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1.
Past changes in phytoplankton assemblages in Lake Baikal over the last 4.5 Ma, both in population and composition, are inferred from the downcore profiles of the relatively stable chlorophyll derivatives steryl esters of pyropheophorbides a and b (steryl chlorine esters; SCEs) in the 0–200 m section of the BDP-98 drill core, supplemented by the data on biogenic silica (BSi) and total organic carbon (TOC) contents. SCEs-a and -b dominate among sedimentary chlorophyll derivatives in the BDP-98 sediments except for the upper few meters, indicating their high stability during diagenetic alteration of sediments. The depth (age) profiles of SCEs-a are consistent with BSi and TOC profiles and are interpreted as reflecting primary productivity of the lake in the past. Baikal proxies reveal close correlation with marine oxygen isotope records (MIS stratigraphy). These observations confirm that climate change in the northern hemisphere has been a primary factor controlling the total phytoplankton productivity in Lake Baikal during the last several million years.Among SCEs-a, C30 (dinostanol)-SCE-a, a marker of dinoflagellates was identified by GC–MS analysis. SCE-b, a marker of green algae, was identified by its UV–vis spectrum. The ratio of C30-SCE-a to total SCEs-a (TSCEs-a) was higher during 4.5–4.2 and 1.7–1.3 Ma, suggesting that dinoflagellates proliferated preferentially in those periods. The early Pleistocene maximum of this ratio corresponds to the broad minimum of diatom abundance previously suggested to have recorded a prolonged regional cooling. An abrupt increase in the SCE-b/TSCEs-a ratio was observed at 2.5–2.6 Ma, indicating that green algae containing chlorophyll b have proliferated in Lake Baikal during this period. This interval has also been suggested to contain evidence for a significant regional cooling based on minima of diatom abundance and BSi in sediments. The depth profile of C27Δ5 (cholesterol)-SCE-a relative to TSCEs-a showed a trend similar to that of BSi, suggesting that C27Δ5-SCE-a/TSCEs-a ratio is a potential marker of diatoms in Lake Baikal.Certain mismatches between the Lake Baikal profiles of biological indicators and the marine oxygen isotope records, as well as the slight temporal offsets between different Lake Baikal biological marker signals suggest that the regional component of climatic and/or lacustrine environmental changes also have played a role in determining the composition of the Lake Baikal Plio-Pleistocene phytoplankton assemblage.  相似文献   

2.
Temperature and H2O activity can be determined with high precision using metamorphic mineral assemblages that define both a dehydration equilibrium and a temperature-sensitive cation-exchange equilibrium. Such determinations are obtained by applying the Gibbs method and then integrating two resulting differential equations, as illustrated here for the assemblage garnet-chlorite-quartz. The first equation, a geothermometer that monitors temperature based upon Fe–Mg exchange between garnet and chlorite, was calibrated using rocks at Pecos Baldy, New Mexico: 0=0.05 P(bars)–19.02 T(K)+4607 ln K D+24,156 with errors of ±8°C based upon analytical precision. The second equation monitors differences in the activity of water between specimens (1) and (2): 0=(0.1 X Mg–chl, 1 – 2.05)(P 2 – P 1) +[–33.02+5.96 ln(X Fe–chl, 1/X alm, 1)][T 2–T 1 –2.67 RT 1ln[a(H2O)2/a(H2O)1] +5.96 T 1ln(X Fe–chl, 2 X alm, 1/X Fe–chl, 1 X alm, 2).For samples equilibrated at the same pressure and temperature, microprobe analytical errors of 1% limit precision to ±0.01 a(H2O). For samples equilibrated at the same pressure but variable temperature, uncertainty of ±8°C limits precision to ±0.06 a(H2O). Extreme presure sensitivity requires that the H2O-barometer be applied only to rocks where pressure gradients are absent or well-constrained. The geothermometer gives temperatures in agreement with two other garnet-chlorite geothermometers (Dickenson and Hewitt 1986; Ghent et al. 1987) and with garnet-biotite geothermometry (ferry and Spear 1978) over the temperature range 350–520°C. Application of the relative H2O barometer shows variations in the activity of water approaching 0.30 in several study areas. Either pelitic schists commonly equilibrate with a fluid that is not pure H2O, or some pelitic rocks undergo metamorphism in the absence of a free fluid phase.  相似文献   

