Dissolved Ba Concentrations Research Articles

Dissolved Barium Causes Toxicity to Groundwater Cyclopoida.

Barium (Ba) dissolution and mobilization in groundwater are predominantly controlled by sulfate because of the low solubility of barium sulfate (BaSO4) minerals. Naturally present at low concentrations in groundwater, elevated concentrations of Ba can occur as a result of anthropogenic activities, including use of barite in drill operations, and geogenic sources such as leaching from geological formations. No toxicity data exist for Ba with groundwater organisms (stygofauna) to assess the risk of elevated Ba concentrations. The present study measured Ba toxicity to two stygobiont Cyclopoida species: one collected from Wellington and the other from Somersby, New South Wales, Australia. Toxicity was measured as cyclopoid survival over 2, 4, 7, 14, 21, and 28 days in waters of varying sulfate concentration (<1-100 mg SO4/L). When sulfate was present, dissolved Ba concentrations decreased rapidly in toxicity test solutions forming a BaSO4 precipitate until dissolved sulfate was depleted. Barium in excess of sulfate remained in the dissolved form. The toxicity of Ba to cyclopoids was clearly attributed to dissolved Ba. Precipitated Ba was not toxic to the Wellington cyclopoid species. Toxicity values for dissolved Ba for the Wellington and Somersby cyclopoid species included a (21-day) no-effect concentration of 3.3 mg/L and an effective concentration to cause 5% mortality of 4.8 mg/L (at 21 days). Elevated dissolved Ba concentrations due to anthropogenic and/or biogeochemical processes may pose a risk to groundwater organisms. Further toxicity testing with other stygobiont species is recommended to increase the data available to derive a guideline value for Ba that can be used in contaminant risk assessments for groundwaters. Environ Toxicol Chem 2024;00:1-14. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Stable Barium Isotope Fractionation in Pore Waters of Estuarine Sediments

AbstractThe development of stable barium (Ba) isotope measurements provides a novel tool to investigate the geochemical cycling of Ba in the ocean and its sediments. In sediment pore waters, gradients of dissolved Ba concentrations result from various diagenetic processes. The distribution and fractionation of Ba isotopes in the pore waters are expected to further improve our understanding of these early diagenetic control mechanisms. Here, we present pore water profiles of dissolved stable Ba isotopic signatures (δ138Bapw) from shallow water sediments covering the entire Pearl River Estuary (PRE) in Southern China. We find pronounced depth‐dependent Ba isotope variations generally showing a shift from heavy to light δ138Bapw signatures from the sediment surface down to 15 cm depth. These gradients are well reproduced by a diffusion‐reaction model, which generates an apparent fractionation factor (138ε) of −0.60 ± 0.10‰ pointing to preferential removal of low‐mass Ba isotopes from the pore water during solution‐solid phase interactions. Consequently, the combined diagenetic processes induce the highest δ138Bapw values of +0.5 to +0.7‰ in the pore waters of the topmost sediment layer. Although the detrital fraction dominates the Ba content in the PRE surface sediments, the determined gradients of pore water Ba isotopes, together with concentration variations of Ba and other redox‐sensitive elements such as manganese (Mn), show that non‐detrital excess Ba carriers including Mn oxides and authigenic barite clearly affect the post‐depositional Ba dynamics. Stable Ba isotopes are thus a potentially powerful tracer of Ba geochemistry during early sediment diagenesis in estuarine depositional environments.

Chemical and isotopic evolution of flowback fluids from the Utica Gas Shale Play, Eastern Ohio USA

