Patterns of Pacific decadal variability recorded by Indian Ocean corals

We investigate Pacific Decadal Oscillation (PDO) signals recorded by two bimonthly resolved coral δ¹⁸O series from La Réunion and Ifaty (West Madagascar), Indian Ocean from 1882 to 1993. To isolate the main PDO frequencies, we apply a band pass filter to the time series passing only periodicities from 16 to 28 years. We investigate the covariance patterns of the coral time series with sea surface temperature (SST) and sea level pressure (SLP) of the Indian and Pacific Oceans. In addition, the empirical orthogonal functions of the filtered SST and SLP fields (single and coupled) are related to the filtered coral times series. The covariance maps show the typical PDO pattern for SST and SLP, confirming the coupling between the Indian and Pacific Oceans. Both corals show the strongest signal in boreal summer. The La Réunion (Ifaty) coral better records SST (SLP) than SLP (SST) pattern variability. We suggest that the filtered La Réunion coral δ¹⁸O represents δ¹⁸O of seawater that varies with the South Equatorial Current, which, in turn, is linked with the SST PDO. The filtered Ifaty coral δ¹⁸O represents SST and is remotely linked with the SLP PDO variability. A combined coral record of the Ifaty and La Réunion boreal summer δ¹⁸O series explains about 64% of the variance of the coupled SST/SLP PDO time series. AGU OS06 special issue “Ocean’s role in climate change—a paleo perspective”.     

Molecular isotopic evidence of environmental and ecological changes across the Cenomanian–Turonian boundary in the Levant Platform of central Jordan

We evaluated the structure of planktonic communities and paleoenvironmental conditions throughout the Cenomanian–Turonian Oceanic Anoxic Event (OAE2) by studying bulk geochemical properties and the molecular isotopic composition of source-specific hydrocarbons from organic-rich sediments deposited in an intrashelf basin at the Levant Platform, central Jordan. High concentrations of desmethyl and 4-methylsteranes as well as dinosteranes indicate that marine algae including dinoflagellates were the main primary producing organisms. The presence of 2-methylhopanes and ¹³C-enriched hopanes, in addition to isotopically enriched aryl isoprenoids, evidenced the contribution of cyanobacteria and green sulfur bacteria, respectively. Additionally, variable but fairly low δ¹⁵N values during OAE2 suggest the occurrence of diazotrophy as a likely important process fueling primary production during OAE2 in this stratified/anoxic continental platform. Variations in the relative contribution of biomarkers revealed changes in planktonic communities associated with sea level change and water column stratification. OAE2 was characterized by strong stratification, anoxic bottom waters and a deep chemocline, as evidenced by high gammacerane and homohopane indices and the absence of photic zone euxinia (PZE) markers, respectively. However, the presence of isorenieratane and its derivatives in post-OAE black shales points to a shoaling of the chemocline and to PZE. This interval was also characterized by an exceptionally high abundance of chlorophyll-derived pristane and phytane (up to 2 mg g^?1 TOC), likely as a result of highly enhanced primary production and organic matter preservation. Remarkably, this high productivity event co-occurs with an exceptionally high abundance of calcispheres reported elsewhere to be part of a global bio-event.     

Aptian (Lower Cretaceous) biostratigraphy and cephalopods from north central Tunisia

Thick Aptian deposits in north central Tunisia comprise hemipelagic lower Aptian, reflecting the sea-level rise of OAE 1a, and an upper Aptian shallow marine environment characterized by the establishment of a carbonate platform facies. Carbon stable isotope data permit recognition of the OAE 1a event in the Djebel Serdj section. Cephalopods are rare throughout these successions, but occurrences are sufficient to date the facies changes and the position of the OAE1a event. Ammonite genera include lower Aptian Deshayesites, Dufrenoyia, Pseudohaploceras, Toxoceratoides and ?Ancyloceras; and upper Aptian Zuercherella, Riedelites and Parahoplites. Correlation of carbon isotope data with those of other Tethyan sections is undertaken together with the integration of planktonic foraminiferal data.     

Genesis of sediment-hosted stratiform copper–cobalt mineralization at Luiswishi and Kamoto, Katanga Copperbelt (Democratic Republic of Congo)

