Hydrochemical Atlas of the Arctic Ocean

Introduction: Chemical composition of water determines its physical properties and character of processes proceeding in it: freezing temperature, volume of evaporation, density, color, transparency, filtration capacity, etc. Presence of chemical elements in water solution confers waters special physical properties exerting significant influence on their circulation, creates necessary conditions for development and inhabitance of flora and fauna, and imparts to the ocean waters some chemical features that radically differ them from the land waters (Alekin & Liakhin, 1984). Hydrochemical information helps to determine elements of water circulation, convection depth, makes it easier to distinguish water masses and gives additional knowledge of climatic variability of ocean conditions. Hydrochemical information is a necessary part of biological research. Water chemical composition can be the governing characteristics determining possibility and limits of use of marine objects, both stationary and moving in sea water. Subject of investigation of hydrochemistry is study of dynamics of chemical composition, i.e. processes of its formation and hydrochemical conditions of water bodies (Alekin & Liakhin 1984). The hydrochemical processes in the Arctic Ocean are the least known. Some information on these processes can be obtained in odd publications. A generalizing study of hydrochemical conditions in the Arctic Ocean based on expeditions conducted in the years 1948-1975 has been carried out by Rusanov et al. (1979). The "Atlas of the World Ocean: the Arctic Ocean" contains a special section "Hydrochemistry" (Gorshkov, 1980). Typical vertical profiles, transects and maps for different depths - 0, 100, 300, 500, 1000, 2000, 3000 m are given in this section for the following parameters: dissolved oxygen, phosphate, silicate, pH and alkaline-chlorine coefficient. The maps were constructed using the data of expeditions conducted in the years 1948-1975. The illustrations reflect main features of distribution of the hydrochemical elements for multi-year period and represent a static image of hydrochemical conditions. Distribution of the hydrochemical elements on the ocean surface is given for two seasons - winter and summer, for the other depths are given mean annual fields. Aim of the present Atlas is description of hydrochemical conditions in the Arctic Ocean on the basis of a greater body of hydrochemical information for the years 1948-2000 and using the up-to-date methods of analysis and electronic forms of presentation of hydrochemical information. The most wide-spread characteristics determined in water samples were used as hydrochemical indices. They are: dissolved oxygen, phosphate, silicate, pH, total alkalinity, nitrite and nitrate. An important characteristics of water salt composition - "salinity" has been considered in the Oceanographic Atlas of the Arctic Ocean (1997, 1998). Presentation of the hydrochemical characteristics in this Hydrochemical Atlas is wider if compared with that of the former Atlas (Gorshkov, 1980). Maps of climatic distribution of the hydrochemical elements were constructed for all the standard depths, and seasonal variability of the hydrochemical parameters is given not only for the surface, but also for the underlying standard depths up to 400 m and including. Statistical characteristics of the hydrochemical elements are given for the first time. Detailed accuracy estimates of initial data and map construction are also given in the Atlas. Calculated values of mean-root deviations, maximum and minimum values of the parameters demonstrate limits of their variability for the analyzed period of observations. Therefore, not only investigations of chemical statics are summarized in the Atlas, but also some elements of chemical dynamics are demonstrated. Digital arrays of the hydrochemical elements obtained in nodes of a regular grid are the new form of characteristics presentation in the Atlas. It should be mentioned that the same grid and the same boxes were used in the Atlas, as those that had been used by creation of the US-Russian climatic Oceanographic Atlas. It allows to combine hydrochemical and oceanographic information of these Atlases. The first block of the digital arrays contains climatic characteristics calculated using direct observational data. These climatic characteristics were not calculated in the regions without observations, and the information arrays for these regions have gaps. The other block of climatic information in a gridded form was obtained with the help of objective analysis of observational data. Procedure of the objective analysis allowed us to obtain climatic estimates of the hydrochemical characteristics for the whole water area of the Arctic Ocean including the regions not covered by observations. Data of the objective analysis can be widely used, in particular, in hydrobiological investigations and in modeling of hydrochemical conditions of the Arctic Ocean. Array of initial measurements is a separate block. It includes all the available materials of hydrochemical observations in the form, as they were presented in different sources. While keeping in mind that this array contains some amount of perverted information, the authors of the Atlas assumed it necessary to store this information in its primary form. Methods of data quality control can be developed in future in the process of hydrochemical information accumulation. It can be supposed that attitude can vary in future to the data that were rejected according to the procedure accepted in the Atlas. The hydrochemical Atlas of the Arctic Ocean is the first specialized and electronic generalization of hydrochemical observations in the Arctic Ocean and finishes the program of joint efforts of Russian and US specialists in preparation of a number of atlases for the Arctic. The published Oceanographic Atlas (1997, 1998), Atlas of Arctic Meteorology and Climate (2000), Ice Atlas of the Arctic Ocean prepared for publication and Hydrochemical Atlas of the Arctic Ocean represent a united series of fundamental generalizations of empirical knowledge of Arctic Ocean nature at climatic level. The Hydrochemical Atlas of the Arctic Ocean was elaborated in the result of joint efforts of the SRC of the RF AARI and IARC. Dr. Ye. Nikiforov was scientific supervisor of the Atlas, Dr. R. Colony was manager on behalf of the USA and Dr. L. Timokhov - on behalf of Russia.