Hydraulic fracturing flowback fluids were collected from two Utica/Point Pleasant well pads in eastern Ohio. One site was in the wet gas zone (UPPW), while the site ∼50 km south consisted of four wells on the same pad in the dry gas zone (UPPS). Samples of input fluids also were collected before and during hydraulic fracturing. Flowback fluids are Na-Ca-Cl brines with total dissolved salt (TDS) concentrations that increase over several months from ∼100 to 200 g/L. The slightly higher TDS of the dry gas fluids are in part due to recycled flowback used as input fluids, and in part due to lower volume of water used in hydraulic fracturing. Concentrations of most major ions (Ca2+, Mg2+, Na+, Sr2+, Fe, Mn, Cl−, Br−) are similar for the five wells sampled, although small but systematic changes occur in the major element ratios over time.Most notably, an increase in the Sr/Cl ratio corresponds to an increase in the 87Sr/86Sr ratio in the fluids, suggesting interactions with a more radiogenic Sr source in the subsurface. Dissolved Ba concentrations and Ra activities were different between the two sites, reflecting a high SO42− fluid used at the UPPW site, and water-rock reactions occurring during hydraulic fracturing at the UPPS site.Water oxygen (δ18O) and hydrogen (δD) isotopes for input fluids used in the UPPW4 well and fresh water used for the UPPS wells fall on the Global Meteoric waterline (GMWL). Flowback fluids from both sites are relatively enriched in δ18O and δD compared to the input, but do not appear to follow a simple mixing trend, suggesting reaction and isotopic exchange with carbonates and fractionation due to imbibition in the rock. Cl isotopes, δ37Cl in the FP fluids varied from ∼ −0.43 to +0.13‰, the largest variation was observed in the earlier stages of flowback, while in the later stages δ37Cl exhibited a small but systematic increase over time, suggesting diffusion control of isotopic composition.Some of the trace species measured (dissolved Fe, Mn, thiosulfate and organic acids) do not follow the same trends as the major ions, suggesting contributions from input fluids, or microbially mediated reactions are exerting control on their concentrations. Input water chemistry exerts an important control on the Sr and Ba concentrations in flowback water. High SO42− in the input fluids used for hydraulically fracturing the wet gas well leads to precipitation of barite-celestite in flowback fluids.

Dissolved and Particulate Barium Distributions Along the US GEOTRACES North Atlantic and East Pacific Zonal Transects (GA03 and GP16): Global Implications for the Marine Barium Cycle

AbstractProcesses controlling dissolved barium (dBa) were investigated along the GEOTRACES GA03 North Atlantic and GP16 Eastern Tropical Pacific transects, which traversed similar physical and biogeochemical provinces. Dissolved Ba concentrations are lowest in surface waters (∼35–50 nmol kg−1) and increase to 70–80 and 140–150 nmol kg−1 in deep waters of the Atlantic and Pacific transects, respectively. Using water mass mixing models, we estimate conservative mixing that accounts for most of dBa variability in both transects. To examine nonconservative processes, particulate excess Ba (pBaxs) formation and dissolution rates were tracked by normalizing particulate excess 230Th activities. Th‐normalized pBaxs fluxes, with barite as the likely phase, have subsurface maxima in the top 1,000 m (∼100–200 μmol m−2 year−1 average) in both basins. Barite precipitation depletes dBa within oxygen minimum zones from concentrations predicted by water mass mixing, whereas inputs from continental margins, particle dissolution in the water column, and benthic diffusive flux raise dBa above predications. Average pBaxs burial efficiencies along GA03 and GP16 are ∼37% and 17%–100%, respectively, and do not seem to be predicated on barite saturation indices in the overlying water column. Using published values, we reevaluate the global freshwater dBa river input as 6.6 ± 3.9 Gmol year−1. Estuarine mixing processes may add another 3–13 Gmol year−1. Dissolved Ba inputs from broad shallow continental margins, previously unaccounted for in global marine summaries, are substantial (∼17 Gmol year−1), exceeding terrestrial freshwater inputs. Revising river and shelf dBa inputs may help bring the marine Ba isotope budget more into balance.

Assessing the utility of barium isotopes to trace Eurasian riverine freshwater inputs to the Arctic Ocean

Tracing riverine freshwater transport pathways within the Arctic Ocean is key to understanding changes in Arctic Ocean freshwater inventories. Dissolved Ba concentrations have been used in this capacity but are compromised by non-conservative processes. To assess the potential for Ba isotopes to provide insights into the impact of such processes on Arctic Ocean dissolved Ba inventories, Ba concentration and isotope data for surface seawater samples from the Siberian Shelf and Bering Sea/Strait are presented. These samples capture the mixing of riverine freshwater discharged by the rivers Yenisey, Lena and Ob, with Atlantic and Pacific derived seawater, which are traced by relationships between salinity, Ba concentration and δ138/134Ba. The δ138/134Ba of net river inputs, following modification by estuarine processes, are constrained to be 0.31 ± 0.04‰, 0.20 ± 0.06‰ and 0.23 ± 0.04‰, for the rivers Yenisey, Lena and Ob respectively. These values are used to estimate an average δ138/134Ba for Eurasian river freshwater input to the Arctic Ocean of 0.23 ± 0.04‰. The Ba concentration and δ138/134Ba of Lena River freshwater transported across the Laptev Sea are modified by non-conservative processes. These non-conservative processes do not result in distinctive modification of dissolved Ba concentration-δ138/134Ba mixing relationships between Eurasian riverine freshwater and Arctic seawater, which unfortunately limits the potential of Ba isotopes to improve tracing riverine freshwater sources in the central Arctic Ocean basins using dissolved Ba inventories. More generally the results of this study help advance understanding of Ba isotope cycling in the environment and their development as an emerging tracer of marine processes.

