20th Century sea-level change along the eastern US: Unravelling the contributions from steric changes, Greenland ice sheet mass balance and Late Pleistocene glacial loading

We have considered the influence of ocean temperature and salinity changes, mass changes of the Greenland ice sheet (GIS) and the isostatic response of the solid earth to the most recent glacial cycle on 20th century sea-level change along the US east coast with the intention of better understanding the observed signal as well as determining the potential of the tide gauge data for constraining the recent (past 50–100 yr) mass balance of the GIS and earth viscosity structure. Our results show that the signal due to steric changes is large and displays a complex spatial variation which can account for a significant portion of the observed signal. In contrast, that due to changes in the GIS is relatively small and insensitive to the specific geometry of the mass balance model adopted. As a consequence, the tide gauge data alone are not capable of providing useful constraints on either the magnitude or form of recent GIS mass balance. Our inference of mantle viscosity structure based on the tide gauge data was affected dramatically when the steric effect was accounted for: An earth model with an upper mantle viscosity of 8 × 10¹⁹ Pa s and a lower mantle viscosity of 5 × 10²² Pa s produced the best fit to the steric-corrected data; the optimal fit to the uncorrected data was obtained for upper and lower mantle viscosities of 5 × 10²⁰ Pa s and 10²² Pa s, respectively.     

Temporal–compositional trends over short and long time-scales in basalts of the Big Pine Volcanic Field, California

Primitive basaltic single eruptions in the Big Pine Volcanic Field (BPVF) of Owens Valley, California show systematic temporal–compositional variation that cannot be described by simple models of fractional crystallization, partial melting of a single source, or crustal contamination. We targeted five monogenetic eruption sequences in the BPVF for detailed chemical and isotopic measurements and ⁴⁰Ar/³⁹Ar dating, focusing primarily on the Papoose Canyon sequence. The vent of the primitive (Mg# = 69) Papoose Canyon sequence (760.8 ± 22.8 ka) produced magmas with systematically decreasing (up to a factor of two) incompatible element concentrations, at roughly constant MgO (9.8 ± 0.3 (1σ) wt.%) and Na₂O. SiO₂ and compatible elements (Cr and Ni) show systematic increases, while ⁸⁷Sr/⁸⁶Sr systematically decreases (0.7063–0.7055) and ε_Nd increases (− 3.4 to − 1.1). ¹⁸⁷Os/¹⁸⁸Os is highly radiogenic (0.20–0.31), but variations among four samples do not correlate with other chemical or isotopic indices, are not systematic with respect to eruption order, and thus the Os system appears to be decoupled from the dominant trends. The single eruption trends likely result from coupled melting and mixing of two isotopically distinct sources, either through melt-rock interaction or melting of a lithologically heterogeneous source. The other four sequences, Jalopy Cone (469.4 ± 9.2 ka), Quarry Cone (90.5 ±17.6 ka), Volcanic Bomb Cone (61.6 ± 23.4 ka), and Goodale Bee Cone (31.8 ± 12.1 ka) show similar systematic temporal decreases in incompatible elements. Monogenetic volcanic fields are often used to decipher tectonic changes on the order of 10⁵–10⁶ yr through long-term changes in lava chemistry. However, the systematic variation found in Papoose Canyon (10⁰–10² yr) nearly spans that of the entire volcanic field, and straddles cutoffs for models of changing tectonic regime over much longer time-scales. Moreover, ten new ⁴⁰Ar/³⁹Ar ages combined with chemistry from all BPVF single eruption sequences show the long-term trend of BPVF evolution comprises the overlapping, temporal–compositional trends of the monogenetic vents. This suggests that the single eruption sequences contain the bulk of the systematic chemical variation, whereas their aggregate compositions define the long-term trend of volcanic field evolution.     

