Sulfur-isotope analyses of gypsium samples from the Southeast Greenland margin, southern Alaska and Gulf of Alaska (Table 1)

Gypsum grains were identified in Miocene-Pleistocene sediment cores from two deep-water ODP sites, Site 918 off the SE Greenland margin and Site 887 in the Gulf of Alaska, and in Holocene sediment cores from shallow-water localities in Disenchantment Bay and Muir Inlet in southern Alaska. Although initial morphologic and textural observations suggested a complex system in which the gypsum may have had more than one origin, quantitative sulfur isotope analyses of the gypsum provide evidence of its detrital nature. d34S values in gypsum from southern Alaska range between +0.0 and +7.1 per mil. Gypsum has d34S values between -27.1 and -27.5 per mil in the Gulf of Alaska and values between -28.5 and +0.2 per mil off the SE Greenland margin. All of these isotopic signatures are too highly depleted in d34S to have precipitated from seawater, present or past. In addition there is no significant change in d34S values for gypsum crystals with differing physical characteristics (abraded vs. unabraded) from the same stratigraphic horizon, suggesting all the gypsum is detrital regardless of the degree of abrasion. The isotopic and physical evidence, in combination with the onshore geology the environmental setting, and site characteristics of the gypsum-bearing marine localities, lead us to propose that the ultimate source of the gypsum is precipitation from freeze-induced terrestrial sediment or soil brines. Furthermore the combined evidence suggests that the subsequent occurrence of gypsum in glacimarine sediments results from ice-rafting (by icebergs or sea ice) of the frozen regolith and/or, in the proximal glacimarine setting of southern Alaska, very rapid burial via turbidity currents.

Mineralogy ol late Quaternary marine sediments from the West and East Greenland shelves offshore from early Tertiary basalt outcrops

We use quantitative X-ray diffraction to determine the mineralogy of late Quaternary marine sediments from the West and East Greenland shelves offshore from early Tertiary basalt outcrops. Despite the similar basalt outcrop area (60 000-70 000 km**2), there are significant differences between East and West Greenland sediments in the fraction of minerals (e.g. pyroxene) sourced from the basalt outcrops. We demonstrate the differences in the mineralogy between East and West Greenland marine sediments on three scales: (1) modern day, (2) late Quaternary inputs and (3) detailed down-core variations in 10 cores from the two margins. On the East Greenland Shelf (EGS), late Quaternary samples have an average quartz weight per cent of 6.2 ± 2.3 versus 12.8 ± 3.9 from the West Greenland Shelf (WGS), and 12.02 ± 4.8 versus 1.9 ± 2.3 wt% for pyroxene. K-means clustering indicated only 9% of the samples did not fit a simple EGS vs. WGS dichotomy. Sediments from the EGS and WGS are also isotopically distinct, with the EGS having higher eNd (-18 to 4) than those from the WGS (eNd = -25 to -35). We attribute the striking dichotomy in sediment composition to fundamentally different long-term Quaternary styles of glaciation on the two basalt outcrops.

The syntheses of the marine metabolites 3-bromoverongiaquinol and 5-monobromocavernicolin

An efficient synthesis of the marine metabolite 3-bromoverongiaquinol (1) and the first total synthesis of 5-monobromocavernicolin (2), both isolated from the marine sponge Aplysina cavernicola, have been described based on the 1,2 addition of the lithium enolate of N,O-bistrimethylsilylacetamide (BSA, 4) to 1,4-benzoquinone (3). Bromination and purification of the crude product on silica gel chromatography provided 3-bromoverongiaquinol (1) in 50% overall yield. Under alkaline conditions, the crude product of the bromination reaction was converted to 5-monobromocavernicolin (2) in 20% yield which was also obtained in 13% yield (25% yield based on recovered starting material) from 3-bromoverongiaquinol (1).