Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Geochemistry on sediment profile PS69/335

During RV Polarstern cruise ANT-XXIII/4 in 2006, a gravity core (PS69/335-2) and a giant box core (PS69/335-1) were retrieved from Maxwell Bay off King George Island (KGI). Comprehensive geochemical (bulk parameters, quantitative XRF, Inductively Coupled Plasma Mass Spectrometry) and radiometric dating analyses (14C, 210Pb) were performed on both cores. A comparison with geochemical data from local bedrock demonstrates a mostly detrital origin for the sediments, but also points to an overprint from changing bioproductivity in the overlying water column in addition to early diagenetic processes. Furthermore, ten tephra layers that were most probably derived from volcanic activity on Deception Island were identified. Variations in the vertical distribution of selected elements in Maxwell Bay sediments further indicate a shift in source rock provenance as a result of changing glacier extents during the past c. 1750 years that may be linked to the Little Ice Age and the Medieval Warm Period. Whereas no evidence for a significant increase in chemical weathering rates was found, 210Pb data revealed that mass accumulation rates in Maxwell Bay have almost tripled since the 1940s (0.66 g cm-2 yr-1 in AD 2006), which is probably linked to rapid glacier retreat in this region due to recent warming.

(Table 1) Chloride concentrations in water obtained from observation wells on Helgoland Dune, North Sea

The hydrogeological conditions are unfavourable for a sufficient supply of drinking-water. The small size of the catchment area, the large hydraulic gradient inside the steep 'Buntsandstein'-cliff and the low geodetic level of the 'Dune Island' and the foreshore at the eastern foot of the cliff do not allow the formation and recharge of a sufficiently exploitable geodetic freshwater dome over the underlying saltwater. This means that until recently the provision of sufficient drinking-water for the island's inhabitants, for its garrison as well as for visiting ships was a problem. This problem has now been solved by the desalination of seawater.

Barium measured on water bottle samples during POLARSTERN cruise ARK-XXII/2 (SPACE)

Dissolved barium has been shown to have the potential to distinguish Eurasian from North American (NA) river runoff. As part of the ARK-XXII/2 Polarstern expedition in summer 2007, Ba was analyzed in the Barents, Kara, Laptev seas, and the Eurasian Basins as well as the Makarov Basin up to the Alpha and Mendeleyev Ridges. By combining salinity, d18O and initial phosphate corrected for mineralization with oxygen (PO4*) or N/P ratios we identified the water mass fractions of meteoric water, sea ice meltwater, and marine waters of Atlantic as well as Pacific origin in the upper water column. In all basins inside the lower halocline layer and the Arctic intermediate waters we find Ba concentrations close to those of the Fram Strait branch of the lower halocline (41-45 nM), reflecting the composition of the incoming Atlantic water. A layer of upper halocline water (UHW) with higher Ba concentrations (45-55 nM) is identified in the Makarov Basin. Atop of the UHW, the Surface Mixed Layer (SML), including the summer and winter mixed layers, has high concentrations of Ba (58-67 nM). In the SML of the investigated area of the central Arctic the meteoric fraction can be identified by assuming a conservative behavior of Ba to be primarily of Eurasian river origin. However, in productive coastal regions biological removal compromises the use of Ba to distinguish between Eurasian and NA rivers. As a consequence, the NA river water fraction is underestimated in productive surface waters or waters that have passed a productive region, whereas this fraction is overestimated in subsurface waters containing remineralised Ba, particularly when these waters have passed productive shelf regions. Especially in the Laptev Sea and small regions in the Barents Sea, Ba concentrations are low in surface waters. In the Laptev Sea exceptionally high Ba concentrations in shelf bottom waters indicate that Ba is removed from surface waters to deep waters by biological activity enhanced by increasing ice-free conditions as well as by scavenging by organic matter of terrestrial origin. We interpret high Ba concentrations in the UHW of the Makarov Basin to result from enrichment by remineralisation in bottom waters on the shelf of the Chukchi Sea and therefore the calculated NA runoff is an artefact. We conclude that no NA runoff can be demonstrated unequivocally anywhere during our expedition with the set of tracers considered here. Small contributions of NA runoff may have been masked by Ba depletion and could only be resolved by supportive tracers on the uptake history. We thus suggest that Ba has to be used with care as it can put limits but not yield quantitative water mass distributions. Only if the extra Ba inputs exceed the cumulative biological uptake the signal can be unequivocally attributed to NA runoff.