Calibrations for benthic foraminiferal Mg/Ca paleothermometry and the carbonate ion hypothesis

Benthic foraminiferal magnesium/calcium ratios were determined on one hundred and forty core-top samples from the Atlantic Ocean, the Norwegian Sea, the Indian Ocean, the Arabian Sea and the Pacific Ocean, mostly at sites with bottom water temperatures below 5 °C. Mg/Ca ratios are consistently lower, by  0.2 mmol/mol, in samples cleaned using oxidative and reductive steps than using oxidative cleaning. Differences between Cibicidoides species have been identified: Mg/Ca of Cibicidoides robertsonianus > Cibicidoides kullenbergi > Cibicidoides wuellerstorfi. Comparison with bottom water temperatures support observations of lowered Mg/Ca of C. wuellerstorfi at temperature below  3 °C compared with values predicted by published calibrations and from other Cibicidoides species. Hydrographic data shows that carbonate ion saturation (Δ[CO₃²⁻]) decreases rapidly below this temperature. An empirical sensitivity of Δ[CO₃²⁻] on Mg/Ca has been established for C. wuellerstorfi of 0.0086 ± 0.0006 mmol/mol/μmol/kg. A novel application using modern temperatures and Last Glacial Maximum temperatures derived via pore fluid modelling supports a carbonate ion saturation state effect on Mg incorporation. This may significantly affect calculated δ¹⁸O_seawater obtained from foraminiferal δ¹⁸O and Mg/Ca temperature.     

Glacier hydrochemistry, solute provenance, and chemical denudation at a surge-type glacier in Kuannersuit Kuussuat, Disko Island, West Greenland

In 1995–1998, Han 11 km terrestrial surge of Kuannersuit Glacier, an outlet glacier of the largest ice cap on Disko Island, West Greenland, affected the catchment dramatically. In order to estimate solute fluxes and provenances, bulk meltwaters were sampled at the main subglacial outlet during the initial part of the quiescent phase. The hydrochemistry is significantly influenced by a subglacial basaltic weathering regime with absence of carbonate minerals. The results show that marine and aerosol derived solutes have minimal contribution to the total ion content, whereas sequestration of atmospheric CO₂ associated with carbonation of Ca-rich feldspar and reactive volcanic glass is more dominant than previously reported from glacierized catchments. Application of a sampling strategy dividing water samples into four groups to determine the content of dissolved HCO₃⁻ and CO₃²⁻ shows that the cationic equivalent weathering rate range is 683–860 Σmeq⁺ m⁻² a⁻¹ and solute flux ranges between 76 and 98 t km⁻² a⁻¹. The crustal denudation rate is estimated to 26 t km⁻² a⁻¹, and the transient CO₂ drawdown amounts to 8500–13700 kg C km⁻² a⁻¹.     

REE diffusion in calcite

Chemical diffusion of four rare-earth elements (La, Nd, Dy and Yb) has been measured in natural calcite under anhydrous conditions, using rare-earth carbonate powders as the source of diffusants. Experiments were run in sealed silica capsules along with finely ground calcite to ensure stability of the single-crystal samples during diffusion anneals. Rutherford backscattering spectroscopy (RBS) was used to measure diffusion profiles. The following Arrhenius relations were obtained over the temperature range 600–850°C: D_La =2.6×10⁻¹⁴ exp(−147±14 kJ mol⁻¹/RT) m² s⁻¹, D_Nd =2.4×10⁻¹⁴ exp(−150±13 kJ mol⁻¹/RT) m² s⁻¹, D_Dy =2.9×10⁻¹⁴ exp(−145±25 kJ mol⁻¹/RT) m² s⁻¹, D_Yb =3.9×10⁻¹² exp(−186±23 kJ mol⁻¹/RT) m² s⁻¹. In contrast to previous findings for refractory silicates (e.g. zircon), differences in transport rates among the REE are not pronounced over the range of temperature conditions investigated in this study. Diffusion of the REE is significantly slower than diffusion of the divalent cations Sr and Pb and slower than transport of Ca and C at temperatures above 650°C. Fine-scale zoning and isotopic and REE chemical signatures may be retained in calcites under many conditions if diffusion is the dominant process affecting alteration.     

