Anthropogenic contributions to atmospheric Hg, Pb and As accumulation recorded by peat cores from southern Greenland and Denmark dated using the C “bomb pulse curve”

Mercury concentrations are clearly elevated in the surface and sub-surface layers of peat cores collected from a minerotrophic (“groundwater-fed”) fen in southern Greenland (GL) and an ombrotrophic (“rainwater-fed”) bog in Denmark (DK). Using ¹⁴C to precisely date samples since ca. AD 1950 using the “atmospheric bomb pulse,” the chronology of Hg accumulation in GL is remarkably similar to the bog in DK where Hg was supplied only by atmospheric deposition: this suggests not only that Hg has been supplied to the surface layers of the minerotrophic core (GL) primarily by atmospheric inputs, but also that the peat cores have preserved a consistent record of the changing rates of atmospheric Hg accumulation. The lowest Hg fluxes in the GL core (0.3 to 0.5 μg/m²/yr) were found in peats dating from AD 550 to AD 975, compared to the maximum of 164 μg/m²/yr in AD 1953. Atmospheric Hg accumulation rates have since declined, with the value for 1995 (14 μg/m²/yr) comparable to the value for 1995 obtained by published studies of atmospheric transport modelling (12 μg/m²/yr).The greatest rates of atmospheric Hg accumulation in the DK core are also found in the sample dating from AD 1953 and are comparable in magnitude (184 μg/m²/yr) to the GL core; again, the fluxes have since gone into strong decline. The accumulation rates recorded by the peat core for AD 1994 (14 μg/m²/yr) are also comparable to the value for 1995 obtained by atmospheric transport modelling (18 μg/m²/yr). Comparing the Pb/Ti and As/Ti ratios of the DK samples with the corresponding crustal ratios (or “natural background values” for preanthropogenic peat) shows that the samples dating from 1953 also contain the maximum concentration of “excess” Pb and As. The synchroneity of the enrichments of all three elements (Hg, Pb, and As) suggests a common source, with coal-burning the most likely candidate. Independent support for this interpretation was obtained from the Pb isotope data (²⁰⁶Pb/²⁰⁷Pb = 1.1481 ± 0.0002 in the leached fraction and 1.1505 ± 0.0002 in the residual fraction) which is too radiogenic to be explained in terms of gasoline lead alone, but compares well with values for U.K. coals. In contrast, the lowest values for ²⁰⁶Pb/²⁰⁷Pb in the DK profile (1.1370 ± 0.0003 in the leached fraction and 1.1408 ± 0.0003 in the residual fraction) are found in the sample dating from AD 1979: this shows that the maximum contribution of leaded gasoline occurred approximately 25 yr after the zenith in total anthropogenic Pb deposition.     

Structural, chemical, and isotopic microanalytical investigations of graphite from supernovae

We report the results of coordinated ion microprobe and transmission electron microscope (TEM) studies of presolar graphites from the KE3 separate (1.65-1.72 g/cm³) of the Murchison CM2 meteorite. Isotopic analysis of individual graphites (1-12 μm) with the ion microprobe shows many to have large ¹⁸O excesses combined with large silicon isotopic anomalies, indicative of a supernova (SN) origin. Transmission electron microscopy (TEM) of ultramicrotome slices of these SN graphites revealed a high abundance (25-2400 ppm) of internal titanium carbides (TiCs), with a single graphite in some cases containing hundreds of TiCs. Isotopic compositions of individual TiCs by nanoscale resolution secondary ion mass spectrometry (NanoSIMS) confirmed their presolar origin. In addition to TiCs, composite TiC/Fe grains (TiCs with attached iron-nickel subgrains) and solitary kamacite internal grains were found. In the composite grains, the attached iron phase (kamacite [0-24 at. % Ni] or taenite [up to 60 at. % Ni]) was epitaxially grown onto one or more TiC faces. In contrast to the denser Murchison KFC1 graphites, no Zr-Ti-Mo carbides were observed. The average TiC diameters were quite variable among the SN graphites, from 30 to 232 nm, and were generally independent of the host graphite size. TiC grain morphologies ranged from euhedral to anhedral, with the grain surfaces exhibiting variable degrees of corrosion, and sometimes partially amorphous rims (3 to 15 nm thick). Partially amorphous rims of similar thickness were also observed on some solitary kamacite grains. We speculate that the rims on the internal grains are most plausibly the result of atom bombardment caused by drift of grains with respect to the ambient gas, requiring relative outflow speeds ∼100 km/s (i.e., a few percent of the SN mass outflow speed).Energy dispersive X-ray spectrometry (EDXS) of TiCs revealed significant V in solid solution, with an average V/Ti ratio over all TiCs of ∼83% of the solar value of 0.122. Significant variations about the mean V/Ti ratio were also seen among TiCs in the same graphite, likely indicating chemical equilibration with the surrounding gas over a range of temperatures. In general, the diversity in internal TiC properties suggests that TiCs formed first and had substantially diverse histories before incorporation into the graphite, implying some degree of turbulent mixing in the SN outflows.In most graphites, there is a decrease in the number density of TiCs as a function of increasing radial dis- tance, caused by either preferential depletion of TiCs from the gas or an acceleration of graphite growth with decreasing ambient temperature. In several graphites, TiCs showed a trend of larger V/Ti ratios with increasing distance from the graphite center, an indication of progressive equilibration with the surrounding gas before they were sequestered in the graphites. In all but one graphite, no trend was seen in the TiC size vs. distance from the graphite center, implying that appreciable TiC growth had effectively stopped before the graphites formed, or else that graphite growth was rapid compared to TiC growth. Taken together, the chemical variations among internal grains as well as the presence of partially amorphous rims and epitaxial Fe phases on some TiCs clearly indicate that the phase condensation sequence was TiC, followed by the iron phases (only found in some graphites) and finally graphite. Since graphite typically condenses at a higher temperature than iron at low pressures (<10⁻³ bars) in a gas with C > O and otherwise solar composition, the observed condensation sequence implies a relative iron enrichment in the gas or greater supersaturation of graphite relative to iron.The TEM observations allow inferences to be made about the physical conditions in the gas from which the grains condensed. Given the TiC sizes and abundances, the gas was evidently quite dusty. From the observed TiC size range of ∼20 nm to ∼500 nm (assuming ∼1 yr growth time and T ∼ 1800°K), we infer minimum Ti number densities in the gas to be ∼7 × 10⁴ to ∼2 × 10⁶ atoms/cc, respectively. Although the gas composition is clearly not solar, for scale, these number densities would correspond to a pressure range of ∼0.2 μbar to ∼5.0 μbar in a gas of solar composition. They also correspond to minimum TiC grain number densities of ∼3 × 10⁻⁴ to ∼0.2 grains/cc, assuming complete condensation of Ti in TiC. We estimate the maximum ratio of mean TiC grain separation distance in the gas to grain diameter from the Ti number densities as ∼3 × 10⁵ to ∼1 × 10⁶.     

Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

Spectral and Multiscale Signal-to-Noise Thresholding of Spherical Vector Fields

The basic concepts of spectral and multiscale selective reconstruction of (geophysically relevant) vector fields on the sphere from error-affected data is outlined in detail. The reconstruction mechanism is formulated under the assumption that spectral as well as multiscale approximation is well-representable in terms of only a certain number of expansion coefficients at the various resolution levels. It is shown that spectral denoising by means of orthogonal expansions in terms of vector spherical harmonics reflects global a priori information of the noise (e.g., in form of a covariance tensor field), whereas multiscale signal-to-noise thresholding can be performed under locally dependent noise information within a multiresolution analysis in terms of spherical vector wavelets. An application of the multiscale formalism to Earth's magnetic field determination is presented.     

Source of trace element variability in Great Barrier Reef corals affected by the Burdekin flood plumes

Massive corals in the Great Barrier Reef, analyzed at high-resolution for Sr/Ca (thermal ionization mass spectrometry) and trace elements such as Ba and Mn (laser ablation inductively coupled plasma mass spectrometry), can provide continuous proxy records of dissolved seawater concentrations, as well as sea surface temperature (SST). A 10-yr record (1989 to 1998) from Pandora Reef, an inshore reef regularly impacted by the freshwater plumes of the Burdekin River, is compared with an overlapping record from a midshelf reef, away from runoff influences. Surface seawater samples, taken away from river plumes, show little variability for Sr/Ca (8484 ± 10 μmol/mol) and Ba (33.7 ± 0.7 nmol/kg). Discrete Ba/Ca peaks in the inshore coral coincide with flood events. The magnitude of this Ba/Ca enrichment is most likely controlled by the amount of suspended sediments delivered to the estuary, which remains difficult to monitor. The maximum flow rate at peak river discharge is used here as a proxy for the sediment load and is shown to be strongly correlated with coral Ba/Ca (r = 0.97). After the wet summer of 1991, the coral Ba/Ca flood peak is followed by a plateau that lingers for several months after dissipation of plume waters, signifying an additional flux of Ba that may originate from submarine groundwater seeps and/or mangrove reservoirs. Both Mn and Y are enriched by a factor of ∼5 in inshore relative to midshelf corals. Mn/Ca ratios show a seasonal cycle that follows SST (r = 0.7), not river discharge, with an additional high variability in summer suggesting a link with biological activity. P and Cd show no significant seasonal variation and are at a low level at both inshore and midreef locations. However, leaching experiments suggest that part of the coral P is not lattice bound.     

Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.     

