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.

The effects of pre- and postnatal depression in fathers: a natural experiment comparing the effects of exposure to depression on offspring

Background: Depression in fathers in the postnatal period is associated with an increased risk of behavioural problems in their offspring, particularly for boys. The aim of this study was to examine for differential effects of depression in fathers on children's subsequent psychological functioning via a natural experiment comparing prenatal and postnatal exposure. Methods:In a longitudinal population cohort study (the Avon Longitudinal Study of Parents and Children (ALSPAC)) we examined the associations between depression in fathers measured in the prenatal and postnatal period (measured using the Edinburgh Postnatal Depression Scale), and later behavioural/emotional and psychiatric problems in their children, assessed at ages 31/2 and 7 years. Results: Children whose fathers were depressed in both the prenatal and postnatal periods had the highest risks of subsequent psychopathology, measured by total problems at age 31/2 years (Odds Ratio 3.55; 95% confidence interval 2.07, 6.08) and psychiatric diagnosis at age 7 years (OR 2.54; 1.19, 5.41). Few differences emerged when prenatal and postnatal depression exposure were directly compared, but when compared to fathers who were not depressed, boys whose fathers had postnatal depression only had higher rates of conduct problems aged 31/2 years (OR 2.14; 1.22, 3.72) whereas sons of the prenatal group did not (OR 1.41; .75, 2.65). These associations changed little when controlling for maternal depression and other potential confounding factors. Conclusions: The findings of this study suggest that the increased risk of later conduct problems, seen particularly in the sons of depressed fathers, maybe partly mediated through environmental means. In addition, children whose fathers are more chronically depressed appear to be at a higher risk of emotional and behavioural problems. Efforts to identify the precise mechanisms by which transmission of risk may occur should be encouraged to enable the development of focused interventions to mitigate risks for young children.

Towards a European tephrochronological framework for Termination 1 and the Early Holocene

The record of deposition of tephras in Europe and the North Atlantic during the period 18.5–8.0 P>14P>C ka BP (the Last Termination and Early Holocene) is reviewed. Altogether, 34 tephras originating from four main volcanic provinces (Iceland, the Eifel district, the Massif Central and Italy) have been identified so far in geological sequences spanning this time–interval. Most of the records have been based, until very recently, on observations of visible layers of tephras. Here, we report on the potential for extending the areas over which some of the tephras can be traced by the search for layers of micro–tephra, which are not visible to the naked eye, and on the use of geochemical methods to correlate them with known tephra horizons. This approach has greatly extended the area in Northern Europe over which the Vedde Ash can be traced. The same potential exists in southern Europe, which is demonstrated for the first time by the discovery of a distinct layer of micro–tephra of the Neapolitan Yellow Tuff in a site in the Northern Apennines in Italy, far to the north of the occurrences of visible records of this tephra. The paper closes by considering the potential for developing a robust European tephrostratigraphy to underpin the chronology of records of the Last Termination and Early Holocene, thereby promoting a better understanding of the nature, timing and environmental effects of the abrupt climatic changes that characterized this period.

Early–Middle Holocene vegetation history, climate change and human activities at Lago Riane (Ligurian Apennines, NW Italy)

The radiocarbon-dated palaeoecological study of Lago Riane (Ligurian Apennines, NW Italy) presented here forms part of a wider investigation into the relationships between Holocene vegetation succession, climate change and human activities in the northern Apennines. The record of vegetation history from Lago Riane indicates that, since the end of the last glaciation, climate change and prehistoric human activities, combined with several local factors, have strongly influenced the pattern and timing of natural vegetation succession. The pollen record indicates an important change in vegetation cover at Lago Riane at ~8500–8200 cal. years b.p., coincident with a well-known period of rapid climate change. At ~6100 cal. years b.p., Fagus woodland colonised Lago Riane during a period of climate change and expansion of Late Neolithic human activities in the upland zone of Liguria. A marked decline in Abies woodland, and the expansion of Fagus woodland, at ~4700 cal. years b.p., coincided with further archaeological evidence for pastoralism in the mountains of Liguria during the Copper Age. At ~3900–3600 cal. years b.p. (Early to Middle Bronze Age transition), a temporary expansion of woodland at Lago Riane has been provisionally attributed to a decline in human pressure on the environment during a period of short-term climate change

Statistical decadal predictions for sea surface temperatures: a benchmark for dynamical GCM predictions

