Long-term chemical characterization of aerosols at CVAO from 2007 to 2011

The first long-term aerosol sampling and chemical characterization results from measurements at the Cape Verde Atmospheric Observatory (CVAO) on the island of São Vicente are presented and are discussed with respect to air mass origin and seasonal trends. In total 671 samples were collected using a high-volume PM10 sampler on quartz fiber filters from January 2007 to December 2011. The samples were analyzed for their aerosol chemical composition, including their ionic and organic constituents. Back trajectory analyses showed that the aerosol at CVAO was strongly influenced by emissions from Europe and Africa, with the latter often responsible for high mineral dust loading. Sea salt and mineral dust dominated the aerosol mass and made up in total about 80% of the aerosol mass. The 5-year PM10 mean was 47.1 ± 55.5 µg/m**2, while the mineral dust and sea salt means were 27.9 ± 48.7 and 11.1 ± 5.5 µg/m**2, respectively. Non-sea-salt (nss) sulfate made up 62% of the total sulfate and originated from both long-range transport from Africa or Europe and marine sources. Strong seasonal variation was observed for the aerosol components. While nitrate showed no clear seasonal variation with an annual mean of 1.1 ± 0.6 µg/m**3, the aerosol mass, OC (organic carbon) and EC (elemental carbon), showed strong winter maxima due to strong influence of African air mass inflow. Additionally during summer, elevated concentrations of OM were observed originating from marine emissions. A summer maximum was observed for non-sea-salt sulfate and was connected to periods when air mass inflow was predominantly of marine origin, indicating that marine biogenic emissions were a significant source. Ammonium showed a distinct maximum in spring and coincided with ocean surface water chlorophyll a concentrations. Good correlations were also observed between nss-sulfate and oxalate during the summer and winter seasons, indicating a likely photochemical in-cloud processing of the marine and anthropogenic precursors of these species. High temporal variability was observed in both chloride and bromide depletion, differing significantly within the seasons, air mass history and Saharan dust concentration. Chloride (bromide) depletion varied from 8.8 ± 8.5% (62 ± 42%) in Saharan-dust-dominated air mass to 30 ± 12% (87 ± 11%) in polluted Europe air masses. During summer, bromide depletion often reached 100% in marine as well as in polluted continental samples. In addition to the influence of the aerosol acidic components, photochemistry was one of the main drivers of halogenide depletion during the summer; while during dust events, displacement reaction with nitric acid was found to be the dominant mechanism. Positive matrix factorization (PMF) analysis identified three major aerosol sources: sea salt, aged sea salt and long-range transport. The ionic budget was dominated by the first two of these factors, while the long-range transport factor could only account for about 14% of the total observed ionic mass.

Particle concentration and size distribution in the NGRIP ice core

A novel laser microparticle detector used in conjunction with continuous sample melting has provided a more than 1500 m long record of particle concentration and size distribution of the NGRIP ice core, covering continuously the period approximately from 9.5-100 kyr before present; measurements were at 1.65 m depth resolution, corresponding to approximately 35-200 yr. Particle concentration increased by a factor of 100 in the Last Glacial Maximum (LGM) compared to the Preboreal, and sharp variations of concentration occurred synchronously with rapid changes in the delta18O temperature proxy. The lognormal mode µ of the volume distribution shows clear systematic variations with smaller modes during warmer climates and coarser modes during colder periods. We find µ ~ 1.7 µm diameter during LGM and µ ~ 1.3 µm during the Preboreal. On timescales below several 100 years µ and the particle concentration exhibit a certain degree of independence present especially during warm periods, when µ generally is more variable. Using highly simplifying considerations for atmospheric transport and deposition of particles we infer that (1) the observed changes of µ in the ice largely reflect changes in the size of airborne particles above the ice sheet and (2) changes of µ are indicative of changes in long range atmospheric transport time. From the observed size changes we estimate shorter transit times by roughly 25% during LGM compared to the Preboreal. The associated particle concentration increase from more efficient long range transport is estimated to less than one order of magnitude.

