Climate variability in the southwest Pacific during the Last Termination (20-10 kyr BP)

The degree to which palaeoclimatic changes in the Southern Hemisphere co-varied with events in the high latitude Northern Hemisphere during the Last Termination is a contentious issue, with conflicting evidence for the degree of ‘teleconnection’ between different regions of the Southern Hemisphere. The available hypotheses are difficult to test robustly, however, because there are few detailed palaeoclimatic records in the Southern Hemisphere. Here we present climatic reconstructions from the southwestern Pacific, a key region in the Southern Hemisphere because of the potentially important role it plays in global climate change. The reconstructions for the period 20–10 kyr BP were obtained from five sites along a transect from southern New Zealand, through Australia to Indonesia, supported by 125 calibrated 14C ages. Two periods of significant climatic change can be identified across the region at around 17 and 14.2 cal kyr BP, most probably associated with the onset of warming in the West Pacific Warm Pool and the collapse of Antarctic ice during Meltwater Pulse-1A, respectively. The severe geochronological constraints that inherently afflict age models based on radiocarbon dating and the lack of quantified climatic parameters make more detailed interpretations problematic, however. There is an urgent need to address the geochronological limitations, and to develop more precise and quantified estimates of the pronounced climate variations that clearly affected this region during the Last Termination.

Magnitude of climate variability during middle Pliocene warmth: a palaeoclimate modelling study

The nature and magnitude of climatic variability during the period of middle Pliocene warmth (ca 3.29–2.97 Ma) is poorly understood. We present a suite of palaeoclimate modelling experiments incorporating an advanced atmospheric general circulation model (GCM), coupled to a Q-flux ocean model for 3.29, 3.12 and 2.97 Ma BP. Astronomical solutions for the periods in question were derived from the Berger and Loutre BL2 astronomical solution. Boundary conditions, excluding sea surface temperatures (SSTs) which were predicted by the slab-ocean model, were provided from the USGS PRISM2 2°×2° digital data set. The model results indicate that little annual variation (0.5°C) in SSTs, relative to a ‘control’ experiment, occurred during the middle Pliocene in response to the altered orbital configurations. Annual surface air temperatures also displayed little variation. Seasonally, surface air temperatures displayed a trend of cooler temperatures during December, January and February, and warmer temperatures during June, July and August. This pattern is consistent with altered seasonality resulting from the prescribed orbital configurations. Precipitation changes follow the seasonal trend observed for surface air temperature. Compared to present-day, surface wind strength and wind stress over the North Atlantic, North Pacific and Southern Ocean remained greater in each of the Pliocene experiments. This suggests that wind-driven gyral circulation may have been consistently greater during the middle Pliocene. The trend of climatic variability predicted by the GCM for the middle Pliocene accords with geological data. However, it is unclear if the model correctly simulates the magnitude of the variation. This uncertainty is derived from, (a) the relative insensitivity of the GCM to perturbation in the imposed boundary conditions, (b) a lack of detailed time series data concerning changes to terrestrial ice cover and greenhouse gas concentrations for the middle Pliocene and (c) difficulties in representing the effects of ‘climatic history’ in snap-shot GCM experiments.

Ab initio prediction of the infrared-absorption spectrum of the C2Cl radical

The three lowest (1(2)A('), 2(2)A('), and 1(2)A(')) potential-energy surfaces of the C2Cl radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio using a large basis set and multireference configuration-interaction techniques. The electronic ground state is confirmed to be bent with a very low barrier to linearity, due to the strong nonadiabatic electronic interactions taking place in this system. The rovibronic energy levels of the (CCCl)-C-12-C-12-Cl-35 isotopomer and the absolute absorption intensities at a temperature of 5 K have been calculated, to an upper limit of 2000 cm(-1), using diabatic potential-energy and dipole moment surfaces and a recently developed variational method. The resulting vibronic states arise from a strong mixture of all the three electronic components and their assignments are intrinsically ambiguous. (c) 2005 American Institute of Physics.

