Lead, sulphate, and aluminium concentrations and lead crustal enrichment factors in Mt. Logan ice core during pre-anthropogenic to modern periods

A high-resolution, 8000 year-long ice core record from the Mt. Logan summit plateau (5300 m asl) reveals the initiation of trans-Pacific lead (Pb) pollution by ca. 1730, and a >10-fold increase in Pb concentration (1981-1998 mean = 68.9 ng/l) above natural background (5.6 ng/l) attributed to rising anthropogenic Pb emissions from Asia. The largest rise in North Pacific Pb pollution from 1970-1998 (end of record) is contemporaneous with a decrease in Eurasian and North American Pb pollution as documented in ice core records from Greenland, Devon Island, and the European Alps. The distinct Pb pollution history in the North Pacific is interpreted to result from the later industrialization and less stringent abatement measures in Asia compared to North America and Eurasia. The Mt. Logan record shows evidence for both a rising Pb emissions signal from Asia and a trans-Pacific transport efficiency signal related to the strength of the Aleutian Low.

Chemical composition and isotopic ratios of basic lavas from Iceland and the surrounding ocean floor

Major and trace dement data are used to establish the nature and extent of spatial and temporal chemical variations in basalts erupted in the Iceland region of the North Atlantic Ocean. The ocean floor samples are those recovered by legs 38 and 49 of the Deep Sea Drilling Project. Within each of the active zones on Iceland there are small scale variations in the light rare earth elements and ratios such as K/Y: several central complexes and their associated fissure swarms erupt basalts with values of K/Y distinct from those erupted at adjacent centres; also basalts showing a wide range of immobile trace element ratios occur together within single vertical sections and ocean floor drill holes. Although such variations can be explained in terms of the magmatic processes operating on Iceland they make extrapolations from single basalt samples to mantle sources underlying the outcrop of the sample highly tenuous. 87Sr/86Sr ratios measured for 25 of the samples indicate a total range from 0.7028 in a tholeiite from the Reykjanes Ridge to 0.7034 in an alkali basalt from Iceland and are consistent with other published ratios from the region. A positive correlation between 87Sr/86Sr and Ce/Yb ratios indicates the existence of systematic isotopic and elemental variations in the mantle source region. An approximately fivefold variation in Ce/Yb ratio observed in basalts with the same 87Sr/86Sr ratio implies that different degrees and types of partial melting have been involved in magma genesis from a single mantle composition. 87Sr/86Sr ratios above 0.7028, Th/U ratios close to 4 and La/Ta ratios close to 10 distinguish most basalts erupted in this part of the North Atlantic Ocean from normal mid-ocean ridge basalt (N-type MORB) - although N-type MORB has been erupted at extinct spreading axes just to the north and northeast of Iceland as well as the presently active Iceland-Jan Mayen Ridge. Comparisons with the hygromagmatophile element and radiogenic isotope ratios of MORB and the estimated primordial mantle indicate that the mantle sources producing Iceland basalts have undergone previous depletion followed by more recent enrichment events. A veined mantle source region is proposed in preference to the mantle plume model to explain the chemical variations.

Auxiliary material and basic geochemical and benthic foraminiferal stable isotope data for the interval bracketing Eocene Thermal Maximum 2 (ETM2) at DSDP Sites 401 and 550 in the northeastern Atlantic Ocean

Ever since its discovery, Eocene Thermal Maximum 2 (ETM2; ~53.7 Ma) has been considered as one of the "little brothers" of the Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) as it displays similar characteristics including abrupt warming, ocean acidification, and biotic shifts. One of the remaining key questions is what effect these lesser climate perturbations had on ocean circulation and ventilation and, ultimately, biotic disruptions. Here we characterize ETM2 sections of the NE Atlantic (Deep Sea Drilling Project Sites 401 and 550) using multispecies benthic foraminiferal stable isotopes, grain size analysis, XRF core scanning, and carbonate content. The magnitude of the carbon isotope excursion (0.85-1.10 per mil) and bottom water warming (2-2.5°C) during ETM2 seems slightly smaller than in South Atlantic records. The comparison of the lateral d13C gradient between the North and South Atlantic reveals that a transient circulation switch took place during ETM2, a similar pattern as observed for the PETM. New grain size and published faunal data support this hypothesis by indicating a reduction in deepwater current velocity. Following ETM2, we record a distinct intensification of bottom water currents influencing Atlantic carbonate accumulation and biotic communities, while a dramatic and persistent clay reduction hints at a weakening of the regional hydrological cycle. Our findings highlight the similarities and differences between the PETM and ETM2. Moreover, the heterogeneity of hyperthermal expression emphasizes the need to specifically characterize each hyperthermal event and its background conditions to minimalize artifacts in global climate and carbonate burial models for the early Paleogene.