Accurate decadal climate predictions could be used to inform adaptation actions to a changing climate. The skill of such predictions from initialised dynamical global climate models (GCMs) may be assessed by comparing with predictions from statistical models which are based solely on historical observations. This paper presents two benchmark statistical models for predicting both the radiatively forced trend and internal variability of annual mean sea surface temperatures (SSTs) on a decadal timescale based on the gridded observation data set HadISST. For both statistical models, the trend related to radiative forcing is modelled using a linear regression of SST time series at each grid box on the time series of equivalent global mean atmospheric CO2 concentration. The residual internal variability is then modelled by (1) a first-order autoregressive model (AR1) and (2) a constructed analogue model (CA). From the verification of 46 retrospective forecasts with start years from 1960 to 2005, the correlation coefficient for anomaly forecasts using trend with AR1 is greater than 0.7 over parts of extra-tropical North Atlantic, the Indian Ocean and western Pacific. This is primarily related to the prediction of the forced trend. More importantly, both CA and AR1 give skillful predictions of the internal variability of SSTs in the subpolar gyre region over the far North Atlantic for lead time of 2 to 5 years, with correlation coefficients greater than 0.5. For the subpolar gyre and parts of the South Atlantic, CA is superior to AR1 for lead time of 6 to 9 years. These statistical forecasts are also compared with ensemble mean retrospective forecasts by DePreSys, an initialised GCM. DePreSys is found to outperform the statistical models over large parts of North Atlantic for lead times of 2 to 5 years and 6 to 9 years, however trend with AR1 is generally superior to DePreSys in the North Atlantic Current region, while trend with CA is superior to DePreSys in parts of South Atlantic for lead time of 6 to 9 years. These findings encourage further development of benchmark statistical decadal prediction models, and methods to combine different predictions.

Climate on the Southern Black Sea coast during the Holocene: implications from the Sofular Cave record

We present the updated Holocene section of the Sofular Cave record from the southernBlackSeacoast (northern Turkey); an area with considerably different present-day climate compared to that of the neighboring Eastern Mediterranean region. Stalagmite δ13C, growth rates and initial (234U/238U) ratios provide information about hydrological changes above the cave; and prove to be more useful than δ18O for deciphering Holocene climatic variations. Between ∼9.6 and 5.4 ka BP (despite a pause from ∼8.4 to 7.8 ka BP), the Sofular record indicates a remarkable increase in rainfall amount and intensity, in line with other paleoclimate studies in the Eastern Mediterranean. During that period, enhanced summertime insolation either produced much stronger storms in the following fall and winter through high sea surface temperatures, or it invoked a regional summer monsoon circulation and rainfall. We suggest that one or both of these climatic mechanisms led to a coupling of the BlackSea and the Mediterranean rainfall regimes at that time, which can explain the observed proxy signals. However, there are discrepancies among the Eastern Mediterranean records in terms of the timing of this wet period; implying that changes were probably not always occurring through the same mechanism. Nevertheless, the Sofular Cave record does provide hints and bring about new questions about the connection between regional and large scale climates, highlighting the need for a more extensive network of high quality paleoclimate records to better understand Holoceneclimate.

Wildfire responses to abrupt climate change in North America

It is widely accepted, based on data from the last few decades and on model simulations, that anthropogenic climate change will cause increased fire activity. However, less attention has been paid to the relationship between abrupt climate changes and heightened fire activity in the paleorecord. We use 35 charcoal and pollen records to assess how fire regimes in North America changed during the last glacial–interglacial transition (15 to 10 ka), a time of large and rapid climate changes. We also test the hypothesis that a comet impact initiated continental-scale wildfires at 12.9 ka; the data do not support this idea, nor are continent-wide fires indicated at any time during deglaciation. There are, however, clear links between large climate changes and fire activity. Biomass burning gradually increased from the glacial period to the beginning of the Younger Dryas. Although there are changes in biomass burning during the Younger Dryas, there is no systematic trend. There is a further increase in biomass burning after the Younger Dryas. Intervals of rapid climate change at 13.9, 13.2, and 11.7 ka are marked by large increases in fire activity. The timing of changes in fire is not coincident with changes in human population density or the timing of the extinction of the megafauna. Although these factors could have contributed to fire-regime changes at individual sites or at specific times, the charcoal data indicate an important role for climate, and particularly rapid climate change, in determining broad-scale levels of fire activity.

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.

