Temporal–spatial variation and source analysis of carbon and nitrogen in a tidal wetland of Luoyuan Bay

Carbon and nitrogen are important elements in biogeochemical studies of tidal wetlands. Three wetland zones in Luoyuan Bay in the Fujian province were chosen for this study; the Spartina alterniflora flat zone with Spartina alterniflora growing, the silt zone with no Spartina alterniflora growing and the Spartina alterniflora-silt flat zone – a transition zone between the two. The spatial and seasonal variations of total organic carbon (TOC), total nitrogen (TN), stable isotopes of organic material (δ¹³C, δ¹⁵N), C/N ratio, average particle size and sediment composition in surface and vertical sediments of different ecological zones were analyzed. Carbon and nitrogen accumulation and particle size effects in the different ecological zones were discussed and the indicators of δ¹³C and C/N ratios were also compared. TOC, TN, δ¹³C contents, C/N ratios, and average particle size varied within the ranges of 0.611–1.133%, 0.053–0.090%, ?22.60 to ?18.92‰, 12.3–15.7, and 6.4–8.7 μm, respectively. Sediments were mainly silt-sized. Besides δ¹⁵N values, the other parameters, such as TOC, TN, δ¹³C contents, C/N ratios, and average particle size showed an obvious zonal distribution in surface sediments. The distribution of TOC and TN contents reflected the distribution of Spartina alterniflora within the bay. The profile and seasonal variations of these parameters in different ecological zones indicated that variations in the Spartina alterniflora flat and transition zones were complex because of the effect of Spartina alterniflora. Vertical and seasonal variations were sampled in the silt flat area. The profile and seasonal variations of TOC, TN and δ¹³C were similar in the transition zone and the Spartina alterniflora flat zone. Seasonal concentrations of TOC, TN and δ¹³C decreased from autumn > spring > winter > summer. The seasonal variation of carbon and nitrogen in the sediments may be influenced by temperature, particle size, plankton and benthos. The particle size effect was significant in the surface sediments and profile sediments of the transition zone. However, other factors had a greater effect on the distributions of TOC and TN in the Spartina alterniflora flat and silt flat zones. C/N ratios in sediments of the Spartina alterniflora flat, transition zone and silt flat were close to or > 12, indicating that the organic material source was dominated by terrestrial inputs. However, δ¹³C values decreased from the Spartina alterniflora flat zone > transition zone > silt flat zone indicating that the organic material source was predominantly from marine inputs. Thus the indications from C/N ratios and δ¹³C were different. There was no clear relationship between C/N ratios and δ¹³C values and a better relationship between δ¹³C values and TOC concentrations suggested that δ¹³C values provided a better indication of the organic source. Limited amounts of organic material came from Spartina alterniflora. This study has provided basic data for researching biogeochemical processes of biogenic elements in tidal wetlands and vegetation restoration, and has also provided a reference for assessing and protecting the environment and ecological systems in wetlands.     

The oxygen isotope composition of planktonic foraminifera from the Guaymas Basin,Gulf of California: Seasonal,annual, and interspecies variability

Sediment trap samples collected over a seven-year period (February 1991–October 1997) from Guaymas Basin in the Gulf of California were used to study the oxygen isotope composition of five species of planktonic foraminifera, Globigerinoides ruber (white), Globigerina bulloides, Neogloboquadrina dutertrei, Pulleniatina obliquiloculata, and Globorotalia menardii. The δ¹⁸O data were analyzed for temporal and interspecies variability and were compared to local hydrography to evaluate the use of each species in reconstructing past oceanographic applications. The two surface dwelling species, G. ruber and G. bulloides displayed the lowest δ¹⁸O values (～ 0.0 to ? 5.0‰), while δ¹⁸O values for the thermocline dwelling N. dutertrei, P. obliquiloculata, and G. menardii were higher (～ 0.0 to ? 2.0‰). The δ¹⁸O of G. ruber most accurately records measured sea surface temperatures (SSTs) throughout the year. G. bulloides δ¹⁸O tracks SSTs during the winter–spring upwelling period but for the remainder of the year records slightly colder, subsurface temperatures. The difference between the δ¹⁸O of the surface dwelling species, G. ruber and G. bulloides, and that of the thermocline dwelling species, N. dutertrei, P. obliquiloculata, and G. menardii, was used to estimate the surface to thermocline temperature gradient. During the winter these δ¹⁸O differences are small (～ 0.50‰) reflecting a well-mixed water column. These interspecies δ¹⁸O differences increase during the summer (～ 1.90‰) in response to the strong thermal stratification that exists at this time of year.     

