarbon biomarkers. Microbial communities included heterotrophic bacteria, cyanobacteria, chemoautotrophic bacteria, as well as green sulfur bacteria. Higher inputs of terrigenous organic matter occurred during deposition of the Upper Oligocene units of the Maikop Formation from Angeharan mountains. The terpenoid hydrocarbon composition argues for angiosperm dominated vegetation in the Shamakhy–Gobustan area.High primary bioproductivity resulted in a stratified water column and the accumulation of organic matter rich sediments in the Lower Oligocene units of the Maikop Formation. Organic carbon accumulation during this period occurred in a permanently (salinity-) stratified, mesohaline environment with free H₂S in the water column. This is indicated by low pristane/phytane ratios of all sediments (varying from 0.37–0.69), lower methylated-(trimethyltridecyl)chromans ratio in the lower units and their higher contents of aryl isoprenoids and highly branched isoprenoid thiophenes. Subsequently, the depositional environment changed to normal marine conditions with oxygen deficient bottom water. The retreat of the chemocline towards the sediment–water interface and enhanced oxic respiration of OM during deposition of the Upper Oligocene Maikop sediments is proposed.Parallel depth trends in δ¹³C of total OM, n-alkanes, isoprenoids and steranes argue for changes in the regional carbon cycle, associated with the changing environmental conditions. Increased remineralisation of OM in a more oxygenated water column is suggested to result in low TOC and hydrocarbon contents, as well as ¹⁵N enriched total nitrogen of the Upper Oligocene units.     

Temporal trends of aliphatic and polyaromatic hydrocarbons in the Bohai Sea, China: Evidence from the sedimentary record

This work reports the historical trends and sources of aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) in two ²¹⁰Pb dated sediment cores extracted from the central mud areas of Bohai Sea (Bohai). The TOC/TN ratio of the bulk organic matter (OM) and the composition of the n-alkanes suggest that the sedimentary organic matter was of mixed marine and terrigenous sources. The coarser sediment grain size and decreasing C/N ratios since ∼1976 could be attributed to the relocation of the Yellow River mouth causing a decreased influence of Yellow River derived sediments and associated OM into the central Bohai. The concentration of total 16 PAHs in the two cores ranged from 34.2-202 ng/g (mean, 91.5) for BC1, and from 53.3-186 ng/g (mean, 103) for BC2, with a high abundance of 2-3 ring PAHs. Perylene in the two cores mainly originated from terrigenous sources via riverine discharge and thus could be potentially related to changes in the sediment load from the Yellow River into the Bohai over time. Petroleum inputs could be revealed by ratios of methylphenanthrenes to phenanthrene (MP/P) and the patterns of more stable geochemical biomarkers (hopanes and steranes) along the two cores, in addition to the presence of unresolved complex mixtures (UCM) in the surface layers. Source diagnostic ratios of PAHs indicated a pyrogenic origin from biomass and coal combustion with a minor petroleum contribution. Downcore trends of compositional PAHs profiles were in agreement with the socio-economic development in China in the past decades. This temporal variation of sedimentary PAHs can also reflect a different evolution stage of energy structure in China as compared with those of the western developed countries.     

长江口沉积物碳氮元素地球化学特征及有机质来源分析

根据对长江口水下三角洲上部(CJ16)和口门浅滩(CJ19)柱状样的粒度、总有机碳(TOC)、总氮(TN)和有机碳同位素(δ13C)以及长江口表层样TOC的测定,得出其粒度及碳氮元素特征,利用C/N和δ13C分析有机质来源及不同来源的贡献率。研究结果表明:(1)沉积物中有机碳含量在0.19%～1.17%之间,CJ16柱中有机碳含量比CJ19柱略高;总氮含量均比较少,且变化幅度小;C/N比值在5～17间变化;CJ16柱的δ13C值在24.70‰～22.86‰间变化,CJ19柱为24.88‰～22.37‰,且CJ19柱δ13C值在36 cm以上段较下段明显增大,推测可能与南汇边滩互花米草(C4植物)的引种有关;(2)长江口表层沉积物TOC的含量范围为0.17%～1.16%,平均值为0.52%;(3)粒度特征显示长江口主要以粉砂和粘土为主,砂含量较少,粒度与长江口TN、TOC含量有较好的相关性;(4)C/N和δ13C值的特征均显示该区有机质为陆源和海洋混合,利用C/N比值估算出来自陆源的有机碳比例在CJ16柱约为40%,而在CJ19柱中约为60%;根据δ13C值估算出CJ16柱陆源和海源两种有机质来源几乎是各占一半的比例,CJ19柱来自陆源的有机碳占总有机碳的60%,与用C/N比值法测得的结果较一致。上述结果显示长江口的不同空间位置碳氮元素分布特征不同,沉积记录受到粒度、河口区物源的影响,还受到陆源和海源不同有机质来源输入的影响。     

