Sodium fluoride ion-pairs in seawater

Laboratory investigations were conducted on the formation of NaF° ion-pairs at the ionic strength of seawater using specific ion electrodes. Sodium and fluoride ion electrodes produced results which are consistent with the ion-pairing model for these ionic interactions. The stoichiometric association constant for NaF°, $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$, was determined at 15, 25, and 35°C. It was assumed that $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$ was a function of temperature, pressure, and ionic strength but not of solution composition. The value for $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$ at 25°C and I = 0.7 m is 0.045 ± 0.006. $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$ increased with decreasing temperature. This result was used to recompute values of $\text{K}{}^1{}_{\mathrm{<mtext>MgF</mtext>}}$ and $\text{K}{}^1{}_{\mathrm{<mtext>CaF</mtext>}}$ accounting for the presence of NaF° ion-pairs. The value for $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$ indicates that 1.1% of the fluoride in seawater is ion-paired with sodium at 25°C and 35‰ salinity. This fraction increases to approximately 2% at the lower temperatures found in the deep ocean. The percentage of free fluoride in natural seawater was measured at 15, 25, and 35°C to verify the speciation calculated from equilibrium constants.     

Early diagenesis in rapidly accumulating sediments on the Alboran slope, ODP site 976

 The oxidation and reduction that occur during early diagenesis of sediments has been studied in the interstitial waters of a rapidly accumulating sedimentary sequence from the Mediterranean margin of Spain. A series of reactions that are mediated by progressively lower free energy derived from oxidation of organic matter is evident in the sedimentary sequence. Iron and manganese are rapidly reduced. Phosphate and alkalinity maxima at a subbottom depth of 15 m indicate maximal organic matter degradation. Methane first appears at ∼20 m subbottom after sulfate is depleted, and its concentrations quickly climb. Received: 27 October 1997 / Revision received: 4 March 1998     

Resolving cosmic structure formation with the Millennium-II Simulation

We present the Millennium-II Simulation (MS-II), a very large N -body simulation of dark matter evolution in the concordance Λ cold dark matter (ΛCDM) cosmology. The MS-II assumes the same cosmological parameters and uses the same particle number and output data structure as the original Millennium Simulation (MS), but was carried out in a periodic cube one-fifth the size  (100  h ⁻¹ Mpc)  with five times better spatial resolution (a Plummer equivalent softening of  1.0  h ⁻¹ kpc  ) and with 125 times better mass resolution (a particle mass of  6.9 × 10⁶  h ⁻¹ M_⊙  ). By comparing results at MS and MS-II resolution, we demonstrate excellent convergence in dark matter statistics such as the halo mass function, the subhalo abundance distribution, the mass dependence of halo formation times, the linear and non-linear autocorrelations and power spectra, and halo assembly bias. Together, the two simulations provide precise results for such statistics over an unprecedented range of scales, from haloes similar to those hosting Local Group dwarf spheroidal galaxies to haloes corresponding to the richest galaxy clusters. The 'Milky Way' haloes of the Aquarius Project were selected from a lower resolution version of the MS-II and were then resimulated at much higher resolution. As a result, they are present in the MS-II along with thousands of other similar mass haloes. A comparison of their assembly histories in the MS-II and in resimulations of 1000 times better resolution shows detailed agreement over a factor of 100 in mass growth. We publicly release halo catalogues and assembly trees for the MS-II in the same format within the same archive as those already released for the MS.     

Effects of seed particle size and composition on heterogeneous nucleation of n-nonane

Heterogeneous nucleation of supersaturated n-nonane vapour on seed particles of different size and composition has been investigated using a fast expansion chamber. Monodisperse seed particle sizes were ranging from about 4 nm up to about 24 nm in diameter. By using different types of particle generators WO_x, Ag and (NH₄)₂SO₄ particles were generated. For direct comparison between different particle compositions overlapping sizes have been generated for WO_x and Ag at about 7 nm particle diameter as well as for Ag and (NH₄)₂SO₄ at about 15 nm. Nucleation temperature was kept constant at about 278 K. Experimental data were compared to Kelvin equation and Fletcher theory including the effect of line tension. It was found that heterogeneous nucleation of n-nonane seems to be independent of seed particle composition and starts well below the Kelvin curve. Good agreement was achieved with Fletcher theory including the effect of line tension.     