Tree age,site and climate controls on tree ring cellulose δ18O: A case study on oak trees from south-western France

A main concern of dendroclimatic reconstruction is to distinguish in the tree ring proxy the influence of the climate variables of interest from other controlling factors. In order to investigate age, site and climate controls on tree ring width and cellulose δ¹⁸O, measurements have been performed in nearby groups of young (145 years old) and older (310–405 years old) oak trees in south-western France, covering the period 1860–2010.Within a given site, inter-tree deviations are small, pointing to a common climatic signal. Despite a similar inter-annual variability, the average level of cellulose δ¹⁸O in the young tree group is ∼0.8‰ higher than in the old trees. Such offsets might be caused by different soil properties and differences in the fraction of the source water used by trees from different depths. The δ¹⁸O of water in the top soil layer is directly related to the current growing season precipitation, while deeper water can have a lower and more constant δ¹⁸O. Local cave drip waters at 10 m depth indeed show a constant isotopic composition, which corresponds to pluri-annual mean precipitation.A 2‰ increasing trend is observed in cellulose δ¹⁸O of young trees in the first 30 years of growth, during a period when no trend is visible in older trees. This increase can be quantitatively explained by humidity gradients under the forest canopy, and a changing microclimate around the crown as trees grow higher.While relationships between tree ring width and climate appear complex, the isotopic composition of cellulose is strongly correlated with summer maximum temperature, relative humidity and evapotranspiration (r ≈ 0.70). Weaker correlations (r ≈ 0.40) are identified with precipitation δ¹⁸O from a 15-year long local record and from the REMOiso model output. These results imply that leaf water enrichment has a stronger control on the inter-annual variability of cellulose δ¹⁸O than the δ¹⁸O of precipitation.This study demonstrates the suitability of oak tree ring cellulose δ¹⁸O for reconstructing past summer climate variability in south-western France, provided that the sampling and pooling strategy accounts for the fact that trees from different sites and of different age can introduce non-climatic signals.     

Magnesium and strontium compositions of recent symbiont-bearing benthic foraminifera

Minor and trace elements in foraminiferal carbonates are potential paleo-proxies of climate, nutrient and seawater composition. There are very few reports of trace element composition of symbiont-bearing, larger foraminifera that are known to be important constituents of shallow-marine, modern and ancient carbonates. In this paper we examine the range of variation in Mg and Sr content of Recent species of these foraminifera from a lagoon of Lakshadweep Atoll (Indian Ocean) and Akajima Islands, Japan. Two hyaline species, Amphistegina lessonii and Neorotalia calcar,and two porcellaneous species, Amphisorus hemprichii and Marginopora vertebralis were collected live from Lakshadweep islands. Mg / Ca in these foraminifera is of an order of magnitude higher than the values reported for planktonic and symbiont-free benthic foraminifera. The Sr / Ca values are, however, comparable with the reported values in other foraminiferal taxa and they are found to vary within a narrow range. Electron-probe micro-analysis of three symbiont-bearing benthic species indicates spatial heterogeneity of high orders in Mg / Ca composition in all the species. The annual variation in temperature and pH of the lagoon water cannot explain the observed amplitude of the compositional variation. The photosynthesis and respiration of the symbionts and host foraminifera are possibly the major cause of compositional heterogeneity in individual tests, as has also been recently postulated for symbiont-bearing planktonic foraminiferal species. It highlights the need to isolate biological factors and necessitates species-specific paleotemperature scale in paleoclimatic analysis. We also analyzed δ¹⁸O, δ¹³C, Ca, Mg and Sr in carefully dissected chambers of a reef-dwelling, porcellaneous benthic foraminifer, Marginopora kudakajimaensis, collected live in four seasons. A moderate positive correlation is observed between Mg / Ca and temperature. However, large inter- and intra-test variation in Mg limits the precision of Mg / Ca as palaeotemperature proxy. The Sr / Ca of the test calcite is unrelated to temperature of the sea water. The δ¹³C of M. kudakajimaensis does not correlate with δ¹⁸O, Mg / Ca or Sr / Ca.     

