Comparison of gas with liquid chromatography for the determination of benzenepolycarboxylic acids as molecular tracers of black carbon

Existing methods for black carbon (BC) quantification measure different parts of the BC continuum, which complicates the calculation of a global BC budget. Benzenepolycarboxylic acids (BPCA) are used as molecular markers to quantify and characterize BC in soils and sediments using gas chromatography for BPCA separation (GC-BPCA). Recently, this method was refined for BC analysis in seawater using high performance liquid chromatography (LC-BPCA), which omits the cleaning steps and derivatization necessary in GC analysis. As yet it is not clear whether the two analytical methods yield similar results. Here we apply both methods to a suite of laboratory produced charcoals derived from wood and grass. We found systematically lower total BPCA-C contents and larger analytical variability for all tested charcoals when using GC-BPCA compared to LC-BPCA, the latter giving 1.5 ± 0.3 times higher yields for the charcoal samples formed at 275-700 °C. At lower and higher pyrolysis temperatures the differences between the two analytical methods were larger. The main reason for the differences between the two methods is the loss of BPCA during sample preparation for GC analysis. We propose a correction factor of 1.5 to account for at least part of these losses. No qualitative biases, i.e. towards more or less functionalized BPCAs, were observed between the two methods. The relative contribution of mellitic acid C to total BPCA-C, a measure for the degree of condensation of BC, was the same in the two analytical techniques. Qualitative differences between wood and grass charcoals as detected by both methods were small.     

Evaluation of cosmogenic 3He and 21Ne production rates in olivine and pyroxene from two Pleistocene basalt flows,western Grand Canyon,AZ, USA

Combining cosmogenic ³He and ²¹Ne (³He_c and ²¹Ne_c) measurements on both pyroxene and olivine from the Pleistocene Bar Ten flows (85–107 ka) greatly increases our ability to evaluate the accuracy of ³He_c and ²¹Ne_c production rates and, therefore, ³He_c and ²¹Ne_c surface exposure ages. Comparison of ³He_c and ²¹Ne_c age-pairs yielded by experimentally determined production rates and composition-based model calculations indicates that the former give more accurate surface exposure ages than the latter in this study. However, experimental production rates should be adjusted to the composition of the minerals being analyzed to obtain the best agreement between ³He_c and ²¹Ne_c ages for any given sample. ²¹Ne_c/³He_c values are 0.400 ± 0.029 and 0.204 ± 0.014 for olivine and pyroxene, respectively, in Bar Ten lava flows, in agreement with previously published values, and indicate that ²¹Ne_c/³He_c in olivine and pyroxene is not affected by erosion and remains constant with latitude, elevation, and time (up to 10 Myr). Samples with ²¹Ne_c/³He_c that do not agree with these values may indicate the presence of non-cosmogenic helium and/or neon. The neon three-isotope diagram can also indicate whether or not all excess neon in mineral separates comes from cosmogenic sources. An error-weighted regression for olivine defines a spallation line [y = (1.033 ± 0.031)x + (0.09876 ± 0.00033)], which is indistinguishable from that for pyroxene (Schäfer et al., 1999). We have derived a production rate of 25 ± 8 at/g/yr for ²¹Ne_c in clinopyroxene (En_43–44) based on the ⁴⁰Ar/³⁹Ar age of the upper Bar Ten flow. Our study indicates that the production rate of ²¹Ne_c in olivine may be slightly higher than previously determined. Cosmogenic ³He and ²¹Ne remain extremely useful, particularly when paired, in determining accurate eruption ages of young olivine- and pyroxene-rich basaltic lava flows.     

Atmospheric Pb and Cd input into the Baltic Sea: a new estimate based on measurements

Bulk deposition samples were collected during a summer (1997) and a winter (1998) measurement campaign at four coastal stations along the southern Baltic Sea coast and on the Island of Gotland. The data were used to construct Pb and Cd deposition fields over the Baltic Sea. A weak gradient with decreasing deposition rates from the southwest towards the east and north was obtained for Pb. In the case of Cd, the spatial distribution pattern was characterized by an extreme deposition maximum at the Polish station on the Hel Peninsula. The total atmospheric input of Pb and Cd into the Baltic Sea was 550 and 33 t/year, respectively, and exceeds the riverine input by approximately about 50%. Previous measurement-based estimates were higher by a factor 2–3 and indicate a decrease of the atmospheric deposition during the past 10–15 years. The comparison with modelled deposition data yielded partly large differences and was impaired by the fact that 1990 emission inventories were used whereas our measurements were performed in 1997/1998.Relating our deposition estimate and the Pb/Cd input by rivers to the mean concentrations in Baltic Sea water, residence times of 0.29 and 3.6 years were obtained for Pb and Cd, respectively.     