Energy partitioning during seismic slip in pseudotachylyte-bearing faults (Gole Larghe Fault, Adamello, Italy)

The determination of the earthquake energy budget remains a challenging issue for Earth scientists, as understanding the partitioning of energy is a key towards the understanding the physics of earthquakes. Here we estimate the partition of the mechanical work density into heat and surface energy (energy required to create new fracture surface) during seismic slip on a location along a fault. Earthquake energy partitioning is determined from field and microstructural analyses of a fault segment decorated by pseudotachylyte (solidified friction-induced melt produced during seismic slip) exhumed from a depth of ~ 10 km—typical for earthquake hypocenters in the continental crust. Frictional heat per unit fault area estimated from the thickness of pseudotachylytes is ~ 27 MJ m^− 2. Surface energy, estimated from microcrack density inside clast (i.e., cracked grains) entrapped in the pseudotachylyte and in the fault wall rock, ranges between 0.10 and 0.85 MJ m^− 2. Our estimates for the studied fault segment suggest that ~ 97–99% of the energy was dissipated as heat during seismic slip. We conclude that at 10 km depth, less than 3% of the total mechanical work density is adsorbed as surface energy on the fault plane during earthquake rupture.     

Andesitic magma degassing investigated through H2O vapour–melt partitioning of halogens at Soufrière Hills Volcano, Montserrat (Lesser Antilles)

Magma degassing at Soufrière Hills Volcano (SHV) is characterised by an almost permanent SO₂ flux and a HCl production rate which mainly depends on dome growth rate. Degassing processes have been studied through textural, H₂O and halogen analyses of clasts collected between 1995 and 2006 on the dome and in pyroclastic flows and vulcanian eruption deposits. Cl, Br and I are strongly depleted in melts during H₂O degassing with no significant Cl–Br–I fractionation, whereas F is almost unaffected. All magmas erupted at SHV have followed a multi-step degassing path from the magma chamber up to a shallow depth ( 1 km, P  20 MPa). From that depth, however, effusive and explosive paths are distinct; vulcanian eruptions are the result of closed system degassing (CSD), while effusive dome growth is the result of CSD up to a very shallow depth (≤ 200 m, P  5–2 MPa) followed by open system degassing (OSD). CSD is modelled using the H₂O solubility law, the perfect gas law and partition coefficients of halogens between a rhyolitic melt and H₂O vapour (d_v − lⁱ). Gas loss characteristic of OSD is modelled using a Rayleigh law. Degassing induced crystallisation is introduced through the ratio of crystallisation and degassing rates, which ranges from 150–500. d_v − l^Cl for OSD ranges between 50–300, increasing with melt Cl content. For CSD, the lower effective d_v − l^Cl ( 20) is attributed to kinetic effects.

Dome forming activity has a greater impact on atmospheric chemistry than vulcanian eruptions because OSD is much more efficient at extracting halogens. The model shows that HCl flux is a good proxy for the dome forming eruption rate. Comparison between model and measured gas compositions suggests a high HBr–BrO conversion rate (BrO/Total Br  1/3) in the SHV gas plume.

The degassing behaviour of Cl, Br and I implies similar Cl/Br ( 160) and Br/I ( 90) in initial melts, volcanic clasts and high temperature gases. The low Cl/Br at SHV compared to other island arcs ( 250–300) is attributed to a shallow, pre-eruptive Br enrichment. The almost permanent dome extrusion at SHV since 1995 has likely had a significant regional atmospheric impact because of the very efficient effusive degassing and the high conversion rate of halogens into reactive species within the gas plume.     

Can biomass burning produce a globally significant carbon-isotope excursion in the sedimentary record?

Negative carbon-isotope excursions have been comprehensively studied in the stratigraphic record but the discussion of causal mechanisms has largely overlooked the potential role of biomass burning. The carbon-isotopic ratios (δ¹³C) of vegetation, soil organic matter and peat are significantly lower than atmospheric carbon dioxide (CO₂), and thereby provide a source of low ¹³C CO₂ when combusted. In this study, the potential role of biomass burning to generate negative carbon isotope excursions associated with greenhouse climates is modeled. Results indicate that major peat combustion sustained for 1000 yr increases atmospheric CO₂ from 2.5× present atmospheric levels (PAL) to 4.6× PAL, and yields a pronounced negative δ¹³C excursion in the atmosphere ( 2.4‰), vegetation ( 2.4‰) and the surface ocean ( 1.2‰), but not for the deep ocean ( 0.9‰). Release of CO₂ initiates a short-term warming of the atmosphere (up to 14.4 °C, with a duration of 1628 yr), which is consistent with the magnitude and length of an observed Toarcian excursion event. These results indicate that peat combustion is a plausible mechanism for driving negative δ¹³C excursions in the rock record, even during times of elevated pCO₂.     

