Atmospheric deposition and isotope biogeochemistry of zinc in ombrotrophic peat

Zinc isotope ratios were measured in the top sections of dated ombrotrophic peat cores in Finland to investigate their potential as proxies for atmospheric sources and to constrain post depositional processes affecting the geochemical record. The peat deposits were located in Hietajärvi, a background site well away from any point pollution source and representing ‘background’ conditions, in Outokumpu, next to a mining site, and in Harjavalta, next to a smelter. Measured total concentrations, calculated excess concentrations and mass balance considerations suggest that zinc is subjected to important biogeochemical cycling within the peat. Significant isotopic variability was found in all three peat bogs, with heavier zinc in the deeper and lighter zinc in the upper sections. Isotope ratios and concentrations correlated in the two peats located next to dominant point sources, i.e. the smelting and mining site, suggesting that zinc isotopes trace pollution sources. Concentration and isotope peaks were offset from the period of mining and smelting activity, supporting migration of zinc down the profile. The δ⁶⁶Zn_JMC (where δ⁶⁶Zn = [(⁶⁶Zn/⁶⁴Zn)_sample/(⁶⁶Zn/⁶⁴Zn)_JMC-standard − 1] × 10³) of the top section sample at the remote Hietajärvi site was 0.9‰ and we suggest this represents the regional background isotope signature of atmospheric zinc. The deeper sections of the peat cores show isotopically heavier zinc than any potential atmospheric source, indicating that post depositional processes affected the isotopic records. The large variations encountered (up to 1.05‰ for δ⁶⁶Zn) and Rayleigh modelling imply that multiple fractionation of zinc during diagenetic alterations occurs and nutrient recycling alone cannot explain the fractionation pattern.We propose that zinc isotopes are amenable to identify different atmospheric zinc sources, including zinc derived from anthropogenic activities such as mining and smelting, but multiple biogeochemical processes seriously affect the record and they need to be evaluated and assessed carefully if zinc isotopes are used in terrestrial paleorecords.     

Millennial timescale carbon cycle and climate change in an efficient Earth system model

A new Earth system model, GENIE-1, is presented which comprises a 3-D frictional geostrophic ocean, phosphate-restoring marine biogeochemistry, dynamic and thermodynamic sea-ice, land surface physics and carbon cycling, and a seasonal 2-D energy-moisture balance atmosphere. Three sets of model climate parameters are used to explore the robustness of the results and for traceability to earlier work. The model versions have climate sensitivity of 2.8–3.3°C and predict atmospheric CO₂ close to present observations. Six idealized total fossil fuel CO₂ emissions scenarios are used to explore a range of 1,100–15,000 GtC total emissions and the effect of rate of emissions. Atmospheric CO₂ approaches equilibrium in year 3000 at 420–5,660 ppmv, giving 1.5–12.5°C global warming. The ocean is a robust carbon sink of up to 6.5 GtC year⁻¹. Under ‘business as usual’, the land becomes a carbon source around year 2100 which peaks at up to 2.5 GtC year⁻¹. Soil carbon is lost globally, boreal vegetation generally increases, whilst under extreme forcing, dieback of some tropical and sub-tropical vegetation occurs. Average ocean surface pH drops by up to 1.15 units. A Greenland ice sheet melt threshold of 2.6°C local warming is only briefly exceeded if total emissions are limited to 1,100 GtC, whilst 15,000 GtC emissions cause complete Greenland melt by year 3000, contributing 7 m to sea level rise. Total sea-level rise, including thermal expansion, is 0.4–10 m in year 3000 and ongoing. The Atlantic meridional overturning circulation shuts down in two out of three model versions, but only under extreme emissions including exotic fossil fuel resources.     