Stable oxygen and carbon isotopes of live benthic foraminifera from the Bay of Biscay: Microhabitat impact and seasonal variability

We determined the stable oxygen and carbon isotopic composition of live (Rose Bengal stained) benthic foraminifera (> 150 μm size fraction) of seven taxa sampled along a downslope transect between 140 to 2000 m water depth in the Bay of Biscay. At the five stations, Hoeglundina elegans, Cibicidoides pachydermus, Uvigerina peregrina, Uvigerina mediterranea preferentially occupy shallow infaunal niches, whereas Melonis barleeanus and Uvigerina elongatastriata occupy an intermediate infaunal microhabitat, and Globobulimina spp. live in a deep infaunal niche close to the zero oxygen boundary.When compared with δ¹⁸O values of calcite formed in equilibrium with bottom waters, U. peregrina forms its test in close equilibrium with bottom water δ¹⁸O. All other foraminiferal taxa calcify with a constant offset to calculated equilibrium calcite. There is no systematic relationship between the foraminiferal microhabitat depth and the Δδ¹⁸O between foraminiferal and equilibrium calcite. We calculated correcting factors for the various taxa, which are needed for constructing multispecies-based oxygen isotope records in paleoceanographic studies of the study area.The δ¹³C values of foraminiferal taxa investigated in this study do neither record bottom water δ¹³C_DIC in a 1 : 1 relationship nor with a constant offset, but appear to be mainly controlled by microhabitat effects. The increase of δ¹³C values of shallow infaunal taxa with increasing water depth reflects the decrease of the exported flux of organic carbon along the bathymetric transect and early diagenetic processes in the surface sediment. This is particularly the case for the shallow infaunal U. peregrina. The δ¹³C values of deep infaunal Globobulimina spp. are much less dependent on the exported organic matter flux. We suggest that the Δδ¹³C between U. peregrina and Globobulimina spp. can shed light on the various pathways of past degradation of organic detritus in the benthic environments.At a station in 550 m water depth, where periodic eutrophication of sediment surface niches was demonstrated previously, we performed a two-year seasonal survey of the isotopic composition of foraminiferal faunas. No marked seasonal changes of the stable carbon isotopic composition of shallow, intermediate and deep infaunal foraminiferal taxa were observed. Thus, the δ¹³C values of foraminiferal individuals belonging to the > 150 μm fraction may result from rather long-term calcification processes lasting for several weeks or months, which limit the impact of ephemeral ¹²C enrichment of shallow infaunal niches on the isotope chemistry of adult individuals during eutrophic periods. Only highly opportunistic taxa reproducing or calcifying during phytoplankton bloom periods and the subsequent deposits of phytoplankton remains in the benthic environment may exhibit a particularly low δ¹³C, indicative of such short productive periods.     

Fluxes and isotopic composition of planktonic foraminifera off Hainan Island,northern South China Sea: Implications for paleoceanographic studies

Planktonic foraminifera collected from a sediment trap deployed off Hainan in the northwestern South China Sea (SCS-NW) between July 2012 and April 2013 were studied to evaluate their seasonal variability and ecology as well as to infer the factors controlling their shell fluxes. The total planktonic foraminifera flux, as well as the fluxes of the dominant species (Globigerinoides ruber, Globigerinoides sacculifer and Neogloboquadrina dutertrei), showed three distinct maxima during SW-monsoon in August 2012, the SW-NE intermonsoon in October 2012 and the NE-monsoon in December 2012–February 2013. These periods were characterized by upwelling, aerosol fallout, and intense wind mixing, respectively, from which the foraminiferal assemblages benefitted, as indicated by the close correlation between wind speed, sea surface temperature (SST), chlorophyll a concentration (Chl-a), δ¹⁸O of G. ruber and the shell fluxes. The correlation also suggests that temperature and food availability might have been the primary drivers of the observed changes in foraminiferal abundance. The offset between the SST deduced from flux-weighted of G. ruber δ¹⁸O and annual mean SST is only ∼0.3 °C, much lower than ∼5.2 °C between the summer and winter temperature, indicating a balanced seasonality bias in the shell flux. The linear regression between the satellite-derived sea surface temperature and G. ruber δ¹⁸O reveals the strong potential of this species, at least in the studied region, as an ecological indicator for past oceanic environments.     

Paleoceanography of the Mauritanian margin during the last two climatic cycles: From planktonic foraminifera to African climate dynamics