Hydrochemistry, water level, and discharge of water from Samoylov Island, Lena Delta, northeastern Siberia, in 2008

Although ponds make up roughly half of the total area of surface water in permafrost landscapes, their relevance to carbon dioxide emissions on a landscape scale has, to date, remained largely unknown. We have therefore investigated the inflows and outflows of dissolved organic and inorganic carbon from lakes, ponds, and outlets on Samoylov Island, in the Lena Delta of northeastern Siberia in September 2008, together with their carbon dioxide emissions. Outgassing of carbon dioxide (CO2) from these ponds and lakes, which cover 25% of Samoylov Island, was found to account for between 74 and 81% of the calculated net landscape-scale CO2 emissions of 0.2-1.1 g C/m**2/d during September 2008, of which 28-43% was from ponds and 27-46% from lakes. The lateral export of dissolved carbon was negligible compared to the gaseous emissions due to the small volumes of runoff. The concentrations of dissolved inorganic carbon in the ponds were found to triple during freezeback, highlighting their importance for temporary carbon storage between the time of carbon production and its emission as CO2. If ponds are ignored the total summer emissions of CO2-C from water bodies of the islands within the entire Lena Delta (0.7-1.3 Tg) are underestimated by between 35 and 62%.

Chemistry and mineralogy of ODP Leg 124 sediment samples

From X-ray mineralogical studies and chemical analyses of the whole rocks and the fine fractions (<2 µm) of ten to fifteen samples at each site of ODP Leg 124, two major sources were identified in the sedimentary components of the Celebes and Sulu basins: (1) a terrestrial and continental contribution; (2) a volcanic influx that gives way to well-defined volcanic units or to a dilute contamination, consisting of coarse-grained minerals (Plagioclase, pyroxene, olivine, spinel) or a smectitic-rich fraction produced by the alteration of volcanic glasses and ashes. The continental signature increases the amount of quartz in the rocks and the phyllitic association is complex: micas, kaolinite, disordered interstratified clay-minerals. The chemical compositions of the bulk rocks and the fractions <2 µm are more potassic and aluminum-rich. The volcanic imprint depends on the grain-size and chemical properties of the components. Ca/Na contents highly variable compared to the K content of the bulk composition are due to the presence of coarse-grained volcanic Plagioclase. The fractions <2 µm are more magnesian than in the continental regime. The diagenesis is revealed by the crystallization of zeolites, the fixation of magnesium into the smectites that depletes the pore fluids in this element. Smectitization of the disordered interstratified clay minerals enriches the alkalinity of the pore fluids. Some deep formations of the Sulu Basin are affected by a thermal event, but no thermal event was recognized in the Celebes Basin.

Barium in sediments and pore waters of several ODP Leg 170 and Leg 205 sites

Barium concentrations were measured on 17 pore fluid and 13 sediment samples from Sites 1253 and 1254 drilled offshore Costa Rica during Ocean Drilling Program (ODP) Leg 205. An additional 83 pore fluid and 29 sediment samples were analyzed for Ba concentrations from Sites 1039 and 1040 drilled during ODP Leg 170 offshore Costa Rica. Sites 1039/1253 and 1040/1254 are part of a transect across the Middle America Trench offshore Nicoya Peninsula. The entire incoming sediment section is being underthrust beneath the margin, providing an ideal setting to examine Ba cycling in the shallow levels of the subduction zone. Results from these analyses indicate that a significant amount of Ba is liberated from the mineral barite (BaSO4) in the uppermost hemipelagic sediments arcward of the trench. The shallow distillation of Ba may impact the amount of sedimentary Ba reaching the deeper subduction zone.

Annual variations in composition of the North Dvina River water

New data on elemental composition of particulate matter from the North Dvina River are presented. In May (period of snowmelt flood) it is similar to the upper layer of the continental crust due to active erosion of crust material in the catchment area. In August (summer low water period) impact of biogenic components increases and elevated concentrations of Cd, Sb, Mn, Zn, Pb, and Cu are observed. At other seasons no significant increase in heavy and rare earth element concentrations is observed.

Biogeochemistry and microbiology of groundwater during acetate and bicarbonate amendment to an alluvial aquifer

These data are from a field experiment conducted in a shallow alluvial aquifer along the Colorado River in Rifle, Colorado, USA. In this experiment, bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Data include names and location data for boreholes, geochemical data for all the boreholes between June 1, 2010 and January 1, 2011, microarray data provided as signal to noise ratio (SNR) for individual microarray probes, microarray data provided as signal to noise ratio (SNR) by Genus.