Prehistoric Pinus woodland dynamics in an upland landscape in northern Scotland: the roles of climate change and human impact

Pollen, microscopic charcoal, palaeohydrological and dendrochronological analyses are applied to a radiocarbon and tephrochronologically dated mid Holocene (ca. 8500–3000 cal B.P.) peat sequence with abundant fossil Pinus (pine) wood. The Pinus populations on peat fluctuated considerably over the period in question. Colonisation by Pinus from ca. 7900–7600 cal B.P. appears to have had no specific environmental trigger; it was probably determined by the rate of migration from particular populations. The second phase, at ca. 5000–4400 cal B.P., was facilitated by anthropogenic interference that reduced competition from other trees. The pollen record shows two Pinus declines. The first at ca. 6200–5500 cal B.P. was caused by a series of rapid and frequent climatic shifts. The second, the so-called pine decline, was very gradual (ca. 4200–3300 cal B.P.) at Loch Farlary and may not have been related to climate change as is often supposed. Low intensity but sustained grazing pressures were more important. Throughout the mid Holocene, the frequency and intensity of burning in these open Pinus–Calluna woods were probably highly sensitive to hydrological (climatic) change. Axe marks on several trees are related to the mid to late Bronze Age, i.e., long after the trees had died.

Influence of climate change and trophic coupling across four trophic levels in the Celtic Sea

Climate change has had profound effects upon marine ecosystems, impacting across all trophic levels from plankton to apex predators. Determining the impacts of climate change on marine ecosystems requires understanding the direct effects on all trophic levels as well as indirect effects mediated by trophic coupling. The aim of this study was to investigate the effects of climate change on the pelagic food web in the Celtic Sea, a productive shelf region in the Northeast Atlantic. Using long-term data, we examined possible direct and indirect ‘bottom-up’ climate effects across four trophic levels: phytoplankton, zooplankton, mid-trophic level fish and seabirds. During the period 1986–2007, although there was no temporal trend in the North Atlantic Oscillation index (NAO), the decadal mean Sea Surface Temperature (SST) in the Celtic Sea increased by 0.66±0.02°C. Despite this, there was only a weak signal of climate change in the Celtic Sea food web. Changes in plankton community structure were found, however this was not related to SST or NAO. A negative relationship occurred between herring abundance (0- and 1-group) and spring SST (0-group: p = 0.02, slope = −0.305±0.125; 1-group: p = 0.04, slope = −0.410±0.193). Seabird demographics showed complex species–specific responses. There was evidence of direct effects of spring NAO (on black-legged kittiwake population growth rate: p = 0.03, slope = 0.0314±0.014) as well as indirect bottom-up effects of lagged spring SST (on razorbill breeding success: p = 0.01, slope = −0.144±0.05). Negative relationships between breeding success and population growth rate of razorbills and common guillemots may be explained by interactions between mid-trophic level fish. Our findings show that the impacts of climate change on the Celtic Sea ecosystem is not as marked as in nearby regions (e.g. the North Sea), emphasizing the need for more research at regional scales.

Isotopic Assessment of Sources of Surface Water Nitrate within the Oldman River Basin, Southern Alberta, Canada

Concentrations and isotopic compositions of NO-3 from the Oldman River (OMR) and some of its tributaries (Alberta, Canada) have been determined on a monthly basis since December 2000 to assess temporal and spatial variations of riverine NO-3 sources within the OMR basin. For the OMR sites, NO-3 -N concentrations reached up to 0.34 mg L-1, d15N-NO-3 values varied between –0.3 and +13.8‰, and d18O-NO-3 values ranged from –10.0 to +5.7‰. For the tributary sites, NO-3 -N concentrations were as high as 8.81 mg L-1, d15N-NO-3 values varied between –2.5 and +23.4‰, and d18O-NO-3 values ranged from –15.2 to +3.4‰. Tributaries in the western, relatively pristine forested part of the watershed add predominantly NO-3 to the OMR with d15N-NO-3 indicative of soil nitrification. In contrast, tributaries in the eastern agriculturally-urban-industrially-used part of the basin contribute NO-3 with d15N-NO-3 values of about +16‰ indicative of manure and/or sewage derived NO-3. This difference in d15N-NO-3 values of tributaries was found to be independent of the season, but rather indicates a spatial change in the NO-3 source, which correlates with land use changes within the OMR basin. As a consequence of tributary influx, d15N-NO-3 values in the Oldman River increased from +6‰ in the downstream direction (W to E), although [NO-3 -N] increased only moderately (generally

