Geochemistry of rare earth elements in cobalt-rich crusts from the Mid-Pacific M seamount

Rare earth elements (RFEs) and major elements of 25 cobalt-rich crusts obtained from different depths of Mid-Pacific M seamount were analyzed using inductively coupled plasma-atomic emission spectrometer and gravimetric method. The results showed that they were hydrogenous crusts with average Sigma REE content of 2084.69 mu g/g and the light REE (LREE)/heavy REE (HREE) ratio of 4.84. The shale-normalized PEE patterns showed positive Ce anomalies. The total content of strictly trivalent REEs increased with water depth. The Ce content and LREE/HREE ratios in Fe-Mn crusts above 2000 in were lower than those below 2000 m. The change in RE E with water depth could be explained by two processes: adsorptive scavenging by setting matters and behaviors of REE in seawater. However, the Ce abundance took no obvious correlation with water depth reflects the constant Ce flux. The Cc in crusts existed mainly as Ce(IV), implying that the oxidative-enriching process was controlled by kinetic factors.

Element enrichment and U-series isotopic characteristics of the hydrothermal sulfides at Jade site in the Okinawa Trough

The geochemical and U-series isotopic characteristics of hydrothermal sulfide samples from the Jade site (127A degrees 04.5'E, 27A degrees 15'N, water depth 1300-1450 m) at Jade site in the Okinawa Trough were analyzed. In the hydrothermal sulfide samples bearing sulfate (samples HOK1 and HOK2), the LREEs are relatively enriched. All the hydrothermal sulfide samples except HOK1 belong to Zn-rich hydrothermal sulfide. In comparison with Zn-rich hydrothermal sulfides from other fields, the contents of Zn, Pb, Ag, Cd, Au and Hg are higher, the contents of Fe, Al, Cr, Co, Ni, Sr, Te, Cs, Ti and U lower, and the Pb-210 radioactivity ratios and Pb-210/Pb ratios very low. In the hydrothermal sulfide mainly composed of sphalerite, the correlations between rare elements Hf and U, and Hf and Mn as well as that between dispersive elements Ga and Zn, are strongly positive; also the contents of Au and Ag are related to Fe-sulfide, because the low temperature promotes enrichment of Au and Ag. Meanwhile, the positive correlations between Fe and Bi and between Zn and Cd are not affected by the change of mineral assemblage. Based on the Pb-210/Pb ratios of hydrothermal sulfide samples (3.99x10(-5)-5.42x10(-5)), their U isotopic composition (U-238 content 1.15-2.53 ppm, U-238 activity 1.07-1.87 dpm/g, U-234 activity 1.15-2.09 dpm/g and U-234/U-238 ratio 1.07-1.14) and their Th-232 and Th-230 contents are at base level, and the chronological age of hydrothermal sulfide at Jade site in the Okinawa Trough is between 200 and 2000 yr.

Tide-influenced acidic hydrothermal system offshore NE Taiwan

Elemental sulfur and hydrogen sulfide emitted offshore of northeastern Taiwan known to local fishermen for generations, but never studied until recently, are found to have originated from a cluster of shallow (< 30 m depth) hydrothermal vents. Among the mounds is a massive 6 m high chimney with a diameter of 4 m at the base composed of almost pure sulfur and discharging hydrothermal fluid containing sulfur particles. The sulfur in the chimney has a delta(34)S= 1.1 parts per thousand that is isotopically lighter than seawater. A yellow smoker at shallow depths with such characteristics has never been reported on anywhere else in the world. Gas discharges from these vents are dominated by CO2 (> 92%) with small amounts of H2S. Helium isotopic ratios 7.5 times that of air indicate that these gases originate from the mantle. High temperature hydrothermal fluids have measured temperatures of 78-116 degrees C and pH (25 degrees C) values as low as 1.52, likely the lowest to be found in world records. Low temperature vents (30-65 degrees C) have higher pH values. Continuous temperature records from one vent show a close correlation with diumal tides, suggesting rapid circulation of the hydrothermal fluids. (c) 2005 Elsevier B.V. All rights reserved.