3.
The chemical structure, source(s), and formation pathway(s) of kerogen-like organic matter (KL) were investigated in recent sediments from the northwestern Black Sea, off the Danube delta. Three sections from a sediment core collected at the mouth of the Sulina branch of the delta, under an oxic water column, were examined: S0 (0–0.5 cm bsf), S10 (10–13 cm bsf), and S20 (20–25 cm bsf). The bulk geochemical features of these sediments (total organic carbon, organic C/N atomic ratio, δ13Corg) were determined. Thereafter, KL was isolated from the samples, as the insoluble residue obtained after HF/HCl treatment. KL chemical composition was investigated via spectroscopic (FTIR, solid state 13C and 15N NMR) and pyrolytic (Curie point pyrolysis–gas chromatography–mass spectrometry) methods, and the morphological features were examined by scanning and transmission electron microscopy. Similar morphological features and chemical composition were observed for the three KLs and they suggested that the selective preservation of land-plant derived material as well as of resistant aliphatic biomacromolecules (probably derived from cell walls of freshwater microalgae) was the main process involved in KL formation. Besides, some melanoidin-type macromolecules (formed via the degradation-recondensation of products mainly derived from proteinaceous material) and/or some encapsulated proteins also contributed to the KL chemical structure.  相似文献   

4.
This report extends our previous studies by investigating oxic and anoxic alteration of chlorophyll in 13 species of microalgae incubated between 3 and 10 years. The experiments were designed to investigate the alteration of chlorophyll as cells senescence, die and decompose. They mimic the initiation of diagenesis without the intervention of (non-microbial) grazing or photochemistry.Anoxic (dark) incubation provided two new observations and substantiated numerous other chlorophyll-a (CHLa) alteration reactions: (i) vinyl reduction, giving meso-CHLa and several derivatives, occurred, adding to observations on the phorbide/deoxophylloerythroetioporphyrin (DPEP) routes; (ii) room temperature anoxic incubation of a diatom (Navicula sp.) for 5.5 years resulted in production of purpurporphyrin-18 free acid (PurPorph-18-FA), a functionalized porphyrin and direct precursor of a specific C-30 β-H etioporphyrin. Oxic conditions typically led to high amounts of the allomers of CHLa, pheophorbide-a, and pheophytin-a, as well as to the appearance of purpurin-18 (PUR18) and/or its phytyl ester (PE). Mg-PUR18-PE, chlorin-p6-PE (the hydrolysis product of PUR18-PE) and two forms of chlorin-e6 (PE and free acid) were also often present.Such experiments have proved quite valuable for investigation of senescence/death induced alteration of the chlorophylls. In this manner, the processes can be better understood, vs. reactions occurring during grazing (heterotrophy) and early diagenesis in sediments. Various routes to specific ETIO series porphyrins from the chlorophyll-a nucleus are suggested on the basis of these data.  相似文献   

5.
The behaviour of synthetic Mg-ferrite (MgFe2O4) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K0=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by a0+a1*(T–298)+a2/(T–298)2, where a0=9.1(1) 10–6 K–1, a1=4.9(2) 10–9 K–2 and a2= 5.1(5) 10–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol–1 and =–17.6(± 1.2) kJ mol–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe2O4, which shows that the high-pressure transition from spinel to orthorombic CaMn2O4-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe2O3.  相似文献   

