Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

Effect of simulated ocean acidification on the acute toxicity of Cu and Cd to Tigriopus japonicus

Heavy metals pollution in marine environments has caused great damage to marine biological and ecological systems. Heavy metals accumulate in marine creatures, after which they are delivered to higher trophic levels of marine organisms through the marine food chain, which causes serious harm to marine biological systems and human health. Additionally, excess carbon dioxide in the atmosphere has caused ocean acidification. Indeed, about one third of the CO2 released into the atmosphere by anthropogenic activities since the beginning of the industrial revolution has been absorbed by the world's oceans, which play a key role in moderating climate change. Modeling has shown that, if current trends in CO2 emissions continue, the average pH of the ocean will reach 7.8 by the end of this century, corresponding to 0.5 units below the pre-industrial level, or a three-fold increase in H+ concentration. The ocean pH has not been at this level for several millions of years. Additionally, these changes are occurring at speeds 100 times greater than ever previously observed. As a result, several marine species, communities and ecosystems might not have time to acclimate or adapt to these fast changes in ocean chemistry. In addition, decreasing ocean pH has the potential to seriously affect the growth, development and reproduction reproductive processes of marine organisms, as well as threaten normal development of the marine ecosystem. Copepods are an important part of the meiofauna that play an important role in the marine ecosystem. Pollution of the marine environment can influence their growth and development, as well as the ecological processes they are involved in. Accordingly, there is important scientific value to investigation of the response of copepods to ocean acidification and heavy metals pollution. In the present study, we evaluated the effects of simulated future ocean acidification and the toxicological interaction between ocean acidity and heavy metals of Cu and Cd on T. japonicus. To accomplish this, harpacticoids were exposed to Cu and Cd concentration gradient seawater that had been equilibrated with CO2 and air to reach pH 8.0, 7.7, 7.3 and 6.5 for 96 h. Survival was not significantly suppressed under single sea water acidification, and the final survival rates were greater than 93% in both the experimental groups and the controls. The toxicity of Cu to T. japonicus was significantly affected by sea water acidification, with the 96h LC50 decreasing by nearly threefold from 1.98 to 0.64 mg/L with decreasing pH. The 96 h LC50 of Cd decreased with decreasing pH, but there was no significant difference in mortality among pH treatments. The results of the present study demonstrated that the predicted future ocean acidification has the potential to negatively affect survival of T. japonicus by exacerbating the toxicity of Cu. The calculated safe concentrations of Cu were 11.9 (pH 7.7) and 10.5 (pH 7.3) µg/L, which were below the class I value and very close to the class II level of the China National Quality Standard for Sea Water. Overall, these results indicate that the Chinese coastal sea will face a