Last glacial vegetation of northern Eurasia

In order to investigate the potential role of vegetation changes in megafaunal extinctions during the later part of the last glacial stage and early Holocene (42–10 ka BP), the palaeovegetation of northern Eurasia and Alaska was simulated using the LPJ-GUESS dynamic vegetation model. Palaeoclimatic driving data were derived from simulations made for 22 time slices using the Hadley Centre Unified Model. Modelled annual net primary productivity (aNPP) of a series of plant functional types (PFTs) is mapped for selected time slices and summarised for major geographical regions for all time slices. Strong canonical correlations are demonstrated between model outputs and pollen data compiled for the same period and region. Simulated aNPP values, especially for tree PFTs and for a mesophilous herb PFT, provide evidence of the structure and productivity of last glacial vegetation. The mesophilous herb PFT aNPP is higher in many areas during the glacial than at present or during the early Holocene. Glacial stage vegetation, whilst open and largely treeless in much of Europe, thus had a higher capacity to support large vertebrate herbivore populations than did early Holocene vegetation. A marked and rapid decrease in aNPP of mesophilous herbs began shortly after the Last Glacial Maximum, especially in western Eurasia. This is likely implicated in extinction of several large herbivorous mammals during the latter part of the glacial stage and the transition to the Holocene.

Antarctic Peninsula ice sheet evolution during the Cenozoic Era

The Antarctic Peninsula region is currently undergoing rapid environmental change, resulting in the thinning, acceleration and recession of glaciers and the sequential collapse of ice shelves. It is important to view these changes in the context of long-term palaeoenvironmental complexity and to understand the key processes controlling ice sheet growth and recession. In addition, numerical ice sheet models require detailed geological data for tuning and testing. Therefore, this paper systematically and holistically reviews published geological evidence for Antarctic Peninsula Ice Sheet variability for each key locality throughout the Cenozoic, and brings together the prevailing consensus of the extent, character and behaviour of the glaciations of the Antarctic Peninsula region. Major contributions include a downloadable database of 186 terrestrial and marine calibrated dates; an original reconstruction of the LGM ice sheet; and a new series of isochrones detailing ice sheet retreat following the LGM. Glaciation of Antarctica was initiated around the Eocene/Oligocene transition in East Antarctica. Palaeogene records of Antarctic Peninsula glaciation are primarily restricted to King George Island, where glacigenic sediments provide a record of early East Antarctic glaciations, but with modification of far-travelled erratics by local South Shetland Island ice caps. Evidence for Neogene glaciation is derived primarily from King George Island and James Ross Island, where glaciovolcanic strata indicate that ice thicknesses reached 500–850 m during glacials. This suggests that the Antarctic Peninsula Ice Sheet draped, rather than drowned, the topography. Marine geophysical investigations indicate multiple ice sheet advances during this time. Seismic profiling of continental shelf-slope deposits indicates up to ten large advances of the Antarctic Peninsula Ice Sheet during the Early Pleistocene, when the ice sheet was dominated by 40 kyr cycles. Glacials became more pronounced, reaching the continental shelf edge, and of longer duration during the Middle Pleistocene. During the Late Pleistocene, repeated glacials reached the shelf edge, but ice shelves inhibited iceberg rafting. The Last Glacial Maximum (LGM) occurred at 18 ka BP, after which transitional glaciomarine sediments on the continental shelf indicate ice-sheet retreat. The continental shelf contains large bathymetric troughs, which were repeatedly occupied by large ice streams during Pleistocene glaciations. Retreat after the LGM was episodic in the Weddell Sea, with multiple readvances and changes in ice-flow direction, but rapid in the Bellingshausen Sea. The late Holocene Epoch was characterised by repeated fluctuations in palaeoenvironmental conditions, with associated glacial readvances. However, this has been subsumed by rapid warming and ice-shelf collapse during the twentieth century.

Terrestrial biosphere changes over the last 120 kyr and their impact on ocean δ 13C

A new global synthesis and biomization of long (>40 kyr) pollen-data records is presented, and used with simulations from the HadCM3 and FAMOUS climate models to analyse the dynamics of the global terrestrial biosphere and carbon storage over the last glacial–interglacial cycle. Global modelled (BIOME4) biome distributions over time generally agree well with those inferred from pollen data. The two climate models show good agreement in global net primary productivity (NPP). NPP is strongly influenced by atmospheric carbon dioxide (CO2) concentrations through CO2 fertilization. The combined effects of modelled changes in vegetation and (via a simple model) soil carbon result in a global terrestrial carbon storage at the Last Glacial Maximum that is 210–470 Pg C less than in pre-industrial time. Without the contribution from exposed glacial continental shelves the reduction would be larger, 330–960 Pg C. Other intervals of low terrestrial carbon storage include stadial intervals at 108 and 85 ka BP, and between 60 and 65 ka BP during Marine Isotope Stage 4. Terrestrial carbon storage, determined by the balance of global NPP and decomposition, influences the stable carbon isotope composition (δ13C) of seawater because terrestrial organic carbon is depleted in 13C. Using a simple carbon-isotope mass balance equation we find agreement in trends between modelled ocean δ13C based on modelled land carbon storage, and palaeo-archives of ocean δ13C, confirming that terrestrial carbon storage variations may be important drivers of ocean δ13C changes.

