The influence of the organic aerosol component on CCN supersaturation spectra for different aerosol types

Abstract This paper describes the effect of the presence of water-soluble organic compounds (WSOC) in aerosol particles on the aerosol critical supersaturation as defined by the Köhler theory and on cloud condensation nuclei (CCN) number concentration. Taking into account both the soluble mass increase and the surface tension depression due to WSOC, we calculated a substantial decrease of the aerosol critical supersaturation, which results in a large increase in CCN number concentration. CCN supersaturation spectra were computed for three different aerosol types: marine, rural and urban. The increase of CCN number concentration in the presence of WSOC (with respect to the case when only the inorganic aerosol compounds are considered) varies with aerosol type, with an increase up to 13% in the marine case, up to 97% in the rural case, and up to 110% in the urban case, for the supersaturation range typical of atmospheric conditions.     

Applying the bootstrap technique for studying soil redistribution by caesium-137 measurements at basin scale

Abstract

The use of the bootstrap technique to estimate the reference level of¹³⁷ Cs in an uneroded site is tested. The analysis is developed using ¹³⁷Cs measurements made in a small experimental Sicilian basin. In the reference area the ¹³⁷Cs activity is normally distributed with a known sample mean value, m equal to 94.4 mBq cm^?2. The influence of¹³⁷ Cs reference site sampling was determined generating samples having a fixed size, N and six different values of the sample coefficient of variation, CV, by a Monte Carlo technique. Then, for each size N, the probability distribution of the mean μ of the sequences generated by Monte Carlo technique is defined. The soil redistribution is determined, both at morphological unit and basin scale, using the proportional method of Martz & de Jong for calculating the net soil loss. The analysis showed that the spatial distribution of the net soil loss E _i, and the basin value E _b are independent of the sample size, N, and the coefficient of variation, CV, of the samples drawn from the reference area, if the bootstrap technique is applied for estimating the mean μ(μ) to use as reference value. The soil redistribution is also examined using as reference value the quantiles μ2.5, μ25, μ75, μ97.5 corresponding to a frequency F(μ) equal to 2.5, 25, 75 and 97.5%, respectively. In conclusion, the analysis established that a robust estimate of the reference value can be obtained even in fields where a small number of samples was drawn (high CV of the ¹³⁷Cs activity of the field samples), using the bootstrap technique for generating sequences of reference values having known mean value m (the mean value of the ¹³⁷Cs activity of the drawn field samples) and large sample size (N = 50).     

Evidence of Saharan dust in upper Pleistocene reworked palaeosols of North‐west Sardinia,Italy: palaeoenvironmental implications

A multi‐disciplinary approach was followed to investigate two thick palaeosol strata that alternate with wind‐blown dominated deposits developed along the Alghero coast (North‐west Sardinia, Italy). Optically stimulated luminescence ages reveal that both palaeosols were developed during cooler drier periods: the first one at around 70 ka Marine Isotope Stage 4 and the latter around 50 ka (Marine Isotope Stage 3). In contrast, the pedological features indicate that the palaeosols underwent heavy weathering processes under warm humid to sub‐humid conditions, characteristic of the Sardinian climate during the last interglacial stage (Marine Isotope Stage 5e). To reconcile this apparent data discrepancy, a range of sedimentological and pedological analyses were conducted. These analyses reveal that the palaeosols possess a complex history, with accumulation and weathering occurring during Marine Isotope Stage 5e, and erosion, colluviation and final deposition taking place during the following cold stages. Thus, even if these reddish palaeosols were last formed during the glacial period, the sediments building up these strata probably record the climate of the last interglacial stage (Marine Isotope Stage 5e). Trace element and X‐ray diffraction analyses, together with scanning electron microscope images, reveal the presence of Saharan dust in the parent material of the palaeosols. However, no evidence of any far‐travelled African dust has been observed in the Marine Isotope Stage 4–3 aeolian deposits. It is possible to conclude that in the West Mediterranean islands, Saharan dust input, even if of modest magnitude, is preserved preferentially in soils accumulated and weathered during interglacial stages.     