Dissolved Argon Changes the Rate of Diffusion in Room Temperature Ionic Liquids: Effect of the Presence and Absence of Argon and Nitrogen on the Voltammetry of Ferrocene

This work explores the effects of argon and nitrogen, two electrochemically and chemically inert gases frequently used in sample preparation of room temperature ionic liquid (RTIL) solutions, on the eelectrochemical characterization of ferrocene (Fc) dissolved in the RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C(2)mim][NTf2]). Remarkably, chronoamperometrically determined diffusion coefficients of Fc in [C(2)mim][NTf2] are found to increase from 4.8 (+/- 0.2) x 10(-11) m(2) s(-1) under vacuum conditions to 6.6 (+/- 0.5) x 10(-11) m(2) s(-1) in an atmosphere of 1 atm Ar. In contrast, exposing a vacuum-purified sample to an atmosphere of 1 atm N-2 resulted in no significant change in the measured diffusion coefficient of Fc. The effect of dissolved argon on diffusion transport is unexpected and has implications in electrochemistry and elsewhere. Fc was found to volatilize under vacuum conditions. We propose, however, that evacuation of the cell by vacuum prior to electrochemical measurements being carried out is the only way to ensure that no contamination of the sample occurs, and use of an in situ method of determining the diffusion coefficient and concentration of Fc dispells,any ambiguity associated with Fc depletion by vacuum.

Climate change-linked range expansion of Nathusius' pipistrelle bat, Pipistrellus nathusii (Keyserling & Blasius, 1839)

Aim To examine the effect of climate change on the occurrence and distribution of Pipistrellus nathusii (Nathusius' pipistrelle) in the United Kingdom (UK).Location We modelled habitat and climatic associations of P. nathusii in the UK and applied this model to the species' historical range in continental Europe.Methods A binomial logistic regression model was constructed relating the occurrence of P. nathusii to climate and habitat characteristics using historical species occurrence records (1940-2006) and CORINE land cover data. This model was applied to historical and projected climate data to examine changes in suitable range (1940-2080) of this species. We tested the predictive ability of the model with known records in the UK after 2006 and applied the model to the species' known range in Europe.Results The distribution of P. nathusii was related positively to the area of water bodies, woodland and small areas of urbanization, and negatively related to the area of peat/heathland. Species records were associated with higher minimum temperatures, low seasonal variation in temperature and intermediate rainfall. We found that suitable areas have existed in the UK since the 1940s and that these have expanded. The model had high predictive power when applied to new records after 2006, with a correct classification rate of 70%, estimated by receiver operating characteristic analysis. Based on climate projections, our model suggests a potential twofold increase in the area suitable for P. nathusii in the UK by 2050. The single most influential climate variable contributing to range increase was the projected increase in minimum temperature. When applied to Europe, the model predictions had best predictive capability of known records in western areas of the species' range, where P. nathusii is present during the winter.Main conclusions We show that a mobile, migratory species has adapted its range in response to recent climate change on a continental scale. We believe this may be the first study to demonstrate a case of range change linked to contemporary climate change in a mammal species in Europe.

Late Holocene climate change in central Sweden inferred from lacustrine stable isotope data

Stable isotopes (delta O-18 and delta C-13) of lacustrine carbonates (Chara spp. algae and Pisidium spp. molluscs) from a lake sedimentary sequence in central Sweden were analysed to infer changes in lake hydrology and climate during the late Holocene. Results from analysis of lake water isotopes (delta O-18 and delta H-2) show that Lake Blektjarnen water isotope composition is responsive to the balance between evaporation and input water (E/l ratio). A high E/l ratio results from a dry and probably warmer climate, decreasing the relative importance of precipitation input. Under such conditions evaporation and atmospheric equilibration probably enrich lake water in O-18 and C-13, respectively, which is reflected in the isotopic composition of the carbonates in the lake. From the relatively positive Chara delta O-18 values we infer that conditions were dry and warm between 4400 and 4000 cal. a BP, whereas more negative values indicate that conditions were wetter and probably cooler between 4000 and 3000 cal. a BP. A drier climate is inferred from more positive values between 2500 and 1000 cal. a BP. However, a successive depletion after ca. 1750 cal. a BP, also detected in several other delta O-18 records (carbonate and diatom), suggest increasingly wetter conditions in Scandinavia after that time, which is probably related to increased strength of the zonal flow.

