On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

Trace element composition of peridotites from the southern Mariana forearc: Insights into the geochemical effects of serpentinization and/or seafloor weathering

Peridotites from the southern Mariana forearc were sampled on the landward trench slope of the Izu-Bonin-Mariana (IBM) subduction zone by dredging. These mantle wedge peridotites underwent hydration by fluid derived from a dehydrated descending slab, and later interacted with seawater after emplacement at or near the seafloor. This study investigates how these two different rock-fluid interaction processes influenced trace element distribution in the southern Mariana forearc peridotites. We measured trace element concentrations of peridotites from the southern Mariana forearc. The southern Mariana forearc peridotites are characterized by a distinct seawater-like REE pattern with an obvious negative Ce anomaly, and La shows good correlation with other REEs (except Ce). In addition, there is a great enrichment of U, Pb, Sr and Li elements, which show a distinct positive anomaly relative to adjacent elements in the multi-element diagram. For the seawater-like REE pattern, we infer that REEs are mainly influenced by seawater during peridotite-seawater interactions after their emplacement at or near the seafloor, by serpentinization or by marine weathering. Furthermore, the anomalous behavior of Ce, compared with other rare earth elements in these samples, may indicate that they have undergone reactions involving Ce (IV) when the peridotites interacted with seawater. Positive U, Pb, Sr and Li anomalies are inferred to be related to seawater and/or fluids released during dehydration of the subducting slab.

Geochemical properties of the variolitic andesite from Susong in the Dabie orogenic belt, China

The variolitic andesite from the Susong County in the Dabie Mountains implies that it was erupted in water. The mineralogy of the varioles is primarily radiate plagioclase (albite sind oligoclase), with little pyroxene, hornblende and quartz (derived from alteration). The pyroxene, hornblende and quartz are in the interstices between plagiocalse. The matrix consists of glass, hornblende, chlorite, epidote and zoisite. It is clearly subjected an extensive alteration. The andesite has an uncommon chemical composition. The SiO2 content is about 56.8%, TiO2 = 0.9%, MgO = 6.4%, Fe2O3 (tot) = 6.7%similar to 7.6%, 100Mg/(Mg + Fe) = 64.1 similar to 66.2. Mg-# is significantly high. The andesite has high abundances of large-lithophile trace elements (e.g. K, Ba. Sr, LREE), e.g. La/Nb = 5.56 similar to 6.07, low abundances of high-strength-field elements (HFSE e.g. Ta, Nb, P, Ti), particularly Ta and Nb strongly depleted. These are consistent with the characteristics of subduction-related magmas. In the spider diagram of trace elements, from Ce to right hand, the abundances of elements decrease quickly, showing a character of the continental margins. There has a strong punishment of light-rare-earth elements, with a significant diffraction of REEs (the mean value of (La/Yb)(N) is 32.84). No Eu anomaly, but there are anomaly high (La/Yb)(N) = 28.63 similar to 36.74, (La/Y)(N) = 70.33 similar to 82.4. The elements Y and Yb are depleted greatly, Y<20 g/g, Y-N = 2.74 similar to 2.84, Yb-N = 2.18 similar to 2.35. From the La-(La/Sm) diagram, the andesite is derived from partial melting. But the epsilone value of Nd is - 18.7 similar to -19.2, so that the material source may be the mantle materials affected by the crustal materials. The Nd model age is 1.9 Ga indicating that the variolitic basaltic andesite was resulted from the mantle wedge of North China block, which had the Nd model age of 2.5Ga, when the Yangze block which had the Nd model age of 1.7Ga subducted beneath it. So the variolitic andesite has characteristics of the island-are volconic rocks oil a continental basement in the vicinity of the destructive continental margin.

Geochemical anomalies of hydrothermal plume at EPR 13 degrees N

During the DY105-12, 14cruise (RN DAYANG YIHAO, November 2003) on East Pacific Rise (EPR) 12-13 degrees N, the submarine hydrothermal activity was investigated and the CTD hydrocast was carried out at EPR12 degrees 39 ' N - 12 degrees 54 ' N. From the temperature anomalies and the concentrations of magnesium, chlorine, bromine in seawater samples, we discover that magnesium depletes 9.3%-22.4%, chlorine and bromine enrich 10.3%-28.7% and 10.7%-29.0% respectively relative to normal seawater at the stations which have chemistry anomalies, moreover temperature and chemistry anomalies are at the same layer. The depletion of magnesium in the plume may be caused by a fluid lacking of magnesium which rises after the hydrothermal fluid reaches the equilibrium with ambient seawater, the enrichment of chlorine and bromine might be the result of inputting later brine which is generated by phase separation due to hydrothermal activity. In addition, the Br/CI ratio in the abnormal layers at the survey area is identical to that in seawater, which implies that halite dissolution (or precipitation) occurs neither when the fluid is vented nor when hydrothermal fluid entraining ambient seawater rises to form plume. From the abnormal instance at E55 station, it is very possible that there might exist a new hydrothermal vent site.

Geochemical character and material source of sediments in the eastern Philippine Sea

Based upon analyses of grain-size, rare earth element (REE) compositions, elemental occurrence phases of REE, and U-series isotopic dating, the sediment characteristics and material sources of the study area were examined for the recently formed deep-sea clays in the eastern Philippine Sea. The analytical results are summarized as follows. (1) Low accumulation rate, poor sorting and roundness, and high contents of grains coarser than fine silt indicate relatively low sediment input, with localized material source without long distance transport. (2) The REE Contents are relatively high. Shale-normalized patterns of REE indicate weak enrichment in heavy REE (HREE), Ce-passive anomaly, and Eu-positive anomaly. (3) Elemental occurrence phases of REE between the sediments with and without crust are similar. REE mainly concentrate in residual phase and then in ferromanganese oxide phase. The light REE (LREE) enrichment, Ce-positive anomaly, and Eu-positive anomaly occur in residual phase. Ferromanganese oxide phase shows the characteristics of relatively high HREE content and Ce-passive anomaly. (4) There are differences in each above mentioned aspect between the sediments with and without ferromanganese crust. (5) Synthesizing the above characteristics and source discriminant analysis, the study sediments are deduced to mainly result from the alteration of local and nearby volcanic materials. Continental materials transported by wind and/or river (ocean) flows also have minor contributions.