6.
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.  相似文献   

7.
The Tin Zebane gabbro–anorthosite layered mafic intrusion represented by plagioclase-rich cumulates forms a set of small lenticular to round-shaped mainly undeformed bodies intruding the Pan-African high-pressure metamorphic rocks from western Hoggar (Tuareg shield, southwest Algeria). The coarse-grained anorthosites are mainly made of slightly zoned bytownite (An86–74) with the higher anorthite content at the cores. Anorthosites are interlayered with leucogabbros and gabbros that show preserved magmatic structures and with olivine gabbros characterised by coronitic textures. The primary assemblage in gabbros includes plagioclase (An93–70), olivine (Fo77–70), zoned clinopyroxene (En43–48Fs05–13Wo41–49 with Al2O3 up to 4.3 wt.%) and rare orthopyroxene (En73–78). Pyroxenes and olivine are commonly surrounded by Ca-amphibole. The olivine–plagioclase contact is usually marked by a fine orthopyroxene–Cr-spinel–amphibole symplectite. A magnesian pigeonite (En70–75Fs19–20Wo6–10) is also involved in corona. The coronitic minerals have equilibrated with the primary mineral rims at P–T–aH2O conditions of 797 ± 42 °C for aH2O=0.5 and 808 ± 44 °C for aH2O=0.6 at 6.2 ± 1.4 kbar. The Tin Zebane gabbroic rocks are depleted in REE with a positive Eu anomaly, high Sr (>10 * chondrite) and Al2O3 concentrations (17–33%) that support plagioclase accumulation with the extreme case represented by the anorthosites. The REE patterns can be modelised using plagioclase, clinopyroxene and orthopyroxene REE signature, without any role played by accessory minerals. High MgO content points to olivine as a major cumulate phase. Anorthositic gabbros Sr and Nd isotopic initial ratios are typical of a depleted mantle source (Sri=0.70257–0.70278; Nd=+5.9 to +7.8). This isotopic signature is identical to that of the 10-km wide 592 Ma old dyke complex composed of alkaline to peralkaline granites and tholeiitic gabbros and one single bimodal complex can be inferred. The source of the Tin Zebane basic rocks corresponds to the prevalent mantle (PREMA). The Tin Zebane complex was emplaced along the mega-shear zone bounding to the west the Archaean In Ouzzal metacraton. The model proposed suggests a linear lithospheric delamination along this rigid and cold terrane due to post-collisional transtensional movements. This allowed the asthenosphere to rise rapidly and to melt by adiabatic pressure release. Transtension along a rigid body allowed these mantle melts to reach the surface rapidly without any crustal contamination.  相似文献   

8.
The climatology and interannual variability of winter phytoplankton was analyzed at the Long Term Ecological Research Station MareChiara (LTER-MC, Gulf of Naples, Mediterranean Sea) using data collected from 1985 to 2006. Background winter chlorophyll values (0.2–0.5 μg chl a dm−3) were associated with the dominance of flagellates, dinoflagellates, and coccolithophores. Winter biomass increases (<5.47 μg chl a dm−3) were often recorded until 2000, generally in association with low-salinity surface waters (37.3–37.9). These blooms were most often caused by colonial diatoms such as Chaetoceros spp., Thalassiosira spp., and Leptocylindrus danicus. In recent years, we observed more modest and sporadic winter biomass increases, mainly caused by small flagellates and small non-colonial diatoms. The resulting negative chl a trend over the time series was associated with positive surface salinity and negative nutrient trends. Physical and meteorological conditions apparently exert a strict control on winter blooms, hence significant changes in winter productivity can be foreseen under different climatic scenarios.  相似文献   

9.
We determined how the species used for calibration affects the accuracy of in situ chlorophyll a (chl a) measurements by fluorometry using single-species cultures and natural phytoplankton populations from Winyah Bay, South Carolina, USA. When a diatom was used for calibration, chl a in a dinoflagellate culture was overestimated by 66 ± 7%, whereas concentrations of a cryptophyte, chlorophyte, and cyanobacterium were underestimated by 16 ± 20%, 40 ± 7%, and 71 ± 33%, respectively. In natural populations, the combination of species-specific and environmentally induced variation in the ratio of fluorescence to chl a (F Chl−1) led to an overestimate by the in situ fluorometer of 40–169% for an April experiment and an underestimate of 4–50% in July. Even when field samples were dominated by diatoms, environmental effects resulted in highly variable predictions of chl a. Thus, while a carefully selected calibration species can improve estimates of in vivo chl a in the laboratory, calibration of in situ fluorometers should be done with natural communities collected from the site of interest.  相似文献   