Barium isotopes in mid-ocean ridge hydrothermal vent fluids: A source of isotopically heavy Ba to the ocean

Mid-ocean ridge (MOR) hydrothermal vent fluids are enriched with dissolved barium, but due to barite (BaSO4) precipitation during mixing between Ba-bearing vent fluids and SO4-bearing seawater, the magnitude of hydrothermal Ba input to the ocean remains uncertain. Deep-ocean Ba isotopes show evidence for non-conservative behavior, which might be explained by input of isotopically heavy hydrothermal Ba. In this study we present the first Ba isotope data in mid-ocean ridge hydrothermal vent fluids and particles from systems on the Mid-Atlantic Ridge (Rainbow 36°N and TAG 26°N), the East Pacific Rise (EPR9–10°N and 13°N) and the Juan de Fuca Ridge (MEF and ASHES). The vent fluids display a wide range of dissolved Ba concentrations from 0.43 to 97.9 μmol/kg and δ138/134Ba values from −0.26 to +0.91‰, but are modified relative to initial composition due to precipitation of barite. Calculated endmember vent fluid δ138/134Ba values, prior to barite precipitation, are between −0.17 and +0.09‰, consistent with the values observed in oceanic basalts and pelagic sediments. Water-rock interaction at depth in the oceanic crust appears to occur without Ba isotope fractionation. During subsequent venting and mixing with seawater, barite precipitation preferentially removes isotopically light Ba from vent fluids with a fractionation factor of Δ138/134Bahyd-barite-fluid = −0.35 ± 0.10‰ (2SE, n = 2). Based on knowledge of barite saturation and isotope fractionation during precipitation, the effective hydrothermal Ba component that mixes with seawater after barite precipitation has completed can be calculated: δ138/134Bahyd = +1.7 ± 0.7‰ (2SD). This value is isotopically heavier than deep ocean waters and may explain the observed non-conservative of Ba isotopes in deep waters. These new constraints on hydrothermal Ba compositions enable the hydrothermal input of Ba to Atlantic deep waters to be assessed at ≈3–9% of the observed Ba. Barium isotopes might be used as a tracer to reconstruct the history of hydrothermal Ba inputs and seawater SO4 concentrations in the past.

Geochemical conditions conducive for retention of trace elements and radionuclides during shale-fluid interactions.

Produced water generated during unconventional oil and gas extractions contains a complex milieu of natural and anthropogenic potentially toxic chemical constituents including arsenic (As), chromium (Cr), and cadmium (Cd), naturally occurring radioactive materials (NORMs) including U and Ra, and a myriad of organic compounds. The human-ecological health risks and challenges associated with the disposal of produced water may be alleviated by understanding geochemical controls on processes responsible for the solubilization of potentially hazardous natural shale constituents to produced water. Here, we investigated, through a series of batch treatments, the leaching behavior of As, Se, Cu, Fe, Ba, Cr, Cd, and radioactive nuclides U, Ra from shale to produced water. Specifically, the effect of four major controls on element mobility was studied: (1) solution pH, (2) ionic strength of the solution, (3) oxic-anoxic conditions, and (4) an additive used in fracking fluid. The mobilization of metals and metalloids from shale was greatest in treatments containing sodium persulfate, an oxidant and a commonly used additive in fracture fluid. In the high ionic strength treatments, dissolved Ba concentrations increased 5-fold compared to low ionic strength treatments. Overall, anoxic conditions superimposed with low pH resulted in the largest increase of dissolved metals and radionuclides such as Ra. Overall, our results suggest that (1) limiting pore water acidification by injection of alkaline fluid in carbonate-low shale and (2) minimizing strong oxidizing conditions in shale formations may result in cost-effective in situ retention of produced water contaminants.