The last 220 ka of the MD03-2705 (18° 05.81′ N–21° 09.19′ W) sedimentary sequence, retrieved off the Cape Verde islands, was investigated using a multiproxy approach. Planktonic foraminifera assemblage analyses, coupled with isotopic measurements (δ¹⁸O) from benthic (Planulina wuellerstorfi) and planktonic (Globigerinoides ruber) foraminifera monospecific samples were conducted along the topmost 11 m of the sequence. High resolution X-ray fluorescence measurements (0.5 cm resolution), giving access to major element ratio, have completed the geochemical analyses along the core. Seasonal and annual past sea surface temperatures (SST) were quantitatively reconstructed. Local sea-surface salinity (SSS) changes were then estimated by coupling SST with planktonic δ¹⁸O data. Our data provide a set of both oceanic and continental markers of environmental changes along the north-western African margin. The major changes detected in our record are discussed in the light of the regional paleoceanographic and paleoclimatic history of the last 220 ka. Coupled oceanographic and atmospheric processes portray the climatic evolution of the area, and show strong links among the regional oceanography (water mass advection), the upwelling dynamics and the Intertropical Convergence Zone (ITCZ) migration. An increased upwelling activity (or influence of upwelling filaments) is noted at the end of the two last glacial periods, probably in response to a more southerly position of the ITCZ. Higher SSS are recorded over the area during arid intervals and were tentatively interpreted as signing a southward shift of the Cape Verde Frontal Zone. A detailed coupling between dust advection and SSS values over the site of study was noted during MIS6.5.     

Climatic dependency of soil organic carbon isotopic composition along the S–N Transect from 34°N to 52°N in central-east Asia

We explored the relationships between surface-soil (1–20 cm) organic carbon isotopic signatures and associated climatic factors in central-east Asia in an attempt to develop transfer functions that can be used to retrieve the paleoclimatic information stored in the thick eolian–paleosol sequences within the area. Our analysis shows that the negative correlation between the surface-soil organic δ¹³C values and the mean annual precipitation is robust (R² = 0.453; n = 196; p < 0.05) and the negative correlation with the growing-season (April–September) precipitation is more significant (R² = 0.4966; n = 196; p < 0.05). Our study further shows that the positive correlation between the surface-soil organic δ¹³C values and mean growing-season aridity is most significant (R² = 0.5805; n = 196; p < 0.05). We have smoothed both the organic δ¹³C values and the mean growing-season aridity values using a 3-point moving-window average-filter method in an attempt to remove some of random errors and found that the positive correlation between the two is further increased (R² =  0.7784; n =  192; p < 0.05). These robust linear relationships demonstrate their value in reconstructing paleoclimate changes in the study area. The documented climatic dependency of the surface-soil carbon isotopic composition in the study area might have resulted both from the humidity-related isotopic enrichment processes of the dominant C₃ plants (stomatal conductance and photosynthetic discrimination) and from the aridity-related abundance of C₄ plants (mainly Chenopodiaceae species) along the S–N bioclimatic gradient.     

Mg/Ca and δ18O in the brackish shallow-water benthic foraminifer Ammonia ‘beccarii’

Specimens of the benthic foraminifer Ammonia beccarii were cultured in the laboratory in order to determine the relation between temperature and Mg/Ca and oxygen isotope values in their tests. Asexual reproduction in this species provides a large number of juveniles that were allowed to grow into maturity at temperatures ranging from 10 to 27 °C and at salinities ranging from 18 to 33 PSU. The Mg/Ca in a calcite increase exponentially and δ¹⁸O decreases linearly with the temperature. Salinity has no significant impact on either Mg/Ca or δ¹⁸O. We show how the combination of these two parameters can be used to reconstruct seawater δ¹⁸O and temperature in shallow marine habitats.     

Carbon and oxygen isotope evidence for high-frequency (104–105 yr) and My-scale glacio-eustasy in Middle Pennsylvanian cyclic carbonates (Gray Mesa Formation), central New Mexico

We combine cyclo- and sequence stratigraphy along with whole rock δ¹³C and conodont apatite δ¹⁸O analysis to document high-frequency (10⁴–10⁵ yr) and My-scale sea-level changes for the Middle Pennsylvanian (Desmoinesian or Moscovian) Gray Mesa Formation of central New Mexico. Approximately 75 subtidal cycles (1–8 m) are grouped into 4 1/2 My-scale depositional sequences (40–80 m). About 50% of the cycles show evidence of prolonged subaerial exposure at cycle tops with the development of calcretes, diagenetic mottling, and regolith intraclasts. High-resolution δ¹³C analysis of whole rock limestones across nine of the cycles indicates that the cycle tops were diagenetically altered by isotopically light, meteoric fluids during sea-level fall and lowstand. These δ¹³C trends support the interpretation that high-frequency sea-level changes were responsible for cycle development.Conodont apatite δ¹⁸O values from sampled cycles indicate that the high-frequency sea-level changes were driven by glacio-eustasy combined with changes in surface seawater temperature (SST). δ¹⁸O values from conodont apatite, spanning parts of three depositional sequences indicate that My-scale glacio-eustasy and/or SST changes controlled sequence development. δ¹⁸O shifts indicate that the magnitudes of 10⁴–10⁵ yr glacio-eustasy were between ～ 55 and 170⁺ m combined with tropical SST changes of ～ 1.5°–6 °C. Calculated My-scale glacio-eustatic oscillations were between ～ 60 and 140 m with SST changes of < 3.5 °C. The most plausible driver for the My-scale paleoclimate changes is long-period obliquity (～ 1.2 My) variations. These calculated high-frequency, glacio-eustatic values are similar or greater than Pleistocene values, and lie within the range estimated for other Middle Pennsylvanian successions using a variety of independent eustatic proxies. The similarity in range of magnitudes between high-frequency and My-scale sea-level changes combined with the large differences in magnitudes between individual high-frequency sea-level oscillations helps explain the lack of systematic cycle-stacking patterns within these Pennsylvanian icehouse sequences.     