K–Ar dating of fault gouge in the northern Sydney Basin, NSW, Australia—implications for the breakup of Gondwana

The occurrence of synkinematic and authigenic clay minerals is a common feature in fault gouges. Few attempts have been made to date fault gouges. We present the first age data in Australia for synkinematic illite–smectite growth in two fault zones of the northern Sydney Basin, NSW. The faults occur at Burwood Beach, NSW in the northern part of the Sydney Basin and are hosted by Early Permian siltstones, tuffs and coals of the Lambton Formation, Newcastle Coal Measures. The faults are 1.5 m apart, show normal displacement and trend N–S with steep easterly dips. Foliated gouge zones, comminution and dilational breccias are developed along both fault surfaces. K–Ar ages extracted from samples in the gouge and tuffs in the damage zones are 172 (6–10 μm) to 119 Ma (<0.4 μm), respectively. Older ages of 272–281 Ma for the coarse fractions (>2 μm), 237–245 Ma for the <2 μm fraction, 218 Ma for the <0.4 μm fraction and 196 Ma for the <0.1 μm fraction have been obtained from siltstones within and outside the damage zone. We believe the younger ages of 196–237 Ma indicate the time at which diagenetic illite–smectite formed and the 122–150 Ma dates from the <2 μm fraction represent the maximum age of gouge formation. The younger ages are thought to reflect the last slip event occurring on the faults, which is related to the rifting and dispersal of the eastern margin of the Australian continent.     

Network‐scale dynamics of grain‐size sorting: implications for downstream fining,stream‐profile concavity,and drainage basin morphology

We explore the link between channel‐bed texture and river basin concavity in equilibrium catchments using a numerical landscape evolution model. Theory from homogeneous sediment transport predicts that river basin concavity directly increases with bed sediment size. If the effective grain size on a river bed governs its concavity, then natural phenomena such as grain‐size sorting and channel armouring should be linked to concavity. We examine this hypothesis by allowing the bed sediment texture to evolve in a transport‐limited regime using a two grain‐size mixture of sand and gravel. Downstream ?ning through selective particle erosion is produced in equilibrium. As the channel‐bed texture adjusts downstream so does the local slope. Our model predicts that it is not the texture of the original sediment mixture that governs basin concavity. Rather, concavity is linked to the texture of the sorted surface layer. Two different textural regimes are produced in the experiments: a transitional regime where the mobility of sand and gravel changes with channel‐bed texture, and a sand‐dominated region where the mobility of sand and gravel is constant. The concavity of these regions varies depending on the median gravel‐ or sand‐grain size, erosion rate, and precipitation rate. The results highlight the importance of adjustments in both surface texture and slope in natural rivers in response to changes in ?uvial and sediment inputs throughout a drainage network. This adjustment can only be captured numerically using multiple grain sizes or empirical downstream ?ning rules. Copyright © 2004 John Wiley & Sons, Ltd.     

Warm-Season Annual to Decadal Temperature Variability for Hokkaido, Japan, Inferred from Maximum Latewood Density and Ring Width Data

We present a warm season (April–September) temperature reconstructionfor Asahikawa, north central Hokkaido, Japan for AD 1557–1990. The reconstruction, which accounts for 34% of the temperature variancefrom 1925–1990, is based on maximum latewood density data from Saghalinspruce (Picea glehnii) growing at timberline (1340–1390 m) at MountAsahidake, Hokkaido. We only present a high frequency (prewhitened or white noise) version of the reconstruction because there is an unexplained offset in the mean between the actual and estimated temperature data for an earlier period of overlap from 1891–1924. The coldest summer in the reconstruction is 1718, forwhich the estimated value is 12.89 ° C, nearly four standard deviations (SD) below the mean. A colder-than-average year is reconstructed for 1641 (13.30° C, nearly 3 SD below mean), following the eruption of Komagatake, Hokkaido which began in July, 1640. The Asahikawa density chronology, shows decadal modes of variation with statistically significant spectral peaks prior to around 1850. A tree-ring width chronology for this same site (AD 1532–1990) is in phase with a tree-ring width record from centralKamchatka prior to around 1850, but out of phase since that time. This pattern suggests, as has been hypothesized for temperature-sensitive tree-ring records from the eastern Pacific sector (Alaska and Patagonia), that a decadal mode of climate variation was more dominant in the Pacific sector prior to about 1850, after which a higher frequency (ENSO-type) mode may have become more pronounced, at least until recent decades. Additional data from the northwestern Pacific is needed to compare to these findings.     

