Concentrations of natural and anthropogenic organohalogens in water and air samples in the Canadian Arctic during IPY (2007-2008)

Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg/L) were as follows: alpha-hexachlorocyclohexane (alpha-HCH) 465-1013, gamma-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg/m**3) were as follows: alpha-HCH 7.5-48, gamma-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4-39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of alpha-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The alpha-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 ± 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 ± 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic alpha-HCH from surface water (EF = 0.457 ± 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means ± SD (and ranges) of net fluxes (ng/m**2/d) were as follows: alpha-HCH 6.8 ± 3.2 (2.7-13), gamma-HCH 0.76 ± 0.40 (0.26-1.4), HCB -9.6 ± 2.7 (-6.1 to -15), DBA 1.2 ± 0.69 (0.04-2.0), and TBA 0.46 ± 1.1 ng/m**2/d (-1.6 to 2.0).

Hexachlorocyclohexanes concentration in air and ocean water

Hexachlorocyclohexanes (HCHs) are ubiquitous organic pollutants derived from pesticide application. They are subject to long-range transport, persistent in the environment, and capable of accumulation in biota. Shipboard measurements of HCH isomers (a-, b- and g-HCH) in surface seawater and boundary layer atmospheric samples were conducted in the Atlantic and the Southern Ocean in October to December of 2008. SumHCHs concentrations (the sum of a-, g- and b-HCH) in the lower atmosphere ranged from 12 to 37 pg/m**3 (mean: 27 ± 11 pg/m**3) in the Northern Hemisphere (NH), and from 1.5 to 4.0 pg/m**3 (mean: 2.8 ± 1.1 pg/m**3) in the Southern Hemisphere (SH), respectively. Water concentrations were: a-HCH 0.33-47 pg/l, g-HCH 0.02-33 pg/l and b-HCH 0.11-9.5 pg/l. Dissolved HCH concentrations decreased from the North Atlantic to the Southern Ocean, indicating historical use of HCHs in the NH. Spatial distribution showed increasing concentrations from the equator towards North and South latitudes illustrating the concept of cold trapping in high latitudes and less interhemispheric mixing process. In comparison to concentrations measured in 1987-1999/2000, gaseous HCHs were slightly lower, while dissolved HCHs decreased by factor of 2-3 orders of magnitude. Air-water exchange gradients suggested net deposition for a-HCH (mean: 3800 pg/m**2/day) and g-HCH (mean: 2000 pg/m**2/day), whereas b-HCH varied between equilibrium (volatilization: <0-12 pg/m**2/day) and net deposition (range: 6-690 pg/m**2/day). Climate change may significantly accelerate the release of "old" HCHs from continental storage (e.g. soil, vegetation and high mountains) and drive long-range transport from sources to deposition in the open oceans. Biological productivities may interfere with the air-water exchange process as well. Consequently, further investigation is necessary to elucidate the long term trends and the biogeochemical turnover of HCHs in the oceanic environment.

Nd, Pb, and Be isotopes of ferromanaganese crusts of the Atlantic Ocean

The isotopic composition of Nd in present-day deep waters of the central and northeastern Atlantic Ocean is thought to fingerprint mixing of North Atlantic Deep Water with Antarctic Bottom Water. The central Atlantic Romanche and Vema Fracture Zones are considered the most important pathways for deep water exchange between the western and eastern Atlantic basins today. We present new Nd isotope records of the deepwater evolution in the fracture zones obtained from ferromanganese crusts, which are inconsistent with simple water mass mixing alone prior to 3 Ma and require additional inputs from other sources. The new Pb isotope time series from the fracture zones are inexplicable by simple mixing of North Atlantic Deep Water and Antarctic Bottom Water for the entire past 33 Myr. The distinct and relatively invariable Nd and Pb isotope records of deep waters in the fracture zones appear instead to have been controlled to a large extent by contributions from Saharan dust and the Orinoco/Amazon Rivers. Thus the previously observed similarity of Nd and Pb isotope time series from the western and eastern North Atlantic basins is better explainable by direct supply of Labrador Seawater to the eastern basin via a northern pathway rather than by advection of North Atlantic Deep Water via the Romanche and Vema Fracture Zones.