The evolution of deepwater dissolved oxygen in the northern South China Sea since 400 ka

The dissolved oxygen (DO) content of the ocean provides potential evidence and clues for the waxing and waning of marine productivity, ocean circulation, global climate change, and the evolution of ecological communities. On the basis of the analysis of the Benthic Foraminiferal Oxygen Index (BFOI), the percentage of epifaunal benthic foraminifers, and the redox-sensitive trace elements (Mo/Al) in Core MD12-3432, we reconstruct the evolution of deep water DO content in the northern South China Sea (SCS) during the past 400 ka and discuss the mechanisms of variable DO content. The results show that the changes of BFOI, Mo/Al, and the percentage of epifaunal benthic foraminifer present a similar pattern, which may reflect the variations of the DO content in seawater since 400 ka. Both variations in BFOI and Mo/Al indicate that the DO content was high during most time of marine isotope stage (MIS) 11 to mid-MIS 6, then decreased in late-MIS 6, and remained stable in MIS 5. It increased in MIS 4 and decreased until MIS 2, and then rose again. The non-synchronous variations between bottom water DO and benthic foraminiferal δ¹⁸O indicate that the DO content is not controlled by glacial-interglacial cyclic environmental variations. Comparing the biomarker productivity index with the DO content of water, we find that the DO content is affected mainly by productivity. Bulimina, Uvigerina and Chilostomella oolina are high productivity species. The accumulation rates of Bulimina and Uvigerina are higher during 61–15 kyr interval, but the accumulation rate of C. oolina is higher during 168–130 kyr. The results infer that different intensity of primary productivity and DO during these two periods. The DO and phytoplankton total (PT) show the opposite relation, which also indicates that the DO is affected by primary productivity, and the combined action of productivity and DO decides the growth of Bulimina, Uvigerina, and C. oolina. Besides the influences of productivity, the change of DO in the ocean is also affected by oceanic circulation.     

Climatic potential of δ18O of Abies spectabilis from the Nepal Himalaya

A 50-year tree-ring δ¹⁸O chronology of Abies spectabilis growing close to the tree line (3850 m asl) in the Nepal Himalaya is established to explore its dendroclimatic potential. Response function analysis with ambient climatic records revealed that tree-ring δ¹⁸O is primarily governed by rainfall during the monsoon season (June–September), and the regression model accounts for 35% of the variance in rainfall. Extreme dry years identified in instrumental weather data are detected in the δ¹⁸O chronology. Further, tree-ring δ¹⁸O is much more sensitive to rainfall fluctuations than other tree-ring parameters such as width and density typically used in dendroclimatology. Correlation analyses with Niño 3.4 SST reveal time-dependent behavior of ENSO–monsoon relationships.     

Suitable sediment fraction for paleoenvironmental reconstruction and assessment of contaminated coastal areas based on benthic foraminifera: A case study from Augusta Harbour (Eastern Sicily,Italy)

Since the 1990s several studies noticed that, along coastal marine areas, the mean size of benthic foraminifera may be reduced due to heavy metal pollution, even if no biometric studies were carried out to quantify this aspect. The Augusta harbour (Sicily, Italy), is characterized by a strong contamination due to several anthropogenic activities, the most important of which are a petrochemical pole and an important industrial harbour. Taking into account the previous studies carried out in the area, which recorded small-sized foraminifera, the present study compared assemblage composition and faunal parameters in the >125 μm and >63 μm fractions of a sediment core collected in the most polluted sector of Augusta harbour. The aim was to understand if the two fractions have comparable environmental significance providing reliable information on the environmental status. In order to quantify the amount of smaller foraminifera in a community and to determine species loss between size fractions, two new indices are used: the Foraminiferal Size Index (FSI) and the Lost Species Index (LSI). Species richness, diversity and composition of the two assemblages were determined to characterize their structure. The results highlighted great depletion and different composition of the >125 μm assemblage with respect to the >63 μm one, showing a selective loss of particular ecological groups (stress-tolerant infaunal taxa). Also the better correlation of Foraminiferal Number (FN) and H’ index of >63 μm fraction with Polychlorobiphenyls (PCBs), Polycyclic Aromatic Hydrocarbons (PAHs), Barium (Ba) and Mercury (Hg), demonstrated the higher reliability of this size fraction for environmental assessment purposes.     