ISOTOPIC CHARACTERISTICS AND AGE DATING OF THE PUMICE IN OKINAWA TROUGH

The data on the isotope compositions of rubidium, strontium and oxygen in the pumice of Okinawa Trough are reported for the first time. The ages of the pumice were successfully dated with the method of U-series disequilibrium. Then, the material source, crystallization evolution of magma and activity cycles of volcanos are explored. Isotopic data show that pumice magma was originally from the mantle, but had undergone a full crystallization differentiation and had been contaminated to a fair extent by crust-derived materials before the magma was erupted out of the sea floor. According to the dating results available so far, the earliest volcanic eruption in Okinawa Trough occurred about 70,000 a ago and the latest eruption was about 10,000 a B.P. During this period, there were three volcanic eruption cycles which were respectively corresponding to the middle Late Pleistocene, the late Late Pleistocene and the Early Holocene.

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze river) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0-2 cm) were 5-10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C-26-C-33 long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC(15) to nC(22) compounds. Long-chain (> C-20) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (< C-20) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk delta(CTOCTOC)-C-13. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.

Major element, trace element, and Sr, Nd and Pb isotope studies of Cenozoic basalts from the South China Sea

The whole rock K-Ar ages of basalts from the South China Sea basin vary from 3.8 to 7.9 Ma, which suggest that intra-plate volcanism after the cessation of spreading of the South China Sea (SCS) is comparable to that in adjacent regions around the SCS, i.e., Leiqiong Peninsula, northern margin of the SCS, Indochina block, and so on. Based on detailed petrographic studies, we selected many fresh basaltic rocks and measured their major element, trace element, and Sr-Nd-Pb isotope compositions. Geochemical characteristics of major element and trace element show that these basaltic rocks belong to alkali basalt magma series, and are similar to OIB-type basalt. The extent of partial melting of mantle rock in source region is very low, and magma may experience crystallization differentiation and cumulation during the ascent to or storing in the high-level magma chamber. Sr-Nd-Pb isotopic data of these basaltic rocks imply an inhomogeneous mantle below the South China Sea. The nature of magma origin has a two end-member mixing model, one is EM2 (Enriched Mantle 2) which may be originated from mantle plume, the other is DMM (Depleted MORB Mantle). Pb isotopic characteristics show the Dupal anomaly in the South China Sea, and combined with newly found Dupal anomaly at Gakkel ridge in Arctic Ocean, this implies that Dupal anomaly is not only limited to South Hemisphere. In variation diagrams among Sr, Nd and Pb, the origin nature of mantle below the SCS is similar to those below Leiqiong peninsula, northern margin of the SCS and Indochina peninsula, and is different from those below north and northeast China. This study provides geochemical constraints on Hainan mantle plume.

Genesis of Th-230 excess in basalts from mid-ocean ridges and ocean islands: Constraints from the global U-series isotope database and major and rare earth element geochemistry

