Investigation of thallium fluxes from subaerial volcanism—Implications for the present and past mass balance of thallium in the oceans

A suite of 34 volcanic gas condensates and particulates from Kilauea (Hawaii), Mt. Etna and Vulcano (Italy), Mt. Merapi (Indonesia), White Island and Mt. Nguaruhoe (New Zealand) were analysed for both Tl isotope compositions and Tl/Pb ratios. When considered together with published Tl-Pb abundance data, the measurements provide globally representative best estimates of Tl/Pb = 0.46 ± 0.25 and ε²⁰⁵Tl = −1.7 ± 2.0 for the emissions of subaerial volcanism to the atmosphere and oceans (ε²⁰⁵Tl is the deviation of the ²⁰⁵Tl/²⁰³Tl isotope ratio from NIST SRM 997 isotope standard in parts per 10,000). Compared to igneous rocks of the crust and mantle, volcanic gases were found to have (i) Tl/Pb ratios that are typically about an order of magnitude higher, and (ii) significantly more variable Tl isotope compositions but a mean ε²⁰⁵Tl value that is indistinguishable from estimates for the Earth’s mantle and continental crust. The first observation can be explained by the more volatile nature of Tl compared to Pb during the production of volcanic gases, whilst the second reflects the contrasting and approximately balanced isotope fractionation effects that are generated by partial evaporation of Tl during magma degassing and partial Tl condensation as a result of the cooling and differentiation of volcanic gases.Mass balance calculations, based on results from this and other recent Tl isotope studies, were carried out to investigate whether temporal changes in the volcanic Tl fluxes could be responsible for the dramatic shift in the ε²⁰⁵Tl value of the oceans at ∼55 Ma, which has been inferred from Tl isotope time series data for ferromanganese crusts. The calculations demonstrate that even large changes in the marine Tl input fluxes from volcanism and other sources are unable to significantly alter the Tl isotope composition of the oceans. Based on modelling, it is shown that the large inferred change in the ε²⁰⁵Tl value of seawater is best explained if the oceans of the early Cenozoic featured significantly larger Tl output fluxes to oxic pelagic sediments, whilst the sink fluxes to altered ocean crust remained approximately constant.     

Thallium isotope variations in an ore-bearing continental igneous setting: Collahuasi Formation, northern Chile

Thallium is a highly incompatible element and a large fraction of the bulk silicate Earth Tl budget is, therefore, expected to reside in the continental crust. Nonetheless, the Tl isotope systematics of continental rocks are essentially unexplored at present. Here, we present new Tl isotope composition and concentration data for a suite of 36 intrusive and extrusive igneous rocks from the vicinity of porphyry Cu deposits in the Collahuasi Formation of the Central Andes in northern Chile. The igneous lithologies of the rocks are variably affected by the hydrothermal alteration that accompanied the formation of the Cu deposits.The samples display Tl concentrations that vary by more than an order of magnitude, from 0.1 to 3.2 μg/g, whilst ε²⁰⁵Tl ranges between −5.1 and +0.1 (ε²⁰⁵Tl is the deviation of the ²⁰⁵Tl/²⁰³Tl isotope ratio of a sample from a standard in parts per 10⁴). These variations are primarily thought to be a consequence of hydrothermal alteration processes, including metasomatic transport of Tl, and formation/breakdown of Tl-bearing minerals, which are associated with small but significant Tl isotope effects. The Tl abundances show excellent correlations with both K and Rb concentrations but no co-variation with Cu. This demonstrates that Tl displays only limited chalcophile affinity in the continental crust of the Collahuasi Formation, but behaves as a lithophile element with a distribution that is primarily governed by partitioning of Tl⁺ into K⁺-bearing phases. Collahuasi samples with propylitic alteration features, which are derived from the marginal parts of the hydrothermal systems, have, on average, slightly lighter Tl isotope compositions than rocks from the more central sericitic and argillic alteration zones. This small but statistically significant difference most likely reflects preferential retention of isotopically heavy Tl in alteration phases, such as white micas and clays, which formed during sericitic and argillic alteration.     