The influence of seawater carbonate ion concentration [CO32−] on the stable carbon isotope composition of the planktic foraminifera species Globorotalia inflata

We sampled the upper water column for living planktic foraminifera along the SW-African continental margin. The species Globorotalia inflata strongly dominates the foraminiferal assemblages with an overall relative abundance of 70–90%. The shell δ¹⁸O and δ¹³C values of G. inflata were measured and compared to the predicted oxygen isotope equilibrium values (δ¹⁸O_eq) and to the carbon isotope composition of the total dissolved inorganic carbon (δ¹³C_DIC) of seawater. The δ¹⁸O of G. inflata reflects the general gradient observed in the predicted δ¹⁸O_eq profile, while the δ¹³C of G. inflata shows almost no variation with depth and the reflection of the δ¹³C_DIC in the foraminiferal shell seems to be covered by other effects. We found that offsets between δ¹⁸O_shell and predicted δ¹⁸O_eq in the surface mixed layer do not correlate to changes in seawater [CO₃²⁻].To calculate an isotopic mass balance of depth integrated growth, we used the oxygen isotope composition of G. inflata to estimate the fraction of the total shell mass that is grown within each plankton tow depth interval of the upper 500 m of the water column. This approach allows us to calculate the Δδ¹³C_{interval added-DIC}; i.e. the isotopic composition of calcite that was grown within a given depth interval. Our results consistently show that the Δδ¹³C_IA-DIC correlates negatively with in situ measured [CO₃²⁻] of the ambient water. Using this approach, we found Δδ¹³C_IA-DIC/[CO₃²⁻] slopes for G. inflata in the large size fraction (250–355 μm) of − 0.013‰ to 0.015‰ (μmol kg^− 1)^− 1 and of − 0.013‰ to 0.017‰ (μmol kg^− 1)^− 1 for the smaller specimens (150–250 μm). These slopes are in the range of those found for other non-symbiotic species, such as Globigerina bulloides, from laboratory culture experiments. Since the Δδ¹³C_IA-DIC/[CO₃²⁻] slopes from our field data are nearly identical to the slopes established from laboratory culture experiments we assume that the influence of other effects, such as temperature, are negligibly small. If we correct the δ¹³C values of G. inflata for a carbonate ion effect, the δ¹³C_shell and δ¹³C_DIC are correlated with an average offset of 2.11.     

Foraminiferal oxygen and carbon isotopes during the last 34 kyr off northern Japan,northwestern Pacific

Oxygen and carbon isotopes of foraminifera were analyzed in core PC4, water depth 1366 m, off northern Japan, near the east side of the Tsugaru Strait (130 m depth) between the open northwestern Pacific Ocean and the Japan Sea. At present, the site is at the confluence of the Tsugaru Warm Current which flows eastwards out of the Sea of Japan through the Tsugaru Strait, the subarctic Oyashio Current and the subtropic Kuroshio Current. During the Last Glacial Maximum (LGM), the Oyashio Current penetrated further to the South and outflow from the Japan Sea was restricted by glacio-eustatic sea level lowering.The isotopic values of the planktic foraminifer Neogloboquadrina pachyderma (sinistral) and the benthic foraminifer Uvigerina akitaensis reflect rapid millennial-scale paleoceanographic changes between 34 and 6 ka. Hydrographic changes during deglaciation were related to events at high northern latitudes, but Holocene hydrographic changes were dominated by local effects, such as the development of the outflow of the Tsugaru Warm Current. High values of planktic δ¹⁸O during the LGM reflect the southward advance of the Oyashio Current. These values decreased by 0.3‰ from 19.4 to 18.9 ka, then increased by 0.5‰ at 18 ka, with highest values between 17.5 and 15 ka. The δ¹⁸O oscillations between 19.4 and 15 ka may reflect millennial-scale warm–cold oscillations during Heinrich event 1. Planktic microfossil data indicate that cold Oyashio waters flowed from the northwestern Pacific into the Japan Sea via the Tsugaru Strait between 17 and 16 ka, consistent with the occurrence of the highest planktic δ¹⁸O values in core PC4. Planktic δ¹⁸O values rapidly decreased by 0.9‰ at 15 ka, possibly reflecting the effects of both a rapid increase in fresh water flux and rising temperatures in the subarctic North Pacific. During the Younger Dryas, cold event planktic δ¹⁸O values increased by 0.5‰, followed by a gradual decrease by 1‰ from the early to middle Holocene, reflecting a gradual increase in eastward outflow via the Tsugaru Strait with sea level rise. Both planktic and benthic foraminiferal δ¹³C values oscillated between 34 and 10 ka, at relatively large amplitudes (about 0.5‰), then remained relatively stable during the last 10 kyr. Several negative planktic and benthic (∼ − 0.7‰) δ¹³C excursions were present in sediment dated between the precipitation of secondary carbonates during episodic methane release possibly associated with methane release from continental margin sediments.     