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states (1(2)A', 2(2)A', 1(2)A '') of the C2Br radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, R-CC = 1.2621 angstrom, R-CBr = 1.7967 angstrom, < CCBr 156.1 degrees, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C2F and C2Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Sigma, Pi(1/2), Pi(3/2) vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5K have been calculated for the (CCBr)-C-12-C-12-Br-79 isotopomer, to an upper limit of 2000 cm(-1), using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.

Measurement of paraben concentrations in human breast tissue at serial locations across the breast from axilla to sternum

The concentrations of five esters of p-hydroxybenzoic acid (parabens) were measured using HPLC-MS/MS at four serial locations across the human breast from axilla to sternum using human breast tissue collected from 40 mastectomies for primary breast cancer in England between 2005 and 2008. One or more paraben esters were quantifiable in 158/160 (99%) of the tissue samples and in 96/160 (60%) all five esters were measured. Variation was notable with respect to individual paraben esters, location within one breast and similar locations in different breasts. Overall median values in nanograms per gram tissue for the 160 tissue samples were highest for n-propylparaben [16.8 (range 0–2052.7)] and methylparaben [16.6 (range 0–5102.9)]; levels were lower for n-butylparaben [5.8 (range 0–95.4)], ethylparaben [3.4 (range 0–499.7)] and isobutylparaben 2.1 (range 0–802.9). The overall median value for total paraben was 85.5 ng g−1 tissue (range 0–5134.5). The source of the paraben cannot be identified, but paraben was measured in the 7/40 patients who reported never having used underarm cosmetics in their lifetime. No correlations were found between paraben concentrations and age of patient (37–91 years), length of breast feeding (0–23 months), tumour location or tumour oestrogen receptor content. In view of the disproportionate incidence of breast cancer in the upper outer quadrant, paraben concentrations were compared across the four regions of the breast: n-propylparaben was found at significantly higher levels in the axilla than mid (P = 0.004 Wilcoxon matched pairs) or medial (P = 0.021 Wilcoxon matched pairs) regions (P = 0.010 Friedman ANOVA).

Comparison of polar ozone loss rates simulated by one-dimensional and three-dimensional models with Match observations in recent Antarctic and Arctic winters

Simulations of ozone loss rates using a three-dimensional chemical transport model and a box model during recent Antarctic and Arctic winters are compared with experimental loss rates. The study focused on the Antarctic winter 2003, during which the first Antarctic Match campaign was organized, and on Arctic winters 1999/2000, 2002/2003. The maximum ozone loss rates retrieved by the Match technique for the winters and levels studied reached 6 ppbv/sunlit hour and both types of simulations could generally reproduce the observations at 2-sigma error bar level. In some cases, for example, for the Arctic winter 2002/2003 at 475 K level, an excellent agreement within 1-sigma standard deviation level was obtained. An overestimation was also found with the box model simulation at some isentropic levels for the Antarctic winter and the Arctic winter 1999/2000, indicating an overestimation of chlorine activation in the model. Loss rates in the Antarctic show signs of saturation in September, which have to be considered in the comparison. Sensitivity tests were performed with the box model in order to assess the impact of kinetic parameters of the ClO-Cl2O2 catalytic cycle and total bromine content on the ozone loss rate. These tests resulted in a maximum change in ozone loss rates of 1.2 ppbv/sunlit hour, generally in high solar zenith angle conditions. In some cases, a better agreement was achieved with fastest photolysis of Cl2O2 and additional source of total inorganic bromine but at the expense of overestimation of smaller ozone loss rates derived later in the winter.

