Fossil vs. non-fossil sources of fine carbonaceous aerosols in four Chinese cities during the extreme winter haze episode of 2013

During winter 2013, extremely high concentrations (i.e., 4–20 times higher than the World Health Organization guideline) of PM2.5 (particulate matter with an aerodynamic diameter < 2.5 μm) mass concentrations (24 h samples) were found in four major cities in China including Xi'an, Beijing, Shanghai and Guangzhou. Statistical analysis of a combined data set from elemental carbon (EC), organic carbon (OC), 14C and biomass-burning marker measurements using Latin hypercube sampling allowed a quantitative source apportionment of carbonaceous aerosols. Based on 14C measurements of EC fractions (six samples each city), we found that fossil emissions from coal combustion and vehicle exhaust dominated EC with a mean contribution of 75 ± 8% across all sites. The remaining 25 ± 8% was exclusively attributed to biomass combustion, consistent with the measurements of biomass-burning markers such as anhydrosugars (levoglucosan and mannosan) and water-soluble potassium (K+). With a combination of the levoglucosan-to-mannosan and levoglucosan-to-K+ ratios, the major source of biomass burning in winter in China is suggested to be combustion of crop residues. The contribution of fossil sources to OC was highest in Beijing (58 ± 5%) and decreased from Shanghai (49 ± 2%) to Xi'an (38 ± 3%) and Guangzhou (35 ± 7%). Generally, a larger fraction of fossil OC was from secondary origins than primary sources for all sites. Non-fossil sources accounted on average for 55 ± 10 and 48 ± 9% of OC and total carbon (TC), respectively, which suggests that non-fossil emissions were very important contributors of urban carbonaceous aerosols in China. The primary biomass-burning emissions accounted for 40 ± 8, 48 ± 18, 53 ± 4 and 65 ± 26% of non-fossil OC for Xi'an, Beijing, Shanghai and Guangzhou, respectively. Other non-fossil sources excluding primary biomass burning were mainly attributed to formation of secondary organic carbon (SOC) from non-fossil precursors such as biomass-burning emissions. For each site, we also compared samples from moderately to heavily polluted days according to particulate matter mass. Despite a significant increase of the absolute mass concentrations of primary emissions from both fossil and non-fossil sources during the heavily polluted events, their relative contribution to TC was even decreased, whereas the portion of SOC was consistently increased at all sites. This observation indicates that SOC was an important fraction in the increment of carbonaceous aerosols during the haze episode in China.

Linking megathrust earthquakes to brittle deformation in a fossil accretionary complex

Seismological data from recent subduction earthquakes suggest that megathrust earthquakes induce transient stress changes in the upper plate that shift accretionary wedges into an unstable state. These stress changes have, however, never been linked to geological structures preserved in fossil accretionary complexes. The importance of coseismically induced wedge failure has therefore remained largely elusive. Here we show that brittle faulting and vein formation in the palaeo-accretionary complex of the European Alps record stress changes generated by subduction-related earthquakes. Early veins formed at shallow levels by bedding-parallel shear during coseismic compression of the outer wedge. In contrast, subsequent vein formation occurred by normal faulting and extensional fracturing at deeper levels in response to coseismic extension of the inner wedge. Our study demonstrates how mineral veins can be used to reveal the dynamics of outer and inner wedges, which respond in opposite ways to megathrust earthquakes by compressional and extensional faulting, respectively.

Wet deposition of fossil and non-fossil derived particulate carbon: insights from radiocarbon measurement

Radiocarbon (14C) measurements of both organic carbon (OC) and elemental carbon (EC) allow a more detailed source apportionment, leading to a full and unambiguous distinction and quantification of the contributions from non-fossil and fossil sources. A thermal-optical method with a commercial OC/EC analyzer to isolate water-insoluble OC (WIOC) and EC for their subsequent 14C measurement was applied for the first time to filtered precipitation samples collected at a costal site in Portugal and at a continental site in Switzerland. Our results show that WIOC in precipitation is dominated by non-fossil sources such as biogenic and biomass-burning emissions regardless of rain origins and seasons, whereas EC sources are shared by fossil-fuel combustion and biomass burning. In addition, monthly variation of WIOC in Switzerland was characterized by higher abundance in warm than in cold seasons, highlighting the importance of biogenic emissions to particulate carbon in rainwater. Samples with high particulate carbon concentrations in Portugal were found to be associated with increased biogenic input. Despite the importance of non-fossil sources, fossil emissions account for approximately 20% of particulate carbon in wet deposition for our study, which is in line with fossil contribution in bulk rainwater dissolved organic carbon as well as aerosol WIOC and EC estimated by the 14C approach from other studies.