Barium concentrations and speciation in surface waters collected from an active barium mining area in Guizhou Province, southwestern China.

Barium (Ba) is a toxic element and can cause serious health effects. Humans have experienced increased exposure to Ba due to its intensive usage in industrial areas and daily life. Anthropogenic activities of Ba mining and the manufacture of Ba containing products introduce the element into surrounding areas, posing environmental concerns. Concentrations of total Ba (TBa) and dissolved Ba (DBa) in water samples collected from active Ba mines in Tianzhu, east Guizhou Province, southwestern China were measured to show the regional dispersion of Ba contamination. Aqueous Ba species in water were calculated using the PHREEQC program. The results showed that TBa and DBa concentrations ranged from 6.7 to 483.1μg/L and from 7.5 to 222.7μg/L, respectively. TBa concentrations presented a high average value of 126.6μg/L and greatly exceeded the reported common value of 10μg/L Ba in surface water set by the Ministry of Environment Protection of China. PHREEQC results indicated that Ba species in water were present as Ba2+, BaSO4, BaHCO3, BaCO3, and BaOH+. The distribution of Ba species in water is controlled by pH and total organic carbon (TOC), and the lower pH (pH < 7) the higher the dissolved fractions. The log K d values (K d , dissolved-particulate distribution coefficients) varied from 2.41 to 6.32. Significant correlations were observed among Ba2+ and K+, Na+, Cl-, NO3-, with Pearson correlation coefficients of 0.425, 0.531, 0.853, 0.612, and 0.329, respectively (p < 0.01). Elevated Ba concentrations in water indicated that the Ba contamination and its distribution pattern in local aquatic ecosystems are derived from Ba mining sites in the Tianzhu area.

Barium isotopes reveal role of ocean circulation on barium cycling in the Atlantic

We diagnose the relative influences of local-scale biogeochemical cycling and regional-scale ocean circulation on Atlantic barium cycling by analysing four new depth profiles of dissolved Ba concentrations and isotope compositions from the South and tropical North Atlantic. These new profiles exhibit systematic vertical, zonal and meridional variations that reflect the influence of both local-scale barite cycling and large-scale ocean circulation. Epipelagic decoupling of dissolved Ba and Si reported previously in the tropics is also found to be associated with significant Ba isotope heterogeneity. As such, we contend that this decoupling originates from the depth segregation of opal and barite formation but is exacerbated by weak vertical mixing. Zonal influence from isotopically-‘heavy’ water masses in the western North Atlantic evidence the advective inflow of Ba-depleted Upper Labrador Sea Water, which is not seen in the eastern basin or the South Atlantic. Meridional variations in Atlantic Ba isotope systematics below 2000m appear entirely controlled by conservative mixing. Using an inverse isotopic mixing model, we calculate the Ba isotope composition of the Ba-poor northern end-member as +0.45‰ and the Ba-rich southern end-member +0.26‰, relative to NIST SRM 3104a. The near-conservative behaviour of Ba below 2000m indicates that Ba isotopes can serve as an independent tracer of the provenance of northern- versus southern-sourced water masses in the deep Atlantic Ocean. This finding may prove useful in palaeoceanographic studies, should appropriate sedimentary archives be identified, and offers new insights into the processes that cycle Ba in seawater.

Dissolved and particulate Barium in the Ganga (Hooghly) River estuary, India: Solute-particle interactions and the enhanced dissolved flux to the oceans