Formation of Fe-oxyhydroxides from the East Pacific Rise near latitude 13 degrees N: Evidence from mineralogical and geochemical data

The mineralogical and geochemical characteristics of Fe-oxyhydroxide samples from one dredge station (long. 103 degrees 54.48'W, lat. 12 degrees 42.30'N, water depth 2655 m) on the East Pacific Rise near lat 13 degrees N were analyzed by XRD, ICP-AES, and ICP-MS. Most Fe-oxyhydroxides are amorphous, with a few sphalerite microlites. In comparison with Fe-oxyhydroxides from other fields, the variable ranges in the chemical composition of Fe-oxyhydroxide samples are very narrow; their Fe, Si, and Mn contents were 39.90%, 8.92%, and 1.59%, respectively; they have high Cu (0.88%-1.85%) and Co (65x10(-6)-704x10(-6)) contents, and contain Co+Cu+Zn+Ni > 1.01%. The trace-element (As, Co, Ni, Cu, Zn, Ba, Sr) and major-element (Fe, Ca, Al, Mg) contents of these samples are in the range of hydrothermal sulfide from the East Pacific Rise near 13 degrees N, reflecting that this type of Fe-oxyhydroxide constitutes a secondary oxidation product of hydrothermal sulfide. The Fe-oxyhydroxide samples from one dredge station on the East Pacific Rise near 13 degrees N are lower in Sigma REE (5.44x10(-6)-17.01x10(-6)), with a distinct negative Ce anomaly (0.12-0.28). The Fe-oxyhydroxide samples have similar chondrite-normalized rare-earth-element (REE) patterns to that of seawater, and they are very different from the REE composition characteristics of hydrothermal plume particles and hydrothermal fluids, showing that the REEs of Fe-oxyhydroxide are a major constituent of seawater and that the Fe-oxyhydroxides can become a sink of REE from seawater. The quick settling of hydrothermal plume particles resulted in the lower REE content and higher Mn content of these Fe-oxyhydroxides, which are captured in part of the V and P from seawater by adsorption. The Fe-oxyhydroxides from one dredge station on the East Pacific Rise near 13 degrees N were formed by secondary oxidation in a low temperature, oxygenated environment. In comparison with the elemental (Zn, Cd, Pb, Fe, Co, Cu) average content of hydrothermal sulfide samples from the East Pacific Rise near 13 degrees N, the Zn, Cd, and Pb contents of the Fe-oxyhydroxides are lower, and their Fe, Co, and Cu contents are higher.

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.

Geochemical characteristics of nitrogen in the southern Yellow Sea surface sediments

Roles and distributions of various forms of nitrogen in biogeochemical cycling in the southern Yellow Sea surface sediments were investigated. The southern Yellow Sea could be divided into three regions (I, II and III) according to the proportion of fine-grained sediment in > 65%, 35-65% and < 35%, respectively. The ratios of different forms of nitrogen contents between each two of the three regions indicated that the nitrogen contents increased with the proportion of fine-grained sediment increasing. The quanta of exchangeable forms of nitrogen were similar in the three regions, while their releasing time increased from regions I to III, indicating that the cycle of nitrogen in fine-grained sediments was shorter than that in coarse-grained sediments. Nitrogen burial fluxes were also similar in these regions, while the burial efficiency increased from regions I to III. The highest burial efficiency was 30.21% in region III, indicating that more than 70% of nitrogen in the southern Yellow Sea surface sediments could be released to take part in biogeochemical recycling. When all the four forms of exchangeable nitrogen (nitrogen in ion exchangeable form (IEF-N), nitrogen in weak acid extractable form (WAEF-N), nitrogen in strong alkali extractable form (SAEF-N) and nitrogen in strong oxidant extractable form (SOEF-N)) were released to take part in recycling, their potential contributions were 80% (SOEF-N), 11% (IEF-N), 6% (SAEF-N), 3% (WAEF-N) respectively, which showed that SOEF-N was the predominant one, and its contribution to biogeochemical cycling was the highest. (c) 2004 Elsevier B.V. All rights reserved.

Organic geochemical studies of sinking particulate material in China sea area(I) - Organic matter fluxes and distributional features of hydrocarbon compounds and fatty acids

Sinking particulate material collected from Nansha Yongshu reef lagoon and the continental shelf of the East China Sea by sediment traps has been analyzed and studied for the first time using organic geochemical method. The results show that about half of the sinking particulate organic matter in the two study areas are consumed before reaching the depth of 5 m to the sea floor and the degree of this consumption in Yongshu reef lagoon is larger than that in the continental shelf of the East China Sea. The distributions of hydrocarbons and fatty acids indicate that the minor difference of biological sources of sinking particulate organic matter exists between Yongshu reel lagoon and the continental shelf of the East China Sea, but they mainly come from marine plankton. Stronger biological and biochemical transformations of sinking particulate organic matter are also observed and the intensity of this transformation in Yongshu reef lagoon is greater than that in the continental shelf of the East China Sea. It is found that the occurrence of C-25 highly branched isoprenoid (HBI) diene may be related to the composition of diatom species.