Stable isotope ratios and chemistry on corals from the Caribbean Sea

Instrumental climate data are limited in length and only available with low spatial coverage before the middle of the 20th century. This is too short to reliably determine and interpret decadal and longer scale climate variability and to understand the underlying mechanisms with sufficient accuracy. A proper knowledge of past variability of the climate system is needed to assess the anthropogenic impact on climate and ecosystems, and also important with regard to long-range climate forecasting. Highly-resolved records of past climate variations that extend beyond pre-industrial times can significantly help to understand long-term climate changes and trends. Indirect information on past environmental and climatic conditions can be deduced from climate-sensitive proxies. Large colonies of massive growing tropical reef corals have been proven to sensitively monitor changes in ambient seawater. Rapid skeletal growth, typically ranging between several millimeters to centimeters per year, allows the development of proxy records at sub-seasonal resolution. Stable oxygen isotopic composition and trace elemental ratios incorporated in the aragonitic coral skeleton can reveal a detailed history of past environmental conditions, e.g., sea surface temperature (SST). In general, coral-based reconstructions from the tropical Atlantic region have lagged behind the extensive work published using coral records from the Indian and Pacific Oceans. Difficulties in the analysis of previously utilized coral archives from the Atlantic, typically corals of the genera Montastrea and Siderastrea, have so far exacerbated the production of long-term high-resolution proxy records. The objective of this study is the evaluation of massive fast-growing corals of the species Diploria strigosa as a new marine archive for climate reconstructions from the tropical Atlantic region. For this purpose, coral records from two study sites in the eastern Caribbean Sea (Guadeloupe, Lesser Antilles; and Archipelago Los Roques, Venezuela) were examined. At Guadeloupe, a century-long monthly resolved multi-proxy coral record was generated. Results present the first d18O (Sr/Ca)-SST calibration equations for the Atlantic braincoral Diploria strigosa, that are robust and consistent with previously published values using other coral species from different regions. Both proxies reflect local variability of SST on a sub-seasonal scale, which is a precondition for studying seasonally phase-locked climate variations, as well as track variability on a larger spatial scale (i.e., in the Caribbean and tropical North Atlantic). Coral Sr/Ca reliably records local annual to interannual temperature variations and is higher correlated to in-situ air temperature than to grid-SST. The warming calculated from coral Sr/Ca is concurrent with the strong surface temperature increase at the study site during the past decades. Proxy data show a close relationship to major climate signals from the tropical Pacific and North Atlantic (the El Niño Southern Oscillation (ENSO) and the North Atlantic Oscillation (NAO)) affecting the seasonal cycle of SST in the North Tropical Atlantic (NTA). Coral oxygen isotopes are also influenced by seawater d18O (d18Osw) which is linked to the hydrological cycle, and capture large-scale climate variability in the NTA region better than Sr/Ca. Results from a quantitative comparison between extreme events in the two most prominent modes of external forcing, namely the ENSO and NAO, and respective events recorded in seasonal coral d18O imply that SST variability at the study site is highly linked to Pacific and North Atlantic variability, by this means supporting the assumptions of observational- and model-based studies which suggest a strong impact of ENSO and NAO forcings onto the NTA region through a modulation of trade wind strength in winter. Results from different spectral analysis tools suggest that interannual climate variability recorded by the coral proxies is II largely dictated by Pacific ENSO forcing, whereas at decadal and longer timescales the influence of the NAO is dominan. tThe Archipelago Los Roques is situated in the southeastern Caribbean Sea, north of the Venezuelan coast. Year-to-year variations in monthly resolved coral d18O of a nearcentury- long Diploria strigosa record are significantly correlated with SST and show pronounced multidecadal variations. About half of the variance in coral d18O can be explained by variations in seawater d18O, which can be estimated by calculating the d18Oresidual via subtracting the SST component from measured coral d18O. The d18Oresidual and a regional precipitation index are highly correlated at low frequencies, suggesting that d18Osw variations are primarily atmospheric-driven. Warmer SSTs at Los Roques broadly coincide with higher precipitation in the southeastern Caribbean at multidecadal time scales, effectively strengthening the climate signal in the coral d18O record. The Los Roques coral d18O record displays a strong and statistically significant relationship to different indices of hurricane activity during the peak of the Atlantic hurricane season in boreal summer and is a particularly good indicator of decadal-multidecadal swings in the latter indices. In general, the detection of long-term changes and trends in Atlantic hurricane activity is hampered due to the limited length of the reliable instrumental record and the known inhomogeneity in the observational databases which result from changes in observing practice and technology over the years. The results suggest that coral-derived proxy data from Los Roques can be used to infer changes in past hurricane activity on timescales that extend well beyond the reliable record. In addition, the coral record exhibits a clear negative trend superimposed on the decadal to multidecadal cycles, indicating a significant warming and freshening of surface waters in the genesis region of tropical cyclones during the past decades. The presented coral d18O time series provides the first and, so far, longest continuous coral-based record of hurricane activity. It appears that the combination of both signals (SST and d18Osw) in coral d18O leads to an amplification of large-scale climate signals in the record, and makes coral d18O even a better proxy for hurricane activity than SST alone. Atlantic hurricane activity naturally exhibits strong multidecadal variations that are associated with the Atlantic Multidecadal Oscillation (AMO), the major mode of lowfrequency variability in the North Atlantic Ocean. However, the mechanisms underlying this multidecadal variability remain controversial, primarily because of the limited instrumental record. The Los Roques coral d18O displays strong multidecadal variability with a period of approximately 60 years that is closely related to the AMO, making the Archipelago Los Roques a very sensitive location for studying low-frequency climate variability in the Atlantic Ocean. In summary, the coral records presented in this thesis capture different key climate variables in the north tropical Atlantic region very well, indicating that fast-growing Diploria strigosa corals represent a promising marine archive for further proxy-based reconstructions of past climate variability on a range of time scales.