The sediment-hosted stratiform Cu–Co mineralization of the Luiswishi and Kamoto deposits in the Katangan Copperbelt is hosted by the Neoproterozoic Mines Subgroup. Two main hypogene Cu–Co sulfide mineralization stages and associated gangue minerals (dolomite and quartz) are distinguished. The first is an early diagenetic, typical stratiform mineralization with fine-grained minerals, whereas the second is a multistage syn-orogenic stratiform to stratabound mineralization with coarse-grained minerals. For both stages, the main hypogene Cu–Co sulfide minerals are chalcopyrite, bornite, carrollite, and chalcocite. These minerals are in many places replaced by supergene sulfides (e.g., digenite and covellite), especially near the surface, and are completely oxidized in the weathered superficial zone and in surface outcrops, with malachite, heterogenite, chrysocolla, and azurite as the main oxidation products. The hypogene sulfides of the first Cu–Co stage display δ³⁴S values (−10.3‰ to +3.1‰ Vienna Canyon Diablo Troilite (V-CDT)), which partly overlap with the δ³⁴S signature of framboidal pyrites (−28.7‰ to 4.2‰ V-CDT) and have ∆³⁴S_SO4-Sulfides in the range of 14.4‰ to 27.8‰. This fractionation is consistent with bacterial sulfate reduction (BSR). The hypogene sulfides of the second Cu–Co stage display δ³⁴S signatures that are either similar (−13.1‰ to +5.2‰ V-CDT) to the δ³⁴S values of the sulfides of the first Cu–Co stage or comparable (+18.6‰ to +21.0‰ V-CDT) to the δ³⁴S of Neoproterozoic seawater. This indicates that the sulfides of the second stage obtained their sulfur by both remobilization from early diagenetic sulfides and from thermochemical sulfate reduction (TSR). The carbon (−9.9‰ to −1.4‰ Vienna Pee Dee Belemnite (V-PDB)) and oxygen (−14.3‰ to −7.7‰ V-PDB) isotope signatures of dolomites associated with the first Cu–Co stage are in agreement with the interpretation that these dolomites are by-products of BSR. The carbon (−8.6‰ to +0.3‰ V-PDB) and oxygen (−24.0‰ to −10.3‰ V-PDB) isotope signatures of dolomites associated with the second Cu–Co stage are mostly similar to the δ¹³C (−7.1‰ to +1.3‰ V-PDB) and δ¹⁸O (−14.5‰ to −7.2‰ V-PDB) of the host rock and of the dolomites of the first Cu–Co stage. This indicates that the dolomites of the second Cu–Co stage precipitated from a high-temperature, host rock-buffered fluid, possibly under the influence of TSR. The dolomites associated with the first Cu–Co stage are characterized by significantly radiogenic Sr isotope signatures (0.70987 to 0.73576) that show a good correspondence with the Sr isotope signatures of the granitic basement rocks at an age of ca. 816 Ma. This indicates that the mineralizing fluid of the first Cu–Co stage has most likely leached radiogenic Sr and Cu–Co metals by interaction with the underlying basement rocks and/or with arenitic sedimentary rocks derived from such a basement. In contrast, the Sr isotope signatures (0.70883 to 0.71215) of the dolomites associated with the second stage show a good correspondence with the ⁸⁷Sr/⁸⁶Sr ratios (0.70723 to 0.70927) of poorly mineralized/barren host rocks at ca. 590 Ma. This indicates that the fluid of the second Cu–Co stage was likely a remobilizing fluid that significantly interacted with the country rocks and possibly did not mobilize additional metals from the basement rocks.     

Sulfur isotope characteristics of metamorphosed Zn–Cu volcanogenic massive sulfides in the Areachap Group, Northern Cape Province, South Africa

Zn- and Cu-rich massive sulfide ores of volcanogenic origin [volcanogenic massive sulfide (VMS) deposits] occur as stratiform/stratabound lenses of variable size hosted by gneisses, amphibolites, and schists of the Areachap Group, in the Northern Cape Province of South Africa. The Areachap Group represents the highly deformed and metamorphosed remnants of a Mesoproterozoic volcanic arc that was accreted onto the western margin of the Kaapvaal Craton during the ∼1.0–1.2 Ga Namaquan Orogeny. Sulfur isotope data (δ³⁴S) are presented for 57 sulfide separates and one barite sample from five massive sulfide occurrences in the Areachap Group. Although sulfides from each site have distinct sulfur isotope values, all δ³⁴S values fall within a very limited range (3.0‰ to 8.5‰). Barite has a δ³⁴S value of 18.5‰, very different from that of associated sulfides. At one of the studied sites (Kantienpan), a distinct increase in δ³⁴S of sulfides is observed from the massive sulfide lens into the disseminated sulfides associated with a distinct footwall alteration zone. Sulfide–sulfide and sulfide–barite mineral pairs which recrystallized together during amphibolite- and lower granulite facies metamorphism are not in isotopic equilibrium. Sulfur isotope characteristics of sulfides and sulfates of the Zn–Cu ores in the Areachap Group are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and unsedimented mid-ocean ridges. It is thus concluded that profound recrystallization and textural reconstitution associated with high-grade regional metamorphism of the massive sulfide ores of the Areachap Group did not result in extensive sulfur isotopic homogenization. This is similar to observations in other metamorphosed VMS deposit districts and confirms that massive sulfide ores remain effectively a closed system for sulfur isotopes for both sulfides and sulfates during metamorphism.     