U,U andTh in seawater

We have developed techniques to determine²³⁸U,²³⁴U and²³²Th concentrations in seawater by isotope dilution mass spectrometry. U measurements are made using a²³³U²³⁶U double spike to correct for instrumental fractionation. Measurements on uranium standards demonstrate that²³⁴U/²³⁸U ratios can be measured accurately and reproducibly.²³⁴U/²³⁸U can be measured routinely to ± 5‰ (2σ) for a sample of 5 × 10⁹ atoms of²³⁴U (3 × 10⁻⁸ g of total U, 10 ml of seawater). Data acquisition time is 1 hour. The small sample size, high precision and short data acquisition time are superior to-counting techniques.²³⁸U is measured to ± 2‰ (2σ) for a sample of 8 × 10¹² atoms of²³⁸U ( 3 × 10⁻⁹ g of U, 1 ml of seawater).²³²Th is measured to ± 20‰ with 3 × 10¹¹²³²Th atoms (10⁻¹⁰ g²³²Th, 1 1 of seawater). This small sample size will greatly facilitate investigation of the²³²Th concentration in the oceans. Using these techniques, we have measured²³⁸U,²³⁴U and²³²Th in vertical profiles of unfiltered, acidified seawater from the Atlantic and²³⁸U and²³⁴U in vertical profiles from the Pacific. Determinations of²³⁴U/²³⁸U at depths ranging from 0 to 4900 m in the Atlantic (7°44′N, 40°43′W) and the Pacific (14°41′N, 160°01′W) Oceans are the same within experimental error (± 5‰,2σ). The average of these²³⁴U/²³⁸U measurements is 144 ± 2‰ (2σ) higher than the equilibrium ratio of 5.472 × 10⁻⁵. U concentrations, normalized to 35‰ salinity, range from 3.162 to 3.281 ng/g, a range of 3.8%. The average concentration of the Pacific samples (31°4′N, 159°1′W) is 1% higher than that of the Atlantic (7°44′N, 40°43′W and 31°49′N, 64°6′W).²³²Th concentrations from an Atlantic profile range from 0.092 to 0.145 pg/g. The observed constancy of the²³⁴U/²³⁸U ratio is consistent with the predicted range of²³⁴U/²³⁸U using a simple two-☐ model and the residence time of deep water in the ocean determined from¹⁴C. The variation in salinity-normalized U concentrations suggests that U may be much more reactive in the marine environment than previously thought.     

Implanted radiogenic and other noble gases in crustal diamonds from Northern Kazakhstan

Noble gases were extracted in steps from grain size fractions of microdiamonds ( < 100 μm) from the Kokchetav Massif, Northern Kazakhstan, by pyrolysis and combustion. The concentration of ⁴He in the diamonds proper (liberated by combustion) shows a 1/r dependence on grain size. For grain diameters > 15 μm the concentration also decreases with the combustion step. Both results are clear evidence that ⁴He has been implanted into the diamonds from -decaying elements in the surrounding matrix. The saturation concentration of ⁴He(5.6 × 10⁻⁴ cm³ STP/g) is among the very highest observed in any terrestrial diamonds. Fission xenon from the spontaneous fission of ²³⁸U accompanies the radiogenic ⁴He; the ¹³⁶Xe_f/⁴He ratio of (2.5 ± 0.3) × 10⁻⁹ agrees well with the production ratio of 2.3 × 10⁻⁹ expected in a reservoir where Th/U 3.3. Radiogenic ⁴⁰Ar is predominantly ( > 90%) set free upon combustion; it also resides in the diamonds and appears to have been incorporated into the diamonds upon their formation.