The importance of three centuries of land-use change for the global and regional terrestrial carbon cycle

Large amounts of carbon (C) have been released into the atmosphere over the past centuries. Less than half of this C stays in the atmosphere. The remainder is taken up by the oceans and terrestrial ecosystems. Where does the C come from and where and when does this uptake occur? We address these questions by providing new estimates of regional land-use emissions and natural carbon fluxes for the 1700–2000 period, simultaneously considering multiple anthropogenic (e.g. land and energy demand) and biochemical factors in a geographically explicit manner. The observed historical atmospheric CO₂ concentration profile for the 1700 to 2000 period has been reproduced well. The terrestrial natural biosphere has been a major carbon sink, due to changes in climate, atmospheric CO₂, nitrogen and management. Due to land-use change large amounts of carbon have been emitted into the atmosphere. The net effect was an emission of 35 Pg C into the atmosphere for the 1700 to 2000 period. If land use had remained constant at its distribution in 1700, then the terrestrial C uptake would have increased by 142 Pg C. This overall difference of including or excluding land-use changes (i.e. 177 Pg C) comes to more than half of the historical fossil-fuel related emissions of 308 Pg C. Historically, global land-use emissions were predominantly caused by the expansion of cropland and pasture, while wood harvesting (for timber and fuel wood) only played a minor role. These findings are robust even when changing some of the important drivers like the extent of historical land-use changes. Under varying assumptions, land-use emissions over the past three centuries could have increased up to 20%, but remained significantly lower than from other sources. Combining the regional land-use and natural C fluxes, North America and Europe were net C sources before 1900, but turned into sinks during the twentieth century. Nowadays, these fluxes are a magnitude smaller than energy- and industry-related emissions. Tropical regions were C neutral prior to 1950, but then accelerated deforestation turned these regions into major C sources. The energy- and industry-related emissions are currently increasing in many tropical regions, but are still less than the land-use emissions. Based on the presented relevance of the land-use and natural fluxes for the historical C cycle and the significance of fossil-fuel emissions nowadays, there is a need for an integrated approach for energy, nature and land use in evaluating possible climate change mitigation policies.     

Changing hillslope and fluvial Holocene sediment dynamics in a Belgian loess catchment

Floodplain deposition is an essential part of the Holocene sediment dynamics of many catchments and a thorough dating control of these floodplain deposits is therefore essential to understand the driving forces of these sediment dynamics. In this paper we date floodplain and colluvial deposition in the Belgian Dijle catchment using accelerator mass spectrometric radiocarbon and optical stimulated luminescence dating. Relative mass accumulation curves for the Holocene were constructed for three colluvial sites and 12 alluvial sites. A database was constructed of all available radiocarbon ages of the catchment and this database was analysed using relative sediment mass accumulation rates and cumulative probability functions of ages and site‐specific sedimentation curves. Cumulative probability functions of ages were split into different depositional environments representing stable phases and phases of accelerated clastic deposition. The results indicate that there is an important variation between the different dated sites. After an initial stable early and middle Holocene phase with mainly peat growth in the floodplains, clastic sedimentation rates increased from 4000 BC on. This first phase was more pronounced and started somewhat earlier for colluvial deposits then for alluvial deposits. The main part of the Holocene deposits, both in colluvial and alluvial valleys, was deposited during the last 1 ka. The sedimentation pattern of the individual dated sites and the catchment‐wide pattern indicate that land use changes are responsible for the main variations in the Holocene sediment dynamics of this catchment, while the field data do not provide indications for a climatological influence on the sediment dynamics. Copyright © 2011 John Wiley & Sons, Ltd.