Zenghui Yu

Heavy metals in Changjiang estuarine and offshore sediments: responding to human activities

The Changjiang (Yangtze) estuarine and offshore sediments were analyzed for total heavy metals concentrations and chemical fractions. Distributions of heavy metals show typical banded diffusion pattern, with high concentrations near the river mouth and following a decreasing trend in the offshore direction. According to chemical fractions, Fe/Mn oxide fraction is the major non-residual fraction in the Changjiang estuarine and offshore sediments. Higher percentage of non-residual fraction of Pb implies that, the industrial contaminations transported via the atmosphere and river input, may affect the non-residual fraction of heavy metals. Over past fifteen years, the concentration of Pb normalizing to Al presents significant increasing trend, corresponding to the effect of human activities. By comparison of heavy metals fractions in 2003 to 2006, it has been realized that increasing water and sediment may cause a higher percentage non-residual fraction of Cu in the southern part of offshore muddy sediments.

Dominance of terrigenous particulate organic carbon in the high-turbidity Shuangtaizihe estuary

Abstract Suspended sediment samples were collected from the high-turbidity Shuangtaizihe estuary to analyze particulate organic carbon (POC) and stable carbon isotope composition (δ13C) of organic materials. The POC values of the Shuangtaizihe estuary are relatively low (1.2–1.4%) but remain stable over the whole salinity range sampled, which suggests the predominance of a terrigenous source over the mass transport of organic materials in the estuary. The δ13C values of particulate organic materials (−25.0 to −23.5‰) are heavy compared to detritus of higher plants (e.g. tree leaves), but similar to other Chinese rivers. The compositional characteristics of POC and δ13C indicate a large and isotopically constant material source from the organic matter reservoir of soils over the drainage basin.

Two possible hydrothermal vents in the northern Okinawa Trough

As the Okinawa Trough is a back-arc basin in early spreading, modern submarine hydrothermal activity and minerallization have many characteristics which have aroused wide attention. Up to now, three well-known hydrothermal venting areas are all located in the middle part of the trough. During two cruise investigations to map and sample the seafloor, numbers ofCalyptogena sp. shells were dredged at two sites in the northern trough with comparatively thicker crust and numerous submarine volcanoes. Based on the fact thatCalyptogena sp. is only observed around the hydrothermal vents and lives on hydrothermal activities, it is predicted that there is the possibility of modern hydrothermal activities in the northern part of the trough. In this note, the shell is carefully characterized and the sample locations with possible hydrothermal activity are given. It is pointed out that the research of biogenic fossils to trace hydrothermal activity changes in venting time, strength fluctuations, evolution in chemical compositions and so on should be stressed in the future in addition to the study of the ecological characteristics of hydrothermal organisms.

Geochemical features of trace and rare earth elements of pumice in middle Okinawa Trough and its indication of magmatic process

Pumice, the most widely distributed volcanic rock in Okinawa Trough, is loose and porous. Since its formation, it has definitely suffered from the denudation of the sea to different degrees. In order to truly reveal the geochemical features of pumice, we choose the method of mineral separation. Firstly, the phenocryst is separated from glass. Then the phenocryst is divided into light and heavy mineral compositions. By ICP-MS (inductively coupled plasma mass spectrometry) analytical technology, the contents of trace and rare earth elements in the whole pumice, the glass and the heavy and light mineral compositions are determined respectively. By researching the elemental geochemical features, the magma dynamic processes are found. It shows that the initial magma for the pumice in Okinawa Trough came from the depleted mantle, from which the N-MORB (normal type of mid-ocean ridge basalt) is formed, homologous with the local basalts. But they are formed in different periods of magma crystal fractionation. Featured with sufficient crystal fractionation for pumice, it is found that the earlier crystallizing minerals are olivine, plagioclase and pyroxene. The pumice magma, formed from the depleted mantle, was mixed with additional subduction-related materials (components), and contaminated with the mass from upper crust when it rose up into the crust. As the Okinawa Trough is a back-arc basin in its early back-arc spreading stage, its magmatism has a series of its own unique characteristics, different from not only the mid-ocean ridge expansion, but also the mature back-arc basin.

Rare earth element geochemistry of hydrothermal deposits from Southwest Indian Ridge

The REE compositions of hydrothermal deposits and basalt samples from the Southwest Indian Ridge (SWIR) were determined with ICP-MS. The results show that there are significant differences between different types of samples although all samples show relative LREE enrichment. The contents of REE in hydrothermal sulfides and alterated rocks samples are lower (from 7.036×10−6 to 23.660×10−6), while those in the white chimney deposits are relatively higher (ranging from 84.496×10−6 to 103.511×10−6). Both of them are lower than basalts. Chondrite-normalized REE distribution patterns show that sulfides and alterated rocks samples are characterized by significant positive Eu anomalies. On the contrary, white chimney deposits have obvious negative Eu anomalies, which may be caused by abundant calcite existing in the white chimney samples. Both the content and distribution pattern of REE in sulfides suggest that REE most possibly is originally derived from hydrothermal fluids, but influenced by the submarine reducing ore-forming environment, seawater convection, mineral compositions as well as the constraint of mineral crystallizations.