Constraints on the magnitude and patterns of ocean cooling at the Last Glacial Maximum - Supplementary material

Observation-based reconstructions of sea surface temperature from relatively stable periods in the past, such as the Last Glacial Maximum, represent an important means of constraining climate sensitivity and evaluating model simulations. The first quantitative global reconstruction of sea surface temperatures during the Last Glacial Maximum was developed by the Climate Long-Range Investigation, Mapping and Prediction (CLIMAP) project in the 1970s and 1980s. Since that time, several shortcomings of that earlier effort have become apparent. Here we present an updated synthesis of sea surface temperatures during the Last Glacial Maximum, rigorously defined as the period between 23 and 19 thousand years before present, from the Multiproxy Approach for the Reconstruction of the Glacial Ocean Surface (MARGO) project. We integrate microfossil and geochemical reconstructions of surface temperatures and include assessments of the reliability of individual records. Our reconstruction reveals the presence of large longitudinal gradients in sea surface temperature in all of the ocean basins, in contrast to the simulations of the Last Glacial Maximum climate available at present.

Crete fault scarp point cloud data

This paper assesses the along strike variation of active bedrock fault scarps using long range terrestrial laser scanning (t-LiDAR) data in order to determine the distribution behaviour of scarp height and the subsequently calculate long term throw-rates. Five faults on Cretewhich display spectacular limestone fault scarps have been studied using high resolution digital elevation model (HRDEM) data. We scanned several hundred square metres of the fault system including the footwall, fault scarp and hanging wall of the investigated fault segment. The vertical displacement and the dip of the scarp were extracted every metre along the strike of the detected fault segment based on the processed HRDEM. The scarp variability was analysed by using statistical and morphological methods. The analysis was done in a geographical information system (GIS) environment. Results show a normal distribution for the scanned fault scarp's vertical displacement. Based on these facts, the mean value of height was chosen to define the authentic vertical displacement. Consequently the scarp can be divided into above, below and within the range of mean (within one standard deviation) and quantify the modifications of vertical displacement. Therefore, the fault segment can be subdivided into areas which are influenced by external modification like erosion and sedimentation processes. Moreover, to describe and measure the variability of vertical displacement along strike the fault, the semi-variance was calculated with the variogram method. This method is used to determine how much influence the external processes have had on the vertical displacement. By combining of morphological and statistical results, the fault can be subdivided into areas with high external influences and areas with authentic fault scarps, which have little or no external influences. This subdivision is necessary for long term throw-rate calculations, because without this differentiation the calculated rates would be misleading and the activity of a fault would be incorrectly assessed with significant implications for seismic hazard assessment since fault slip rate data govern the earthquake recurrence. Furthermore, by using this workflow areas with minimal external influences can be determined, not only for throw-rate calculations, but also for determining samples sites for absolute dating techniques such as cosmogenic nuclide dating. The main outcomes of this study include: i) there is no direct correlation between the fault's mean vertical displacement and dip (R² less than 0.31); ii) without subdividing the scanned scarp into areas with differing amounts of external influences, the along strike variability of vertical displacement is ±35%; iii) when the scanned scarp is subdivided the variation of the vertical displacement of the authentic scarp (exposed by earthquakes only) is in a range of ±6% (the varies depending on the fault from 7 to 12%); iv) the calculation of the long term throw-rate (since 13 ka) for four scarps in Crete using the authentic vertical displacement is 0.35 ± 0.04 mm/yr at Kastelli 1, 0.31 ± 0.01 mm/yr at Kastelli 2, 0.85 ± 0.06 mm/yr at the Asomatos fault (Sellia) and 0.55 ± 0.05 mm/yr at the Lastros fault.