Evolution of the Nile deep‐sea turbidite system during the Late Quaternary: influence of climate change on fan sedimentation

This paper presents an overview of the evolution of the Nile deep‐sea turbidite system during the last 200 kyr, over a series of glacial to interglacial cycles. Six individual deep‐sea fans were identified from an extensive field data set. Each fan comprises a canyon, channel system and terminal lobes. Two of these fan systems were possibly active at the same time, at least during some periods. Large‐scale slope failures destroyed channel segments and caused the formation of new submarine fan systems. These slope failures thus played an important role in the overall evolution of the turbidite system. During the last glacial maximum (ca 25 to 14·8 ka) the central and eastern parts of the Nile deep‐sea turbidite system were relatively inactive. This inactivity corresponds to a lowstand in sea‐level, and a period of arid climate and relatively low sediment discharge from the Nile fluvial system. Rapid accumulation of fluvial flood‐derived deposits occurred across the shallower part of the submarine delta during sea‐level rise between ca 14·8 and 5 ka. The most recent deep‐sea channel–lobe system was very active during this period of rising sea‐level, which is also associated with a wetter continental climate and increased sediment and water discharge from the Nile. Increased sediment deposition in shallower water areas led to occasional large‐scale slope failure. The Nile deep‐sea turbidite system was largely inactive after ca 5 ka. This widespread inactivity is due to retreat of the coastline away from the continental shelf break, and to a more arid continental climate and reduced discharge of sediment from the Nile. The Nile deep‐sea turbidite system may be more active during periods of rising and high sea‐level associated with wetter climates, than during lowstands, and may rapidly become largely inactive during highstands in sea‐level coupled with arid periods. These acute responses to climate change have produced sedimentary/stratigraphic features that diverge from traditional sequence models in their nature and timing. This large‐scale sedimentary system responded to monsoon‐driven climate change and sea‐level change in a system‐wide and contemporaneous manner.     

Dolomite formation in the dynamic deep biosphere: results from the Peru Margin

Early diagenetic dolomite beds were sampled during the Ocean Drilling Programme (ODP) Leg 201 at four reoccupied ODP Leg 112 sites on the Peru continental margin (Sites 1227/684, 1228/680, 1229/681 and 1230/685) and analysed for petrography, mineralogy, δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values. The results are compared with the chemistry, and δ¹³C and ⁸⁷Sr/⁸⁶Sr values of the associated porewater. Petrographic relationships indicate that dolomite forms as a primary precipitate in porous diatom ooze and siliciclastic sediment and is not replacing the small amounts of precursor carbonate. Dolomite precipitation often pre‐dates the formation of framboidal pyrite. Most dolomite layers show ⁸⁷Sr/⁸⁶Sr‐ratios similar to the composition of Quaternary seawater and do not indicate a contribution from the hypersaline brine, which is present at a greater burial depth. Also, the δ¹³C values of the dolomite are not in equilibrium with the δ¹³C values of the dissolved inorganic carbon in the associated modern porewater. Both petrography and ⁸⁷Sr/⁸⁶Sr ratios suggest a shallow depth of dolomite formation in the uppermost sediment (<30 m below the seafloor). A significant depletion in the dissolved Mg and Ca in the porewater constrains the present site of dolomite precipitation, which co‐occurs with a sharp increase in alkalinity and microbial cell concentration at the sulphate–methane interface. It has been hypothesized that microbial ‘hot‐spots’, such as the sulphate–methane interface, may act as focused sites of dolomite precipitation. Varying δ¹³C values from −15‰ to +15‰ for the dolomite are consistent with precipitation at a dynamic sulphate–methane interface, where δ¹³C of the dissolved inorganic carbon would likewise be variable. A dynamic deep biosphere with upward and downward migration of the sulphate–methane interface can be simulated using a simple numerical diffusion model for sulphate concentration in a sedimentary sequence with variable input of organic matter. Thus, the study of dolomite layers in ancient organic carbon‐rich sedimentary sequences can provide a useful window into the palaeo‐dynamics of the deep biosphere.     

Depth and controls of Ca-rhodochrosite precipitation in bioturbated sediments of the Eastern Equatorial Pacific, ODP Leg 201, Site 1226 and DSDP Leg 68, Site 503

The occurrence of early diagenetic Ca‐rhodochrosite [(Mn,Ca)CO₃] is reported in association with ‘griotte’‐type nodular limestones from basinal settings in the geological record; however, without the comparison of analogous modern examples, the controls on precipitation remain speculative. Here the findings of four layers of primary Ca‐rich rhodochrosite recovered from a modern deep‐sea setting in the Eastern Equatorial Pacific, from bioturbated sediments 300 m below sea floor, are reported (Ocean Drilling Program, Leg 201, Site 1226). The mineralogy is similar to cements in burrows recovered during Deep Sea Drilling Project Leg 68 at Eastern Equatorial Pacific Site 503 and from Ca‐rhodochrosite laminae in sediments of the central Baltic Sea. Petrographic relationships and constant oxygen isotopic compositions in the Ca‐rhodochrosite around 5‰ at all depths indicate a shallow burial depth of formation. The onset of 1‰ heavier oxygen isotope composition of Ca‐rhodochrosite at Site 503, about 30 m below the Pliocene/Pleistocene boundary, further suggests that precipitation occurs in the range of 30 m below sea floor. The approximate depth of formation allowed an approximate empirical fractionation factor for marine Ca‐rhodochrosite to be constrained that strongly differs from previously published theoretical values. Based on the approximate precipitation depth, authigenic Ca‐rhodochrosite forms within the SO₄^2?‐reduction zone. Moderately negative δ¹³C values (around ?3‰) and total organic carbon lower than 2 wt% indicate a relatively low contribution of CO₃^2? from organic C mineralization within the expanded redox zonation in the Eastern Equatorial Pacific. It is suggested that the alkalinity is increased by a rise in pH at focused sites of Mn‐reduction coupled with S^2? oxidation. High concentrations of Mn‐oxide can accumulate in layers or burrows because of Mn‐cycling in suboxic sediments as suggested for the Baltic Sea Ca‐rhodochrosites. This study demonstrates how early diagenetic precipitates document biogeochemical processes from past diagenetic systems.     