Mineralogical characteristics of polymetallic sulfides from the Deyin-1 hydrothermal field near 15°S, southern Mid-Atlantic Ridge

A seafloor hydrothermal field, named Deyin-1 later, near 15°S southern Mid-Atlantic Ridge (SMAR) was newly found during the 22nd cruise carried out by the China Ocean Mineral Resources Research & Development Association (COMRA). Sulfide samples were collected at three stations from the hydrothermal field during the 26th cruise in 2012. In this paper, mineralogical characteristics of the sulfides were analyzed with optical microscope, X-ray diffractometer, scanning electron microscope and electron microprobe to study the crystallization sequence of minerals and the process of hydrothermal mineralization. According to the difference of the ore-forming metal elements, the sulfide samples can be divided into three types: (1) the Ferich sulfide, which contains mainly pyrite and chalcopyrite; (2) the Fe-Cu-rich sulfide consisting predominantly of pyrite, chalcopyrite and isocubanite, with lesser amount of sphalerite, marmatite and pyrrhotine; and (3) the Fe-Zn-rich sulfide dominated by pyrite, sphalerite and marmatite, with variable amounts of chalcopyrite, isocubanite, pyrrhotine, marcasite, galena and gratonite. Mineral precipitations in these sulfides are in the sequence of chalcopyrite (isocubanite and possible coarse pyrite), fine pyrite, sphalerite (marmatite), galena, gratonite and then the minerals out of the dissolution. Two morphologically distinct generations (Py-I and Py-II) of pyrite are identified in each of the samples; inclusions of marmatite tend to exist in the coarse pyrite crystals (Py-I). Sphalerite in the Fe-Zn-rich sulfide is characterized by a “chalcopyrite disease” phenomenon. Mineral paragenetic relationships and a wide range of chemical compositions suggest that the environment of hydrothermal mineralization was largely changing. By comparison, the Fe-rich sulfide was formed in a relatively stable environment with a high temperature, but the conditions for the formation of the Fe-Cu-rich sulfide were variable. The Fe-Zn-rich sulfide was precipitated during the hydrothermal venting at relatively low temperature.

Geochemical characteristics of major and trace elements in the Okinawa Trough basaltic glass

The Okinawa Trough (OT) is a back-arc basin at an initial spreading stage that is under the influence of subduction of the Philippine Sea Plate. In this study, we analyzed the geochemical compositions of basaltic glass in the OT and discussed the effects of different magmatic sources, evolution, and subducted components in basalts. Our results showed that the middle and southern regions of the OT exhibit characteristics consistent with an iron-rich tholeiite series. Trace element proportions conform to the typical spider diagram pattern characteristic of back-arc basin basalts, rich in large ion lithophile elements (LILEs) including Rb, Ba, Pb, U, and Th, while depleted in high field-strength elements (HFSEs) including Nb, Ta, Zr, Hf, and Ti. The distribution of rare earth elements (REEs) is also consistent with enrichment by right-leaning light rare earth elements (LREEs). The addition of enriched mantle type I (EMI) materials as well as mantle heterogeneity may have led to variable degrees of enrichment in different regions. The magma source of the middle trough has undergone crystallization towards pyroxene, while development of plagioclase was restricted partly, and the crystallization of spinel and olivine ceased altogether. At the same time, crystallization of the southern OT magma source was dominated by olivine and including the formation of plagioclase, pyroxene, and magnetite (or titanomagnetite). Finally, the results of this study showed that 90% Th, 95% Ba in the southern basalt, 50%–70% Th and 70%–90% Ba in the middle basalt originated from subducted component. Different subducted component influence may be due to different subduction zone structural feature.