In this study, the sources and the cycling of Ba have been evaluated in the Ganga (Hooghly) River estuary using the composition of the suspended sediments and the water samples collected during six seasons of contrasting water discharge over two years (2012 and 2013). In addition, the data on the samples of groundwater from areas adjacent to the estuary, and the industrial effluent water and urban wastewater draining into the estuary are presented. Selective extraction experiments were also performed on the suspended particulate matter of two seasons to assess the distribution of exchangeable concentrations of major ions and Ba. In the mixing zone, the variation patterns of the dissolved Ba concentrations show mid-salinity maxima and are similar to the patterns of variation of the particulate Mg/Al and Mg/Fe, suggesting that the production of dissolved Ba is linked to the adsorption of major ions on to the clay minerals and Fe–Mn oxyhydroxides in the particulate matter. The inference of coupled adsorption–desorption processes is supported by the observations that the particulate Ba/Mg and Ba/K ratios exhibit significant to strong negative correlations with the concentrations of Al, Fe and Mn. The observations of mid-salinity maxima for the concentrations of exchangeable Mg and K, and of the exchangeable Ba concentrations that decrease with salinity provide strong evidence that the solute-particle interactions is the major driver in regulating the dissolved Ba distributions in the estuary. The estimates of the quantity of desorbed Ba based on three different approaches suggest that desorption is sufficient to account for the calculated excess Ba (Baxs) concentrations. The contribution of Ba to the dissolved load via dissolution of the particulate carbonate phases is minor, up to 3% of the maximum Baxs concentrations. The estimates of anthropogenic contributions are insignificant, and account for ⩽2% of maximum Baxs in the estuary. Groundwater contributions are less significant and account for up to 5% of the annual Ba flux from the Hooghly estuary.The estimates of Ba flux show that annually (1.5–1.9)×107moles of Ba is transported by the Hooghly River. About (3.6–4.3)×107moles of Ba is generated annually in the estuary through desorption. Added together, the desorbed and riverine Ba fluxes generate a total Ba flux of (5.1–6.2)×107moles per year. Thus, the solute-particle interactions enhance the riverine Ba flux by >300%. A compilation of the available data shows that the enhancement of the riverine Ba flux and the fractions of desorbed Ba flux scale with (particulate matter flux/water flux) ratio in several estuaries of the world, suggesting that the process of solute-particle interactions is a major driver for the estuarine production of Ba on a global scale. Among the rivers considered in this study, the estuaries of the Hooghly River and the Ganges–Brahmaputra rivers, characterized by very high (sediment flux/water flux) ratio, depict the highest increase in the riverine Ba flux. This unique feature of the Ganga River system is inferred to be resulting from the collective impact of the tectonic activity and the monsoonal rainfall in the catchment areas.

Constraining the oceanic barium cycle with stable barium isotopes

The distribution of barium (Ba) concentrations in seawater resembles that of nutrients and Ba has been widely used as a proxy of paleoproductivity. However, the exact mechanisms controlling the nutrient-like behavior, and thus the fundamentals of Ba chemistry in the ocean, have not been fully resolved. Here we present a set of full water column dissolved Ba (DBa) isotope (δ137BaDBa) profiles from the South China Sea and the East China Sea that receives large freshwater inputs from the Changjiang (Yangtze River). We find pronounced and systematic horizontal and depth dependent δ137BaDBa gradients. Beyond the river influence characterized by generally light signatures (0.0 to +0.3‰), the δ137BaDBa values in the upper water column are significantly higher (+0.9‰) than those in the deep waters (+0.5‰). Moreover, δ137BaDBa signatures are essentially constant in the entire upper 100 m, in which dissolved silicon isotopes are fractionated during diatom growth resulting in the heaviest isotopic compositions in the very surface waters. Combined with the decoupling of DBa concentrations and δ137BaDBa from the concentrations of nitrate and phosphate this implies that the apparent nutrient-like fractionation of Ba isotopes in seawater is primarily induced by preferential adsorption of the lighter isotopes onto biogenic particles rather than by biological utilization. The subsurface δ137BaDBa distribution is dominated by water mass mixing. The application of stable Ba isotopes as a proxy for nutrient cycling should therefore be considered with caution and both biological and physical processes need to be considered. Clearly, however, Ba isotopes show great potential as a new tracer for land–sea interactions and ocean mixing processes.