A new facies model for the Upper Gypsum of Sicily (Italy): chronological and palaeoenvironmental constraints for the Messinian salinity crisis in the Mediterranean

The Upper Gypsum unit of the Caltanissetta Basin (Sicily) records the last phase of the Messinian salinity crisis comprising the so‐called ‘Lago Mare’ event. A new facies analysis study recognizes nine to ten depositional cycles consisting of seven rhythmically interbedded primary gypsum bodies, and two to three sandstone bodies separated by marly terrigenous horizons showing laterally persistent vertical organization. A basal thin gypsum bed is overlain by a cluster of five thicker gypsum bodies. A marly interval containing two distinct sandstone horizons separates this cluster from the overlying uppermost (seventh) gypsum body. The terrigenous Arenazzolo Formation, in turn followed by the lower Pliocene Trubi Formation, is considered here to form the uppermost part of the Upper Gypsum unit. The rhythmic alternation in the sandy marls and gypsum/sandstone bodies records the response of sediments from shelfal to deltaic systems to precession‐driven arid‐wet climate fluctuations causing cyclical changes of both base‐level and water concentration. During wet climate phases (at insolation maxima) marl and sandstone were deposited in a hypohaline environment as suggested by: (i) the typical Lago Mare faunal assemblage and (ii) the negative δ¹⁸O values. During arid phases (at insolation minima) the reduced meteoric supply, recorded by higher δ¹⁸O values in the carbonate, caused the development of a negative hydrological budget leading to evaporite precipitation. At a basinal scale the Upper Gypsum unit unconformably overlies a mainly clastic evaporite unit containing carbonate breccia (the so‐called ‘Calcare di Base’) and/or clastic gypsum. Towards the basin centres, where the basal contact becomes conformable, a primary gypsum cumulate horizon is present. This layer is interpreted as a possible lateral equivalent of the Halite unit present only in the deepest depocentres. Based on astronomical calibration of the depositional cycles, the Upper Gypsum unit, including the Arenazzolo Formation, spans the interval between 5·33 and 5·53 Ma. This new age calibration allows the deposition of the Halite unit to be dated between 5·6 Ma (top of the Lower Evaporites) and 5·55 Ma (base of the Upper Evaporites) corresponding to isotopic stages TG12 and/or TG14.     

Dolomite formation within microbial mats in the coastal sabkha of Abu Dhabi (United Arab Emirates)

Microbial mediation is the only demonstrated mechanism to precipitate dolomite under Earth surface conditions. A link between microbial activity and dolomite formation in the sabkha of Abu Dhabi has, until now, not been evaluated, even though this environment is cited frequently as the type analogue for many ancient evaporitic sequences. Such an evaluation is the purpose of this study, which is based on a geochemical and petrographic investigation of three sites located on the coastal sabkha of Abu Dhabi, along a transect from the intertidal to the supratidal zone. This investigation revealed a close association between microbial mats and dolomite, suggesting that microbes are involved in the mineralization process. Observations using scanning electron microscopy equipped with a cryotransfer system indicate that authigenic dolomite precipitates within the exopolymeric substances constituting the microbial mats. In current models, microbial dolomite precipitation is linked to an active microbial activity that sustains high pH and alkalinity and decreased sulphate concentrations in pore waters. Such models can be applied to the sabkha environment to explain dolomite formation within microbial mats present at the surface of the intertidal zone. By contrast, these models cannot be applied to the supratidal zone, where abundant dolomite is present within buried mats that no longer show signs of intensive microbial activity. As no abiotic mechanism is known to form dolomite at Earth surface conditions, two different hypotheses can reconcile this result. In a first scenario, all of the dolomite present in the supratidal zone formed in the past, when the mats were active at the surface. In a second scenario, dolomite formation continues within the buried and inactive mats. In order to explain dolomite formation in the absence of active microbial metabolisms, a revised microbial model is proposed in which the mineral‐template properties of exopolymeric substances play a crucial role.