³He, on the other hand is mainly released during pyrolysis and hence is apparently carried by ‘contaminants’. The concentration in the diamonds proper is of the order of 4 × 10⁻¹² cm³ STP/g, with a ³He/⁴He ratio of 1 × 10⁻⁸. Excess ²¹Ne, similarly, appears to be present in contaminants as well as in diamonds proper. These two nuclides in the contaminants must have a nucleogenic origin, but it is difficult to explain their high concentrations.     

AMS analysis of I in Japanese soil samples collected from background areas far from nuclear facilities

Analytical procedures in the determination of iodine-129 (half-life: 1.6×10⁷ y) have been studied using accelerator mass spectrometry (AMS), with special references to the separation procedures of iodine from soil samples for the AMS measurement. Iodine was successfully volatilized from soil samples by pyrohydrolysis at 1000 °C and collected in a trap solution. Iodine was purified from the matrix by solvent extraction. Finally, it was precipitated as silver iodide to make a target for AMS. In order to obtain information on the ¹²⁹I/¹²⁷I ratio in a chemical blank (or iodine carrier), we have determined the ratios in several iodine reagents and found that the ratios fell in a narrow range around 1.7×10⁻¹³. The detection limit for soil sample (1 g material) by the present method was about 0.01 mBq/kg or 4×10⁻¹¹ as the ratio of stable iodine (¹²⁹I/¹²⁷I ratio), i.e. these values were much better than that by neutron activation analysis (NAA) used in our previous studies. We have applied this method in the analysis of soil samples collected from different places in Japan. We could successfully determine ¹²⁹I in soil samples with low ¹²⁹I concentrations, which could not be detected by NAA. Sample size necessary for the soil analysis by AMS was only about 0.5 g or less, whereas about 100 g of the sample were required for NAA [Muramatsu, Y., Ohmomo, Y., 1986. Iodine-129 and iodine-127 in environmental samples collected from Tokaimura/ Ibaraki, Japan. Sci. Total Environ. 48, 33-43]. Using this method, new data were obtained for the ¹²⁹I levels in 20 soil samples collected from background areas far from nuclear facilities, and the ranges were 1.4×10⁻⁵−4.5×10⁻³ Bq/kg as ¹²⁹I concentrations and 3.9×10⁻¹¹−2.2×10⁻⁸ as ¹²⁹I/¹²⁷I ratios. These values are useful in understanding the ¹²⁹I levels in Japanese environments. Higher ¹²⁹I concentrations were observed in forest soils than those in field and rice paddy soils should be related to the interception effect of atmospheric ¹²⁹I due to tree canopies. Relatively high ¹²⁹I/¹²⁷I ratios found in rice paddy soils could be explained by their low stable iodine concentrations which were caused by the desorption of stable iodine from the rice paddies during the cultivation.     

Impacts of domestic sewage effluent on phytoplankton from Bedford Basin, eastern Canada

The impact of domestic sewage effluent (SE) on the dynamics of phytoplankton assemblages from Bedford Basin was evaluated in the laboratory. Phytoplankton production and chlorophyll a increased proportionally with SE enrichment. Phytoplankton species composition also changed. The potentially harmful diatoms, Pseudonitzschia spp., present initially in small numbers (600 cells 1⁻¹) in Bedford Basin seawater, and became dominant (3–5×10⁶ cells 1⁻¹) when the seawater was enriched with 0.5–5% untreated SE. With higher proportions of SE, other harmful species such as Fragilaria spp. and Euglena spp. became dominant (7−15×10⁶ and 2.2×10⁴ cells 1⁻¹, respectively). Treatment of SE with UV light or activated charcoal seems to favour growth of benign species, such as Chaetoceros socialis, Skeletonema costatum and Thalassiosira spp., but not harmful species such as Pseudonitzschia spp. Further research on UV treatment of domestic sewage is recommended.     