Effect of tertiary sewage effluent additions on Prymnesium parvum cell toxicity and stable isotope ratios

We investigated the ability of the ichthyotoxic haptophyte Prymnesium parvum to use sewage-originated nutrients applying stable carbon (C) and nitrogen (N) isotope techniques. P. parvum was cultured under N and phosphorus (P) sufficient and deficient conditions in either sewage effluent-based medium or in a nitrate- and phosphate-based control. Cell densities and toxicities were monitored and stable carbon N isotopes signatures (δ¹³C and δ¹⁵N) of P. parvum and the sewage effluent analysed. Nitrogen and P sufficient cultures achieved the highest biomass followed by P and N deficient cultures, regardless of sewage effluent additions. The P deficient cultures with sewage effluent had higher toxicity, estimated as haemolytic activity (9.4 ± 0 × 10^?5 mg Saponin equiv. cell^?1) compared to the P deficient control and to all N deficient and NP sufficient cultures. Nutrient deficient conditions had no effect on the cell δ¹⁵N, but a decreasing effect on δ¹³C in the inorganic N deficient treatment. Growth in sewage-based media was followed by a substantial increase in the cell δ¹⁵N (10.4–16.1‰) compared to the control treatments (2.4–4.9‰), showing that P. parvum is capable of direct use of sewage-originated N, inorganic as well as organic. Uptake of terrestrial derived C in the sewage treatments was confirmed by a decrease in cell δ¹³C, implying that P. parvum is able to utilize organic nutrients in sewage effluent.     

Discriminating the endogenous and exogenous urinary estrogens in human by isotopic ratio mass spectrometry and its potential clinical value

Estrogens were prohibited in the food producing animals by European Union (96/22/EC directive) and added to the Report on Carcinogens in United States since 2002. Due to very low concentration in serum or urine (～pg/mL), the method of control its abuse had not been fully developed.The endogenous estrogens were separated from urines of 18 adult men and women. The exogenous estrogens were chemical reference standards and over the counter preparations. Two patients of dysfunctional uterine bleeding (DUB) administered exogenous estradiol and the urines were collected for 72 h. The urinary estrogens were separated by high-performance liquid chromatography (HPLC) and confirmed. The exogenous and exogenous estrogens were analyzed by gas chromatography combustion isotope ratio mass spectrometry (GC–C–IRMS) to determine the ¹³C/¹²C ratio (δ¹³C‰).The δ¹³C‰ values of reference standard of E1, E2, and E3 were ?29.36 ± 0.72, ?27.98 ± 0.35, ?27.62 ± 0.51, respectively. The δ¹³C‰ values of the endogenous E1, E2, and E3 were ?21.62 ± 1.07, ?22.14 ± 0.98, and ?21.88 ± 1.16, with P < 0.01 (t-test). Two DUB patients’ urinary estradiol δ¹³C‰ values was depleted to ?28.02 ± 0.33 after the administration. The progesterone, 17α-hydroxyprogesterone, pregnanediol, as well as desogestrel and ethinylestradiol from contraceptives were also determined.Stable carbon isotope analysis can distinguish the endogenous and exogenous urinary estrogen in human.     

Effect of salinity and seawater calcite saturation state on Mg and Sr incorporation in cultured planktonic foraminifera