Evaluating adjusted forcing and model spread for historical and future scenarios in the CMIP5 generation of climate models

We utilize energy budget diagnostics from the Coupled Model Intercomparison Project phase 5 (CMIP5) to evaluate the models' climate forcing since preindustrial times employing an established regression technique. The climate forcing evaluated this way, termed the adjusted forcing (AF), includes a rapid adjustment term associated with cloud changes and other tropospheric and land-surface changes. We estimate a 2010 total anthropogenic and natural AF from CMIP5 models of 1.9 ± 0.9 W m−2 (5–95% range). The projected AF of the Representative Concentration Pathway simulations are lower than their expected radiative forcing (RF) in 2095 but agree well with efficacy weighted forcings from integrated assessment models. The smaller AF, compared to RF, is likely due to cloud adjustment. Multimodel time series of temperature change and AF from 1850 to 2100 have large intermodel spreads throughout the period. The intermodel spread of temperature change is principally driven by forcing differences in the present day and climate feedback differences in 2095, although forcing differences are still important for model spread at 2095. We find no significant relationship between the equilibrium climate sensitivity (ECS) of a model and its 2003 AF, in contrast to that found in older models where higher ECS models generally had less forcing. Given the large present-day model spread, there is no indication of any tendency by modelling groups to adjust their aerosol forcing in order to produce observed trends. Instead, some CMIP5 models have a relatively large positive forcing and overestimate the observed temperature change.

Glacial-interglacial temperature change in the tropical West Pacific: a comparison of stalagmite-based paleo-thermometers

In the tropics, geochemical records from stalagmites have so far mainly been used to qualitatively reconstruct changes in precipitation, but several new methods to reconstruct past temperatures from stalagmite material have emerged recently: i) liquid–vapor homogenization of fluid inclusion water ii) noble gas concentrations in fluid inclusion water, iii) the partitioning of oxygen isotopes between fluid inclusion water and calcite, and iv) the abundance of the 13C18O16O (‘clumped’) isotopologue in calcite. We present, for the first time, a direct comparison of these four paleo-thermometers by applying them to a fossil stalagmite covering nearly two glacial–interglacial cycles (Marine Isotope Stages (MIS) 12–9) and to two modern stalagmites, all from northern Borneo. The temperature estimates from the different methods agree in most cases within errors for both the old and recent samples; reconstructed formation temperatures of the recent samples match within 2-sigma errors with measured cave temperatures. However, slight but systematic deviations are observed between noble gas and liquid–vapor homogenization temperatures. Whereas the temperature sensitivity of fluid inclusion δ18O and clumped isotopes is currently debated, we find that the calibration of Tremaine et al. (2011) for fluid inclusion δ18O and a synthetic calcite-based clumped isotope calibration (Ziegler et al., in prep.) yield temperature estimates consistent with the other methods. All methods (with the potential exception of clumped isotopes) show excellent agreement on the amplitude of glacial–interglacial temperature change, indicating temperature shifts of 4–5 °C. This amplitude is similar to the amplitude of Mg/Ca-based regional sea surface temperature records, when correcting for sea level driven changes in cave elevation. Our reconstruction of tropical temperature evolution over the time period from 440 to 320 thousand years ago (ka) adds support to the view that climate sensitivity to varying greenhouse forcing is substantial also in the deep tropics.

Common black coatings - reflectance and ageing characteristics in the 0.32-14.3 mu m wavelength range

The diffuse and regular reflectances of five optically absorbing coatings frequently used in optical systems, were measured over the 0.32-14.3 mu m wavelength range, before and after exposure to heat and intense optical radiation. The measured coatings included Nextel Velvet Black, an anodised coating and NPL Super Black. The anodised coating exhibited substantial variations in its diffuse and regular reflectance values after thermal and simulated solar ageing. Solar and thermal ageing of the Nextel Velvet Black resulted in increases of its reflectance. However, thermal ageing tended to decrease the reflectance of the other paint samples examined. Thermal and solar ageing of the NPL Super Black resulted in only minor changes in its reflectance characteristics. All measurements are traceable to the UK National Standards.