10.
This report extends previous work ([Louda et al., 1998a] and [Louda et al., 1998b]. Chlorophyll degradation during senescence and death. Organic Geochemistry 29, 1233–1251.) in which we detailed type-I (alteration) and -II (destruction) degradation of chlorophyll with representative fresh water phytoplankton. The present study covers similar experiments with marine phytoplankton, namely, a cyanobacterium (“ANA” Anacystis sp), a coccolithophore (“COC” Coccolithophora sp.), a dinoflagellate (“GYM” Gymnodinium sp.) and two diatoms (“CYC” Cyclotella meneghiniana and “THAL” Thalassiosira sp.). Mg loss (‘pheophytinization') was rapid and continuous in all species under room-oxic conditions and slow or sporadic under anoxic conditions. The proportion of dephytylated pigments (pheophorbides-a, chlorophyllides-a), relative to the phytylated forms (chlorophyll-a, pheophytins-a), increased over the first year under room-oxic conditions and in room-anoxic conditions only in “CYC”. Pheophorbide-a was converted to pyropheophorbide-a within 15 months only in “THAL” and “ANA”, and slightly in “COC”. After 9–15 months of oxic incubation, “COC” was found to contain traces of purpurin-18 phytyl ester. Consideration of carotenoid pigments is also included herein. All fucoxanthin containing species, except “THAL”, exhibited conversion of fucoxanthin to fucoxanthinol in room-oxic conditions. Diadinoxanthin was rapidly de-epoxidized to give diatoxanthin within the first 2–4 weeks. Diatoxanthin then disappeared from all species by 15 months with a concurrent increase in a pigment which we tentatively identify as a cis-zeaxanthin. Incubations of pure cultures are found to be an effective way by which to model the early type-I reactions for both chlorophylls and carotenoids. The influence of oxygen during senescence-death and the onset of early diagenesis is of paramount importance. The absence of oxygen and, by inference, aerobic microbiota, retards the breakdown of these pigments dramatically.  相似文献   

11.
Benthic metabolism and nutrient exchange across the sediment-water interface were examined over an annual cycle at four sites along a freshwater to marine transect in the Parker River-Plum Island Sound estuary in northeastern Massachusetts, U.S. Sediment organic carbon content was highest at the freshwater site (10.3%) and decreased along the salinity gradient to 0.2% in the sandy sediments at the marine end of the estuary. C:N ratios were highest in the mid estuary (23:1) and lowest near the sea (11:1). Chlorophyll a in the surface sediments was high along the entire length of the estuary (39–57 mg chlorophyll a m−2) but especially so in the sandy marine sediments (172 mg chlorophyll a m−2). Chlorophyll a to phaeophytin ratios suggested most chlorophyll is detrital, except at the sandy marine site. Porewater sulfide values varied seasonally and between sites, reflecting both changes in sulfate availability as overlying water salinity changed and sediment metabolism. Patterns of sediment redox potential followed those of sulfide. Porewater profiles of inorganic N and P reflected strong seasonal patterns in remineralization, accumulation, and release. Highest porewater NH4 + values were found in upper and mid estuarine sediments, occasionally exceeding 1 mM N. Porewater nitrate was frequently absent, except in the sandy marine sediments where concentrations of 8 μM were often observed. Annual average respiration was lowest at the marine site (13 mmol O2 m−2 d−1 and 21 mmol TCO2 m−2 d−1) and highest in the mid estuary (130 mmol O2 m−2 d−1 and 170 mmol TCO2 m−2 d−1) where clam densities were also high. N2O and CH4 fluxes were low at all stations throughout the year: Over the course, of a year, sediments varied from being sources to sinks of dissolved organic C and N, with the overall spatial pattern related closely to sediment organic content. There was little correlation between PO4 3− flux and metabolism, which we attribute to geochemical processes. At the two sites having the lowest salinities, PO4 3− flux was directed into the sediments. On average, between 22% and 32% of total system metabolism was attributable to the benthos. The mid estuary site was an exception, as benthic metabolism accounted for 95% of the total, which is attributable to high densities of filter-feeding clams. Benthic remineralization supplied from less than 1% to over 190% of the N requirements and 0% to 21% of the P requirements of primary producers in this system. Estimates of denitrification calculated from stoichiometry of C and N fluxes ranged from 0% for the upper and mid estuary site to 35% for the freshwater site to 100% of sediment organic N remineralization at the marine site. We hypothesize that low values in the upper and mid estuary are attributable to enhanced NH4 + fluxes during summer due to desorption of exchangeable ammonium from rising porewater salinity. NH4 + desorption during summer may be a mechanism that maintains high rates of pelagic primary production at a time of low inorganic N inputs from the watershed.  相似文献   

12.
A. Proyer  E. Mposkos  I. Baziotis  G. Hoinkes 《Lithos》2008,104(1-4):119-130
Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti–)clinohumite and phlogopite were observed in calcite–dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO–MgO–Al2O3–SiO2–CO2 (CMAS–CO2) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite–calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and aCO2 ~ 0.01. The thermodynamic model predicts that no matter what activity of CO2, garnet has to be present in aluminous calcite–dolomite-marble at UHP conditions.  相似文献   

