Sulfur and carbon isotopic systematics of Guadalupian‐Lopingian (Permian) mid‐Panthalassa: δ34S and δ13C profiles in accreted paleo‐atoll carbonates in Japan

Immediately before the extinction of the end‐Guadalupian (Middle Permian; ca 260 Ma), a significant change to the global carbon cycle occurred in the superocean Panthalassa, as indicated by a prominent positive δ¹³C excursion called the Kamura event. However, the causes of this event and its connection to the major extinction of marine invertebrates remain unclear. To understand the mutual relationships between these changes, we analyzed the sulfur isotope ratio of the carbonate‐associated sulfate (CAS) and HCl‐insoluble residue, as well as the carbon isotope ratio of bulk organic matter, for the Middle‐Upper Permian carbonates of an accreted mid‐oceanic paleo‐atoll complex from Japan, where the Kamura event was first documented. We detected the following unique aspects of the stable carbon and sulfur isotope records. First, the extremely high δ¹³C values of carbonate (δ¹³C_carb) over +5 ‰ during the Capitanian (late Guadalupian) were associated with large isotopic differences between carbonate and organic matter (Δ¹³C = δ¹³C_carb ? δ¹³C_org). We infer that the Capitanian Kamura event reflected an unusually large amount of dissolved organic matter in the expanded oxygen minimum zone at mid‐depth. Second, the δ³⁴S values of CAS (δ³⁴S_CAS) were inversely correlated with the δ¹³C_carb values during the Capitanian to early Wuchiapingian (early Late Permian) interval. The Capitanian trend may have appeared under increased oceanic sulfate conditions, which were accelerated by intense volcanic outgassing. Bacterial sulfate reduction with increased sulfate concentrations in seawater may have stimulated the production of pyrite that may have incorporated iron in pre‐existing iron hydroxide/oxide. This stimulated phosphorus release, which enhanced organic matter production and resulted in high δ¹³C_carb. Low δ³⁴S_CAS values under high sulfate concentrations were maintained and the continuous supply of sulfate cannot by explained only by the volcanic eruption of the Emeishan Trap, which has been proposed as a cause of the extinction. The Wuchiapingian δ³⁴S_CAS–δ¹³C_carb correlation, likely related to low sulfate concentration, may have been caused by the removal of oceanic sulfate through the massive evaporite deposition.     

Diatom stratigraphy in five offshore sediment cores from the northwestern Baltic proper implying large scale circulation changes during the last 8500 years

Five Holocene sediment cores from the northwestern Baltic proper were analysed for lithology, siliceous microfossil assemblages and geochemical parameters. The data indicate that surface water salinity and redox conditions below the halocline have changed drastically at least four times since the Baltic Sea changed from a fresh water lake (the Ancylus Lake) to a semi-enclosed brackish water sea (the Litorina Sea) c. 8500 yrs BP. These variations appear to be mainly effects of changes in water depth at the thresholds of inlet areas. Based on these changes, and earlier studies of the shoreline displacement in the inlet areas, we propose a tentative model for changes of large scale water circulation in the Baltic Sea during the last c. 8500 yrs.At the transition from fresh to brackish water 8500 ¹⁴C yrs BP, upwelling of nutrient rich bottom water started to occur, causing a slight increase in primary production. Diatom assemblages in sediments indicate a slow rise in surface water salinity during this period.At 7000-6500 ¹⁴C yrs BP, surface water salinity and primary production simultaneously increased, as anoxic bottom conditions were established at depth below the halocline. We suggest that high primary production was caused by increased input of oceanic water, leading to increased upwelling of nutrient rich bottom water. At the anoxic bottoms laminated sediments formed until 5000-4500 ¹⁴C yrs BP. This period (c. 7000-4500 ¹⁴C BP) was contemporaneous with the post-glacial transgression maximum in Öresund, and we suggest it represents the most saline phase of the Baltic Sea post-glacial history.Due to a regression in Öresund starting 4500 ¹⁴C yrs BP, upwelling decreased and the halocline was lowered, resulting in decreased primary productivity and hence oxic deep water conditions. The diatom assemblages of the sediments indicate a lowering of salinity at the beginning of this period.We suggest that the second period of anoxic bottom conditions c. 2000-1500 ¹⁴C yrs BP was caused by a change of dominating inflows from the Öresund to the Belt Sea. This resulted in decreased salinity of the inflowing water which did not penetrate to the deepest parts of the basin as frequently as before. The diatom record indicates both a second lowering of salinity and a change in the large scale water circulation at the beginning of this period.     

