Ba/Ca ratios in benthic foraminifera from recent core tops

The carbon isotope ratio (delta13C) and cadmium content (Cd/Ca) of benthic foraminifera shells have been used to reconstruct deep-water circulation patterns of the glacial oceans. These tracers co-vary with phosphorus in the modern ocean because they are nearly quantitatively regenerated from sinking biological debris in the upper water column. Hence they can be used to reconstruct the distribution of labile nutrients in glacial water masses. Independent constraints on glacial deep-ocean circulation patterns could be provided by a tracer of the distribution of silica and alkalinity, the deeply regenerated constituents of planktonic hard parts. Barium shares key aspects of its behaviour with these refractory nutrients because it is removed from solution in surface waters and incorporated into sinking particles which slowly dissolve deep in the water column and in the sediments. The fractionation of Ba between deep-water masses of the major ocean basins is largely controlled by thermohaline circulation patterns, so Ba conforms to different boundary conditions from Cd and 13C. As Ba substitutes into trigonal carbonates, it is a potential palaeoceano-graphic tracer if the Ba content of foraminifera shells reflects ambient dissolved Ba concentrations. Here we present data from Recent core-top benthic foraminifera which indicate that the Ba content of some recent calcitic benthic foraminifera does co-vary with bottom-water Ba.

Comparison of Ba/Ca and d18OWATER as freshwater proxies: a multi-species core-top study on planktonic foraminifera from the vicinity of the Orinoco River mouth

Past river run-off is an important measure for the continental hydrological cycle and the as-sessment of freshwater input into the ocean. However, paleosalinity reconstructions applying different proxies in parallel often show offsets between the respective methods. Here, we compare the established foraminiferal Ba/Ca and d18OWATER salinity proxies for their capability to record the highly seasonal Orinoco freshwater plume in the eastern Caribbean. For this purpose we obtained a data set comprising Ba/Ca and d18OWATER determined on multiple spe-cies of planktonic foraminifera from core tops distributed around the Orinoco river mouth. Our findings indicate that interpretations based on either proxy could lead to different conclu-sions. In particular, Ba/Ca and d18OWATER diverge in their spatial distribution due to different governing factors. Apparently, the Orinoco freshwater plume is best tracked by Ba/Ca ratios of G. ruber (pink and sensu lato morphotypes), while d18OWATER based on the same species is more related to the local precipitation-evaporation balance overprinting the riverine freshwater contribution. Other shallow dwelling species (G. sacculifer, O. universa) show a muted response to the freshwater discharge, most likely due to their ecological and habitat prefer-ences. Extremely high Ba/Ca ratios recorded by G. ruber are attributed to Ba2+-desorption from suspended matter derived from the Orinoco. Samples taken most proximal to the freshwater source do not show pronounced Ba/Ca or d18OWATER anomalies. Here, the suspension loaded freshwater lid developing during maximum discharge suppresses foraminiferal populations. Both proxies are therefore biased towards dry season conditions at these sites, when surface salinity is only minimally reduced.

Stable isotopes and Mg/Ca ratios on foraminifera and Ba/Ca ratios of sediment core SK168/GC-1

The past variability of the South Asian Monsoon is mostly known from records of wind strength over the Arabian Sea while high-resolution paleorecords from regions of strong monsoon precipitation are still lacking. Here, we present records of past monsoon variability obtained from sediment core SK 168/GC-1, which was collected at the Alcock Seamount complex in the Andaman Sea. We utilize the ecological habitats of different planktic foraminiferal species to reconstruct freshwater-induced stratification based on paired Mg/Ca and d18O analyses and to estimate seawater d18O (d18Osw). The difference between surface and thermocline temperatures (delta T) and d18Osw (delta d18Osw) is used to investigate changes in upper ocean stratification. Additionally, Ba/Ca in G. sacculifer tests is used as a direct proxy for riverine runoff and sea surface salinity (SSS) changes related to monsoon precipitation on land. Our delta d18Osw time series reveals that upper ocean salinity stratification did not change significantly throughout the last glacial suggesting little influence of NH insolation changes. The strongest increase in temperature gradients between the mixed layer and the thermocline is recorded for the mid-Holocene and indicate the presence of a significantly shallower thermocline. In line with previous work, the d18Osw and Ba/Ca records demonstrate that monsoon climate during the LGM was characterized by a significantly weaker southwest monsoon circulation and strongly reduced runoff. Based on our data the South Asian Summer Monsoon (SAM) over the Irrawaddyy strengthened gradually after the LGM beginning at ~18 ka. This is some 3 kyrs before an increase of the Ba/Ca record from the Arabian Sea and indicates that South Asian Monsoon climate dynamics are more complex than the simple N-S displacement of the ITCZ as generally described for other regions. Minimum d18Osw values recorded during the mid-Holocene are in phase with Ba/Ca marking a stronger monsoon precipitation, which is consistent with model simulations.