Toxic effects of copper on larval development of the barnacle Balanus amphitrite

Experiments were conducted to assess the effects of copper on larval development in the barnacle Balanus amphitrite. In the first experiment, we compared the sensitivity of three naupliar stages to copper stress. Molting inhibition occurred at copper concentrations ranging from 32 μg l⁻¹ in nauplius II to 128 g l⁻¹ in nauplius VI. EC₅₀ for molting ranged from 97 μg l⁻¹ in nauplius II to 129 g l⁻¹ in nauplius VI. Decreased survival occurred at 128 μg Cu l⁻¹ in all of the naupliar stages tested, with LC₅₀ ranging from 145 in nauplius II to 213 μg l⁻¹ in nauplius VI. In the second experiment, we examined effects of copper on the development from nauplius II to cyprid. The larvae reached cypris stage only in treatments of 16 μg Cu l⁻¹. Our study therefore showed that molting was a more sensitive endpoint than survival, nauplius II was the most sensitive naupliar stage, and that whole larval development assay was more sensitive than assays using a particular larval stage. The results were discussed with respect to the use of this species in toxicity tests.     

Effects of some environmental parameters on the reproduction and development of a tropical marine harpacticoid copepod Nitocra affinis f. californica Lang

The effects of salinity, temperature, and light conditions on the reproduction and development of harpacticoid copepod, Nitocra affinis f. californica under controlled laboratory conditions were determined. Seven different salinity levels (5, 10, 15, 20, 25, 30, 35 ppt), four temperatures (20, 25, 30, 35 °C), three different light intensities (25, 56, 130 μmol m⁻² s⁻¹) and photoperiods (24 h:0 h, 1 h:23 h, 12 h:12 h LD cycle) were employed in this study. The highest (p < 0.05) overall reproduction and fastest development time were achieved by copepods reared under 30–35 ppt salinity. The optimum temperature required for the maximum reproduction was 30 °C while under 30 °C and 35 °C the copepod development time was shortest (p < 0.05) compared to other temperature levels. The overall reproduction was highest (p < 0.05) and development rate of N. affinis was shortest (p < 0.05) under lowest light intensity (25 μmol m⁻² s⁻¹). Continuous light (24 h:0 h LD) inhibited the egg production while, continuous darkness (1 h:23 h LD) and 12 h:12 h LD significantly favoured the overall reproductive activity of the female. Photoperiods 1 h:23 h and 12 h:12 h LD yielded highest total (p < 0.05) offspring female⁻¹ coupled with highest (p < 0.05) survival percentage. This study illustrated that although N. affinis can tolerate wide range of environmental conditions, prolonged exposure to subnormal environments affect its reproduction and development. This study showed that this species can be mass cultured for commercial purposes and has a potential to be used for toxicity studies due to its high reproductive performance fast development and a wide range of tolerance to environmental conditions.     

Variation in water use efficiency and δC levels in Eucalyptus grandis clones

This study aimed to determine whether the δ¹³C levels in the foliage and twigs of four Eucalyptus grandis clones were related to their water use efficiency (WUE). This relationship has previously been demonstrated in a number of herbaceous species but not in mature trees. The study involved accurate measurements of tree trunk growth and water use over a period of 4 months, with subsequent isotopic analysis of mature foliage from the north and south side of the canopy, and young leaves from the top of the canopy.

The water use efficiencies were found to vary from 5.97 × 10⁻³ to 12.3 × 10⁻³ m³ m⁻³. Significant differences were observed between clonal-mean water use efficiencies averaged over six sampling periods. The average δ¹³C of the mature and young foliage was found to be significantly correlated with WUE. However, the correlation was weak, suggesting that the relationship between δ¹³C and WUE is more complex in trees than suggested in the literature on crop plants. It is suggested that differences between sample trees in carbon allocation and leaf-to-air vapour pressure deficits may account for the poor correlation between δ¹³C and WUE in the four E. grandis clones studied.     

Intermittent exposure to reduced oxygen levels affects prey size selection and consumption in swimming crab Thalamita danae Stimpson