The effects of a constant volume deformation on the magnetization of an artificial sediment

Anhysteretic remanent magnetization (DC field = 1 Oe, peak AC field = 1000 Oe) was given to an artificial sediment consisting of a kaolinite matrix and a 0.03% magnetic fraction of needle-shaped magnetite grains. The mean grain size of the clay flakes and the magnetite needles was approximately 0.5 μm. This sediment was subjected to plane strain while maintaining constant volume. The axis of maximum compression was shortened by as much as 331/3%, which produced no significant change in the direction of magnetization with a decrease in intensity of 28%. A continuous deformation model, in which the magnetite needles are embedded in a plastically deforming linearly homogeneous medium, failed to explain these results. A discontinuous deformation model was more successful. In this model, deformation occurs mainly in shear zones bounding blocks which translate along the shears. Only those magnetite grains in the shear zones rotate, and from symmetry considerations no net change in the direction of magnetization is predicted. Because magnetite grains rotate in opposite directions in complementary sets of shears, the model predicts a decrease in intensity comparable to that which was observed.     

Lithium in spilites

During spilitisation the abundance of Li increases from about 12 ppm in normal basaltic rocks to an average of 75 ppm, with some spilites containing up to 190 ppm. This is relatively far greater than the increase of <50% in Na. Also the ratio CaO/Al₂O₃ decreases from about 1.0 to <0.1 and the H₂O content increases markedly.Alteration of this kind requires waters rich in both Na and Li, with the material added having a ratio 10⁵ Li/Na of about 750: the ratio for seawater is 1.8 but most subsurface waters have higher ratios and are more likely agents of spilitisation.Volcanic hydrothermal brines have suitable Li and Na abundances and are known to have reacted with fresh basalts to produce spilitic alteration: in cases of spilitisation of volcanogenic sediments, reaction with non-volcanic brines may have occurred. In both cases the waters must initially have high CO₂ and low Ca activities.     

The UV-Visible Absorption Cross-Sections and Atmospheric Photolysis Rate of HOI

The UV-visible absorption cross-sections of HOI have been recorded over the wavelength range 278-494 nm and at 298 K following generation of HOI in the gas phase using laser flash photolysis. The gas phase reaction of OH with I₂ was used to produce HOI, and the absorption spectrum of HOI was calibrated relative to the consumption of I₂. The HOI spectrum recorded exhibits 2 broad absorption maxima of = 3.99 × 10^-19 cm² and = 2.85 × 10^-19 cm², centred at 338.4 nm and 404.8 nm respectively. The spectrum is adequately described by a parameterisation consisting of two semi-logarithmic Gaussian distribution functions. The HOI spectrum is more intense than that recorded in previous work of Jenkin, but is in good agreement with more recent work by Bauer et al. The parameterised HOI absorption spectrum recorded in this work was used in a radiative model to calculate the atmospheric photolysis rate (J-value) of HOI. These results indicate that, under most sunlit conditions, HOI has a lifetime with respect to solar photolysis of the order of minutes. Experiments attempting to generate HOI by the reaction of O atoms with C₂H₅I led to complex absorption spectra containing a negative contribution to the absorption from the photolytic removal of an unidentified species. In addition, evidence was found for adsorption and desorption of an iodine-containing species in the reaction vessel. This behaviour is rationalised in terms of the disproportionation of HOI to I₂O, and an uncalibrated spectrum tentatively attributed to I₂O has been recorded.