Pinus nigra (European black pine) as the dominant species of the last glacial pinewoods in south-western to central Iberia: a morphological study of modern and fossil pollen

Aim Our aim was to discriminate different species of Pinus via pollen analysis in order to assess the responses of particular pine species to orbital and millennial-scale climate changes, particularly during the last glacial period. Location Modern pollen grains were collected from current pine populations along transects from the Pyrenees to southern Iberia and the Balearic Islands. Fossil pine pollen was recovered from the south-western Iberian margin core MD95-2042. Methods We measured a set of morphological traits of modern pollen from the Iberian pine species Pinus nigra, P. sylvestris, P. halepensis, P. pinea and P. pinaster and of fossil pine pollen from selected samples of the last glacial period and the early to mid-Holocene. Classification and regression tree (CART) analysis was used to establish a model from the modern dataset that discriminates pollen from the different pine species and allows identification of fossil pine pollen at the species level. Results The CART model was effective in separating pollen of P. nigra and P. sylvestris from that of the Mediterranean pine group (P. halepensis, P. pinea and P. pinaster). The pollen of Pinus nigra diverged from that of P. sylvestris by having a more flattened corpus. Predictions using this model suggested that fossil pine pollen is mainly from P. nigra in all the samples analysed. Pinus sylvestris was more abundant in samples from Greenland stadials than Heinrich stadials, whereas Mediterranean pines increased in samples from Greenland interstadials and during the early to mid-Holocene. Main conclusions Morphological parameters can be successfully used to increase the taxonomic resolution of fossil pine pollen at the species level for the highland pines (P. nigra and P. sylvestris) and at the group of species level for the Mediterranean pines. Our study indicates that P. nigra was the dominant component of the last glacial south-western/central Iberian pinewoods, although the species composition of these woodlands varied in response to abrupt climate changes.

Constraints on barium isotope fractionation during aragonite precipitation by corals

We present a barium (Ba) isotope fractionation study of marine biogenic carbonates (aragonitic corals). The major aim is to provide first constraints on the Ba isotope fractionation between modern surface sea water and coral skele- ton. Mediterranean surface sea water was found to be enriched in the heavy Ba isotopes compared to previously reported values for marine open ocean authi- genic and terrestrial minerals. In aquarium experiments with a continuous sup- ply of Mediterranean surface water, the Ba isotopic composition of the bulk sample originating from cultured, aragonitic scleractinian corals (d137/134Ba between +0.16 +/- 0.12permil and +0.41 +/-0.12permil) were isotopically identical or lighter than that of the ambient Mediterranean surface sea water (d137/134Ba = +0.42 +/- 0.07permil, 2SD), which corresponds to an empirical maximum value of Ba isotope fractionation of D137/134Bacoral-seawater = -0.26 +/- 0.14permil at 25°C. This maximum Ba isotope fractionation is close and identical in direction to previous results from inorganic precipitation experiments with aragonite- structured pure BaCO3 (witherite). The variability in measured Ba concentrations of the cultured corals is at odds with a uniform distribution coefficient, DBa/Ca, thus indicating stronger vital effects on isotope than element discrimination. This observation supports the hypothesis that the Ba isotopic compositions of these corals do not result from simple equilibrium between the skeleton and the bulk sea water. Complementary coral samples from natural settings (tropical shallow-water corals from the Bahamas and Florida and cold- water corals from the Norwegian continental shelf) show an even wider range in d137/134Ba values (+0.14 +/- 0.08permil and +0.77 +/- 0.11permil), most probably due to additional spatial and/or temporal sea water heterogeneity, as indicated by recent publications.

Younger Dryas and Allerød summer temperatures at Gerzensee (Switzerland) inferred from fossil pollen and cladoceran assemblages