Table 1: U-Pb analyses of zircons and monazites of paragneisses which belong to the high grade metamorphic basement of Wilson Terrane

Samples of high grade metamorphic basement rocks of Wilson Terrane cropping out in the Deep Freeze Range and on Kay Island were collected during GANOVEX VI to study their isotopic evolution. The age and origin of granulite facies gneisses and of their migmatite host rocks are especially of interest for the interpretation of the geological and tectonic development of North Victoria Land. Another important research aspect is the influence of the polyphase metamorphic evolution on the isotopic systems of whole rocks and minerals like zircon, garnet, orthopyroxene, amphibole and feldspar.

(Table 1) Sr, Nd, and Pb isotopic composition of ODP Leg 129 basalts

Basaltic rocks recovered from three drill sites in the western Pacific during Ocean Drilling Program Leg 129 have fairly distinct Sr, Nd, and Pb isotopic compositions. The Cretaceous alkali olivine dolerites from Site 800 in the northern part of Pigafetta Basin have fairly low 87Sr/86Sri (0.70292-0.70320) and 143Nd/144Ndi (0.51277-0.51281) and high present-day Pb isotopic ratios (206Pb/204Pb = 20.53-21.45; 207Pb/204Pb = 15.70-15.77; 208Pb/204Pb = 40.02-40.68). The Middle Jurassic tholeiites from Site 801 in the southern part of the basin have low 87Sr/86Sri (0.70237-0.70248), high 143Nd/144Ndi (0.51298-0.51322), and moderate present-day Pb isotopic ratios (206Pb/204Pb = 18.20-19.12; 207Pb/204Pb = 15.47-15.60; 208Pb/204Pb = 37.56-38.18); isotopic compositions of the alkali olivine basalts overlying the tholeiites fall between those of the tholeiites and Site 800 dolerites. The Cretaceous tholeiites from Site 802 in the East Mariana Basin have high 87Sr/86Sri (0.70360-0.70372), fairly low 143Nd/144Ndi (0.51277-0.51280), and fairly low and homogeneous present-day Pb isotopic ratios (206Pb/204Pb = 18.37-18.39; 207Pb/204Pb = 15.49-15.51; 208Pb/204Pb = 38.34-38.39). Isotopic compositions of Site 801 tholeiites are indistinguishable from those of modern mid-ocean ridge basalts, consistent with the proposal that these tholeiites are a part of the oldest Pacific crust. The diverse isotopic compositions of the younger basalts appear to be the result of Jurassic Pacific plate migration over the geologically anomalous south-central Pacific region, wherein they acquired their distinct isotopic compositions. The anomalous region was volcanically more active during the Cretaceous than at present.

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.