Portunid crabs Thalamita danae (carapace width: 46–56 mm) were exposed to low oxygen level (4.0 mg O₂ l⁻¹) and hypoxia (1.5 mg O₂ l⁻¹) for 6 h each day with three size classes (large: 15.0–19.9 mm, medium: 10.0–14.9 mm, small: 5.0–9.9 mm) of mussels Brachidontes variabilis offered as food. Consumption rate, prey size preference, and prey handling including breaking time, handling time, eating time and prey value, were studied during the time the crabs were exposed to reduced oxygen levels and results were compared with the crabs maintained at high oxygen level (8.0 mg O₂ l⁻¹) throughout the experiment. Consumption of mussels from all size classes was significantly higher at high oxygen level than at reduced oxygen levels. No mussel size preference was observed for crabs exposed to 4.0 or 8.0 mg O₂ l⁻¹ but those crabs exposed to 1.5 mg O₂ l⁻¹ preferred medium mussels. Both breaking time and handling time increased with mussel size but did not vary with oxygen level. Prey value of each mussel consumed (mg dry wt eaten crab⁻¹ s⁻¹) was calculated by dividing the estimated dry weight of the mussel by the observed handling time. Mean prey value varied significantly with mussel size, with values obtained for large mussels being higher than small mussels at 4.0 and 8.0 mg O₂ l⁻¹; the effect of oxygen level, however, was insignificant. In view of portunid crabs as major predators of mussels, results may help explain dominance of mussels in eutrophic harbours in Hong Kong.     

Martian mantle mineralogy investigated by the Lu–Hf and Sm–Nd systematics of shergottites

Chemical heterogeneities in the Martian mantle are believed to result from the crystallization of a magma ocean in the first 100 million years of its history. Shergottite meteorites from Mars are thought to retain a compositional record of such early differentiation and the resulting mineralogy at different depths. The coupled ¹⁷⁶Lu–¹⁷⁶Hf and ¹⁴⁷Sm–¹⁴³Nd isotope systematics in 9 shergottites are used here to investigate these issues. Three compositional groups in the shergottites display distinct isotope systematics. One group, commonly termed as depleted, is characterized by positive ¹⁷⁶Hf_i from + 46.2 to + 50.4 and ¹⁴³Nd_i from + 36.2 to + 39.1. Another, termed as enriched, has negative ¹⁷⁶Hf_i = − 16.5 to − 13.2 and ¹⁴³Nd_i = − 7.0 to − 6.5. The third group is intermediate between the depleted and enriched groups with positive ¹⁷⁶Hf_i = + 30.0 to + 33.4 and ¹⁴³Nd_i = + 16.9. Together, they describe mixing curves between ¹⁷⁶Hf/¹⁷⁷Hf, ¹⁴³Nd/¹⁴⁴Nd, Lu/Hf, and Sm/Nd, implying that they sample two distinct sources in the Martian mantle. All shergottites are characterized by (Sm/Nd)_source < (Sm/Nd)_sample, but (Lu/Hf)_source > (Lu/Hf)_sample. This decoupling can be explained by two successive partial melting episodes in the depleted shergottite source and localized in the Martian upper mantle. The genesis of shergottites can be modeled using non-modal equilibrium partial melting in a source initially composed of 60% olivine, 21% clinopyroxene, 9% orthopyroxene, and 10% garnet, with degrees of partial melting of 8.8% and 3.9%, respectively, for the two successive events. The enriched end-member of the shergottite mixing curve is best modeled by late-stage quenched residual melt resulting from the crystallization of a magma ocean. The depleted shergottite source may be modeled as a mixture of cumulates and residual melt, as convection in the Martian magma ocean is expected to reduce the incompatible trace element heterogeneity in the final solidified layers. Consequently, equilibrium crystallization is preferred to model the crystallization of the Martian magma ocean. The models that best explain the shergottite data are those where the magma ocean is at a depth of at least 1350 km in Mars.     

Towards a classification of organic enrichment in marine sediments based on biogeochemical indicators

A nomogram is developed to show that pH, redox potentials (Eh_NHE) and measures of dissolved sulfides (H₂S + HS⁻ + S²⁻)(total free S²⁻) can be used to classify organic enrichment impacts in marine sediments. The biogeochemical cycle of sulfur in marine sediments is described to show that changes in macrobenthic infauna community structure associated with high levels of organic matter supply result from stress due to oxygen deficiency (hypoxia and anoxia) and toxic effects of S²⁻. The changes reflect enhancement of microbial sulfate reduction under conditions of high organic matter sedimentation and the progressive formation of hypoxic–anoxic conditions measured by decreased Eh_NHE and increased concentrations of S²⁻. The nomogram provides a basis for classification of the oxic status of marine sediments based on changes in inter-related biological and biogeochemical variables along an organic enrichment gradient.     