Geochemical features of sulfides from the Deyin-1 hydrothermal field at the southern Mid-Atlantic Ridge near 15°S

In this study, geochemical compositions of elements in sulfide samples collected from the Deyin-1 hydrothermal field near the 15°S southern Mid-Atlantic Ridge (SMAR) were analyzed by the X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) to examine the enrichment regulations of ore-forming elements and hydrothermal mineralization. These sulfide precipitates can be classified macroscopically into three types: Fe-rich sulfide, Fe-Cu-rich sulfide and Fe-Zn-rich sulfide, and are characterized by the enrichment of base metal elements along with a sequence of Fe>Zn>Cu. Compared with sulfides from other hydrothermal fields on MAR, Zn concentrations of sulfides in the research area are significantly high, while Cu concentrations are relatively low. For all major, trace or rare-earth elements (REE), their concentrations and related characteristic parameters exhibit significant variations (up to one or two orders of magnitude), which indicates the sulfides from different hydrothermal vents or even a same station were formed at different stages of hydrothermal mineralization, and suggests the variations of chemical compositions of the hydrothermal fluid with respect to time. The hydrothermal temperatures of sulfides precipitation decreased gradually from station TVG10 (st.TVG10) to st.TVG12, and to st.TVG11, indicating that the precipitation of hydrothermal sulfides is subjected to conditions changed from high temperature to low temperature, and that the hydrothermal activity of study area was at the late stage of a general trend of evolution from strong to weak. The abnormally low concentrations of REE in sulfides and their similar chondrite-normalized REE patterns show that REEs in all sulfides were derived from a same source, but underwent different processes of migration or enrichment, or sulfides were formed at different stages of hydrothermal mineralization. The sulfides collected from the active hydrothermal vent were mainly attributed to precipitating directly from the hydrothermal fluid, while those collected from the extinct hydrothermal chimney might have already been altered by the seawater. Generally, ore-forming elements in the sulfides can be divided into three groups: Fe-based element group, Cu-based element group and Zn-based element group. The first group includes Fe, Mn, Cr, Mo, Sn, Rb and bio-enriching elements, such as P and Si, reflecting the similar characteristics to Fe in the study area. And the second group contains Cu, W, Co, Se, Te and Bi, suggesting the similar behavior with Cu. Moreover, the third group includes Zn, Hf, Hg, Cd, Ta, Ga, Pb, As, Ag, Ni and Sb, which indicates the geochemical characteristics of most dispersed trace elements controlled by Zn-bearing minerals to some extent.

Heavy metals in suspended matters during a tidal cycle in the turbidity maximum around the Changjiang (Yangtze) Estuary

In order to discuss the content distributions and fluxes of heavy metals in suspended matters during a tidal cycle in the turbidity maximum around the Changjiang (Yangtze) Estuary, the contents of heavy metals (Zn, Pb, Cd, Co and Ni) have been analyzed. During a tidal cycle, the average contents of heavy metals are in the order of Zn>Ni>Pb>Co≫Cd. The average contents in ebb tide are generally higher than that in flood tide. However, at the inshore Sta. 11, influenced by the contamination from the nearby waste treatment plant, the average contents of Zn and Ni in flood tide are higher than those in ebb tide and at the offshore Sta. 10, the content of Cd in flood tide higher than that in ebb tide due to marine-derived materials. The five heavy metals, mainly terrigenous, are transported towards east-northeast, and settle down with suspended matters in the area between Sta. 11 and Sta. 10. Influenced by marine-derived materials, the flux value of Cd does not alter significantly with obviously changing in flux direction towards northwest. The source of heavy metals, the salinity of water and the concentration of suspended matters are the main factors controlling the content distributions of heavy metals during a tidal cycle. There is a positive correlation between the contents of heavy metals (Zn, Pb, Co and Ni) and the salinity of water, while the opposite correlation between the contents and the concentrations of suspended matters. Because of marine-derived materials, the content of Cd is not correlated with the concentration of suspended matters and the salinity of water.

Distribution of tetraether lipids in sulfide chimneys at the Deyin hydrothermal field, southern Mid-Atlantic Ridge: Implication to chimney growing stage

This study presents analysis of four chimney samples in terms of glycerol dialkyl glycerol tetraether lipids (GDGTs), representing different growing stages of sulfide chimneys at the Deyin hydrothermal field, the southern mid-Atlantic ridge. The modified Bligh-Dyer method was used for lipid extraction and purification. GDGTs were analyzed with an Agilent 1200 series liquid chromatograph and 6460A triple quadrupole mass spectrometer. Our results showed that the intact polar GDGTs were more abundant than the core GDGTs in the 4 samples. The intact polar isoprenoidal GDGT-0 was the dominant composition (>70% of isoprenoidal GDGTs), indicating input of thermophilic Euryarchaeota. Most branched GDGTs were likely originated from the in situ thermophilic bacteria. However, the intact polar GDGTs in the sample at the late growing stage was similar to that in normal marine sediments, suggesting that the archaea mainly came from the planktonic Thaumarchaeota input. Our results suggested that the ratio of H-GDGTs to iGDGTs could be considered as a proxy to differentiated growing stages of a chimney. This study shed light on how to assess hydrothermal venting and sulfide chimneys in deep marine environments with a biomarker method in terms of different groups of GDGTs.