Linear- and unimodal-based inference models for mean summer temperatures (partial least squares, weighted averaging, and weighted averaging partial least squares models) were applied to a high-resolution pollen and cladoceran stratigraphy from Gerzensee, Switzerland. The time-window of investigation included the Allerød, the Younger Dryas, and the Preboreal. Characteristic major and minor oscillations in the oxygen-isotope stratigraphy, such as the Gerzensee oscillation, the onset and end of the Younger Dryas stadial, and the Preboreal oscillation, were identified by isotope analysis of bulk-sediment carbonates of the same core and were used as independent indicators for hemispheric or global scale climatic change. In general, the pollen-inferred mean summer temperature reconstruction using all three inference models follows the oxygen-isotope curve more closely than the cladoceran curve. The cladoceran-inferred reconstruction suggests generally warmer summers than the pollen-based reconstructions, which may be an effect of terrestrial vegetation not being in equilibrium with climate due to migrational lags during the Late Glacial and early Holocene. Allerød summer temperatures range between 11 and 12°C based on pollen, whereas the cladoceran-inferred temperatures lie between 11 and 13°C. Pollen and cladocera-inferred reconstructions both suggest a drop to 9–10°C at the beginning of the Younger Dryas. Although the Allerød–Younger Dryas transition lasted 150–160 years in the oxygen-isotope stratigraphy, the pollen-inferred cooling took 180–190 years and the cladoceran-inferred cooling lasted 250–260 years. The pollen-inferred summer temperature rise to 11.5–12°C at the transition from the Younger Dryas to the Preboreal preceded the oxygen-isotope signal by several decades, whereas the cladoceran-inferred warming lagged. Major discrepancies between the pollen- and cladoceran-inference models are observed for the Preboreal, where the cladoceran-inference model suggests mean summer temperatures of up to 14–15°C. Both pollen- and cladoceran-inferred reconstructions suggest a cooling that may be related to the Gerzensee oscillation, but there is no evidence for a cooling synchronous with the Preboreal oscillation as recorded in the oxygen-isotope record. For the Gerzensee oscillation the inferred cooling was ca. 1 and 0.5°C based on pollen and cladocera, respectively, which lies well within the inherent prediction errors of the inference models.

The palaeolimnology of Soppensee (Central Switzerlabnd), as evidenced by diatom, pollen, and fossil-pigment analyses

The development of Soppensee (Central Switzerland, 596 m a.s.l.) has been reconstructed using algal remains such as diatoms, chlorophytes and fossil pigments, as well as the pollen and spores of macrophytes. Sediment accumulation in Soppensee began at the end of the last glacial period, approximately 15,000 yrs ago. During the Oldest Dryas biozone (> 12,700 radiocarbon yrs B.P.) the lake had low primary productivity. After reforestation with birch and later pine, around 12,700 B.P., phases of summer anoxia occurred in the lake. These anoxic conditions were most probably caused by additional carbon input from the catchment, as well as longer phases of stratification due to reduced wind exposure caused by the sheltering effect of increased tree cover. From the Younger Dryas biozone (10,800 to 10,000 radiocarbon yrs B.P.) onwards, Soppensee became meromictic for several millennia.

The recent eutrophication of Baldeggersee (Switzerland) as assessed by fossil diatom assemblages

Diatom analyses with an annual resolution were carried out on varves of the hypertrophic Baldeggersee (Central Swiss Plateau) for the timespan ad 1885 to 1993. They reveal seven major changes in the dominant planktonic diatoms. As a result of progressive nutrient enrichment, Baldeggersee changed in the 1910s from a Cyclotella to a Tabellaria fenestrata dominated assemblage, and eventually in the 1950s to a Stephanodiscus parvus dominated diatom assemblage. The timing and direction of diatom-assemblage changes in the varved sediment compare well with sedimentological and limnological observations. Partitioning of the variance in the diatom data revealed that TP is a stronger explanatory variable than temperature for these changes. A diatom-inferred total phosphorus (TP) reconstruction indicates three major steps in eutrophication, occurring at 1909, the mid-1950s and the mid-1970s. Comparison with TP measurements in the water column demonstrates that the diatom-TP inference model used is able to hindcast past TP concentrations reliably. The major steps in eutrophication led to decreases in diatom diversity and also resulted in a progressive increase of calcite grain-size. The lake restoration programme established since 1982 shows no direct impact on the composition of the diatom assemblages. However, the decrease in phosphorus loads since the mid-1970s is reflected in the diatom assemblages and in decreasing diatom-inferred TP concentrations.

Precious Corals (Coralliidae) from North-Western Atlantic Seamounts

Two new species belonging to the precious coral genus Corallium were collected during a series of exploratory cruises to the New England and Corner Rise Seamounts in 2003-2005. One red species, Corallium bathyrubrum sp. nov., and one white species, C. bayeri sp. nov., are described. Corallium bathyrubrum is the first red Corallium to be reported from the western Atlantic. An additional species, C. niobe Bayer, 1964 originally described from the Straits of Florida, was also collected and its description augmented.