Large thallium isotopic variations in iron meteorites and evidence for lead-205 in the early solar system

Lead-205 decays to ²⁰⁵Tl with a half-life of 15 Myr and should have been present in the early solar system according to astrophysical models. However, despite numerous attempts, Tl isotopic measurements of meteorites have been unable to demonstrate convincingly its former presence. Here, we report large (∼5‰) variations in Tl isotope composition in metal and troilite fragments from a range of iron meteorites that were determined at high precision using multiple collector inductively coupled plasma mass spectrometry. The Tl isotopic compositions of seven metal samples of the IAB iron meteorites Toluca and Canyon Diablo define a correlation with ²⁰⁴Pb/²⁰³Tl. When interpreted as an isochron, this corresponds to an initial ²⁰⁵Pb/²⁰⁴Pb ratio of (7.4 ± 1.0) × 10⁻⁵. Alternative explanations for the correlation, such as mixing of variably mass-fractionated meteorite components or terrestrial contamination are harder to reconcile with independent constraints. However, troilite nodules from Toluca and Canyon Diablo contain Tl that is significantly less radiogenic than co-existing metal with isotope compositions that are variable and decoupled from ²⁰⁴Pb/²⁰³Tl. These effects are similar to those recently reported by others for Fe and Ni isotopes in iron meteorite sulfides and appear to be the result of kinetic stable isotope fractionation during diffusion. Though it cannot conclusively be shown that the metal fragments are unaffected by the secondary processes that disturbed the troilites, mass balance modeling indicates that the alteration of the troilites is unlikely to have significantly affected the Tl isotope compositions of the co-existing metals. It is therefore reasonable to conclude that the IAB metal isochron is a product of the in situ decay of ²⁰⁵Pb. If the I-Xe ages of IAB silicate inclusions record the same event as the ²⁰⁵Pb-²⁰⁵Tl chronometer then crystallization of the IAB metal was probably completed between 10 and 20 Myr after the condensation of the first solids. This implies an initial solar system ²⁰⁵Pb/²⁰⁴Pb of (1.0-2.1) × 10⁻⁴, which is in excellent agreement with recently published astrophysical predictions. Similar calculations yield an initial solar system Tl isotope composition of ε²⁰⁵Tl = −2.8 ± 1.7. The Tl isotopic composition and concentration of the silicate Earth depends critically on the timing and mechanism of core formation and Earth’s volatile element depletion history. Modeling of the Earth’s accretion and core formation using the calculated initial solar system Tl isotope composition and ²⁰⁵Pb/²⁰⁴Pb, however, does not yield reasonable results for the silicate Earth unless either the Earth lost Tl and Pb late in its accretion history or the core contains much higher concentrations of Pb and Tl than are found in iron meteorites.     

Iron isotope systematics in estuaries: The case of North River, Massachusetts (USA)

Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22 μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high-resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ⁵⁶Fe values (with an average of 0.43 ± 0.04‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ⁵⁶Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ⁵⁶Fe values vary from −0.09‰ at no flocculation to ∼0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ⁵⁶Fe composition of rivers can also be characterized by more positive δ⁵⁶Fe values (up to 0.3‰) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe-isotopes during continental run-off.     