Based on Th-230-U-238 disequilibrium and major element data from mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs), this study calculates mantle melting parameters, and thereby investigates the origin of Th-230 excess. (Th-230/U-238) in global MORBs shows a positive correlation with Fe-8, P (o), Na-8, and F-melt (Fe-8 and Na-8 are FeO and Na2O contents respectively after correction for crustal fractionation relative to MgO = 8 wt%, P (o)=pressure of initial melting and F (melt)=degree of melt), while Th-230 excess in OIBs has no obvious correlation with either initial mantle melting depth or the average degree of mantle melting. Furthermore, compared with the MORBs, higher (Th-230/U-238) in OIBs actually corresponds to a lower melting degree. This suggests that the Th-230 excess in MORBs is controlled by mantle melting conditions, while the Th-230 excess in OIBs is more likely related to the deep garnet control. The vast majority of calculated initial melting pressures of MORBs with excess Th-230 are between 1.0 and 2.5 GPa, which is consistent with the conclusion from experiments in recent years that D (U)> D (Th) for Al-clinopyroxene at pressures of > 1.0 GPa. The initial melting pressure of OIBs is 2.2-3.5 GPa (around the spinel-garnet transition zone), with their low excess Ra-226 compared to MORBs also suggesting a deeper mantle source. Accordingly, excess Th-230 in MORBs and OIBs may be formed respectively in the spinel and garnet stability field. In addition, there is no obvious correlation of K2O/TiO2 with (Th-230/U-238) and initial melting pressure (P (o)) of MORBs, so it is proposed that the melting depth producing excess Th-230 does not tap the spinel-garnet transition zone. OIBs and MORBs in both (Th-230/U-238) vs. K2O/TiO2 and (Th-230/U-238) vs. P (o) plots fall in two distinct areas, indicating that the mineral phases which dominate their excess Th-230 are different. Ce/Yb-Ce curves of fast and slow ridge MORBs are similar, while, in comparison, the Ce/Yb-Ce curve for OIBs shows more influence from garnet. The mechanisms generating excess Th-230 in MORBs and OIBs are significantly different, with formation of excess Th-230 in the garnet zone only being suitable for OIBs.

Geochemical and isotopic characteristics of volcanic rocks from the northern East China Sea shelf margin and the Okinawa Trough

Volcanic rocks both from the northern East China Sea (NECS) shelf margin and the northern Okinawa Trough are subalkaline less aluminous, and lower in High Field Strength Elements (HFSE). These rocks are higher in Large Ion Lithophile Elements (LILE), thorium and uranium contents, positive lead anomalies, negative Nb-Ta anomalies, and enrichment in Light Rare Earth Elements (LREE). Basalts from the NECS shelf margin are akin to Indian Ocean Mid-Ocean Ridge Basalt (MORB), and rhyolites from the northern Okinawa Trough have the highest Pb-207/Pb-208 and Pb-208/Pb-204 ratios. The NECS shelf margin basalts have lower Sr-87/Sr-86 ratios, epsilon(Nd) and sigma O-18 than the northern Okinawa Trough silicic rocks. According to K-40-Ar-40 isotopic ages of basalts from the NECS shelf margin, rifting of the Okinawa Trough may have been active since at least 3.65-3.86 Ma. The origin of the NECS shelf margin basalt can be explained by the interaction of melt derived from Indian Ocean MORB-like mantle with enriched subcontinental lithosphere. The basalts from both sides of the Okinawa Trough may have a similar origin during the initial rifting of the Okinawa Trough, and the formation of basaltic magmas closely relates to the thinning of continental crust. The source of the formation of the northern Okinawa Trough silicic rocks was different from that of the middle Okinawa Trough, which could have been generated by the interaction of basaltic melt with an enriched crustal component. From the Ryukyu island arc to East China, the Cenozoic basalts have apparently increasing trends of MgO contents and ratios of LREE to Heavy Rare Earth Elements (HREE), suggesting that the trace element variabilities of basalts may have been influenced by the subduction of the Philippine Sea plate, and that the effects of subduction of the Philippine Sea plate on the chemical composition of basaltic melts have had a decreasing effect from the Ryukyu island arc to East China.

Isotopic feature and uranium dating of the volcanic rocks in the Okinawa Trough

Volcanic rocks from the northern and middle Okinawa Trough were dated by uranium-series dating method. Differential fractions using magnetic procedure were designed to separate samples. New report on the ages and isotopic data of rocks in the northern trough (especially black pumice) was discussed. Based on the uranium dates and Sr-Nd isotopic ratio, magmatic evolution process of the Okinawa Trough was noted. Firstly, there have been wide silicic volcanic activities in the Okinawa Trough from late Pleistocene to present, and the volcanic rocks can be divided into three subgroups. Secondly, magma generally came from PREMA source area under the Okinawa Trough. Magmatic evolution in the northern trough was similar to the middle, but different to the south. Finally, volcanic activities indicated that opening of the southern Okinawa Trough did not happen due to the collision between Luson Arc and Eurasian Plate until the early Pleistocene.