The impact of Eurasian dust storms and anthropogenic emissions on atmospheric nutrient deposition rates in forested Japanese catchments and adjacent regional seas

Bulk precipitation and stream water chemistry data from 1993 to 2005 are used to analyze the relationship between Eurasian dust storms and nutrient deposition rates in the Kutsuki experimental forest (near Lake Biwa). From 2000 to 2005, atmospheric deposition, total nitrogen (TN), total phosphorus (TP) and dissolved silica (DSi) deposition rates increased by 26%, 132%, and 38%, respectively in the Kutsuki experimental forest. These TN and TP increases are associated with three seasonal factors: the increasing frequency and intensity of Eurasian spring dust events (March/April); the annual typhoon period (late August/September); and autumn/early winter (October to December) monsoons. The annual typhoon and monsoon winter periods are drivers for atmospheric TP and DSi deposition due to the correlation between the deposition and precipitation. In addition, increased spring dust deposition is a primarily driver for TN deposition changes. Increased emissions from urbanized areas in China (and likely Korea) affect the chemical properties of aerosols reaching downwind Japanese regions. Aerosol processes are responsible for increasing TN in aerosols, which are affected primarily by anthropogenic emissions. From 2000 to 2005, coal burning emissions from East Asia have contributed to an increase in TP (and possibly DSi) deposition rates. The observed increase in nutrient deposition did not noticeably impact short-term (5 year) stream water fluxes in the Kutsuki experimental forest. Due to plant uptake, the forest ecosystem retained atmospherically deposited N and P. Finally, the observed increases in nutrient deposition rates over the East China Sea and the Sea of Japan may significantly influence intra-annual net primary production. It is recommended that earth system modelling incorporate changes in atmospheric nutrient deposition rates and their impacts on the regional carbon cycle as well as aquatic and terrestrial ecosystems.     

Spatiotemporal variation of stable isotopic composition in precipitation: Post‐condensational effects in a humid area

In the present study, a 2‐year dataset on δ¹⁸O and δ²H in precipitation is used to investigate hydrometeorologic controls on the isotopic compositions in a temperate maritime climate. Data was collected in Denmark along a transect of Six sampling stations across a landscape with a small topographic gradient and predominant westerly winds. Data showed the local meteoric water line for this region is expressed by the equation δ²H = 7.4δ¹⁸O + 5.4‰. A significant trend correlating enriched isotopic values to humidities around 70% during dry season and more depleted isotopic values to humidities around 90% during wet season was derived from the dataset. Temperature was found to only influence the isotopic composition in a secondary way, whereas no significant relationship was obtained for precipitation amount and evapotranspiration. It is suggested that subcloud post‐condensation exchange strongly influences the isotopic composition at the study site. A simple model of evaporation on falling rain was applied with the aim to reproduce observational data and show the potential influence of changing humidity conditions on precipitation compositions. The rather simple model approach did not fully explain the observational data, but it highlights the drastic isotopic changes from a falling raindrop that potentially can occur due to its release into a dryer atmosphere. This study shows that regional conditions and especially humidity can alter the isotopic composition in precipitation substantially even in regions without major topographic and hydrometeorologic gradients.     

Changes in dissolved silica mobilization into river systems draining North America until the period 2081–2100

Dissolved silica (DSi) is an important control on algae abundance and species composition both in freshwater and marine ecosystems. Although continental and global budgets for DSi exist, understanding of the spatial variability of DSi cycles needs to be improved on those scales. In this study, an empirical model of DSi mobilization into river systems is extrapolated on a 1.4 km² grid to North America. To analyze changes in DSi mobilization patterns, DSi mobilization is estimated regionally for present day runoff and a runoff projection ensemble for the period 2081–2100. The model predicts present day annual DSi fluxes for the monitored area within 6% of the calculated fluxes. Possible biases by processes not directly represented by applied geodata are discussed (e.g. land use and ecosystem influences) and found to be only minor on the regional scale. Uncertainty of the results is discussed based on a literature review. The projected DSi-mobilization rates at high latitudes for the present day conditions may be overestimated. However, the projected change rate for the period 2081–2100 might even be underestimated, due to e.g. increased thawing in certain permafrost regions, which was not included in the model.     

Coupling spatial geochemical and lithological information to distinguish silicate and non-silicate chemical weathering fluxes

Lithological maps have been proved to be a useful tool to evaluate regional and global matter fluxes from chemical weathering. However, lithological classes provide aggregated information of mineralogical, geochemical, sedimentary or diagenetic properties. Thus, using a limited number of lithological classes introduces by their definition a bias to the analysis of weathering fluxes, specifically in the case of multilithological catchments. Here it is shown that the coupling of geochemical with lithological information may help to better identify the sources of the weathering fluxes, using the example of dissolved Ca to better distinguish weathering rates of silicate and non-silicate minerals.