Iodine-129 concentrations in marginal seas of the north Pacific and Pacific-influenced waters of the Arctic Ocean

Water sampling during the 1993 IV Russian–US Joint Expedition to the Bering and Chukchi Seas (BERPAC) indicates that Pacific Ocean burdens of the long-lived radionuclide ¹²⁹I are relatively low in the Pacific-influenced Arctic, particularly compared to high latitude waters influenced by the North Atlantic. These low concentrations occur despite the presence of potential submerged anthropogenic sources in the East Sea (Sea of Japan), and in the northwest Pacific Ocean, east of the Kamchatka Peninsula. The concentration of ¹²⁹I entering the Arctic Ocean through Bering Strait, 0.7×10⁸ atoms kg⁻¹, is only slightly higher than observed in deep Pacific waters. Similar concentrations (0.44–0.76×10⁸ atoms kg⁻¹) measured in Long Strait indicate no significant transfer of ¹²⁹I eastward into the Chukchi Sea in the Siberian Coastal Current from the Siberian marginal seas to the west. However, the concentrations reported here are more than an order of magnitude higher than the Bering Strait input concentration estimated (1.0×10⁶ atoms kg⁻¹) from bomb fallout mass balances, which supports other existing evidence for a significant atmospheric deposition term for this radionuclide in surface ocean waters. Near-bottom water samples collected in productive waters of the Bering and Chukchi Seas also suggest that sediment regeneration may locally elevate ¹²⁹I concentrations, and impact its utility as a water mass tracer. As part of this study, two deep ¹²⁹I profiles were also measured in the East Sea in 1993–1994. The near-surface concentration of ¹²⁹I ranged from 0.12 to 0.31×10⁸ atoms kg⁻¹. The ¹²⁹I concentration showed a steady decrease with depth, although because of active deep water ventilation, the entire 3000 m water column exceeded natural concentrations of the radionuclide. Atom ratios of ¹²⁹I/¹³⁷Cs in the East Sea also suggest an excess of ¹²⁹I above bomb fallout estimates, also possibly resulting from atmospheric deposition ultimately originating from nuclear facilities.     

Origin and age of thermal waters in Cieplice Spa, Sudeten, Poland, inferred from isotope, chemical and noble gas data

Isotope and hydrochemical data of the thermal water system in Cieplice laskie Zdrój (Spa) indicate the existence of two subsystems that greatly differ in volume and which meet at the fault zones of a granitic horst, where they discharge at an altitude of about 340m. One of the subsystems is very small (about 4 × 10³ m³) as indicated by the tritium age of the order of 10 years and a low outflow rate. Its recharge area found from the δ¹⁸O and δD values, is about 200m above the springs, most probably on the slopes of the foothills of the Karkonosze Mountains south-southwest of the spa. The large subsystem contains water which is free of tritium and whose ¹⁴C content is from 1 to 8 pmc with δ¹³C = −8.0 to −9.2‰. The isotopic composition of this water reflects either the climatic effect (low-altitude recharge during a cooler pre-Holocene climate) or the altitude effect (recharge in the early Holocene period at about 1000m at the heights of the Karkonosze assuming that the ¹⁴C concentration is strongly reduced by exchange with calcite in veins). For the former hypothesis, the recharge area of this water is probably either at the foot of the southeastern slopes of the Kaczawa Mountains or/and at the foot of the Rudawy Janowickie Mountains, to the east of Cieplice. The noble gas temperatures are more consistent with the pre-Holocene recharge. Similarly, the ⁴He excess and ⁴⁰Ar/³⁶Ar ratio support the hypothesis of a pre-Holecene age. The constant ³He/⁴He ratio of 26 × 10⁻⁸ for highly different helium contents indicates crustal origin of helium. For the pre-Holocene age of water its volume is calculated at >- 10⁹m³ (stagnant water in micropores and mobile water in fractures) and the hydraulic conductivity of the host granite massif is estimated at about 7 × 10⁻⁸ ms⁻¹. Two outflows from this subsystem have different and variable fractions of a modern water component (bomb age), most probably originating from the bank infiltration of a nearby stream.