Nd, Sr and Pb isotopic composition of eolian dust deposited in the central North Pacific

The silicate fractions of recent pelagic sediments in the central north Pacific Ocean are dominated by eolian dust derived from central Asia. An 11 Myr sedimentary record at ODP Sites 885/886 at 44.7°N, 168.3°W allows the evaluation of how such dust and its sources have changed in response to late Cenozoic climate and tectonics. The extracted eolian fraction contains variable amounts (>70%) of clay minerals with subordinate quartz and plagioclase. Uniform Nd isotopic compositions (epsilon-Nd =38.6 to 310.5) and Sm/Nd ratios (0.170-0.192) for most of the 11 Myr record demonstrate a well-mixed provenance in the basins north of the Tibetan Plateau and the Gobi Desert that was a source of dust long before the oldest preserved Asian loess formed. epsilon-Nd values of up to 36.5 for samples 62.9 Ma indicate <=35 wt% admixture of a young, Kamchatka-like volcanic arc component. The coherence of Pb and Nd in the erosional cycle allows us to constrain the Pb isotopic composition of Asian loess devoid of anthropogenic contamination to 206Pb/204Pb =18.97 +/- 0.06, 207Pb/204Pb =15.67 +/- 0.02, 208Pb/204Pb =39.19 +/- 0.11. 87Sr/86Sr (0.711-0.721) and Rb/Sr ratios (0.39-1.1) vary with dust mineralogy and provide an age indication of ~250 Ma. 40Ar/39Ar ages of six dust samples are uniform around 200 Ma and match the K-Ar ages of modern dust deposited on Hawaii. These data reflect the weighted age average of illite formation. Changes from illite- smectite with significant kaolinite to illite- and chlorite-rich, kaolinite-free assemblages since the late Pliocene document changes in the intensity of chemical weathering in the source region. Such weathering evidently did not disturb the K-Ar systematics, and only induced scatter in the Rb-Sr data. We propose that when smectite forms at the expense of illite, K and Ar are quantitatively lost from what becomes smectite, but are quantitatively retained in adjacent illite layers. 40Ar/39Ar age data, therefore, are insensitive to smectite formation during chemical weathering but date the diagenetic growth of illite, the major K-bearing phase in the dust. Over the past 12 Myr, the dust flux to the north Pacific increased by more than an order of magnitude, documenting a substantial drying of central Asia. This climatic change, however, did not alter the ultimate source of the dust, and neoformational products of chemical weathering always remained subordinate to assemblages reworked by mechanical erosion in dust deposited in eastern Asia and the Pacific Ocean.

Alkali contents, Sr isotope and U-Th-Pb data for ocean crust vein minerals from DSDP Holes 27-261, 61-462A, and 72-516F

Cation exchange experiments (ammonium acetate and cation resin) on celadonite-smectite vein minerals from three DSDP holes demonstrate selective removal of common Sr relative to Rb and radiogenic Sr. This technique increases the Rb/Sr ratio by factors of 2.3 to 22 without significantly altering the age of the minerals, allowing easier and more precise dating of such vein minerals. The ages determined by this technique (Site 261 - 121.4+/-1.6 m.y.; Site 462A - 105.1+/-2.8 m.y.; Site 516F - 69.9+/-2.4 m.y.) are 34, 54 and 18 m.y. younger, respectively, than the age of crust formation at the site; in the case of site 462A, the young age is clearly related to off-ridge emplacement of a massive sill/flow complex. At the other sites, either the hydrothermal circulation systems persisted longer than for normal crust (10-15 m.y.), or were reactivated by off-ridge igneous activity. Celadonites show U and Pb contents and Pb isotopic compositions little changed from their basalt precursors, while Th contents are significantly lower. Celadonites thus have unusually high alkali/U,Th ratios and low Th/U ratios. If this celadonite alteration signature is significantly imprinted on oceanic crust as a whole, it will lead to very distinctive Pb isotope signatures for any hot spot magmas which contain a component of aged subducted recycled oceanic crust. Initial Sr isotope ratios of ocean crust vein minerals (smectite, celadonite, zeolite, calcite) are intermediate between primary basalt values and contemporary sea water values and indicate formation under seawaterdominated systems with effective water/rock ratios of 20-200.