Relative abundance of pteropod species of the plankton pump samples in the surface water of the eastern North Atlantic Ocean (Table 4)

Plankton pump samples and plankton tows (size fractions between 0.04 mm and 1.01 mm) from the eastern North Atlantic Ocean contain the following shell- and skeleton-producing planktonic and nektonic organisms, which can be fossilized in the sediments: diatoms, radiolarians, foraminifers, pteropods, heteropods, larvae of benthic gastropods and bivalves, ostracods, and fish. The abundance of these components has been mapped quantitatively in the eastern North Atlantic surface waters in October - December 1971. More ash (after ignition of the organic matter, consisting mostly of these components) per cubic meter of water is found close to land masses (continents and islands) and above shallow submarine elevations than in the open ocean. Preferred biotops of planktonic diatoms in the region described are temperate shallow water and tropical coastal upwelling areas. Radiolarians rarely occur close to the continent, but are abundant in pelagic warm water masses, even near islands. Foraminifers are similar to the radiolarians, rarer in the coastal water mass of the continent than in the open ocean or off oceanic islands. Their abundance is highest outside the upwelling area off NW Africa. Molluscs generally outnumber planktonic foraminifers, implying that the carbonate cycle of the ocean might be influenced considerably by these animals. The molluscs include heteropods, pteropods, and larvae of benthic bivalves and gastropods. Larvae of benthic molluscs occur more frequently close to continental and island margins and above submarine shoals (in this case mostly guyots) than in the open ocean. Their size increases, but they decrease in number with increasing distance from their area of origin. Ostracods and fish have only been found in small numbers concentrated off NW Africa. All of the above-mentioned components occur in higher abundances in the surface water than in subsurface waters. They are closely related to the hydrography of the sampled water masses (here defined through temperature measurements). Relatively warm water masses of the southeastern branches of the Gulf Stream system transport subtropical and southern temperate species to the Bay of Biscay, relatively cool water masses of the Portugal and Canary Currents carry transitional faunal elements along the NW African coast southwards to tropical regions. These mix in the northwest African upwelling area with tropical faunal elements which are generally assumed to live in the subsurface water masses and which probably have been transported northwards to this area by a subsurface counter current. The faunas typical for tropical surface water masses are not only reduced due to the tongue of cool water extending southwards along the coast, but they are also removed from the coastal zone by the upwelling subsurface water masses carrying their own shell and skeleton assemblages. Tropical water masses contain much more shelland skeleton-producing plankters than subtropical and temperate ones. The climatic conditions found at different latitudes control the development and intensity of a separate continental coastal water mass with its own plankton assemblages. Extent of this water mass and steepness of gradients between the pelagic and coastal environment limit the occurrence of pelagic plankton close to the continental coast. A similar water mass in only weakly developed off oceanic islands.