Centennial-scale climate change from decadally-paced explosive volcanism: a coupled sea ice-ocean mechanism

Northern Hemisphere summer cooling through the Holocene is largely driven by the steady decrease in summer insolation tied to the precession of the equinoxes. However, centennial-scale climate departures, such as the Little Ice Age, must be caused by other forcings, most likely explosive volcanism and changes in solar irradiance. Stratospheric volcanic aerosols have the stronger forcing, but their short residence time likely precludes a lasting climate impact from a single eruption. Decadally paced explosive volcanism may produce a greater climate impact because the long response time of ocean surface waters allows for a cumulative decrease in sea-surface temperatures that exceeds that of any single eruption. Here we use a global climate model to evaluate the potential long-term climate impacts from four decadally paced large tropical eruptions. Direct forcing results in a rapid expansion of Arctic Ocean sea ice that persists throughout the eruption period. The expanded sea ice increases the flux of sea ice exported to the northern North Atlantic long enough that it reduces the convective warming of surface waters in the subpolar North Atlantic. In two of our four simulations the cooler surface waters being advected into the Arctic Ocean reduced the rate of basal sea-ice melt in the Atlantic sector of the Arctic Ocean, allowing sea ice to remain in an expanded state for?>?100 model years after volcanic aerosols were removed from the stratosphere. In these simulations the coupled sea ice-ocean mechanism maintains the strong positive feedbacks of an expanded Arctic Ocean sea ice cover, allowing the initial cooling related to the direct effect of volcanic aerosols to be perpetuated, potentially resulting in a centennial-scale or longer change of state in Arctic climate. The fact that the sea ice-ocean mechanism was not established in two of our four simulations suggests that a long-term sea ice response to volcanic forcing is sensitive to the stability of the seawater column, wind, and ocean currents in the North Atlantic during the eruptions.     

Inter-annual and seasonal variations in the air–sea CO2 balance in the central Baltic Sea and the Kattegat

We estimated the net annual air–sea exchange of carbon dioxide (CO₂) using monitoring data from the East Gotland Sea, Bornholm Sea, and Kattegat for the 1993–2009 period. Wind speed and the sea surface partial pressure of CO₂ (pCO₂^w), calculated from pH, total alkalinity, temperature, and salinity, were used for the flux calculations. We demonstrate that regions in the central Baltic Sea and the Kattegat alternate between being sinks (−) and sources (+) of CO₂ within the −4.2 to +5.2 mol m⁻² yr⁻¹ range. On average, for the 1994–2008 period, the East Gotland Sea was a source of CO₂ (1.64 mol m⁻² yr⁻¹), the Bornholm Sea was a source (2.34 mol m⁻² yr⁻¹), and the Kattegat was a sink (−1.16 mol m⁻² yr⁻¹). Large inter-annual and regional variations in the air–sea balance were observed. We used two parameterizations for the gas transfer velocity (k) and the choice varied the air–sea exchange by a factor of two. Inter-annual variations in pCO₂^w between summers were controlled by the maximum concentration of phosphate in winter. Inter-annual variations in the CO₂ flux and gas transfer velocity were larger between winters than between summers. This indicates that the inter-annual variability in the total flux was controlled by winter conditions. The large differences between the central Baltic Sea and Kattegat were considered to depend partly on the differences in the mixed layer depth.     

Comparative assessment of Japan's long-term carbon budget under different effort-sharing principles

This article assesses Japan's carbon budgets up to 2100 in the global efforts to achieve the 2?°C target under different effort-sharing approaches based on long-term GHG mitigation scenarios published in 13 studies. The article also presents exemplary emission trajectories for Japan to stay within the calculated budget.