Organic carbon accumulation over the last 16 kyr off Vancouver Island,Canada: evidence for increased marine productivity during the deglacial

The organic carbon content of marine sediments is commonly used as a proxy for export production. However, in continental margin sediments a large fraction of the organic matter may be of terrestrial origin, and it is necessary to correct the total organic carbon data accordingly. Radiocarbon dating of bulk organic carbon, organic geochemistry and isotope data (δ¹³C and δ¹⁵N) are used here to characterize the type of organic matter present in Core JT96-09 collected at a water depth of 920 m on the slope off Western Canada. The quantities of marine and terrestrial organic carbon are then estimated using the δ¹³C data. The 16 kyr record obtained from Core JT96-09 suggests that accumulation of total organic carbon was highest during the late glacial and deglacial, but geochemical data indicate that as much as 70% of this carbon is terrestrial in origin. When the palaeo-record is corrected for this terrigenous input it is observed that accumulation of marine organic matter, and presumably marine export production, increased at the end of the last glacial contemporaneous with the Bølling, and that it peaked during the Allerød. Data from other palaeoproductivity proxies (i.e., bio-barium, opal and alkenones) also indicate relatively high productivity during the deglacial. These results indicate a return to modern upwelling conditions and high marine export production at ∼14.3 calendar kyr BP and a period of enhanced upwelling, relative to the present, during the Allerød.     

Carbon Geochemistry of Gas Hydrate‐associated Sediments in the Southwestern Taiwan Basin

Marine gas hydrates, one of the largest methane reservoirs on Earth, may greatly affect the deep sea sedimentary environment and biogeochemistry; however, the carbon geochemistry in gas hydrate-bearing sediments is poorly understood. In this study, we investigated the carbon variables in sediment core 973-3 from the southwestern Taiwan Basin in the South China Sea to understand the effect of environmental factors and archaeal communities on carbon geochemistry. The carbon profiles suggest the methanogenesis with the incerase of dissolved inorganic carbon(DIC) and high total organic carbon(TOC)(mean = 0.46%) originated from terrigenous organic matter(mean δ~(13)C_(TOC) value of-23.6‰) driven by the abundant methanogen ‘Methanosaeta and Methanomicrobiales'. The active anaerobic oxidation of methane is characterized by the increase of DIC and inorganic carbon(IC), and the depleted δ~(13)C_(IC), coupled with the increase of TOC and the decrease of δ~(13)C_(TOC) values owing to the methanotroph ‘Methanosarcinales/ANME' in 430–840 cm. Environmental factors and archaeal communities in core 973-3 are significantly correlated to carbon variables owing to methane production and oxidation. Our results indicate that the carbon geochemical characteristics are obviously responding to the formation and decomposition of gas hydrates. Furthermore, pH, Eh and grain size, and Methanosaeta greatly affect the carbon geochemistry in gas hydrate-associated sediments.     