Less ice on the Baltic reduces the extent of hypoxic bottom waters and sedimentary phosphorus release

A significant relation was established between the maximum extent of sea ice covering the Baltic Sea and the hypoxic area in the deeper parts of the Baltic Proper, with a lag of 2 years: for the period 1970–2000, less ice was correlated with a smaller anoxic area. At the same time, maximum ice extent is subject to a long-term climate-related decline, due to higher air temperatures and an increased frequency of westerly winds. Together, this suggests that the hypoxic area will decrease in the coming decades. Internal sedimentary phosphorus-loading is closely related to the hypoxic area and hence would decrease as well. Wind strength variability did not have a significant additive effect to the variance in hypoxic area already explained by sea ice extent. The observed lag is in agreement with the order of magnitude of estimated residence times in the shallower sub-basins feeding the Baltic Proper, where ice extent varies most.     

下-中奥陶统之交陆架周期性缺氧：来自美国犹他州的遗迹沉积学证据?

美国犹他州中西部、北美下-中奥陶统之交重要剖面上的遗迹沉积学证据表明，在奥陶纪生物爆发的重要时期─早、中奥陶世之交和重要生态领域─陆架区，存在持续3.4 Ma、周期性的陆架缺氧事件。主要的遗迹沉积学证据包括：低的遗迹化石分异度，非常浅的生物扰动层厚度和潜穴深度（小于4 cm, 现代陆架区大于20 cm），稀少的居住滤食迹，遗迹化石和遗迹组构的分布与风暴事件层密切相关；细小的Chondrites 阶层占据较浅或最浅的生态阶层 （中生代以来，细小的Chondrites 阶层总是占据最深的生态阶层）；地层序列具轨道旋回地层结构，并且富含呈黄铁矿假象的褐铁矿结核。早古生代较低的大气氧水平，快速和高幅度的奥陶纪耗氧生物大辐射，早、中奥陶世之交陆架区快速和高幅度的海进和温暖的陆架环境可能是导致早、中奥陶世之交陆架环境周期性缺氧的主要原因。轨道旋回地层的研究表明，这次周期性缺氧事件始于473.27 Ma, 结束于 469.87 Ma，持续时间约3.4 Ma，如果早、中奥陶世之交的同位素年龄值为473.0 Ma。早、中奥陶世之交陆架环境周期性缺氧事件的发现，给正确认识奥陶纪生物辐射、古生代演化生物群起源环境和显生宙生物集群绝灭与缺氧关系增添了新资料。     

Quantitative inferences of past hypolimnetic anoxia and nutrient levels from a Canadan Precambrian Shield lake