Carbon Isotopic Fractionation of CFCs during Abiotic and Biotic Degradation

Carbon stable isotope ((13)C) fractionation in chlorofluorocarbon (CFC) compounds arising from abiotic (chemical) degradation using zero-valent iron (ZVI) and biotic (landfill gas attenuation) processes is investigated. Batch tests (at 25 °C) for CFC-113 and CFC-11 using ZVI show quantitative degradation of CFC-113 to HCFC-123a and CFC-1113 following pseudo-first-order kinetics corresponding to a half-life (t(1/2)) of 20.5 h, and a ZVI surface-area normalized rate constant (k(SA)) of -(9.8 ± 0.5) × 10(-5) L m(-2) h(-1). CFC-11 degraded to trace HCFC-21 and HCFC-31 following pseudo-first-order kinetics corresponding to t(1/2) = 17.3 h and k(SA) = -(1.2 ± 0.5) × 10(-4) L m(-2) h(-1). Significant kinetic isotope effects of e(‰) = -5.0 ± 0.3 (CFC-113) and -17.8 ± 4.8 (CFC-11) were observed. Compound-specific carbon isotope analyses also have been used here to characterize source signatures of CFC gases (HCFC-22, CFC-12, HFC-134a, HCFC-142b, CFC-114, CFC-11, CFC-113) for urban (UAA), rural/remote (RAA), and landfill (LAA) ambient air samples, as well as in situ surface flux chamber (FLUX; NO FLUX) and landfill gas (LFG) samples at the Dargan Road site, Northern Ireland. The latter values reflect biotic degradation and isotopic fractionation in LFG production, and local atmospheric impact of landfill emissions through the cover. Isotopic fractionations of ?(13)C ~ -13‰ (HCFC-22), ?(13)C ~ -35‰ (CFC-12) and ?(13)C ~ -15‰ (CFC-11) were observed for LFG in comparison to characteristic solvent source signatures, with the magnitude of the isotopic effect for CFC-11 apparently similar to the kinetic isotope effect for (abiotic) ZVI degradation.

Nineteenth and twentieth century sea-level changes in Tasmania and New Zealand

Positive deviations from linear sea-level trends represent important climate signals if they are persistent and geographically widespread. This paper documents rapid sea-level rise reconstructed from sedimentary records obtained from salt marshes in the Southwest Pacific region (Tasmania and New Zealand). A new late Holocene relative sea-level record from eastern Tasmania was dated by AMS(14)C (conventional, high precision and bomb-spike), Cs-137, Pb-210, stable Pb isotopic ratios, trace metals, pollen and charcoal analyses. Palaeosea-level positions were determined by foraminiferal analyses. Relative sea level in Tasmania was within half a metre of present sea level for much of the last 6000 yr. Between 1900 and 1950 relative sea level rose at an average rate of 4.2 +/- 0.1 mm/yr. During the latter half of the 20th century the reconstructed rate of relative sea-level rise was 0.7 +/- 0.6 mm/yr. Our study is consistent with a similar pattern of relative sea-level change recently reconstructed for southern New Zealand. The change in the rate of sea-level rise in the SW Pacific during the early 20th century was larger than in the North Atlantic and could suggest that northern hemisphere land-based ice was the most significant melt source for global sea-level rise. (C) 2011 Elsevier B.V. All rights reserved.

Comparative growth rates and internal banding periodicity of maerl species (Corallinales, Rhodophyta) from northern Europe