Re-OS and Pb isotope ratios of sediments from Saanich Inlet, Western Canada

Re-Os and Pb-Pb isotopic analysis of reduced varved sediments cored in the deeper basin of Saanich Inlet (B.C.) are presented. From core top to 61 cm down-core, spanning approximately the last 100 yrs of sedimentation, 187Os/188Os ratio and Os concentration respectively increase from ~0.8 to ~0.9 and from 55 to 60 ppt, whereas Re concentration decreases from 3600 to 2600 ppt. Re correlates with Corg (R2=0.6) throughout the entire section, whereas Os follows Re and Corg trends deeper down-core, suggesting a decoupling of a Re- and Os-geochemistry during burial and/or very early diagenesis. No systematic compositional differences are observed between seasonal laminae. 204Pb-normalized lead isotope ratios increase from sediment surface down to 7 cm down-core, then decrease steadily to pre-industrial levels at ~50 cm down-core. This pattern illustrates the contamination from leaded gasoline until the recent past. The measured Pb isotopic ratios point primarily toward gasoline related atmospheric lead from the USA. The osmium isotopic values measured are significantly lower than those of modern seawater-Os. In comparison with other anoxic environments, the osmium content of Saanich Inlet sediments is low, and its Os isotopic composition suggests significant inputs from unradiogenic sources (detrital and/or dissolved). Ultramafic lithologies in the watershed of the Fraser River are suspected to contribute to sedimentary inputs as well as to the input of dissolved unradiogenic osmium in the water of Saanich Inlet. The presence of some unradiogenic Os from anthropogenic contamination cannot be discounted near the core top, but since deeper, pre-anthropogenic levels also yielded unradiogenic Os results, one is led to conclude that the overall low 187Os/188Os ratios result from natural geochemical processes. Thus, the bulk sediment of Saanich Inlet does not appear to record 187Os/188Os composition of the marine end-member of the only slightly below normal salinity, fjord water. The low seawater-derived Os content of the sediment, coupled with unradiogenic Os inputs from local sources, explains the overall low isotopic values observed. As a consequence, such near-shore anoxic sediments are unlikely to record changes in the past ocean Os isotopic composition.

Pb-, Sr-, and Nd-isotopic composition of basaltic rocks from the Lau Basin

New Pb, Sr, and Nd isotope data are presented for 64 samples from the six backarc sites drilled during Leg 135. Systematic changes in Pb and Sr compositions illustrate significant isotopic variations between and within sites as well as provide two key pieces of information. First, a recent influx of asthenosphere with Indian Ocean mantle affinities has occurred and has successfully displaced older "Pacific" asthenosphere from the mantle underlying the backarc region. Second, clear evidence exists for mixing between these two asthenospheric end-members and at least one "arc-like" component. The latter was not the same as most material currently erupting in the Tofua Arc, but it must have had a more radiogenic Pb-isotope signature, perhaps similar to rocks analyzed from the islands of Tafahi, and Niuatoputapu. A comparison between the isotopic variations and the tectonic setting of the drill sites reveals consistent and important information regarding the mantle dynamics beneath the evolving backarc basin. We propose a model in which the source of upwelling magmas changes from Pacific to Indian Ocean asthenosphere with the propagation of seafloor spreading, a model with important implications for the rate of mantle influx into this region. Although the chemistries of backarc magmas have been profoundly influenced by this process, an additional consequence is the advection of Indian Ocean asthenosphere into the sub-arc mantle source. The isotopic compositions of arc rocks from the vicinity have been reevaluated on the basis of the proposed mantle advection model. We suggest that the slab-derived flux of trace elements into the arc wedge has remained relatively uniform with time (i.e., ~40 Ma), so that the change in arc chemistry results from mantle source substitution, rather than from differences in the composition of the downgoing plate.

Geochemistry and radiogenic isotopes of ODP Hole 157-953C lavas

The Canary Island primitive basaltic magmas are thought to be derived from an HIMU-type upwelling mantle containing isotopically depleted (NMORB)-type component having interacted with an enriched (EM)-type component, the origin of which is still a subject of debate. We studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6-90.0 mol.% Fo, 1,722-3,915 ppm Ni, 1,085-1,552 ppm Mn, 1,222-3,002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr-Nd-Pb isotope compositions (87Sr/86Sr = 0.70315-0.70331, 143Nd/144Nd = 0.51288-0.51292, 206Pb/204Pb = 19.55-19.93, 207Pb/204Pb = 15.60-15.63, 208Pb/204Pb = 39.31-39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model (Sobolev et al., 2007, Science Vol 316) in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an end member composition for peridotite with 87Sr/86Sr = 0.70337, 143Nd/144Nd = 0.51291, 206Pb/204Pb = 19.36, 207Pb/204Pb = 15.61 and 208Pb/204Pb = 39.07 (EM-type end member), and pyroxenite with 87Sr/86Sr = 0.70309, 143Nd/144Nd = 0.51289, 206Pb/204Pb = 20.03, 207Pb/204Pb = 15.62 and 208Pb/204Pb = 39.84 (HIMU-type end member). Mixing of melts from these end members in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite derived melt fractions can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low-silica rocks from the western Canary Islands (Gurenko et al., 2009, doi:10.1016/j.epsl.2008.11.013), at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center.