Planktic foraminiferal abundance and stable oxygen isotope ratios of sediment cores from the Southern California Borderlands

A variety of evidence suggests that average sea surface temperatures (SSTs) during the last glacial maximum in the California Borderlands region were significantly colder than during the Holocene. Planktonic foraminiferal delta18O evidence and average SST estimates derived by the modern analog technique indicate that temperatures were 6°-10°C cooler during the last glacial relative to the present. The glacial plankton assemblage is dominated by the planktonic foraminifer Neogloboquadrina pachyderma (sinistral coiling) and the coccolith Coccolithus pelagicus, both of which are currently restricted to subpolar regions of the North Pacific. The glacial-interglacial average SST change determined in this study is considerably larger than the 2°C change estimated by Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP) [1981]. We propose that a strengthened California Current flow was associated with the advance of subpolar surface waters into the Borderlands region during the last glacial.

Hexachlorocyclohexanes concentration in air and ocean water

Hexachlorocyclohexanes (HCHs) are ubiquitous organic pollutants derived from pesticide application. They are subject to long-range transport, persistent in the environment, and capable of accumulation in biota. Shipboard measurements of HCH isomers (a-, b- and g-HCH) in surface seawater and boundary layer atmospheric samples were conducted in the Atlantic and the Southern Ocean in October to December of 2008. SumHCHs concentrations (the sum of a-, g- and b-HCH) in the lower atmosphere ranged from 12 to 37 pg/m**3 (mean: 27 ± 11 pg/m**3) in the Northern Hemisphere (NH), and from 1.5 to 4.0 pg/m**3 (mean: 2.8 ± 1.1 pg/m**3) in the Southern Hemisphere (SH), respectively. Water concentrations were: a-HCH 0.33-47 pg/l, g-HCH 0.02-33 pg/l and b-HCH 0.11-9.5 pg/l. Dissolved HCH concentrations decreased from the North Atlantic to the Southern Ocean, indicating historical use of HCHs in the NH. Spatial distribution showed increasing concentrations from the equator towards North and South latitudes illustrating the concept of cold trapping in high latitudes and less interhemispheric mixing process. In comparison to concentrations measured in 1987-1999/2000, gaseous HCHs were slightly lower, while dissolved HCHs decreased by factor of 2-3 orders of magnitude. Air-water exchange gradients suggested net deposition for a-HCH (mean: 3800 pg/m**2/day) and g-HCH (mean: 2000 pg/m**2/day), whereas b-HCH varied between equilibrium (volatilization: <0-12 pg/m**2/day) and net deposition (range: 6-690 pg/m**2/day). Climate change may significantly accelerate the release of "old" HCHs from continental storage (e.g. soil, vegetation and high mountains) and drive long-range transport from sources to deposition in the open oceans. Biological productivities may interfere with the air-water exchange process as well. Consequently, further investigation is necessary to elucidate the long term trends and the biogeochemical turnover of HCHs in the oceanic environment.