(Table 2) Ba/Ca ratios of Cibicides wuellerstorfi and Orbulina universa from Bahaman sediment cores

This geochemical investigation utilizes Ba/Ca in the benthic foraminifer Cibicides wuellerstorfi from cores taken from the Bahama Banks and the Caribbean Sea to reconstruct changes in basal thermocline ventilation (800-1000 m) and middepth thermohaline circulation (1000-2000 m) in the western North Atlantic during the last glacial period, focusing on the deglacial transition. Previous studies show that an increase in ventilation of the North Atlantic subtropical gyre during the Last Glacial Maximum (LGM) caused a 30-60% decrease in labile nutrients within the thermocline layer. Using foraminiferal Ba/Ca as a proxy of refractory nutrients, increased ventilation during the LGM produced a depletion of less than 20% compared to Holocene values. Following glaciation, the production of Glacial North Atlantic Intermediate Water (GNAIW) shut down owing to the presence of meltwater in the surface ocean, which resulted in a decrease in ventilation, as seen by an enrichment of barium in the basal thermocline. GNAIW was subsequently replaced by barium-rich southern component water in the middepth western North Atlantic. Foraminiferal Ba/Ca data suggest a 38% contribution from southern component water to a depth as shallow as 1475 m and a 14% contribution at 1123 m during deglaciation.

Table 2. Lead and Ba concentrations and Pb isotopic compositions measured in Law Dome ice cores

Lead isotopic compositions and Pb and Ba concentrations have been measured in ice cores from Law Dome, East Antarctica, covering the past 6500 years. 'Natural' background concentrations of Pb (ab. 0.4 pg/g) and Ba (ab. 1.3 pg/g) are observed until 1884 AD, after which increased Pb concentrations and lowered 206Pb/207Pb ratios indicate the influence of anthropogenic Pb. The isotopic composition of 'natural' Pb varies within the range 206Pb/207Pb=1.20-1.25 and 208Pb/207Pb=2.46-2.50, with an average rock and soil dust Pb contribution of 8-12%. A major pollution event is observed at Law Dome between 1884 and 1908 AD, elevating the Pb concentration four-fold and changing 206Pb/207Pb ratios in the ice to ab. 1.12. Based on Pb isotopic systematics and Pb emission statistics, this is attributed to Pb mined at Broken Hill and smelted at Broken Hill and Port Pirie, Australia. Anthropogenic Pb inputs are at their greatest from 1900 to 1910 and from ab. 1960 to ab. 1980. During the 20th century, Ba concentrations are consistently higher than 'natural' levels and are attributed to increased dust production, suggesting the influence of climate change and/or changes in land coverage with vegetation.

Victoria Land Antarctica Pb and Ba concentrations and Pb isotope ratios 1872-1994 CE

Pb and Ba concentrations and Pb isotopic compositions are reported for firn core and snow pit samples from Victoria Land, Antarctica, dating from 1872 AD to 1994 AD. From variations in Pb/Ba ratios and Pb isotopic compositions, two periods of major Pb enhancements were identified, from 1891 to 1908 AD and from 1948 to 1994 AD. The earlier pollution event is attributed to Pb emissions from non-ferrous metal production and coal combustion in the Southern Hemisphere and is in excellent agreement with coincident pollution inputs reported in firn/ice cores from two other regions of Antarctica, at Coats Land and Law Dome. Using Pb isotopic systematics, it was calculated that ~50% of Pb deposited in Victoria Land in 1897 originated from anthropogenic emission sources. The more recent period of Pb enhancements, from 1948 to 1994 AD, corresponds to the introduction and widespread use of gasoline alkyl Pb additives in automobiles in the Southern Hemisphere, with anthropogenic Pb inputs averaging 60% of total Pb but with large uncertainty. Intra- and inter-annual variations in Pb concentrations and isotopic compositions were evaluated in snow pits samples corresponding to the period 1991-1994. Substantial variations in Pb/ Ba and 206Pb/207Pb ratios were detected but the absence of a regular seasonal pattern for these parameters suggests that the transport and deposition of aerosols to the Antarctic ice sheet are complex and vary from year to year.

Pb and Ba concentrations and Pb isotope ratios in EPICA Dome C ice 2-217 ky BP

A record of Pb isotopic compositions and Pb and Ba concentrations are presented for the EPICA Dome C ice core covering the past 220 ky, indicating the characteristics of dust and volcanic Pb deposition in central East Antarctica. Lead isotopic compositions are also reported in a suite of soil and loess samples from the Southern Hemisphere (Australia, Southern Africa, Southern South America, New Zealand, Antarctica) in order to evaluate the provenance of dust present in Antarctic ice. Lead isotopic compositions in Dome C ice support the contention that Southern South America was an important source of dust in Antarctica during the last two glacial maxima, and furthermore suggest occasional dust contributions from local Antarctic sources. The isotopic signature of Pb in Antarctic ice is altered by the presence of volcanic Pb, inhibiting the evaluation of glacial-interglacial changes in dust sources and the evaluation of Australia as a source of dust to Antarctica. Consequently, an accurate evaluation of the predominant source(s) of Antarctic dust can only be obtained from glacial maxima, when dust-Pb concentrations were greatest. These data confirm that volcanic Pb is present throughout Antarctica and is emitted in a physical phase that is free from Ba, while dust Pb is transported within a matrix containing Ba and other crustal elements.