Simulation of the Earth's radiation budget by the European Centre for Medium-Range Weather Forecasts 40-year reanalysis (ERA40)

The radiation budget simulated by the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year reanalysis (ERA40) is evaluated for the period 1979–2001 using independent satellite data and additional model data. This provides information on the quality of the radiation products and indirect evaluation of other aspects of the climate produced by ERA40. The climatology of clear-sky outgoing longwave radiation (OLR) is well captured by ERA40. Underestimations of about 10 W m−2 in clear-sky OLR over tropical convective regions by ERA40 compared to satellite data are substantially reduced when the satellite sampling is taken into account. The climatology of column-integrated water vapor is well simulated by ERA40 compared to satellite data over the ocean, indicating that the simulation of downward clear-sky longwave fluxes at the surface is likely to be good. Clear-sky absorbed solar radiation (ASR) and clear-sky OLR are overestimated by ERA40 over north Africa and high-latitude land regions. The observed interannual changes in low-latitude means are not well reproduced. Using ERA40 to analyze trends and climate feedbacks globally is therefore not recommended. The all-sky radiation budget is poorly simulated by ERA40. OLR is overestimated by around 10 W m−2 over much of the globe. ASR is underestimated by around 30 W m−2 over tropical ocean regions. Away from marine stratocumulus regions, where cloud fraction is underestimated by ERA40, the poor radiation simulation by ERA40 appears to be related to inaccurate radiative properties of cloud rather than inaccurate cloud distributions.

Short-range urban dispersion experiments using fixed and moving sources

Four perfluorocarbon tracer dispersion experiments were carried out in central London, United Kingdom in 2004. These experiments were supplementary to the dispersion of air pollution and penetration into the local environment (DAPPLE) campaign and consisted of ground level releases, roof level releases and mobile releases; the latter are believed to be the first such experiments to be undertaken. A detailed description of the experiments including release, sampling, analysis and wind observations is given. The characteristics of dispersion from the fixed and mobile sources are discussed and contrasted, in particular, the decay in concentration levels away from the source location and the additional variability that results from the non-uniformity of vehicle speed. Copyright © 2009 Royal Meteorological Society

Pyrohydrolysis-IRMS determination of silicate chlorine stable isotope compositions. Application to oceanic crust and meteorite samples

This contribution describes the optimization of chlorine extraction from silicate samples by pyrohydrolysis prior to the precise determination of Cl stable-isotope compositions (637 Cl) by gas source, dual inlet Isotope Ratio Mass Spectrometry (IRMS) on CH(3)Clg. The complete method was checked on three international reference materials for Cl-content and two laboratory glass standards. Whole procedure blanks are lower than 0. 5 mu mol, corresponding to less than 10 wt.% of most of the sample chloride analysed. In the absence of international chlorine isotope rock, we report here Cl extracted compared to accepted Cl contents and reproducibilities on Cl and delta Cl-37 measurements for the standard rocks. After extraction, the Cl contents of the three international references compared within error with the accepted values (mean yield = 94 +/-10%) with reproducibilities better than 12% (10). The laboratory glass standards - andesite SO100DS92 and phonolite S9(2) - were used specifically to test the effect of chloride amount on the measurements. They gave Cl extraction yields of 100 +/-6% (1 sigma-; n = 15) and 105 +/- 8% (1 sigma-; n = 7), respectively, with delta Cl-37 values of -0.51 0.14%o and -0.39 0.17%o (1g). In summary, for silicate samples with Cl contents between 39 and 9042 ppm, the Pyrohydrolysis/HPLC method leads to overall CI extraction yields of 100 8%, reproducibilities on Cl contents of 7% and on delta Cl-37 measurements of 0.12%o (all 1 sigma). The method was further applied to ten silicate rocks of various mineralogy and chemistry (meteorite, fresh MORB glasses, altered basalts and setpentinized peridotites) chosen for their large range of Cl contents (70-2156 ppm) and their geological significance. delta Cl-37 values range between -2.33 and -0.50%o. These strictly negative values contrast with the large range and mainly positive values previously reported for comparable silicate samples and shown here to be affected by analytical problems. Thus we propose a preliminary, revised terrestrial CI cycle, mainly dominated by negative and zero delta Cl-37 values. (C) 2007 Elsevier B.V. All rights reserved.