A coupled model study on ENSO, MJO and Indian summer monsoon rainfall relationships

Summary In this paper, we have tried to understand the ENSO, MJO and Indian summer monsoon rainfall relationships from observation as well as from coupled model results. It was the general feeling that El-Niño years are the deficient in Indian monsoon rainfall and converse being the case for the La-Niña years. Recent papers by several authors noted the failure of this relationship. We find that the model output does confirm a breakdown of this relationship. In this study we have seen that a statistically defined modified Indian summer monsoon rainfall (MISMR) index, a linearly regressed ISMR index and dynamical Webster index (WBSI), shows an inverse relationship with ENSO index during the entire period of integration (1987 to 1999). It is also seen from this study that the amplification of the MJO signals were large and the ENSO signals were less pronounced during the years of above normal ISMR. The MJO signal amplitudes were small and ENSO signals were strong during the years of deficient ISMR. It has been noted that here is a time lag between the MJO and ENSO signal in terms of their modulation aspect. If time lag is added with the ENSO signal then both signals maintain the amplitude modulation theory. A hypothesis is being proposed here to define a relationship between MJO and ENSO signals for the entire period between 1987 and 1999.Received September 18, 2002; revised November 22, 2002; accepted December 20, 2002 Published online: May 8, 2003     

Evolution of the equatorial and dipole modes of the sea-surface temperature in the Tropical Atlantic at decadal scale

Summary ?One hundred and thirty six years (1856–1991) of monthly sea-surface temperature (SST) data in the Tropical Atlantic Ocean are used to investigate the propagating signals of the SST at a decadal (DD) time scale. The first and the third evolving modes show a relationship between the equatorial and the inter-hemispheric patterns, one evolving into the other mode and vice-versa. These modes describe two different evolutions of the SST at DD time-scale. The first EEOF features a 12-year period oscillatory regime with a strong 2-year duration inter-hemispheric pattern evolving into a weak 1-year duration equatorial pattern and vice-versa. This mode exhibits also a northward displacement of the anomalies in the band 15° S–15° N. The third EEOF also shows an oscillatory regime, but with a period of 10 years and with a relatively strong 2-year duration equatorial pattern evolving into a weak 1-year duration inter-hemispheric pattern and vice-versa. For this mode, the SST anomalies show a southward displacement in the band 15° S–15° N. These results have not yet been documented in previous works and explain some of the previous findings on the DD variability in the Tropical Atlantic. Received December 31, 2001; revised April 9, 2002; accepted September 4, 2002 Published online: March 20, 2003     

Turbulence Statistics Inside and Over Forest: Influence on Footprint Prediction

Observations of wind statistics within and above a Scots pine forest are comparedwith those predicted from an analytical second-order closure model. The roughnesssublayer (RSL) effects, and the influence of stability on similarity functions, arestudied using observations. The commonly accepted forms of similarity functionsdescribe the influence of diabatic effects above the RSL well. According to earlierstudies they are expected also to apply within the RSL. As an exception, the averagewind speed normalised with friction velocity was found to be invariant with stabilityclose to the canopy top under unstable conditions. Lagrangian stochastic trajectorysimulations were used to evaluate the influence of canopy turbulence profiles onfootprint prediction. The main uncertainty was found to arise from parameterisationof the random forcing term in the Lagrangian velocity equation. The influence ofdiabatic conditions was studied, and it was found that thermal stability affectssignificantly the footprint function above the forest canopy, but significantuncertainty exists because of uncertainties in the formulation of stability functions.     

Description and evaluation of the bergen climate model: ARPEGE coupled with MICOM

A new coupled atmosphere–ocean–sea ice model has been developed, named the Bergen Climate Model (BCM). It consists of the atmospheric model ARPEGE/IFS, together with a global version of the ocean model MICOM including a dynamic–thermodynamic sea ice model. The coupling between the two models uses the OASIS software package. The new model concept is described, and results from a 300-year control integration is evaluated against observational data. In BCM, both the atmosphere and the ocean components use grids which can be irregular and have non-matching coastlines. Much effort has been put into the development of optimal interpolation schemes between the models, in particular the non-trivial problem of flux conservation in the coastal areas. A flux adjustment technique has been applied to the heat and fresh-water fluxes. There is, however, a weak drift in global mean sea-surface temperature (SST) and sea-surface salinity (SSS) of respectively 0.1 °C and 0.02 psu per century. The model gives a realistic simulation of the radiation balance at the top-of-the-atmosphere, and the net surface fluxes of longwave, shortwave, and turbulent heat fluxes are within observed values. Both global and total zonal means of cloud cover and precipitation are fairly close to observations, and errors are mainly related to the strength and positioning of the Hadley cell. The mean sea-level pressure (SLP) is well simulated, and both the mean state and the interannual standard deviation show realistic features. The SST field is several degrees too cold in the equatorial upwelling area in the Pacific, and about 1 °C too warm along the eastern margins of the oceans, and in the polar regions. The deviation from Levitus salinity is typically 0.1 psu – 0.4 psu, with a tendency for positive anomalies in the Northern Hemisphere, and negative in the Southern Hemisphere. The sea-ice distribution is realistic, but with too thin ice in the Arctic Ocean and too small ice coverage in the Southern Ocean. These model deficiencies have a strong influence on the surface air temperatures in these regions. Horizontal oceanic mass transports are in the lower range of those observed. The strength of the meridional overturning in the Atlantic is 18 Sv. An analysis of the large-scale variability in the model climate reveals realistic El Niño – Southern Oscillation (ENSO) and North Atlantic–Arctic Oscillation (NAO/AO) characteristics in the SLP and surface temperatures, including spatial patterns, frequencies, and strength. While the NAO/AO spectrum is white in SLP and red in temperature, the ENSO spectrum shows an energy maximum near 3 years.