Barium and carbon fluxes in the Canadian Arctic Archipelago

The seasonal and spatial variability of dissolved Barium (Ba) in the Amundsen Gulf,southeastern Beaufort Sea, was monitored over a full year from September 2007 to September 2008. Dissolved Ba displays a nutrient・type behavior: the maximum water column concentration is located below the surface layer. The highest Ba concentrations are typically observed at river mouths, the lowest concentrations are found in water masses of Atlantic origin. Barium concentrations decrease eastward through the Canadian Arctic Archipelago. Barite (BaSO 4 ) saturation is reached at the maximum dissolved Ba concentrations in the subsurface layer, whereas the rest of the water column is undersaturated. A three end‐member mixing model comprising freshwater from sea・ice melt and rivers, as well as upper halocline water, is used to establish their relative contributions to the Ba concentrations in the upper water column of the Amundsen Gulf. Based on water column and riverine Ba contributions, we assess the depletion of dissolved Ba by formation and sinking of biologically bound Ba (bio・Ba), from which we derive an estimate of the carbon export production. In the upper 50 m of the water column of the Amundsen Gulf, riverine Ba accounts for up to 15% of the available dissolved Ba inventory, of which up to 20% is depleted by bio-Ba formation and export. Since riverine inputs and Ba export occur concurrently, the seasonal variability of dissolved Ba in the upper water column is moderate. Assuming a fixed organic carbon to bio・Ba flux ratio, carbon export out of the surface layer is estimated at 1.8 ・ 0.45 mol C m −2 yr −1 . Finally, we propose a climatological carbon budget for the Amundsen Gulf based on recent literature data and our findings, the latter bridging the surface and subsurface water carbon cycles.

Dissolved barium and radium isotopes in the Chao Phraya River estuarine mixing zone in Thailand

New data on dissolved Ba, 226Ra and 228Ra were obtained in the Chao Phraya River estuarine mixing zone in 1996. Although desorption of Ba from river-suspended sediments gives rise to elevated dissolved Ba concentrations in the low salinity ( S<5) zone, two types of mixing trend in the higher salinity ( S>10) region have been observed depending upon the sampling periods. Under a dinofragellates ( Noctiluca) red tide condition in January, significant biological removal of dissolved Ba took place in the mid-salinity ( S=10 –16) region, whereas under normal condition in July and November, the dissolved Ba followed a conservative linear mixing trend. 226Ra is also supplied to the coastal waters by desorption from river-transported sediments in a delayed fashion compared to Ba, at least, in the latter seasons, whereas 228Ra is predominantly supplied by diffusion from underlying sediments to the water largely in the higher salinity ( S>15) region. These geochemical observations in July and November fit well to the previous studies done for other estuarine environments. Total riverine fluxes to the Gulf of Thailand were estimated to be 6.2×10 6 mol Ba/yr and 1.5×10 13 dpm 226Ra/yr, about half of which is contributed by the Chao Phraya River. Although there is a sign indicating that ground water input may be contributing to the fluxes of 226Ra and Ba, we were unable to quantify them due to lack of information on the exchange rate of the coastal waters with open seawater.

Barium peaks at glacial terminations in sediments of the equatorial Atlantic Ocean—relicts of deglacial productivity pulses?

In sediment cores recovered from oligotrophic settings of the western and eastern north-equatorial Atlantic Ocean, Ceará Rise and Sierra Leone Rise, distinct peaks of excess barium were detected at glacial/interglacial transitions. These Ba maxima are unrelated to any other potential productivity proxy, e.g. organic carbon, carbonate or opal. Moreover, they coincide with minima in organic carbon contents. Despite the lack of correlation between excess barium and organic carbon, we ascribe these Ba spikes to pulses of productivity that occurred during glacial/interglacial transitions. The discrepancy between barium and organic carbon in these transitional sediment intervals is attributed to the action of downward-progressing oxidation fronts during deglacial nonsteady-state depositional conditions. The oxidation fronts were initiated due to the overall low sedimentation rates prevailing in the study areas and an increase in bottom water oxygen concentrations at the onset of enhanced NADW production during interglacial periods. The fronts led to a very efficient oxidation of the organic carbon initially present leaving peaks in solid phase barium as relicts of these short-time productivity events. This assumption is supported by the depth arrangement of the solid phase peaks of Ba, Fe, and Mn along the 6/5 oxygen isotope stage boundary in sediments of the Ceará Rise which show striking similarities to the distribution of these elements in oxidized sapropel intervals in eastern Mediterranean sediments. It remains unclear whether productivity was proportional to the magnitude of the Ba excess maxima. Possibly, higher dissolved Ba concentrations in intermediate and deep waters during glacial/interglacial transitions caused the precipitation of barite to increase out of proportion of the (postulated) deglacial productivity pulses.