Geochemical analysis of sediments and interstitial water in sediment cores from the North-West African continental margin and from the Central Pacific

A. Continental slope sediments off Spanish-Sahara and Senegal contain up to 4% organic carbon and up to 0.4% total nitrogen. The highest concentrations were found in sediments from water depths between 1000 and 2000 m. The regional and vertical distribution of organic matter differs significantly. Off Spanish-Sahara the organic matter content of sediment deposited during glacial times (Wuerm, Late Riss) is high whereas sediments deposited during interglacial times (Recent, Eem) are low in organic matter. Opposite distribution was found in sediments off Senegal. The sediments contain 30 to 130 ppm of fixed nitrogen. In most sediments this corresponds to 2-8 % of the total nitrogen. Only in sediments deposited during interglacial times off Spanish-Sahara up to 20 % of the total nitrogen is contained as inorganically bound nitrogen. Positive correlations of the fixed nitrogen concentrations to the amounts of clay, alumina, and potassium suggest that it is primarily fixed to illites. The amino acid nitrogen and hexosamine nitrogen account for 17 to 26 % and 1.3 to 2.4 %, respectively of the total nitrogen content of the sediments. The concentrations vary between 200 and 850 ppm amino acid nitrogen and 20 to 70 ppm hexosamine nitrogen, both parallel the fluctiations of organic matter in the sediment. Fulvic acids, humic acids, and the total organic matter of the sediments may be clearly differentiated from one another and their amino acid and hexosamine contents and their amino acid composition: a) Fulvic acids contain only half as much amino acids as humic acids b) The molar amino acid/hexosamine ratios of the fulvic acids are half those of the humic acids and the total organic matter of the sediment c) The amino acid spectra of fulvic acids are characterized by an enrichment of aspartic acid, alanine, and methionine sulfoxide and a depletion of glycine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine, and arginine compared to the spectra of the humic acids and those of the total organic matter fraction of the sediment. d) The amino acid spectra of the humic acids and those of the total organic matter fraction of the sediments are about the same with the exception that arginine is clearly enriched in the total organic matter. In general, as indicated by the amino compounds humic acids resemble closer the total organic matter composition than the low molecular fulvic acids do. This supports the general idea that during the course of diagenesis in reducing sediments organic matter stabilizes from a fulvic-like structure to humic-like structure and finally to kerogen. The decomposition rates of single aminio acids differ significantly from one another. Generally amino acids which are preferentially contained in humic acids and the total organic matter fraction show a smaller loss with time than those preferably well documented in case of the basic amino acids lysine and arginine which- although thermally unstable- are the most stable amino acids in the sediments. A favoured incorporation of these compounds into high molecular substances as well as into clay minerals may explain their relatively high "stability" in the sediment. The nitrogen loss from the sediments due to the activity of sulphate-reducing bacteria amounts to 20-40 % of the total organic nitrogen now present. At least 40 % of the organic nitrogen which is liberated by sulphate-reducing bacteria can be explained ny decomposition of amino acids alone. B. Deep-sea sediments from the Central Pacific The deep-seas sediments contain 1 to 2 orders of magnitude less organic matter than the continental slope sediments off NW Africa, i.e. 0.04 to 0.3 % organic carbon. The fixed nitrogen content of the deep-sea sediments ranges from 60 to 270 ppm or from 20 to 45 % of the total nitrogen content. While ammonia is the prevailing inorganic nitrogen compound in anoxic pore waters, nitrate predominates in the oxic environment of the deep-sea sediments. Near the sediment/water interface interstital nitrate concentrations of around 30 µg-at. N/l were recorded. These generally increase with sediment depth by 10 to 15 µg-at. NO3- N/l. This suggests the presence of free oxygen and the activity of nitrifying bacteria in the interstitial waters. The ammonia content of the interstitial water of the oxic deep-sea sediments ranges from 2 to 60 µg-at. N/l and thus is several orders of magnitude less than in anoxic sediments. In contrast to recorded nitrate gradients towards the sediments/water interface, there are no ammonia concentration gradients. However, ammonia concentrations appear to be characteristic for certain regional areas. It is suggested that this regional differentiation is caused by ion exchange reactions involving potassium and ammonium ions rather than by different decomposition rates of organic matter. C. C/N ratios All estimated C/N ratios of surface sediments vary between 3 and 9 in the deep-sea and the continental margin, respectively. Whereas the C/N ratios generally increase with depth in the sediment cores off NW Africa they decrease in the deep-sea cores. The lowest values of around 1.3 were found in the deeper sections of the deep-sea cores, the highest of around 10 in the sediments off NW Africa. The wide range of the C/N ratios as well as their opposite behaviour with increasing sediment depth in both the deep-sea and continental margin sediment cores, can be attributed mainly to the combination of the following three factors: 1. Inorganic and organic substances bound within the latticed of clay minerals tend to decrease the C/N ratios. 2. Organic matter not protected by absorption on the clay minerals tends to increase C/N ratios 3. Diagenetic alteration of organic matter by micro-organisms tends to increase C/N ratios through preferential loss of nitrogen The diagenetic changes of the microbially decomposable organic matter results in both oxic and anoxic environments in a preferential loss of nitrogen and hence in higher C/N ratios of the organic fraction. This holds true for most of the continental margin sediments off NW Africa which contain relatively high amounts of organic matter so that factors 2 and 3 predominate there. The relative low C/N ratios of the sediments deposited during interglacial times off Spanish-Sahara, which are low in organic carbon, show the increasing influence of factor 1 - the nitrogen-rich organic substances bound to clay minerals. In the deep-sea sediments from the Central Pacific this factor completely predominates so that the C/N rations of the sediments approach that of the substance absorbed to clay minerals with decreasing organic matter content. In the deeper core sections the unprotected organic matter has been completely destroyed so that the C/N ratios of the total sediments eventually fall into the same range as those of the pure clay mineral fraction.