Lithium isotopic composition and concentration of the upper continental crust

The Li isotopic composition of the upper continental crust is estimated from the analyses of well-characterized shales, loess, granites and upper crustal composites (51 samples in total) from North America, China, Europe, Australia and New Zealand. Correlations between Li, δ⁷Li, and chemical weathering (as measured by the Chemical Index of Alteration (CIA)), and δ⁷Li and the clay content of shales (as measured by Al₂O₃/SiO₂), reflect uptake of heavy Li from the hydrosphere by clays. S-type granites from the Lachlan fold belt (-1.1 to -1.4‰) have δ⁷Li indistinguishable from their associated sedimentary rocks (-0.7 to 1.2‰), and show no variation in δ⁷Li throughout the differentiation sequence, suggesting that isotopic fractionation during crustal anatexis and subsequent differentiation is less than analytical uncertainty (±1‰, 2σ). The isotopically light compositions for both I- and S-type granites from the Lachlan fold belt (-2.5 to + 2.7 ‰) and loess from around the world (-3.1 to + 4.5‰) reflect the influence of weathering in their source regions. Collectively, these lithologies possess a limited range of Li isotopic compositions (δ⁷Li of −5‰ to + 5‰), with an average (δ⁷Li of 0 ± 2‰ at 1σ) that is representative of the average upper continental crust. Thus, the Li isotopic composition of the upper continental crust is lighter than the average upper mantle (δ⁷Li of + 4 ± 2‰), reflecting the influence of weathering on the upper crustal composition. The concentration of Li in the upper continental crust is estimated to be 35 ± 11 ppm (2σ), based on the average loess composition and correlations between insoluble elements (Ti, Nb, Ta, Ga and Al₂O₃, Th and HREE) and Li in shales. This value is somewhat higher than previous estimates (∼20 ppm), but is probably indistinguishable when uncertainties in the latter are accounted for.     

Heterogeneous magnesium isotopic composition of the upper continental crust

High-precision Mg isotopic data are reported for ∼100 well-characterized samples (granites, loess, shales and upper crustal composites) that were previously used to estimate the upper continental crust composition. Magnesium isotopic compositions display limited variation in eight I-type granites from southeastern Australia (δ²⁶Mg = −0.25 to −0.15) and in 15 granitoid composites from eastern China (δ²⁶Mg = −0.35 to −0.16) and do not correlate with SiO₂ contents, indicating the absence of significant Mg isotope fractionation during differentiation of granitic magma. Similarly, the two S-type granites, which represent the two end-members of the S-type granite spectrum from southeastern Australia, have Mg isotopic composition (δ²⁶Mg = −0.23 and −0.14) within the range of their potential source rocks (δ²⁶Mg = −0.20 and +0.15) and I-type granites, suggesting that Mg isotope fractionation during crustal anatexis is also insignificant. By contrast, δ²⁶Mg varies significantly in 19 A-type granites from northeastern China (−0.28 to +0.34) and may reflect source heterogeneity.Compared to I-type and S-type granites, sedimentary rocks have highly heterogeneous and, in most cases, heavier Mg isotopic compositions, with δ²⁶Mg ranging from −0.32 to +0.05 in nine loess from New Zealand and the USA, from −0.27 to +0.49 in 20 post-Archean Australian shales (PAAS), and from −0.52 to +0.92 in 20 sedimentary composites from eastern China. With increasing chemical weathering, as measured by the chemical index of alternation (CIA), δ²⁶Mg values show a larger dispersion in shales than loess. Furthermore, δ²⁶Mg correlates negatively with δ⁷Li in loess. These characteristics suggest that chemical weathering significantly fractionates Mg isotopes and plays an important role in producing the highly variable Mg isotopic composition of sedimentary rocks.Based on the estimated proportions of major rock units within the upper continental crust and their average MgO contents, a weighted average δ²⁶Mg value of −0.22 is derived for the average upper continental crust. Our studies indicate that Mg isotopic composition of the upper crust is, on average, mantle-like but highly heterogeneous, with δ²⁶Mg ranging from −0.52 to +0.92. Such large isotopic variation mainly results from chemical weathering, during which light Mg isotopes are lost to the hydrosphere, leaving weathered products (e.g., sedimentary rocks) with heavy Mg isotopes.     

Nutrient biogeochemistry in an upwelling-influenced estuary of the Pacific northwest (Tillamook Bay,Oregon, USA)