Parameter sensitivity and predictive uncertainty in a new water quality model, Q(2)

A new dynamic model of water quality, Q(2), has recently been developed, capable of simulating large branched river systems. This paper describes the application of a generalized sensitivity analysis (GSA) to Q(2) for single reaches of the River Thames in southern England. Focusing on the simulation of dissolved oxygen (DO) (since this may be regarded as a proxy for the overall health of a river); the GSA is used to identify key parameters controlling model behavior and provide a probabilistic procedure for model calibration. It is shown that, in the River Thames at least, it is more important to obtain high quality forcing functions than to obtain improved parameter estimates once approximate values have been estimated. Furthermore, there is a need to ensure reasonable simulation of a range of water quality determinands, since a focus only on DO increases predictive uncertainty in the DO simulations. The Q(2) model has been applied here to the River Thames, but it has a broad utility for evaluating other systems in Europe and around the world.

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 2 - The sediment phase

This article investigates the temporal and spatial controls on sediment-phosphorus (P) dynamics in two contrasting sub-catchments of the River Kennet, England. Suspended sediment (collected under representative flow conditions) and size-fractionated bedload (collected weekly for one year) from the Rivers Lambourn and Enborne was analysed for a range of physico-chemical determinands. Total P concentrations were highest in the most mobile fractions of sediment: suspended sediment, fine silt and clay and organic matter (mean concentrations of 1758, 1548 and 1440 mug P g(-1) dry sediment, respectively). Correlation analysis showed significant relationships between total P and total iron (n = 110), total manganese (n = 110), organic matter (n = 110) and specific surface area (n = 28) in the Lambourn (r(2) 0.71, 0.68, 0.62 and 0.52, respectively) and between total P and total iron (n = 110), total manganese (n = 110) and organic matter (n = 110) in the Enborne (r(2) 0.74, 0.85 and 0.68, respectively). These data highlight the importance of metal oxyhydroxide adsorption of P on fine particulates and organic matter. However, high total P concentrations in the granule gravel and coarse sand size fraction during the summer period (mean concentration 228 mug P g(-1) dry sediment) also highlight the role of calcite co-precipitation on P dynamics in the Lambourn. P to cation ratios in Lambourn sediment indicated that fine silt and clay and granule gravel and coarse sand size fractions were potential sources of P release to the water column during specific periods of the summer and autumn. In the Enborne, however, only the granule gravel and coarse sand size fraction had high ratios and a slow, constant release of P was observed. In addition, scanning electron microscopy work confirmed the association of P with calcite in the Lambourn and P with iron on clay particles in the Enborne. The study highlighted the importance of the chemical and physical properties of the sediment in influencing the mechanisms controlling P storage and release within river channels. (C) 2004 Elsevier B.V. All rights reserved.

A glacier inventory for the Buordakh Massif, Cherskiy Range, northeast Siberia, and evidence for recent glacier recession

The Buordakh Massif, in the Cherskiy Range of northeast Siberia, contains mountains over 3000 in and, despite its and climate, numerous glaciers. This paper presents a glacier inventory for the region and documents some 80 glaciers, which range in size from 0.1 to 10.4 km(2) (total glacierized area is ca. 70 km(2)). The inventory is based on mapping derived from Landsat 7 ETM+ satellite imagery from August 2001, augmented with data from field investigations obtained at that time. The glaciers in this region are of the 'firn-less,' cold, continental type, and their mass balance relies heavily on the formation of superimposed ice. The most recent glacier maximum extents have also been delineated, and these are believed to date from the Little Ice Age (ca. A.D. 1550-1850). Glacier areal extent has reduced by some 14.8 km(2) (ca. 17%) since this most. recent maximum. Of the 80 glaciers catalogued, 49 have undergone a measurable retreat from their most recent maximum extent.