(Table A1) Isotopic ratios of Sr, Nd, and Pb for sediments in ODP Leg 138 sites

The provenance of eolian dust supplied to deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation. Specifically, measuring temporal changes in dust provenance can shed light on changes in the mean position of the Intertropical Convergence Zone (ITCZ), a region acting as a barrier separating wind-blown material derived from northern versus southern hemisphere sources. Here we have analyzed Nd, Sr, and Pb isotope ratios in the operationally-defined detrital component extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110°W from 3°S to 7°N (ODP Leg 138, sites 848-853). Sr isotope results show that barite Sr has a significant influence on 87Sr/86Sr isotope ratios of samples in the upwelling zone of the EEP. However, sites located >3° or more away from the equator (sites 852 and 853) are believed to not be affected by barite Sr and provide useful detrital Sr signals. 208Pb/206Pb and 207Pb/206Pb ratios in all cores fall into the Pb-isotope space of five potential dust sources (Asia, North and Central/South America, Sahara, and Australia), with no distinct isotopic fingerprinting of the dominant source(s). epsilon-Nd values were most valuable for discerning detrital source provenance, and their values at all sites, ranging from ~5.46 to ~3.25, were more unradiogenic for sediments deposited during the last glacial than for those deposited during the Holocene. There are distinct latitudinal trends in the epsilon-Nd values, with more radiogenic values further south and less radiogenic values further north, excluding site 848. This distinction holds true for both Holocene and last glacial periods. For the most southerly site, 848, we invoke, for the first time, a distinct southern hemisphere Australian source as being responsible for the unradiogenic Nd isotope ratios. Both average last glacial and Holocene epsilon-Nd values show similar sharp gradients along the transect between 5.29°N and 2.77°N, suggesting little movement of the glacial ITCZ in the EEP. However, during the deglacial, this gradient is stronger and shifted further north between 5.29°N and 7.21°N, suggesting a more northerly, possibly stronger, deglacial ITCZ.

Pb isotope and geochemical record of Arctic sediments

Elemental and Pb isotope measurements were performed on leachates and residues from surface sediments and two <50 cm cores (MC04 and MC16) collected along a NE-SW transect through Fram Strait. Geochemical and isotopic properties of residues from surface sediments define three distinct spatial domains within the Strait: 1) the easternmost edge of the Strait; 2) the eastern part of the Strait off the Svalbard margins; and 3) the western part of the Strait, influenced by supplies from Svalbard, the Nordic seas with possible contributions from northwestern Siberian margins, and sea ice and water outflow from the Arctic, respectively. Core MC16, in the third domain beneath the outflowing Arctic waters, spans the Last Glacial Maximum present interval. Sediments from this core were leached to obtain detrital (residues) and exchangeable (leachates) fractions. Detrital supplies to core MC16 are believed to originate mainly from melting of the overlying sea ice and thus can be used to document changes in Arctic sedimentary sources. Detrital 206Pb/204Pb and 208Pb/206Pb ratios illustrate two mixing trends, Trends A and B, corresponding to the pre- and post-Younger Dryas (YD) intervals, respectively. These trends represent binary mixtures with a common end-member (Canadian margins) and either a Siberian (Trend A) or Greenland (Trend B) margin end-member. The YD is marked by an isotopic excursion toward the Canadian end-member, suggesting a very active Beaufort Gyre possibly triggered by massive drainage of the Laurentide ice sheet. Pb isotope compositions of leachates, thought to represent the signature of the overlying water masses, define a unique linear trend coincident with Trend A. This suggests that water masses acquired their signature through exchange with particulate fluxes along the Canadian and Siberian continental margins.