13.
The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S1 to S6) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D1, autumn); August 2001 (D2, winter); October 2001 (D3, spring) and January 2002 (D4, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g− 1) were found in the northern part of the river (S1, average D1–D4), near the mountains and a copper mine, and then decreased downstream to 209 μg g− 1 (S6). Total Zn showed an irregular variation, with higher values at S1 (1290 μg g− 1) and high values in some winter sampling (1384 μg g− 1 S4, S5–D2). Pb showed different trends, increasing from S1 to S6 (17 to 61 μg g− 1), with the highest values in the summer samples (83 μg g− 1, S4–S6, D4), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D1–D4). The highest values of total organic matter, carbonate and conductivity were found in S6, which has the smallest size particles, while at S1 the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g− 1, S1) to 16% (32 μg g− 1, S6); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S1) to 34% (S6), but copper content was lower (214 to 68 μg g− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g− 1, S1 to S6). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S1 were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S6 the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g− 1, respectively).  相似文献   

14.
The unit-cell and atomic parameters of perdeuterated brushite have been extracted from Rietveld analysis of neutron powder diffraction data within the temperature range 4.2 to 470 K. The thermal expansion of brushite is anisotropic, with the largest expansion along the b axis due principally to the effect of the O(1)···D(4) and O(3)···D(2) hydrogen bonds. Expansion along the c axis, influenced by the Ow1···D(5) interwater hydrogen bond, is also large. The high temperature limits for the expansion coefficients for the unit-cell edges a, b and c are 9.7(5) × 10–6, 3.82(9) × 10–5 and 5.54(5) × 10–5 K–1, respectively, and for the cell volume it is 9.7(1) × 10–5 K–1. The angle displays oscillatory variation, and empirical data analysis results in = 1.28(3) × 10–6sin(0.0105 T) K–1, within this temperature range. The evolution of the thermal expansion tensor of brushite has been calculated between 50 T 400 K. At 300 K the magnitudes of the principal axes are 11 = 50(6) × 10–6 K–1, 22 = 26.7(7) × 10–6 K–1 and 33 = 7.0(5) × 10–6 K–1. The intermediate axis, 22, is parallel to b, and using IRE convention for the tensor orthonormal basis, the axes 11 and 33 have directions equal to (–0.228, 0, –0.974) and (–0.974, 0, 0.228) respectively. Under the conditions of these experiments, the onset of dehydration occurred at temperatures above 400 K. Bond valence analysis combined with assessments of the thermal evolution of the bonding within brushite suggests that dehydration is precipitated through instabilities in the chemical environment of the second water molecule.  相似文献   

15.
We carried out reversed piston-cylinder experiments on the equilibrium paragonite = jadeite + kyanite + H2O at 700°C, 1.5–2.5 GPa, in the presence of H2O-NaCl fluids. Synthetic paragonite and jadeite and natural kyanite were used as starting materials. The experiments were performed on four different nominal starting compositions: X(H2O)=1.0, 0.90, 0.75 and 0.62. Reaction direction and extent were determined from the weight change in H2O in the capsule, as well as by optical and scanning electron microscopy (SEM). At X(H2O)=1.0, the equilibrium lies between 2.25 and 2.30 GPa, in good agreement with the 2.30–2.45 GPa reversal of Holland (Contrib Miner Petrol 68:293–301, 1979). Lowering X(H2O) decreases the pressure of paragonite breakdown to 2.10–2.20 GPa at X(H2O)=0.90 and 1.85–1.90 GPa at X(H2O)=0.75. The experiments at X(H2O) = 0.62 yielded the assemblage albite + corundum at 1.60 GPa, and jadeite + kyanite at 1.70 GPa. This constrains the position of the isothermal paragonite–jadeite–kyanite–albite–corundum–H2O invariant point in the system Na2O–Al2O3–SiO2–H2O to be at 1.6–1.7 GPa and X(H2O)~0.65±0.05. The data indicate that H2O activity, a(H2O), is 0.75–0.86, 0.55–0.58, and <0.42 at X(H2O)=0.90, 0.75, and 0.62, respectively. These values approach X(H2O)2, and agree well with the a(H2O) model of Aranovich and Newton (Contrib Miner Petrol 125:200–212, 1996). Our results demonstrate that the presence or absence of paragonite can be used to place limits on a(H2O) in high-pressure metamorphic environments. For example, nearly pure jadeite and kyanite from a metapelite from the Sesia Lanzo Zone formed during the Eo-Alpine metamorphic event at 1.7–2.0 GPa, 550–650°C. The absence of paragonite requires a fluid with low a(H2O) of 0.3–0.6, which could be due to the presence of saline brines.  相似文献   