Pretreatment Method for Nitrogen Isotopic Analysis of Nitrate in Seawater

A suitable method for the pretreutment of dissolved nitrate samples in seawaters for nitrogen isotopic analysis was established. First, the seawater samples were processed by removing nitrite and amonium. Then Devard's alloy was added in sample for conversion of dissolved nitrate to ammonium. The sample was distilled, and then the ammonium condensate was collected with zeolite. after distillation, the collected condensate was filtered and prepared for determining nitropic values. Some tests of the method were conducted. The distillation condition, the influence of salinity on nitrogen isotopic analysis, absorption of ammonium onto zeolite and an improved method on a large volume of seawater were discussed in this study. The results showed that the distillation step had an average recovery of (104.9 +/- 4.2) % (n = 6) when distillating every 300 mL aliquot of the sample under a strong alkaline condition with 0.5 g devard's alloy and a distillation time of 30 min. The nitrogen isotopic fractionation decreased markedly when salinity was increased from 0% to 0.5%; further increase(1% - 3.5%) showed little effect. The adsorption rate of ammonium onto zeolite had a high yield of (95.96 +/- 1.08) % (n = 6) in average. An improved collection method was used to process a large volume of seawater with several distillations, and had good effect on analysis. The method had been applied to analyze water samples collected from Changjiang estuary. The analytical results indicate that the method is suitable for delta N-15 analysis of dissolved nitrate in seawaters. The present method could provide valuable information about the source and cycle mechanism of dissolved nitrogen in estuary waters.

The nitrogen isotopic composition of dissolved nitrate in the Yangtze River (Changjiang) estuary, China

The nitrogen isotopic composition of dissolved nitrate (delta N-15-NO3-) in surface water of the Yangtze River estuary was determined in four seasons of 2006. delta N-15-NO3- ranged from 0.4 parts per thousand to 6.5 parts per thousand and varied with seasons and geographic regions, reflecting the dynamics of nitrogen cycling in the estuarine ecosystem. delta N-15-NO3- was markedly lower in February than in other seasons and exhibited conservative mixing, which was probably attributed to the NO3- being sourced from the atmospheric deposition and agricultural fertilizer. In the upper estuary, the influence of riverine inputs was important during all surveys. in the turbidity maximum zone, nitrification was found with nitrate depleted in N-15 in May, whereas denitrification resulting in heavy delta N-15-NO3- played an important role in August. More enriched delta N-15-NO3- values coinciding with losses of nitrate concentrations based on the conservative mixing model were found in the adjacent marine area in May, and may reflect obvious phytoplankton assimilation of dissolved nitrate. In this manner, delta N-15-NO3- may be a sensitive indicator of nitrogen sources and biogeochemical processing existing in this estuary in conjunction with the variations of dissolved nitrate and other environmental factors. (C) 2009 Elsevier Ltd. All rights reserved.

Carbon isotopic studies of individual lipids in organisms from the Nansha sea area, China