Atmospheric concentrations of organic pollutants in the Arctic between 1993-2006

Continuous and comparable atmospheric monitoring programs to study the transport and occurrence of persistent organic pollutants (POPs) in the atmosphere of remote regions is essential to better understand the global movement of these chemicals and to evaluate the effectiveness of international control measures. Key results from four main Arctic research stations, Alert (Canada), Pallas (Finland), Storhofdi (Iceland) and Zeppelin (Svalbard/Norway), where long-term monitoring have been carried out since the early 1990s, are summarized. We have also included a discussion of main results from various Arctic satellite stations in Canada, Russia, US (Alaska) and Greenland which have been operational for shorter time periods. Using the Digital Filtration temporal trend development technique, it was found that while some POPs showed more or less consistent declines during the 1990s, this reduction is less apparent in recent years at some sites. In contrast, polybrominated diphenyl ethers (PBDEs) were still found to be increasing by 2005 at Alert with doubling times of 3.5 years in the case of deca-BDE. Levels and patterns of most POPs in Arctic air are also showing spatial variability, which is typically explained by differences in proximity to suspected key source regions and long-range atmospheric transport potentials. Furthermore, increase in worldwide usage of certain pesticides, e.g. chlorothalonil and quintozene, which are contaminated with hexachlorobenzene (HCB), may result in an increase in Arctic air concentration of HCB. The results combined also indicate that both temporal and spatial patterns of POPs in Arctic air may be affected by various processes driven by climate change, such as reduced ice cover, increasing seawater temperatures and an increase in biomass burning in boreal regions as exemplified by the data from the Zeppelin and Alert stations. Further research and continued air monitoring are needed to better understand these processes and its future impact on the Arctic environment.

Air concentration of polybrominated diphenyl ethers around the Great Lakes and the Arctic

Atmospheric PBDEs were measured on a monthly basis in 2002-2004 at Point Petre, a rural site in the Great Lakes. Average air concentrations were 7.0 ± 13 pg/m**3 for the sum of 14BDE (excluding BDE-209), and 1.8 ± 1.5 pg/m**3 for BDE-209. Concentrations of 3 dominant congeners (i.e., BDE-47, 99, and 209) were comparable to previous measurements at remote/rural sites around the Great Lakes, but much lower than those at urban areas. Weak temperature dependence and strong linear correlations between relatively volatile congeners suggest importance of advective inputs of gaseous species. The significant correlation between BDE-209 and 183 implies their transport inputs associated with particles. Particle-bound percentages were found greater for highly brominated congeners than less brominated ones. These percentages increase with decreasing ambient temperatures. The observed gas/particle partitioning is consistent with laboratory measurements and fits well to the Junge-Pankow model. Using air mass back-trajectories, atmospheric transport to Point Petre was estimated as 76% for BDE-47, 67% for BDE-99, and 70% for BDE-209 from west-northwest and southwest directions. During the same time period, similar congener profiles and concentration levels were found at Alert in the Canadian High Arctic. Different inter-annual variations between Point Petre and Alert indicate that emissions from other regions than North America could also contribute PBDEs in the Arctic. In contrast to weak temperature effect at Point Petre, significant temperature dependence in the summertime implies volatilization emissions of PBDEs at Alert. Meanwhile, episodic observations in the wintertime were likely associated with enhanced inputs through long-range transport during the Arctic Haze period.

Stable isotope data of sediment cores in the western equatorial Atlantic

In order to reconstruct hydrographic changes during glacial-interglacial cycles for a transequatorial transect we analyzed oxygen isotopes of Globigerinoides sacculifer (without sac-like chamber) and abundances of Globorotalia truncatulinoides (dextral) from FS Meteor cores GeoB 2204-2 (Brazilian continental slope) and GeoB 1523-1 (Ceara Rise). Delta d18O values of G. sacculifer between the two cores were calculated. Modern Delta d18O (G. sacculifer) is ~0.2 per mill between the two core positions, reflecting differences in sea surface salinity (SSS). Higher SSS at GeoB 1523-1 (Ceara Rise) is the result of increased precipitation in the region of the Intertropical Convergence Zone. During glacials the ?18O records from the two cores converge to the same absolute value, resulting in ??18O values of around 0 per mill. Maximum abundances of G. truncatulinoides (dex) correlate with minimum Delta d18O, suggesting a possible increase of SSS at GeoB 1523-1 during stages 2, 3, 4, and 6, which is related to a glacial weakening of the tropical Hadley Cell [Gates, 1976]. Variations in tropical sea surface temperatures are assumed to be low [Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP), 1981].