Paleolimnological analyses were used to infer limnological changes during the past ~ 300 yrs in the west basin of Peninsula Lake, a small (853 ha) Precambrian Shield lake in Ontario, Canada, that has been subjected to moderate cultural disturbances (forest clearance, cottage and resort development). This study represents a pioneering attempt to use sedimentary chironomid assemblages and weighted-averaging models to quantify past hypolimnetic anoxia (expressed as the anoxic factor, AF). Impacts of forest clearance and human land-use on deepwater oxygen availability and surface water quality were assessed by comparing chironomid-inferred AF and diatom-inferred total phosphorus concentration ([TP]) to changes in terrestrial pollen and historical data. This study also discusses the ability of chironomids to quantitatively infer changes in AF.Pre-disturbance chironomid assemblages were stable and dominated by taxa indicative of oxygen-rich hypolimnetic conditions (e.g., Protanypus, Heterotrissocladius, Micropsectra type), while diatoms indicated oligotrophic lake status (diatom inferred [TP] = 5-7 g·l^-1). Chironomids characteristic of lower oxygen availability (e.g., Chironomus, Procladius) increased following land-clearance, road construction, establishment of a grist mill and lakeshore development beginning ca. 1870. Increased abundances of Tanytarsus s. lat., a multigeneric group of mainly littoral chironomids, since 1900, indicated that littoral chironomids may have comprised a greater proportion of fossil assemblages during periods of eutrophication and prolonged anoxia. Abundances of meso-eutrophic diatom taxa (e.g., Fragilaria crotonensis, Asterionella formosa, Aulacoseira ambigua, A. subarctica) increased concurrent with European settlement (ca. 1870) and diatom-inferred [TP] doubled (~ 6-12 g·l^-1), further indicating that naturally-oligotrophic Precambrian Shield lakes were extremely sensitive to initial land-clearance activities.Recent increases in oligotrophic diatom taxa (e.g., Cyclotella stelligera) indicate a shift to more oligotrophic conditions since ca. mid-1960s, with greatest changes since ca. 1980. The chironomids Heterotrissocladius and Micropsectra type also increased at this time suggesting greater deepwater oxygen availability. These recent water-quality improvements, possibly in response to enhanced nutrient removal from detergents and sewage, climate-related reductions in external phosphorus loads, and catchment (but not lake) acidification and reforestation, suggest that habitat for commercially-valuable cold-water fishes has improved in recent decades despite greater recreational lake-use.Paleolimnological assessment of trophic status changes in Peninsula Lake using fossil diatom and chironomid assemblages were in good agreement. Diatom inferences of [TP] and chironomid inferences of AF both suggest that Peninsula Lake was historically oligotrophic, became oligo-mesotrophic after European settlement, and returned to oligotrophy in recent yrs. Chironomid inferences of [TP] consistently underestimated the trophic status of Peninsula Lake, possibly due to its relatively large hypolimnion. These results suggest that AF represents a useful tool for quantitatively reconstructing the past trophic status of deeper, stratified lakes.     

On the ages of flood basalt events

We review available data constraining the extent, volume, age and duration of all major Phanerozoic continental flood basalts (CFB or traps) and oceanic plateaus (OP), together forming the group of large igneous provinces (LIP), going from the smallest Columbia flood basalts at ～16 Ma to the as yet ill-known remnants of a possible trap at ～360 Ma in eastern Siberia. The 16 traps (CFB and OP) reviewed form a rather unimodal distribution with an initial modal volume of the order of 2.5 Mkm³. Most provinces agree with a rather simple first order model in which volcanism may have lasted of the order of 10 Ma, often resulting in continental break-up, but where most of the volume was erupted in about 1 Ma or sometimes less. This makes CFBs/OPs (LIPs) major geodynamic events, with fluxes exceeding the total output of present day hot spots and even possibly exceeding over short times the entire crustal production of mid-ocean ridges. The proposed correlation between trap ages and the ages of several geological events, including mass extinctions and oceanic anoxia, is found to have improved steadily as more data have become available, to the point that the list of trap ages may coincide with many major divisions in the geological time scale. The four largest mass extinctions in the last 260 Ma coincide to the best resolution available with four traps, making a causal connection between the two through some form of catastrophic climatic perturbations the most likely hypothesis. The time sequence of LIPs appears to have been random and there is no robust evidence for long time trends in the corresponding crustal production rate over the last 260 Ma.     