Molecular characterization of dissolved organic matter in pore water of continental shelf sediments

Dissolved organic matter (DOM) in sediment pore water is a complex molecular mixture reflecting various sources and biogeochemical processes. In order to constrain those sources and processes, molecular variations of pore water DOM in surface sediments from the NW Iberian shelf were analyzed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and compared to river and marine water column DOM. Weighted average molecular element ratios of oxygen to carbon ((O/C)_wa) and hydrogen to carbon ((H/C)_wa) provided general information about DOM sources. DOM in local rivers was more oxygenated ((O/C)_wa 0.52) and contained less hydrogen ((H/C)_wa 1.15) than marine pore water DOM (mean (O/C)_wa 0.50, mean (H/C)_wa 1.26). The relative abundance of specific compound groups, such as highly oxygenated aromatic compounds or nitrogen-bearing compounds with low H/C ratios, correspond to a high concentration of lignin phenols (160 μg/g sediment dry weight) and a high TOC/TN ratio (13.3) in the sedimentary organic matter and were therefore assigned to terrestrial sources. The lower degree of unsaturation and a higher relative abundance of nitrogen-bearing compounds in the pore water DOM reflected microbial activity within the sediment. One sampling site on the shelf with a high sediment accumulation, and a humic-rich river sample showed a wide range of sulfur compounds in the DOM, accompanied by a higher abundance of lipid biomarkers for sulfate-reducing bacteria, probably indicating early diagenetic sulfurization of organic matter.     

Palynofacies evidence of dysoxia and upwelling in the Turonian of the Sergipe Basin,Brazil

This paper presents the integrated results of palynofacies and geochemical analyses in Turonian carbonate strata from the Sergipe Basin, Brazil. Forty-three outcrop samples were analyzed from sections of the Cotinguiba Formation in the Votorantim and Rita Cacete quarries. Our results allow for the characterization of the organic matter and interpretation of the environments of deposition. Together with the existing geochemical data, the results allow for recognition of oxic and dysoxic intervals and inferences pertaining to local oceanographic conditions to explain these environmental changes. The palynofacies groups are dominated by marine palynomorphs and amorphous organic matter (AOM), with minor amounts of terrigenous palynomorphs and phytoclasts. The total organic carbon (TOC) and δ¹³C ratio are directly correlated with the dominant palynofacies elements, particularly AOM. The upper section in Rita Cacete quarry has the most complete data set, and the TOC, δ¹³C and marine-derived AOM in this section tend to decrease upsection and serve to differentiate the oxic and dysoxic intervals. The sections also contain abundant, low-diversity dinoflagellate assemblages composed primarily of Trichodinium boltenhagenii, Cribroperidinium? muderongense, Canningia reticulata and Xenascus plotei. The palynofacies and dinoflagellate assemblages indicate deposition in shallow marine to outer neritic environments. The dysoxic events are recognized by an increase in TOC and δ¹³C, high amounts of AOM, an abundance of the low-diversity dinoflagellate assemblages and the lowest amounts of terrestrial components. The changes in marine productivity seem to be related to periods of low-intensity upwelling, which likely decreased the levels of dissolved oxygen in the basin.     

Carbon–sulfur–iron relationships in sedimentary rocks from southwestern Taiwan: influence of geochemical environment on greigite and pyrrhotite formation

The importance of the magnetic iron sulfide minerals, greigite (Fe₃S₄) and pyrrhotite (Fe₇S₈), is often underappreciated in geochemical studies because they are metastable with respect to pyrite (FeS₂). Based on magnetic properties and X-ray diffraction analysis, previous studies have reported widespread occurrences of these magnetic minerals along with magnetite (Fe₃O₄) in two thick Plio-Pleistocene marine sedimentary sequences from southwestern Taiwan. Different stratigraphic zones were classified according to the dominant magnetic mineral assemblages (greigite-, pyrrhotite-, and magnetite-dominated zones). Greigite and pyrrhotite are intimately associated with fine-grained sediments, whereas magnetite is more abundant in coarse-grained sediments. We measured total organic carbon (TOC), total sulfur (TS), total iron (Fe_T), 1N HCl extractable iron (Fe_A), and bulk sediment grain size for different stratigraphic zones in order to understand the factors governing the formation and preservation of the two magnetic iron sulfide minerals. The studied sediments have low TS/Fe_A weight ratios (0.03–0.2), far below that of pyrite (1.15), which indicates that an excess of reactive iron was available for pyritization. Observed low TS (0.05–0.27%) is attributed to the low organic carbon contents (TOC=0.25–0.55%), which resulted from dilution by rapid terrigenous sedimentation. The fine-grained sediments also have the highest Fe_T and Fe_A values. We suggest that under conditions of low organic carbon provision, the high iron activity in the fine-grained sediments may have removed reduced sulfur so effectively that pyritization was arrested or retarded, which, in turn, favored preservation of the intermediate magnetic iron sulfides. The relative abundances of reactive iron and labile organic carbon appear to have controlled the transformation pathway of amorphous FeS into greigite or into pyrrhotite. Compared to pyrrhotite-dominated sediments, greigite-dominated sediments are finer-grained and have higher Fe_A but lower TS. We suggest that diagenetic environments with higher supply of reactive iron, lower supply of labile organic matter, and, consequently, lower sulfide concentration result in relatively high Eh conditions, which favor formation of greigite relative to pyrrhotite.     