The flux of barium to the coastal waters of the southeastern USA: the importance of submarine groundwater discharge

Dissolved Ba concentrations in the inner shelf waters of the South Atlantic Bight (SAB) are two- to three-fold enriched in Ba when compared to Atlantic surface water. We determined that river input could account for about 25% of the observed enrichment. However, salty groundwaters are enriched in Ba by as much as an order of magnitude over calculated river water endmembers. The resultant input of Ba to the coastal environment, via enriched groundwater, is the likely source for the observed Ba enrichment on the inner shelf. The flux of Ba from the inner shelf to the ocean is 70 × 10 3 moles per day. The flux of Ba reaching the inner shelf from salty groundwaters ranges from 25 to 100 × 10 3 moles of Ba per day. Groundwater input of Ba appears to be much more important than river input for the Southeastern coast of the US.

A survey of dissolved barium in the estuaries of major Arctic rivers and adjacent seas

Analyses for dissolved Ba have been performed on water samples obtained from the estuaries of major Arctic rivers and adjacent seas between 1993 and 1996. Complex behavior was observed in the mixing zones between fluvial and oceanic waters. In these areas, riverine dissolved Ba signals were altered by mixing with different shelf water masses and by non-conservative processes such as uptake in association with biological activity and desorption from suspended riverine particles. Despite this complexity, dissolved Ba concentrations [Ba d] measured in samples associated with the Mackenzie River (138–574 nmol L -1) were clearly much higher than those measured in samples associated with any of the Eurasian Arctic rivers (12–175 nmol L -1). While the [Ba d] signatures of Arctic rivers are subject to temporal and seasonal variability, such variability appears to be much smaller than the overall difference between [Ba d] in the Mackenzie River and Eurasian Arctic rivers. These results suggest that Ba can be used to distinguish between North American and Eurasian components of fluvial discharge to the Arctic and thus provide information not available from other oceanographic tracers currently in use.

Biogenic barium fluxes to the deep sea: Implications for paleoproductivity reconstruction

Dymond et al. (1992) have recently proposed an algorithm to reconstruct paleoproductivity from biogenic Ba (bio‐Ba) accumulation rates in sediments. Their equation is based on sediment trap data which indicate that Corg/bio‐Ba ratios in settling particles are higher in the western Atlantic compared to the Pacific. From this observation they have suggested that the flux of bio‐Ba to the seafloor may depend on dissolved Ba concentrations in intermediate and deep waters which are significantly higher in the Pacific compared to the Atlantic. Accordingly, they have introduced a factor related to dissolved Ba concentration in their equation as a variable which strongly influences paleoproductivity estimates. In an attempt to confirm the proposed dependency of bio‐Ba fluxes to the seafloor on dissolved Ba concentrations in seawater we have compiled additional data on organic carbon and bio‐Ba fluxes in the deep sea. These data confirm Dymond et al.'s findings that settling particles have significantly higher Corg/bio‐Ba in the western Atlantic compared to the Pacific. However, we also found lower ratios in traps deployed in the North Atlantic, similar to those found in the Pacific, while in the Panama Basin we found ratios as high as those in the western Atlantic. From these observations we conclude that dissolved Ba concentration is not an important factor in regulating the flux of bio‐Ba to the seafloor. Instead, we propose that high Corg/bio‐Ba ratios found in the western Atlantic, the Panama Basin, the Arabian Sea, and some stations in the Nordic Seas result from the addition of refractory organic carbon from nearby continents, shelves, or slopes. If that is confirmed, the algorithm proposed by Dymond et al. (1992) could be simplified and could provide a powerful means to estimate paleoproductivity. In addition, deviations from the Corg/bio‐Ba ratios in settling particles could be used to estimate the input of continental or shelf‐derived refractory organic matter into the deep sea.

Induction of barite mineralization in the Asiatic clam Corbicula fluminea

Barite crystals were formed on the inner shell surface in 1 week by specimens of Corbicula fluminea exposed to dissolved Ba concentrations of 140–559 µg liter‒1. Prevalences of barite crystals increased directly with initial Ba concentrations over the course of a 28‐d experiment. Barite crystals were not observed on the shell exteriors of any clams analyzed. Results suggest that Ba was concentrated by C. fluminea and periodically purged from the soft tissues into the extrapallial fluids, where it heterogeneously coprecipitated with aragonite on the inner shell surface.

Barium content of benthic foraminifera controlled by bottom-water composition

THE carbon isotope ratio (δ13;C) and cadmium content (Cd/Ca) of benthic foraminifera shells have been used to reconstruct deep-water circulation patterns of the glacial oceans1–7. 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 sediments8. 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 andδ 13C. As Ba substitutes into trigonal carbonates9, 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.