Chemistry of Late Early Triassic Siliceous Claystone ('Toishi-type' Shale) from the Oritate Area, Sambosan Belt, Kyushu, Southwest Japan

Abstract. Inorganic chemical compositions are determined for late Early Triassic siliceous claystone ('Toishi-type' shale) and associated chert from Oritate area, Sambosan Belt, Kyushu, southwest Japan. The siliceous claystone is similar in chemical composition to Post-Archean Australian Shale (PAAS), but is depleted in Ca, Sr, Mn, and Fe and slightly enriched in Cu, Zn, P, and rare earth elements (REEs). The siliceous claystone and associated chert have flat REE patterns with positive Eu anomalies and no distinct Ce anomaly. The siliceous claystone and associated chert have largely constant Ti/Al, Th/Al, and Nb/Al ratios compared to the variable ratios found in siliceous shale and sandstone deposited close to land in a trench setting. This suggests that the claystone and chert were deposited in a deep-sea pelagic environment and were derived mainly from the suspended fraction, including eolian dust and material transported from distant lands, rather than from turbidity currents that occurred close to land. The low Ca contents of the analyzed rocks indicate deposition below the calcium-carbonate compensation depth. The depletion of Mn and Fe, and no distinct Ce anomaly in the Oritate siliceous claystone are also evident, being similar to those in samples from the Sasayama and Kinkazan sections in the Mino-Tanba Belt, where oceanic anoxia developed during the Late Permian to earliest Triassic. This might suggest that oceanic anoxia prevailed through to the late Early Triassic.     

Temporal and spatial distribution of hypoxic/seasonal anoxic zone in Amvrakikos Gulf, Western Greece

Coastal hypoxia and anoxia have become a serious environmental problem in many coastal ecosystems, and recent evidence suggests an increase in the number of systems experiencing hypoxia globally and an increased frequency and duration of hypoxia in many historically hypoxic systems. Eutrophication, low physical energy and large freshwater input are some of the most important factors, which lead to the development of hypoxia in coastal areas. The Amvrakikos Gulf, located in western Greece, is one of the most important protected areas in Greece and in Europe and past studies indicated that some regions of the Gulf experience hypoxia. Despite the importance of the Amvrakikos Gulf ecosystem, little is known about key ecological, chemical, and physical processes in the Gulf and their relationship with oxygen depletion. In the present study, authors try to answer some important questions regarding the distribution and variation of the hypoxic zone. After a year of measurements, it was concluded that according to spatial distribution of DO, the gulf can be divided into two parts, the western and eastern areas, with important differences occurring between them. Within the western area, the water column was well oxygenated during winter and spring and hypoxic conditions occurred only in summer and autumn. The eastern area was hypoxic throughout the year and anoxic conditions occurred only during autumn. In conclusion, taking into account the author’s measurements and previous studies, the seasonally hypoxic eastern area in 1987 converted into a seasonally anoxic area in 2009 and the western part of the gulf, remained seasonally hypoxic, indicating the degradation of the gulf’s environmental state within the last 20 years.     

The role of biogeochemical cycling for the formation and preservation of varved sediments in Soppensee (Switzerland)

We analyzed seasonally aggregated observations of temperature, conductivity, dissolved oxygen and dissolved inorganic carbon from Soppensee (District of Lucerne, Switzerland) for the yrs 1980 to 1993. Holomictic Soppensee is characterized by a strong summer stratification with a thin epilimnion separated from an anoxic hypolimnion by a strong pycnocline formed by thermal and chemical gradients. A vertical one-dimensional model was developed to simulate the observed seasonal cycles of carbon and oxygen. The processes of net community production, mineralization of organic matter, precipitation and dissolution of calcite, gas exchange, in- and outflow, sedimentation and vertical eddy diffusion are included. According to the model, the annual net community production is estimated to about 110 g C m^-2 yr^-1 and the annual net primary production to about 330 to 440 g C m^-2 yr^-1, which is a typical value for eutrophic lakes. A mass balance of the carbon cycle indicates that most of the inflow comes from groundwater which is super-saturated with respect to atmospheric CO₂. Therefore the surface waters exhibit a large capacity for calcite precipitation. The results of the model are used to constrain the conditions that favor the formation of varved sediments in Soppensee during thousands of yrs. Model calculations show that the deep waters would still turn anoxic even if the sedimentation rate of organic matter were decreased to 25%. Several physical factors such as biogenic stabilization of the deep waters due to calcite dissolution and low input of wind energy are responsible for the long term anoxia in Soppensee.