Spatial trends in the geochemical composition of sediments in the Panuco River discharge area, Gulf of Mexico.

Major and trace elements, organic matter, carbonates, loss of ignition, grain size, gravel, sand, silt, clay, and qualitative mineralogical composition were determined on surficial marine sediments sampled during the stormy (February), dry (May), and rainy (September) seasons in the coastal area adjacent to Panuco River discharges into the Gulf of Mexico. The sediments supplied by the river move in a north-east direction, and are deposited in the north-east extreme of the studied area. Terrigenous sediments show a strong association of Al₂O₃ with Fe₂O₃, Na₂O, K₂O, P₂O₅, Rb, Cu, Zn, organic matter, clay, and grain size (Mz). Mineralogical analysis shows that they are formed by quartz, kaolinite, montmorillonite, illite-montmorillonite and biotite. The highest metal concentration of Cu (25 mg/kg), Zn (155 mg/kg), Pb (50 mg/kg) and organic matter (1.26%) was observed in the sampling points located very close to the river mouth. A statistical analysis was done with the information contained in the variables. Five significant factors explain 77% of the total variance: factor 1 is due to sediments from a terrigenous source, factor 2 corresponds to sediments from a biogenous source, factor 3 is associated to sediments with heavy minerals, factor 4 is due to Co concentration, and factor 5 is due to Ni concentration. The sediments supplied from the river had a short-term local impact on the sediment distribution, as observed by the carbonate and heavy mineral concentration of the sediments.     

Enriched stable carbon isotopes in the pore waters of carbonate sediments dominated by seagrasses: Evidence for coupled carbonate dissolution and reprecipitation

Studies of the δ¹³C of pore water dissolved inorganic carbon (δ¹³C-DIC) were carried out in shallow water carbonate sediments of the Great Bahamas Bank (GBB) to further examine sediment-seagrass relationships and to more quantitatively describe the couplings between organic matter remineralization and sediment carbonate diagenesis. At all sites studied δ¹³C-DIC provided evidence for the dissolution of sediment carbonate mediated by metabolic CO₂ (i.e., CO₂ produced during sediment organic matter remineralization); these observations are also consistent with pore water profiles of alkalinity, total DIC and Ca²⁺ at these sites. In bare oolitic sands, isotope mass balance further indicates that the sediment organic matter undergoing remineralization is a mixture of water column detritus and seagrass material; in sediments with intermediate seagrass densities, seagrass derived material appears to be the predominant source of organic matter undergoing remineralization. However, in sediments with high seagrass densities, the pore water δ¹³C-DIC data cannot be simply explained by dissolution of sediment carbonate mediated by metabolic CO₂, regardless of the organic matter type. Rather, these results suggest that dissolution of metastable carbonate phases occurs in conjunction with reprecipitation of more stable carbonate phases. Simple closed system calculations support this suggestion, and are broadly consistent with results from more eutrophic Florida Bay sediments, where evidence of this type of carbonate dissolution/reprecipitation has also been observed. In conjunction with our previous work in the Bahamas, these observations provide further evidence for the important role that seagrasses play in mediating early diagenetic processes in tropical shallow water carbonate sediments. At the same time, when these results are compared with results from other terrigenous coastal sediments, as well as supralysoclinal carbonate-rich deep-sea sediments, they suggest that carbonate dissolution/reprecipitation may be more important than previously thought, in general, in the early diagenesis of marine sediments.