Tillamook Bay, Oregon, is a drowned river estuary that receives freshwater input from 5 rivers and exchanges ocean water through a single channel. Similar to other western United States estuaries, the bay exhibits a strong seasonal change in river discharge in which there is a pronounced winter maximum and summer minimum in precipitation and runoff. The behavior of major inorganic nutrients (phosphorus, nitrogen, and silica) within the watershed is examined over seasonal cycles and under a range of river discharge conditions for October 1997–December 1999. Monthly and seasonal sampling stations include transects extending from the mouth of each river to the mouth of the estuary as well as 6–10 sites upstream along each of the 5 major rivers. Few studies have examined nutrient cycling in Pacific Northwest estuaries. This study evaluates the distributions of inorganic nutrients to understand the net processes occurring within this estuary. Based upon this approach, we hypothesize that nutrient behavior in the Tillamook Bay estuary can be explained by two dominant factors: freshwater flushing time and biological uptake and regeneration. Superimposed on these two processes is seasonal variability in nutrient concentrations of coastal waters via upwelling. Freshwater flushing time determines the amount of time for the uptake of nutrients by phytoplankton, for exchange with suspended particles, and for interaction with the sediments. Seasonal coastal upwelling controls the timing and extent of oceanic delivery of nutrients to the estuary. We suggest that benthic regeneration of nutrients is also an important process within the estuary occurring seasonally according to the flushing characteristics of the estuary. Silicic acid, nitrate, and NH₄ ⁺ supply to the bay appears to be dominated by riverine input. PO₄ ⁻³ supply is dominated by river input during periods of high river flow (winter months) with oceanic input via upwelling and tidal exchange important during other times (spring, summer, and fall months). Departures from conservative mixing indicate that internal estuarine sources of dissolved inorganic phosphorus and nitrogen are also significant over an annual cycle.     

Geochemistry and provenance of bed sediments of the large rivers in the Tibetan Plateau and Himalayan region

We investigated the geochemical characteristics of major, trace and rare earth elements and Sr–Nd isotope patterns of bed sediments from the headwaters and upper reaches of the six large rivers draining the Tibetan Plateau (the Jinsha River—Yangtze, Lancang River—Mekong, Nujiang River—Salween, Huang He—Yellow, Indus, and Yarlung Tsangpo—Brahmaputra). By using Ca/Al versus Mg/Al, La/Sc versus Co/Th, and ⁸⁷Sr/⁸⁶Sr versus ε_Nd (0) binary differentiation diagrams of provenance, some typical contributors to the different catchment sediments can be identified. In the Three-River (the Jinsha, Lancang, and Nujiang Rivers) tectonomagmatic belt, acidic–intermediate-acidic volcanic rocks are very important provenance of sediments. Carbonate rocks and Permian Emeishan basalts are dominant in the Jinsha River. The Yellow River sediments have similar geochemical characteristics with loess in catchments. The Indus and Yarlung Tsangpo Rivers sediments are mainly from ultra-K volcanic rocks and Cenozoic granitoids widely distributed in the Indus–Yarlung suture. The intensity of chemical weathering in these river catchments is evaluated by calculating the chemical indices of alteration (CIA) of sediments and comparing them with bedrocks. The CIA values of the six river sediments are from 46.5 to 69.6, closing to those of bedrocks in the corresponding catchment, which indicates relatively weak chemical weathering intensity. Lithology, climate, and topography affect the chemical weathering intensity in these river catchments.     

Equilibrium thallium isotope fractionation and its constraint on Earth’s late veneer

Equilibrium isotope fractionation of thallium (Tl) includes the traditional mass-dependent isotope fractionation effect and the nuclear volume effect (NVE). The NVE dominates the overall isotope fractionation, especially at high temperatures. Heavy Tl isotopes tend to be enriched in oxidized Tl³⁺-bearing species. Our NVE fractionation results of oxidizing Tl⁺ to Tl³⁺ can explain the positive enrichments observed in ferromanganese sediments. Experimental results indicate that there could be 0.2–0.3 ε-unit fractionation between sulfides and silicates at 1650 °C. It is consistent with our calculation results, which are in the range of 0.17–0.38 ε-unit. Importantly, Tl’s concentration in the bulk silicate Earth (BSE) can be used to constrain the amount of materials delivered to Earth during the late veneer accretion stage. Because the Tl concentration in BSE is very low and its Tl isotope composition is similar with that of chondrites, suggesting either no Tl isotope fractionation occurred during numerous evaporation events, or the Tl in current BSE was totally delivered by late veneer. If it is the latter, the Tl-content-based estimation could challenge the magnitude of late veneer which had been constrained by the amount of highly siderophile elements in BSE. Our results show that the late-accreted mass is at least five-times larger than the previously suggested magnitude, i.e., 0.5 wt% of current Earth’s mass. The slightly lighter ²⁰⁵Tl composition of BSE relative to chondrites is probable a sign of occurrence of Tl-bearing sulfides, which probably were removed from the mantle in the last accretion stage of the Earth.