16.
In order to study the first steps of incorporation of lipids in recent organic-rich sediments into free and bound fractions, we have selected the Santa Barbara Basin, off California. This basin with a maximum of 590 m water depth is characterized by high phytoplankton production in surface waters and a low oxygen content in bottom waters. Sediments show the following features: high sedimentation rate ≈ 4 mm/yr, no bioturbation, and development of a bacterial mat community at the surface with predominance of sulphur-oxidizing bacteria trapping particles, thus preventing re-distribution of sediment, which permit a unique observations of organic sedimentation on a new few years basis.A sediment core has been divided into 2 cm thick slices corresponding to a time resolution of ≈5 years, from 1835 up to 1987. Samples have been analyzed using a multi-parameter approach, such as for plankton species identification, carbon stable isotope ratios and, as reported here, for lipid organic tracers. Organic tracers have been analyzed in the sterol and fatty series for both free and bound compounds by gas chromatography and gas chromatography/mass spectrometry.The incorporation processes of sterols with depth appear different for free and bound compounds. Total free sterol concentrations show high values in surface sediments (≈ 100 μg/g dry sediment), rapidly decrease up to ≈ 10 cm depth and remain at a constant value of 30–40 μg/g. Total bound sterol concentrations show low values in surface sediment (13.6 μg/g), and vary irregularly with depth up to a value of 55 μg/g at 7.3 m, and then remain constant at 25–26 μg/g.Profiles of evolution with depth of free C27, C28 sterols show a regular decrease, whereas C29 sterols show an irregular decrease with anomalies at 7.3 cm (approximately age: 1977–1978) and at 14.1 cm (1962–1964). Profiles of bound compounds are rather different, very regular for C28 sterols, irregular with oscillations for C27 and C29 sterols at 7.3, 12.2 and 18.0 cm (1954–1956), suggesting a different mode of incorporation and probably different inputs for C27, C29 and C28 sterols.The study of the kinetics of degradation of sterols between surface (1987) and 10.5 cm (1968–1972) shows that C27 compounds are degraded at a slight higher rate (0.53 μg/μg of initial C27 concentration/ year) than are C28 and C29 compounds (0.047 μg/μg of initial concentration/year). An intermediate value is found for brassicasterol: 0.049 μg/μg/year.  相似文献   

17.
In-situ synchrotron X-ray diffraction experiments were conducted using the SPEED-1500 multi-anvil press of SPring-8 on stishovite SiO2 and pressure-volume-temperature data were collected at up to 22.5 GPa and 1,073 K, which corresponds to the pressure conditions of the base of the mantle transition zone. The analysis of room-temperature data yielded V0=46.56(1) Å3, KT 0=296(5) GPa and K T =4.2(4), and these properties were consistent with the subsequent thermal equation of state (EOS) analyses. A fit of the present data to high-temperature Birch-Murnaghan EOS yielded (KT /T) P =–0.046(5) GPa K–1 and = a + bT with values of a =1.26(11)×10–5 K–1 and b =1.29(17)×10–8 K–2. A fit to the thermal pressure EOS gives 0=1.62(9)×10–5 K–1, ( K T / T) V =–0.027(4) GPa K–1 and (2P /T 2) V =27(5)×10–7 GPa K–2. The lattice dynamical approach by Mie-Grüneisen-Debye EOS yielded 0=1.33(6), q =6.1(8) and 0=1160(120) K. The strong volume dependence of the thermal pressure of stishovite was revealed by the analysis of present data, which was not detectable by the previous high-temperature data at lower pressures, and this yields ( K T / T) V 0 and q 1. The analyses for the fictive volume for a and c axes show that relative stiffness of c axis to a axis is similar both on compression and thermal expansion. Present EOS enables the accurate estimate of density of SiO2 in the deep mantle conditions.  相似文献   