The literature data allow for an in-depth analysis of four effort-sharing categories. For a 450?ppm CO₂e stabilization level, the remaining carbon budgets for 2014–2100 were negative for the effort-sharing category that emphasizes historical responsibility and capability. For the other three, including the reference ‘Cost-effectiveness’ category, which showed the highest budget range among all categories, the calculated remaining budgets (20th and 80th percentile ranges) would run out in 21–29 years if the current emission levels were to continue. A 550?ppm CO₂e stabilization level increases the budgets by 6–17 years-equivalent of the current emissions, depending on the effort-sharing category. Exemplary emissions trajectories staying within the calculated budgets were also analysed for ‘Equality’, ‘Staged’ and ‘Cost-effectiveness’ categories. For a 450?ppm CO₂e stabilization level, Japan's GHG emissions would need to phase out sometime between 2045 and 2080, and the emission reductions in 2030 would be at least 16–29% below 1990 levels even for the most lenient ‘Cost-effectiveness’ category, and 29–36% for the ‘Equality’ category. The start year for accelerated emissions reductions and the emissions convergence level in the long term have major impact on the emissions reduction rates that need to be achieved, particularly in the case of smaller budgets.

Policy relevance

In previous climate mitigation target formulation processes for 2020 and 2030 in Japan, neither equity principles nor long-term management of cumulative GHG emissions was at the centre of discussion. This article quantitatively assesses how much more GHGs Japan can emit by 2100 to achieve the 2?°C target in light of different effort-sharing approaches, and how Japan's GHG emissions can be managed up to 2100. The long-term implications of recent energy policy developments following the Fukushima nuclear disaster for the calculated carbon budgets are also discussed.     

Holocene climate variability as derived from alkenone sea surface temperature and coupled ocean-atmosphere model experiments

Holocene climate modes are identified by the statistical analysis of reconstructed sea surface temperatures (SSTs) from the tropical and North Atlantic regions. The leading mode of Holocene SST variability in the tropical region indicates a rapid warming from the early to mid Holocene followed by a relatively weak warming during the late Holocene. The dominant mode of the North Atlantic region SST captures the transition from relatively warm (cold) conditions in the eastern North Atlantic and the western Mediterranean Sea (the northern Red Sea) to relatively cold (warm) conditions in these regions from the early to late Holocene. This pattern of Holocene SST variability resembles the signature of the Arctic Oscillation/North Atlantic Oscillation (AO/NAO). The second mode of both tropical and North Atlantic regions captures a warming towards the mid Holocene and a subsequent cooling. The dominant modes of Holocene SST variability emphasize enhanced variability around 2300 and 1000 years. The leading mode of the coupled tropical-North Atlantic Holocene SST variability shows that an increase of tropical SST is accompanied by a decrease of SST in the eastern North Atlantic. An analogy with the instrumental period as well as the analysis of a long-term integration of a coupled ocean-atmosphere general circulation model suggest that the AO/NAO is one dominant mode of climate variability at millennial time scales.     

Microcrater populations on Apollo 17 rocks

Approximately 6000 microcrates were investigated using binocular microscope techniques on Apollo 17 rocks 70215, 72215, 72235, 72395, 72435, 73216, 73218, 73275, 74275, 76135, 76136 and 79155. The crater populations observed have identical characteristics to those obtained from previous missions.Special emphasis was placed on assessing the influence of target properties on the observable crater populations. Although these properties cannot be quantitatively evaluated at present, the empirical results indicate that crater populations on glass, breccia, and crystalline rock surfaces may differ fundamentally. As a consequence, lunar surface exposure ages of individual rocks based on micrometeoroid craters may be subject to criticism.     

Seismically reactivated Hattian slide in Kashmir, Northern Pakistan

The Pakistan 2005 earthquake, of magnitude 7.6, caused severe damage on landscape and infrastructure, in addition to numerous casualties. The event reactivated Hattian Slide, creating a rock avalanche in a location where earlier mass movements had happened already, as indicated by satellite imagery and ground investigation. The slide originated on Dana Hill, in the upper catchment area of Hattian on Karli Stream, a tributary of Jhelum River, Pakistan, and buried the hamlet Dandbeh and several farms nearby. A natural dam accumulated, impounding two lakes, the larger one threatening parts of downstream Hattian Village with flooding. An access road and artificial spillways needed to be constructed in very short time to minimize the flooding risk. As shown by this example, when pointing out the risk of large-scale damage to population and infrastructure by way of hazard indication maps of seismically active regions, and preparing for alleviation of that risk, it is advisable to consider the complete Holocene history of the slopes involved.