     

Iron isotope composition of the suspended matter along depth and lateral profiles in the Amazon River and its tributaries

Samples of suspended matter were collected at different locations, seasons, depths and lateral profiles in the Amazon River and three of its main tributaries, the Madeira, the Solimões and the Negro rivers. Their iron isotope compositions were studied in order to understand the iron cycle and investigate the level of isotopic homogeneity at the river cross-section scale. Samples from four depth profiles and three lateral profiles analyzed show suspended matter δ⁵⁷Fe values (relative to IRMM-14) between −0.501 ± 0.075‰ and 0.196 ± 0.083‰ (2SE). Samples from the Negro River, a blackwater river, yield the negative values. Samples from other stations (whitewater rivers, the Madeira, the Solimões and the Amazon) show positive values, which are indistinguishable from the average composition of the continental crust (δ⁵⁷Fe_IRMM-14 ∼ 0.1‰). Individual analyses of the depth and lateral profiles show no significant variation in iron isotope signatures, indicating that, in contrast to certain chemical or other isotopic tracers, one individual subsurface sample is representative of river deeper waters. This also suggests that, instead of providing detailed information on the riverine iron cycling, iron isotopes of particulate matter in rivers will rather yield a general picture of the iron sources.     

Conservative behaviour of riverine dissolved organic carbon in the Severn Estuary: chemical and geochemical implications

The distribution, variability and chemical behaviour of dissolved organic carbon (DOC) was investigated over 2$\text{1}\text{2}$ years in the Severn Estuary and Bristol Channel, UK. The concentrations of riverine DOC (3.1–7.8 mg C l^?1) covaried with river flow and were invariably conservative in this turbid slowly flushing (~200 days) estuary, indicating that any microbial degradation, chemical flocculation or adsorption processes do not affect the flux of riverine DOC through the estuary. The DOC inputs from the Severn (1.7–2.7 × 10¹⁰ g Cyr^?1) and other rivers (2.6–3.4 × 10¹⁰ g Cyr^?1) are the principal sources of DOC in the estuary and correspond to an export of 0.7–1.1% of the terrestrial productivity from the river catchment to the ocean. This export rate is in accord with recent predictions derived from global compilations of organic inputs from rivers and would imply that the global flux of riverine DOC could be as high as 7.8 × 10¹⁴ g Cyr^?1 which is 5 times greater than some previous estimates.The geochemical significance of a conservative delivery of riverine DOC to the ocean is that irrespective of which flux estimate is considered, such river inputs would make a significant contribution (~SO%) to oceanic DOC, and that the steady-state oceanic DOC flux would have to be significantly greater than present estimates (2.9 × 10¹⁴ g Cyr^?1) which are based on a mean radio carbon age of 3400 yr.An alternative, more realistic DOC flux model, which assumes a polydisperse age distribution about the mean age, is shown to yield the higher oceanic DOC fluxes required. Flocculation and adsorption processes would remove less than 10% and 0.2% respectively of riverine DOC in estuaries.     