Trace elements incorporated in planktonic foraminiferal test carbonate are commonly used as paleoproxies. For instance, Mg/Ca ratios are frequently used for reconstructing sea surface temperature and, together with the foraminiferal stable oxygen isotope ratios, are also used as paleosalinity proxy. Foraminiferal Sr/Ca ratios constitute another example of the application of trace elements in paleostudies since they may reflect the Sr/Ca values of seawater. However, over the past few decades it has been proven that the incorporation of trace elements in foraminiferal calcite is controlled by more than one environmental parameter. To quantify the effect of salinity on Mg and Sr incorporation planktonic foraminifera Globigerinoides sacculifer (sensu stricto) were grown in the laboratory under different environmental conditions. Laboratory experiments allowed us to separate a direct salinity effect from a possible independent impact through differences in the calcite saturation state of the seawater (Ω). Although the temperature effect is more important than the salinity effect, a change of 4 salinity units is equivalent to a 1 °C bias on Mg/Ca-based temperatures. This effect of salinity on Mg incorporation is minor. However, when using Mg/Ca-based temperatures in combination with foraminiferal δ¹⁸O to calculate salinity, it cannot be neglected. The present study shows salinity as the overriding control on Mg incorporation within the range of Ω studied (Ω between 5.25 and 6.50; [CO₃²⁻] between 218 and 270 μmol/kg) at a constant temperature of 26 °C. In contrast, Ω appears to be the main control on foraminiferal Sr incorporation (0.10 mmol/mol per 100 µmol/kg rise in [CO₃²⁻]), whereas salinity has a non significant influence on Sr/Ca.     

Seasonal climatic fluctuations in the Late Triassic tropics—High-resolution oxygen isotope records from aragonitic bivalve shells (Cassian Formation,Northern Italy)

Three megalodontoid bivalves from the Upper Triassic Cassian Formation (N Italy, Dolomites) were sampled for δ¹³C and δ¹⁸O sclerochronology (n = 270). With more than 1000 described invertebrate species, the Cassian Formation has one of the best records of an Early Mesozoic tropical fauna. In addition, the Cassian Formation is one of the very few Triassic occurrences with original aragonite preservation, with all studied shells consisting of pristine aragonite. The presence of aragonite and crossed lamellar as well as fibrous prismatic shell microstructures shown for the first time for Triassic megalodontoids suggests absence or minimal impact of diagenetic alteration. The δ¹³C values range from 3.6 to 5.8‰ and show a distinct cyclicity in two studied shells whereas a third shell shows no obvious cyclicity. In one bivalve specimen, the cycles are somewhat offset from δ¹⁸O cycles and in the other specimen δ¹⁸O and δ¹³C curves are inversely correlated. Seasonal variation in freshwater runoff including nutrient input and subsequent changes in plankton productivity during dry and wet seasons may explain δ¹³C cyclicity. δ¹⁸O values show a pronounced cyclicity within each of the studied shells varying from ? 3.6 to ? 1.4‰. The variations in δ¹⁸O suggest a pronounced seasonality in Late Triassic tropical shallow waters of the western Tethys, with inferred seasonal temperature changes ranging from 24 to 32 °C. Influx of fresh water during the rainy seasons (mega-monsoon) or upwelling might also explain part of the variation in δ¹⁸O. The presented data suggest that the diverse Cassian fauna lived under conditions characterized by warm sea-surface waters with a pronounced seasonality. Similar conditions are reported for some modern tropical settings.     

Kinetic characterization of human phosphopantothenoylcysteine synthetase

Phosphopantothenoylcysteine synthetase (PPCS) catalyzes the formation of phosphopantothenoylcysteine from (R)-phosphopantothenate and l-cysteine with the concomitant consumption of a nucleotide triphosphate. Herein, the human coaB gene encoding PPCS is cloned into pET23a and overexpressed in E. coli BL21(DE3), to yield 10 mg of purified enzyme per liter of culture. Detailed kinetic studies found that this PPCS follows a similar Bi Uni Uni Bi Ping Pong mechanism as previously described for the E. faecalis PPCS, except that the human enzyme can use both ATP and CTP with similar affinity. One significant difference for human PPCS catalysis with respect to ATP and CTP is that the enzyme shows cooperative binding of ATP, measured as a Hill constant of 1.7. PPCS catalysis under CTP conditions displayed Michaelis constants of 265 μM, 57 μM, and 16 μM for CTP, PPA, and cysteine, respectively, with a k_cat of 0.53 ± 0.01 s^? 1 for the reaction. Taking into account the cooperativity under ATP condition, PPCS exhibited Michaelis constants of 269 μM, 13 μM, and 14 μM for ATP, PPA, and cysteine, respectively, with a k_cat of 0.56 s^? 1 for the reaction. Oxygen transfer studies found that ¹⁸O from [carboxyl-¹⁸O] phosphopantothenate is incorporated into the AMP or CMP produced during PPCS catalysis, consistent with the formation of a phosphopantothenoyl cytidylate or phosphopantothenoyl adenylate intermediate, supporting similar catalytic mechanisms under both CTP and ATP conditions. Inhibition studies with GTP and UTP as well as product inhibition studies with CMP and AMP suggest that human PPCS lacks strong nucleotide selectivity.