18.
Rainfall events cause episodic discharges of groundwaters contaminated with septic tank effluent into nearshore waters of the Florida keys, enhancing eutrophication in sensitive coral reef communities. Our study characterized the effects of stormwater discharges by continuously (30-min intervals) measuring salinity, temperature, tidal stage, and dissolved oxygen (DO) along an offshore eutrophication gradient prior to and following heavy rainfall at the beginning of the 1992 rainy season. The gradient included stations at a developed canal system (PP) on Big Pine Key, a seagrass meadow in a tidal channel (PC), a nearshore patch reef (PR), a bank reef at Looe Key National Marine Sanctuary (LK), and a blue water station (BW) approximately 9 km off of Big PIne Key. Water samples were collected at weekly intervals during this period to determine concentrations of total nitrogen (TN), ammonium (NH4 +), nitrate plus nitrite NO3 ? plus NO2 ?), total phosphorus (TP), total dissolved phosphorus (TDP), soluble reactive phosphorus (SRP), and chlorophyll a (chl a). Decreased salinity immediately followed the first major rainfall at Big Pine Key, which was followed by anoxia (DO <0.1 mg I?1), high concentrations of NH4 + (≈24 μM), TDP (≈1.5 μM), and chl a (≈20 μg I?1). Maximum concentration of TDP (≈0.30 μM) also followed the initial rainfall at the PC, PR, and LK stations. In contrast, NH4 + (≈4.0 μM) and chl a (0.45 μg I?1) lagged the rain event by 1–3 wk, depending on distance from shore. The highest and most variable concentrations of NH4 +, TDP, and chl a occurred at PP, and all nutrient parameters correlated positively with rainfall. DO at all stations was positively correlated with tide and salinity and the lowest values occurred during low tide and low salinity (high rainfall) periods. Hypoxia (DO <2.5 mg I?1) was observed at all stations follwing the stormwater discharges, including the offshore bank reef station LK. Our study demonstrated that high frequency (daily) sampling is necessary to track the effects of episodic rainfall events on water quality and that such effects can be detected at considerable distances (12 km) from shore. The low levels of DO and high levels of nutrients and chl a in coastal waters of the Florida Keys demand that special precautions be exercised in the treatment and discharge of wastewaters and land-based runoff in order to preserve sensitive coral reef communities.  相似文献   

19.
The geochemistry of dissolved and suspended loads in river catchments of two low mountain ranges in Central Europe allows comparison of pertinent chemical weathering rates. Distinct differences in lithology, i.e. granites prevailing in the Black Forest compared to Palaeozoic sediments in the Rhenish Massif, provide the possibility to examine the influence of lithology on weathering. Here we determine the origin of river water using the stable isotope ratio δ18OH2O and we quantify the geogenic proportions of sulphate from stable isotope ratios δ34SSO4 and δ18OSO4. Particularly in catchments with abundant pyrite, determination of the geogenic amount of sulphate is important, since oxidation of pyrite leads to acidity, which increases weathering. Our results show that spatially averaged silicate weathering rates are higher for the river catchments Acher and Gutach in the Black Forest (10–12 t/km2/yr) compared to the river catchments of the Möhne dam and the Aabach dam in the Rhenish Massif (2–6 t/km2/yr). Correspondingly, the CO2 consumption by silicate weathering in the Black Forest (334–395 × 103 mol/km2/yr) is more than twice as high as in the Rhenish Massif (28–151 × 103 mol/km2/yr). These higher rates for watersheds of the Black Forest are likely due to steeper slopes leading to higher mechanical erosion with respective higher amounts of fresh unweathered rock particulates and due to the fact that the sediments in the Rhenish Massif have already passed through at least one erosion cycle. Carbonate weathering rates vary between 12 and 38 t/km2/yr in the catchments of the Rhenish Massif. The contribution of sulphuric acid to the silicate weathering is higher in the catchments of the Rhenish Massif (9–16%) than in the catchments of the Black Forest (5–7%) due to abundant pyrite in the sediments of the Rhenish Massif. Three times higher long-term erosion rates derived from cosmogenic nuclides compared to short-term erosion rates derived from river loads in Central Europe point to three times higher CO2 consumption during the past 103 to 104 years.  相似文献   

20.
A stepwise linear regression analysis was carried out on both 0–1 and 0–10 cm surface samples from a transect across the marsh at Little Dipper Harbour, New Brunswick. Only the 0–1 cm surface samples produce statistically reliable results (R2=0.705; R′2=0.609). These results are in sharp contrast to those obtained from British Columbia marshes where infaunal habitat and taphonomic biasing result in 0–10 cm samples producing the best results using stepwise linear regression. The fundamental difference in the apparent preferred habitats of marsh foraminifera in these areas pose difficulties for researchers attempting to develop transfer function training sets that can be applied over wide areas in paleo-sea-level research.  相似文献   

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