Basalt weathering in Central Siberia under permafrost conditions

Chemical weathering of basalts in the Putorana Plateau, Central Siberia, has been studied by combining chemical and mineralogical analysis of solids (rocks, soils, river sediments, and suspended matter) and fluid solution chemistry. Altogether, 70 large and small rivers, 30 soil pore waters and groundwaters and over 30 solids were sampled during July to August 2001. Analysis of multiannual data on discharge and chemical composition of several rivers of the region available from the Russian Hydrological Survey allowed rigorous estimation of mean annual major element concentrations, and dissolved and suspended fluxes associated with basalt weathering. For the rivers Tembenchi and Taimura that drain monolithologic basic volcanic rocks, the mean multiannual flux of total dissolved cations (TDS_c = Ca + Mg + Na + K) corrected for atmospheric input is 5.7 ± 0.5 t/km²/yr. For the largest river Nizhniya Tunguska—draining essentially basic rocks—the TDS_c is 6.1 ± 1.5 t/km²/yr. The overall CO₂ consumption flux associated with basalt weathering in the studied region (∼700,000 km²) achieves 0.08 × 10¹² mol/yr, which represents only 2.6% of the total CO₂ consumption associated with basalt weathering at the Earth’s surface. The fluxes of suspended matter were estimated as 3.1 ± 0.5, 9.0 ± 0.8, and 6.5 ± 2.0 t/km²/yr for rivers Taimura, Eratchimo, and Nizhniya Tunguska, respectively. Based on chemical analyses of river solutes and suspended matter, the relative dissolved versus particulate annual transport of major components is C_inorg ≥ C_org > Na + K > Ca > Mg > Si > Fe ≥ Mn ≥ Ti ≥ Al which reflects the usual order of element mobility during weathering.According to chemical and mineralogical soil and sediment analyses, alteration of basalt consists of (1) replacement of the original basaltic glass by Si-Al-Fe rich amorphous material, (2) mechanical desegregation and grinding of parent rocks, leading to accumulation of “primary” hydrothermal trioctahedral smectite, and (3) transformation of these trioctahedral (oxy)smectites and mixed-layer chlorite-smectite, into secondary dioctahedral smectite accompanied by removal of Ca, Mg, and Fe, and enrichment in Al. No vertical chemical differentiation of fluid and solid phases within the soil profile was identified. All sampled soil pore waters and groundwaters were found to be close to equilibrium with respect to chalcedony, gibbsite, halloysite, and allophanes, but strongly supersaturated with respect to goethite, nontronite, and montmorillonite.Over the annual cycle, the contribution of atmospheric precipitation, permafrost melting, underground reservoirs, litter degradation, and rock and soil mineral weathering for the overall TDS_c transport in the largest river of the region (Nizhniya Tunguska) is 9.3 ± 3, 10 ± 5, 10.5 ± 5, 25 ± 20, and 45 ± 30%, respectively. In the summertime, direct contribution of rocks and soil mineral weathering via solid/fluid interaction does not exceed 20%. The main unknown factors of element mobilization from basalt to the river is litter degradation in the upper soil horizon and parameters of element turnover in the vegetation.     

Hafnium isotopes in Arctic Ocean water

The first isotopic compositions of dissolved hafnium in seawater from across the Arctic Ocean are reported. Most samples from the four sub-basins of the Arctic Ocean have values within error of an average of ε_Hf = +0.8. Combined Hf-Nd isotope compositions do not fall on the well-established positive correlation for mantle and crustal rocks. Instead, Arctic waters have Hf that is more radiogenic than that typically found in rocks with similar Nd isotope compositions, a feature previously found in ferromanganese crusts and waters from the Pacific Ocean. Arctic seawater samples generally fall on the lower part of the ferromanganese crust array, reflecting influences of inputs from Arctic rivers and interactions of shelf waters with underlying sediments. Arctic rivers have much higher Hf concentrations (7-30 pM) than Arctic seawater (0.36-4.2 pM). Water from the Mackenzie River has the least radiogenic Hf, with ε_Hf = −7.1 ± 1.7, and plots furthest away from the ferromanganese crust array, while waters from the Ob, Yenisey, and Lena Rivers have values that are indistinguishable from most Arctic waters. In the Amundsen, Makarov, and Canada basins, Hf concentrations are highest at the surface and lowest in the deeper waters, reflecting the influences of riverine inputs and of waters that have flowed over the extensive Siberian continental shelves and have Nd and Hf characteristics that reflect water-sediment interactions. This is in contrast to the relatively low near surface Hf concentrations reported for locations elsewhere. The Pacific water layer in the Canada Basin exhibits the highest value of ε_Hf = +6.8 ± 1.8, reflecting the Hf isotopic composition of waters entering the Arctic from the Pacific Ocean. Mixing relationships indicate that a substantial fraction of the Hf in the Mackenzie River is lost during estuarine mixing; the behaviour of Hf from other rivers is less constrained.     