Mid- to late Holocene Indian Ocean monsoon variability recorded in four speleothems from Socotra Island, Yemen

Four stalagmites covering the last 7.0 ka were sampled on Socotra, an island in the northern Indian Ocean to investigate the evolution of the northeast Indian Ocean Monsoon (IOM) since the mid Holocene. On Socotra, rain is delivered at the start of the southwest IOM in May–June and at the start of the northeast IOM from September to December. The Haggeher Mountains act as a barrier forcing precipitation brought by the northeast winds to fall preferentially on the eastern side of the island, where the studied caves are located. δ18O and δ13C and Mg/Ca and Sr/Ca signals in the stalagmites reflect precipitation amounts brought by the northeast winds. For stalagmite STM6, this amount effect is amplified by kinetic effects during calcite deposition. Combined interpretation of the stalagmites' signals suggest a weakening of the northeast precipitation between 6.0 and 3.8 ka. After 3.8 ka precipitation intensities remain constant with two superimposed drier periods, between 0 and 0.6 ka and from 2.2 to 3.8 ka. No link can be established with Greenland ice cores and with the summer IOM variability. In contrast to the stable northeast rainy season suggested by the records in this study, speleothem records from western Socotra indicate a wettening of the southwest rainy season on Socotra after 4.4 ka. The local wettening of western Socotra could relate to a more southerly path (more over the Indian Ocean) taken by the southwest winds. Stalagmite STM5, sampled at the fringe between both rain areas displays intermediate δ18O values. After 6.2 ka, similar precipitation changes are seen between eastern Socotra and northern Oman indicating that both regions are affected similarly by the monsoon. Different palaeoclimatologic records from the Arabian Peninsula currently located outside the ITCZ migration pathway display an abrupt drying around 6 ka due to their disconnection from the southwest rain influence. Records that are nowadays still receiving rain by the southwest winds, suggest a more gradual drying reflecting the weakening of the southwest monsoon.

Investigation of the accuracy of historical irradiance products and interannual variability of solar irradiance using Met Office ground data

Met Office station data from 1980 to 2012 has been used to characterise the interannual variability of incident solar irradiance across the UK. The same data are used to evaluate four popular historical irradiance products to determine which are most suitable for use by the UK PV industry for site selection and system design. The study confirmed previous findings that interannual variability is typically 3–6% and weighted average probability of a particular percentage deviation from the mean at an average site in the UK was calculated. This weighted average showed that fewer than 2% of site-years could be expected to fall below 90% of the long-term site mean. The historical irradiance products were compared against Met Office station data from the input years of each product. This investigation has found that all products perform well. No products have a strong spatial trend. Meteonorm 7 is most conservative (MBE = −2.5%), CMSAF is most optimistic (MBE = +3.4%) and an average of all four products performs better than any one individual product (MBE = 0.3%)

Terrestrial biosphere changes over the last 120 kyr

A new global synthesis and biomization of long (> 40 kyr) pollen-data records is presented and used with sim- ulations from the HadCM3 and FAMOUS climate models and the BIOME4 vegetation model to analyse the dynamics of the global terrestrial biosphere and carbon storage over the last glacial–interglacial cycle. Simulated biome distribu- tions using BIOME4 driven by HadCM3 and FAMOUS at the global scale over time generally agree well with those in- ferred from pollen data. Global average areas of grassland and dry shrubland, desert, and tundra biomes show large- scale increases during the Last Glacial Maximum, between ca. 64 and 74 ka BP and cool substages of Marine Isotope Stage 5, at the expense of the tropical forest, warm-temperate forest, and temperate forest biomes. These changes are re- flected in BIOME4 simulations of global net primary pro- ductivity, showing good agreement between the two models. Such changes are likely to affect terrestrial carbon storage, which in turn influences the stable carbon isotopic composi- tion of seawater as terrestrial carbon is depleted in 13C.