Maerl is a type of rhodolith, found in ecologically important beds of high conservation value; a major conservation objective is to establish growth rates. Maerl shows internal banding of controversial periodicity that may contain a high-resolution record of palaeoceanographic-palaeoclimatic data. To investigate growth rates and banding periodicity, we used the vital stain Alizarin Red in combination with scanning electron microscopy (SEM). Three maerl species, Phymatolithon calcareum, Lithothamnion corallioides and L. glaciale, were collected from maerl beds in Ireland. Following staining, maerl was grown in three controlled temperature treatments and at two depths in the field (P. calcareum only), with Corallina officinalis as a control for the stain. Alizarin Red was shown to be a suitable marker for growth in European maerl species and for C. officinalis. The average tip growth rate of P. calcareum from Northern Ireland at 10 m depth and under constant laboratory conditions was c. 0.9 mm yr(-1), double the rates observed at 5 m depth and in L. corallioides. Our measurements and re-examination of reported data allow us to conclude that the three most abundant maerl species in Europe grow about 1 (0.5-1.5) mm per tip per year under a wide range of field and artificial conditions. Internal banding in temperate European maerl revealed by SEM is a result of regular changes in wall thickness; the approximately monthly periodicity of bands in field-grown specimens is consistent with previous suggestions that they may be lunar. The potential for maerl banding to be a high-resolution record of palaeoclimatic and palaeoenvironmental change could be realized with this vital stain in conjunction with isotopic or microgeochemical analyses.

A comparison of nitogen fate and transport in catchments underlain by high and low permeability aquifers using chemical and isotopic tools.

Variability in nitrogen fate and transport in different catchments types is often not considered. This research considers the importance of such nitrogen processes within groundwater pathways in two agricultural catchments in Ireland; a well drained catchment, underlain by karstified Carboniferous limestone, and a poorly drained catchment, underlain by Silurian greywacke.
Depth specific low-flow groundwater sampling was used to evaluate the hydrochemical stratification in groundwater. Groundwater samples, as well as surface water samples, along river courses were analysed for nitrogen species (NO3, NH4 and NO2) and nitrate isotopes (d15N and d18O) as well as field parameters and major ions
.
The dominant nitrate (NO3) groundwater pathway in the poorly drained greywacke catchment is through the shallow weathered bedrock, as indicated by transmissivity values and the ionic and isotopic signatures, and a clear reduction in NO3 concentration is observed with depth. A similar chloride trend would suggest dilution is a major factor, however d15N and d18O isotopic values producing an enrichment ratio of 1.8 indicate that denitrification is also an important process involved in the fate of the NO3 within the groundwater flow system. This consistent trend with depth is in contrast to the stratification pattern observed in the karstified catchment. NO3 was not detected in the shallow groundwater pathway; the dominant groundwater pathway is in the deeper groundwater where there is little change in the nitrate isotope values with depth (d15N values range between 4.1 and 4.6 ‰). This deeper groundwater contributes the dominant proportion of the river flow through a number of springs. As a result, the deeper groundwater, springs and river have a similar ionic signature and NO3 concentration range (23 ± 3 mg/l). Despite this pattern, the NO3 isotopes show a distinct difference in isotopic values between the deeper groundwater in the diffuse karst and the springs indicating some denitrification is occurring during groundwater discharge into the river. Furthermore the isotopes give an indication of the variability of the spatial extent of the springs and the complexities of the fissures through which they are fed. The results of this study clearly show the importance of the geology in the fate and transport of NO3 in agricultural catchments.

A millennial record of environmental change in peat deposits from the Misten bog (East Belgium)

In this study, palaeoenvironmental changes recorded in the top metre of a peat profile (Misten bog, East Belgium) were investigated using a multiproxy approach. Proxies include bulk density, Ti and Si content, pollen, macrofossils, d13C on specific Sphagnum stems, and d13C–d18O on Sphagnum leaves. A high-resolution chronology was generated using 210Pb measurements and 22 14C AMS dates on carefully selected Sphagnum macrofossils. d13C only records large change in mire surface wetness. This is partly due to the fact that the core was taken from the edge of a hummock, which may make it difficult to track small isotopic changes. The d13C signal seems to be dependent upon the Sphagnum species composition. For example, a change between Sphagnum section Cuspidata towards Sphagnum imbricatum causes a significant drop in the d13C values. On the whole, the C and O isotopes record two shallow pool phases during the 8th–9th and the 13th centuries. Pollen and atmospheric soil dust (ASD) fluxes records increased human occupation in the area. There may be some climatic signals in the ASD flux, but they are difficult to decipher from the increasing human impact (land clearance, agriculture) during the last millennium. The variations in the proxies are not always synchronous, suggesting different triggering factors (temperature, wetness, windiness) for each proxy. This study also emphasizes that, compared to studies dealing with pollution using geochemical proxies, palaeoclimatic inferences from peat bogs need as many proxies as possible, together with highly accurate and precise age-models, in order to better understand climate variability and their consequences during the Holocene.