Late Miocene-early Pliocene stable isotope record of benthic foraminifera from ODP Site 177-1088 in the sub-Antarctic South Atlantic

Benthic foraminiferal stable isotope records for the past 11 Myr from a recently drilled site in the sub-Antarctic South Atlantic (Site 1088, Ocean Drilling Program Leg 177, 41°S, 15°E, 2082 m water depth) provide, for the first time, a continuous long-term perspective on deep water distribution patterns and Southern Ocean climate change from the late Miocene through the early Pliocene. I have compiled published late Miocene through Pliocene stable isotope records to place the new South Atlantic record in a global framework. Carbon isotope gradients between the North Atlantic, South Atlantic, and Pacific indicate that a nutrient-depleted watermass, probably of North Atlantic origin, reached the sub-Antarctic South Atlantic after 6.6 Ma. By 6.0 Ma the relative proportion of the northern-provenance watermass was similar to today and by the early Pliocene it had increased to greater than the modern proportion suggesting that thermohaline overturn in the Atlantic was relatively strong prior to the early Pliocene interval of inferred climatic warmth. Site 1088 oxygen isotope values display a two-step increase between ~7.4 Ma and 6.9 Ma, a trend that parallels a published delta18O record of a site on the Atlantic coast of Morocco. This is perhaps best explained by a gradual cooling of watermasses that were sinking in the Southern Ocean. I speculate that relatively strong thermohaline overturn at rates comparable to the present day interglacial interval during the latest Miocene may have provided the initial conditions for early Pliocene climatic warmth. The impact of an emerging Central American Seaway on Atlantic-Pacific Ocean upper water exchange may have been felt in the North Atlantic beginning in the latest Miocene between 6.6 and 6.0 Ma, which would be ~1.5 Myr earlier than previously thought.

Pliocene and Pleistocene abundance of siliceous microfossil assemblages in ODP Leg 127 sites

A close examination of the siliceous microfossil assemblages from the sediments of ODP Leg 127, Japan Sea Sites 794, 795, and 797, reveals that upper Pliocene and Pleistocene assemblages have been subjected to more dissolution than have lower Pliocene assemblages. This conclusion is based on semiquantitative observations of samples processed for diatoms and radiolarians. Although preservation of opaline microfossils in some upper Pliocene and Pleistocene samples is better than others, in general, the poorly preserved state of these assemblages supports the notion that opal dissolution, in response to lowered productivity, is responsible for the paucity of siliceous microfossils in upper Pliocene and Pleistocene sediments. The lithological transition from diatomaceous oozes to silts and clays corresponds to a change between dominantly well preserved to more poorly preserved siliceous assemblages, and is termed the late Pliocene Japan Sea opal dissolution transition zone (ODTZ). The base of the ODTZ is defined as the uppermost occurrence of high abundances of moderately to well preserved valves of the diatom Coscinodiscus marginatus. The dissolution transition zone is characterized by partially dissolved refractory assemblages of radiolarians, the presence of C. marginatus girdles, C. marginatus fragments, siliceous sponge spicules, and a general decrease in weakly silicified, less solution resistant diatoms upward in the section. The top of the dissolution transition zone marks the level where whole C. marginatus valves and C. marginatus fragments are no longer present in significant numbers. Dissolution of the late Pliocene and Pleistocene opaline assemblages is attributed mainly to changes in paleoceanographic circulation patterns and decreased nutrient (dissolved silicon) contents of the water column, and possibly dissolution at the sediment/water interface, rather than to post-depositional dissolution or diagenesis. We suggest that the transition from silica-rich to silica-poor conditions in the Japan Sea was due to fluctuations of deep-water exchange with the Pacific through the Tsugaru Strait between 2.9 and 2.3 Ma.

The hydropolyp fauna of the Red Sea area

46 hydropolyp species of 28 genera and 10 families were sampled during the "Meteor" passage 1964/65 (IIOE) through the Red Sea and its northern and southern exits and on the occasion of several ecological investigations of 29 selected coral reef sections of the central Red Sea and the Gulf of Aqaba. These collections comprise 128 single records of hydropolyp species. Three species and two genera each with one species are doubtful. 25 species, seven genera, one family and one subfamily, together from 49 records have not previously been found in the Red Sea and its exits. Including these newly reported species, the total list increases from 64 species and 112 records to 89 species and 240 single records and 51 additional ones. Scanning microscopical photos, made for the first time for the illustration of the hydropolyps, have been shown to be suitable for a better characterization and diagnosis of the species. Qualified results on the reasons for the horizontal distribution of the species known from the Red Sea area cannot be given because of the low number of samples sporadically distributed through the whole area. In contrast with this fact, the vertical spread of the species sampled seems primarily to be regulated by water exchange and light intensity. For example, four species of hydropolyps are excellent indicators of certain abiotic factors or combinations of them: Gymnangium eximium reacts extremely stenophote-photophobe-rheophil, Eudendrium ramosum moderately stenophote-photophobe-rheophobe, Lytocarpus philippinus moderately stenophote-photophil-rheophil, and Halocordyle disticha var. australis extremely stenophote-photophil but moderately rheophil. Other species have been found throughout all the light zones. Combined with the small size of their colonies their euryphotic behaviour does not allow their use as indicator species.