Carbon isotopes of individual lipids in typical organisms from the Nansha sea area were measured by the GC-IRMS analytical technique. delta(13)C values of saturated fatty acids in different organisms examined are from -25.6parts per thousand to -29.7parts per thousand with the average values ranging from -26.4parts per thousand to -28.2parts per thousand and the variance range of 11.8parts per thousand, between different organisms is also observed. Unsaturated fatty acids have heavy carbon isotopic compositions and the mean differences of 2.9%.9-6.8parts per thousand compared to the same carbon number saturated fatty acids. delta(13)C values of n-alkanes range from -27.5%o to -29.7parts per thousand and their mean values, ranging from -28.6parts per thousand, to -28.9parts per thousand, are very close in different organisms. The mean difference in delta(13)C between the saturated fatty acids and n-alkanes is only 1.5parts per thousand, indicating that they have similar biosynthetic pathways. The carbon isotopic variations between the different carbon-number lipids are mostly within +/-2.0parts per thousand, reflecting that they experienced a biosynthetic process of the carbon chain elongation. At the same time, the carbon isotopic genetic relationships between the biological and sedimentary lipids are established by comparative studies of carbon isotopic compositions of individual lipids in organisms and sediments from the Nansha sea area, which provides scientific basis for carbon isotopic applied research of individual lipids.

Bacterial roles in the formation of high-molecular-weight dissolved organic matter in estuarine and coastal waters: Evidence from lipids and the compound-specific isotopic ratios

High-molecular-weight dissolved organic matter (HMW-DOM, > 1,000 Daltons) is actively involved in the global biogeochemical cycling of many elements, but its carbon sources and detailed formation pathways are still not well understood. In this study, we measured bulk stable carbon and nitrogen isotopic ratios, lipid composition, and compound-specific carbon isotopic ratios of HMW-DOM samples collected from four U.S. estuaries (Boston Harbor/Massachusetts Bay, Delaware/Chesapeake Bay, San Diego Bay, and San Francisco Bay). Analytical results show (1) a fraction of HMW-DOM (lipid associated) in estuarine and coastal waters is derived from bacteria and phytoplankton; (2) this fraction of HMW-DOM is formed by various release processes of bacterial membrane components and bacterial reworking of phytoplankton-derived material; (3) this fraction of HMW-DOM is generally present in all samples from different coastal systems despite variable organic matter inputs and environmental conditions, suggesting an important bacterial role in HMW-DOM formation.

Nitrogen isotopic fractionation during a simulated diatom spring bloom: importance of N-starvation in controlling fractionation

N isotope fractionation (epsilon) was first determined during ambient NO3- depletion in a simulated diatom spring bloom. After 48 h of N-starvation, NH4+ was resupplied to the diatoms in small pulses to simulate grazer-produced N and then epsilon was determined. Large variations in epsilon values were observed: from 2.0-3.6 to 14-0 parts per thousand during NO3- and NH4+ uptake, respectively. This is the first study reporting an epsilon value as low as 0 to 2 parts per thousand for NH4+ uptake and we suggest that greater N demand after N-starvation may have drastically reduced NH3 efflux out of the cells. Thus the N status of the phytoplankton and not the ambient NH4+ concentration may be the important factor controlling epsilon, because, when N-starvation increased, epsilon values for NH4+ uptake decreased within 30 h. This study may thus have important implications for interpreting the delta(15)N of particulate N in nutrient-depleted regimes in temperate coastal oceans.

Environmental changes reflected by sedimentary geochemistry in recent hundred years of Jiaozhou Bay, North China

Sediment geochemical technique was employed to assess how the sediment records reflect the environmental changes of Jiaozhou Bay, a semi-enclosed bay adjacent to Qingdao, China. In the past hundred years, Jiaozhou Bay has been greatly impacted by human interventions. A dated core sediment by Pb-210 chronology was analyzed for trace metals including Li, Cd, Cr, Pb, Cu, Ni, Co, Zn together with C, N, P and BSi. Based on the research, the development of Jiaozhou Bay environment in the past hundred years can be divided into three stages: (1) before the 1980s characterized by relatively low sedimentation rate, weak heavy metal pollution and scarce eutrophication; (2) from the 1980s to 2000, accelerating in the 1990s, during which high sedimentation rates, polluted by heavy metals and the frequent occurrence of red tide; (3) after 2000, the period of the improvement of environment, the whole system has been meliorated including the heavy metal pollution and hypernutrification. (c) 2006 Elsevier Ltd. All rights reserved.