Characterizing Pb mobilization from upland soils to streams using (206)Pb/(207)Pb isotopic ratios

Anthropogenically deposited lead (Pb) binds efficiently to soil organic matter, which can be mobilized through hydrologically mediated mechanisms, with implications for ecological and potable quality of receiving waters. Lead isotopic ((206)Pb/(207)Pb) ratios change down peat profiles as a consequence of long-term temporal variation in depositional sources, each with distinctive isotopic signatures. This study characterizes differential Pb transport mechanisms from deposition to streams at two small catchments with contrasting soil types in upland Wales, U.K., by determining Pb concentrations and (206)Pb/(207)Pb ratios from soil core profiles, interstitial pore waters, and stream water. Hydrological characteristics of soils are instrumental in determining the location in soil profiles of exported Pb and hence concentration and (206)Pb/(207)Pb ratios in surface waters. The highest Pb concentrations from near-surface soils are mobilized, concomitant with high dissolved organic carbon (DOC) exports, from hydrologically responsive peat soils with preferential shallow subsurface flows, leading to increased Pb concentrations in stream water and isotopic signatures more closely resembling recently deposited Pb. In more minerogenic soils, percolation of water allows Pb, bound to DOC, to be retained in mineral horizons and combined with other groundwater sources, resulting in Pb being transported from throughout the profile with a more geogenic isotopic signature. This study shows that (206)Pb/(207)Pb ratios can enhance our understanding of the provenances and transport mechanisms of Pb and potentially organic matter within upland soils.

Conformational Change of Mitochondrial Complex I Increases ROS Sensitivity During Ischemia

Aims: Myocardial ischemia/reperfusion (I/R) is associated with mitochondrial dysfunction and subsequent cardiomyocyte death. The generation of excessive quantities of reactive oxygen species (ROS) and resultant damage to mitochondrial enzymes is considered an important mechanism underlying reperfusion injury. Mitochondrial complex I can exist in two interconvertible states: active (A) and deactive or dormant (D). We have studied the active/deactive (A/D) equilibrium in several tissues under ischemic conditions in vivo and investigated the sensitivity of both forms of the heart enzyme to ROS.

Results: We found that in the heart, t½ of complex I deactivation during ischemia was 10?min, and that reperfusion resulted in the return of A/D equilibrium to its initial level. The rate of superoxide generation by complex I was higher in ischemic samples where content of the D-form was higher. Only the D-form was susceptible to inhibition by H2O2 or superoxide, whereas turnover-dependent activation of the enzyme resulted in formation of the A-form, which was much less sensitive to ROS. The mitochondrial-encoded subunit ND3, most likely responsible for the sensitivity of the D-form to ROS, was identified by redox difference gel electrophoresis.

Innovation: A combined in vivo and biochemical approach suggests that sensitivity of the mitochondrial system to ROS during myocardial I/R can be significantly affected by the conformational state of complex I, which may therefore represent a new therapeutic target in this setting.

Conclusion: The presented data suggest that transition of complex I into the D-form in the absence of oxygen may represent a key event in promoting cardiac injury during I/R.

Time-Resolved DRIFTS, MS, and Resistance Study of SnO2 Materials: The Role of Surface Hydroxyl Groups in Formation of Donor States

Time-resolved DRIFTS, MS, and resistance measurements were used to study the interaction of undoped and Pd-doped SnO2 with H-2 in air and argon at 300 degrees C. Using first-order kinetics, we compare the time constants for the resistance drop and its partial recovery with those of the surface hydroxyl evolution and water formation in the gas phase upon exposure to hydrogen. In the case of the undoped oxide, resistance and bridging hydroxyls (BOHs) evolve similarly, manifesting a fast main drop followed by recovery at a similar rate. The rate of water formation for this material was found to be much slower than that of the main drop in both the resistance and BOHs. In contrast, the resistance change for SnO2-Pd appeared to be similar to that of water formation, and no correlation was found between the evolution of resistance and surface OHs. Isotopic exchange on both materials revealed that water formation occurs via fast and slow hydrogen transfer to surface oxygen species. While the former originates from just-adsorbed hydrogen, the latter appears to proceed from the preadsorbed OHs. Both surfaces exhibit close interaction between chemisorbed oxygen and existing bridging OH groups, indicating that the latter is an intermediate in the hydrogen oxidation and generation of donor states on the surface.