Gotland Deep (Baltic Sea) independent age model based on Palaeomagnetic Secular Variation (PSV) and lead (Pb) deposition profiles

Dating of sediment cores from the Baltic Sea has proven to be difficult due to uncertainties surrounding the 14C reservoir age and a scarcity of macrofossils suitable for dating. Here we present the results of multiple dating methods carried out on cores in the Gotland Deep area of the Baltic Sea. Particular emphasis is placed on the Littorina stage (8 ka ago to the present) of the Baltic Sea and possible changes in the 14C reservoir age of our dated samples. Three geochronological methods are used. Firstly, palaeomagnetic secular variations (PSV) are reconstructed, whereby ages are transferred to PSV features through comparison with varved lake sediment based PSV records. Secondly, lead (Pb) content and stable isotope analysis are used to identify past peaks in anthropogenic atmospheric Pb pollution. Lastly, 14C determinations were carried out on benthic foraminifera (Elphidium spec.) samples from the brackish Littorina stage of the Baltic Sea. Determinations carried out on smaller samples (as low as 4 µg C) employed an experimental, state-of-the-art method involving the direct measurement of CO2 from samples by a gas ion source without the need for a graphitisation step - the first time this method has been performed on foraminifera in an applied study. The PSV chronology, based on the uppermost Littorina stage sediments, produced ten age constraints between 6.29 and 1.29 cal ka BP, and the Pb depositional analysis produced two age constraints associated with the Medieval pollution peak. Analysis of PSV data shows that adequate directional data can be derived from both the present Littorina saline phase muds and Baltic Ice Lake stage varved glacial sediments. Ferrimagnetic iron sulphides, most likely authigenic greigite (Fe3S4), present in the intermediate Ancylus Lake freshwater stage sediments acquire a gyroremanent magnetisation during static alternating field (AF) demagnetisation, preventing the identification of a primary natural remanent magnetisation for these sediments. An inferred marine reservoir age offset (deltaR) is calculated by comparing the foraminifera 14C determinations to a PSV & Pb age model. This deltaR is found to trend towards younger values upwards in the core, possibly due to a gradual change in hydrographic conditions brought about by a reduction in marine water exchange from the open sea due to continued isostatic rebound.

Organic geochemistry of Upper Albian sediments from the Kirchrode I borehole

In the framework of a multidisciplinary research program, an organic geochemical study was carried out on a drill core which comprises a 245 m thick sequence of light-colored, Upper Albian marlstones that were deposited in the central part of the Lower Saxony basin (northern Germany). For part of the Upper Albian sequence, high-resolution measurements of carbonate contents reveal cycles which can be related to earth orbital forcing. Based on these data, sediment accumulation rates were calculated to be in the order of 15 g/m**2/yr. These high accumulation rates contrast with very low organic carbon contents and an extremely poor preservation of the autochthonous organic matter. Most of the sedimentary organic matter is of terrigenous origin and mainly derived from the erosion of older sedimentary rocks. Organic petrography reveals only a very small fraction of marine organic particles. Carbon/sulphur ratios, pristane/phytane ratios as well as the predominance of resedimented organic particles over autochthonous organic particles suggest that aerobic degradation processes rather than anaerobic processes (sulphate reduction) were responsible for the degradation of the organic matter. Furthermore, the scarcity of terrigenous organic particles (vitrinite) indicates that there was little vegetation on nearby land areas. To explain these analytical results, a depositional model was developed which could explain the scarcity of organic matter in the Upper Albian sediments. This model is based on downwelling of oxygen-rich, saline waters of Tethyan origin, which reduces the nutrient content of surface waters and thus primary bioproductivity while degradation of primary organic matter in the water column is enhanced at the same time. These conditions contrast to those which existed in Barremian and early Aptian times in this basin, when limited water exchange with adjacent oceans caused oxygen deficiency and the deposition of numerous organic carbon-rich black shales. The thick, organic matter-poor Upper Albian sequence of northern Germany also contrasts with comparatively thin, time-equivalent, deep-sea black shales from Italy. This discrepancy indicates that local and regional oceanographic factors (at least in this case) have a greater influence on organic matter deposition than global events.