Stable isotope analysis of carbon cycling in the Perdido estuary, Florida

Stable carbon isotope (δ¹³C) analysis was used in the Peridido Estuary, Florida U.S. to determine the predominant carbon source that supports the bacterial assemblage. Stable carbon isotope values were measured in the suspended particulate matter (SPM), dissolved organic and inorganic matter, and bacteria. Stable nitrogen isotope (δ¹⁵N) ratios were measured in SPM and nitrate to assist in understanding carbon cycling through the estuary. Analyses were conducted on samples from riverine, coastal, and anthropogenic sources and compared with samples from the bay. Stable isotope ratio analysis was coupled with estimates of mixing of riverine and coastal waters into the bay. Preliminary observation of the °¹³C data indicates that terrestrial organic matter is the primary carbon source that is assimilated by bacteria in the ecosystem. Stable isotope data from carbon and nitrogen pools in combination with analysis of estuarine current velocities indicates that primary production is an important factor in the carbon cycle. This study demonstrates the importance of stable isotope analysis of multiple carbon and nitrogen pols to assess sources and cycling of organic matter.     

How important is it to integrate riverine suspended sediment chemical composition with depth? Clues from Amazon River depth-profiles

The vertical variability in mineralogical, chemical and isotopic compositions observed in large river suspended sediments calls for a depth-integration of this variability to accurately determine riverine geochemical fluxes. In this paper, we present a method to determine depth-integrated chemical particulate fluxes of large rivers, based on river sampling along depth-profiles, and applied to the Amazon Basin lowland tributaries. The suspended particulate matter (SPM) concentration data from depth-profiles is modeled for a number of individual grain size fractions using the Rouse model, which allows to predict the grain size distribution of suspended sediment throughout the whole river cross-section. Then, using (1) the relationship between grain size distribution and the Al/Si ratio (2) relationships between the Al/Si ratio and the chemical concentrations, the chemical composition of river sediment is predicted throughout the river cross-section, and integrated to yield the depth-integrated chemical particulate flux for a number of chemical elements (e.g. Si, Al, Fe, Na, REEs, …). For elements such as Al, Fe, REEs, Th, the depth-integrated flux is around twice as high as the one calculated from river surface sample characteristics. For Na and Si, the depth-integrated flux is three times higher than the “surface” estimate, due to the enrichment of albite and quartz at the bottom of the river. Depth-integrated ⁸⁷Sr/⁸⁶Sr composition of suspended sediment, also predictable using this method, differs by more than 10⁻³ from the surface sample composition.Finally, potential implications of depth-integrated estimates of Amazon sediment chemistry are explored. Depth-integration of particulate ⁸⁷Sr/⁸⁶Sr isotopic ratios is necessary for a reliable use of Sr isotopes as a provenance tracer. The concept of steady-state weathering of a large river basin is revisited using depth-integrated sediment composition. This analysis shows that, in the Amazon Basin river, the previously observed discrepancy between (1) weathering intensities of channel surface sediment and (2) silicate-derived dissolved fluxes is only slightly accounted for by the vertical variability of suspended sediment weathering intensities. This observation confirms that most large rivers basins are not eroding at steady-state.     

Biological uptake and accumulation of silica on the Amazon continental shelf

Water column and seabed samples were obtained from 92 stations on the Amazon continental shelf during October of 1979. Uptake of silica near and southeast of the river mouth began at a salinity of 8%. and accounted for 17% of the riverine silica flux to this region. Uptake northwest of the river mouth began at a salinity of 20%. and resulted in 33% removal of the riverine silica flux. Examination of filtered suspended solids revealed abundant diatoms in the surface waters, including Coscinodiscus. Skeletonema, Synedra. and Thalassiosira. The biological uptake of silica appears to be dependent on three factors: turbidity, turbulence, and nutrient availability. There was no evidence of abiological removal of silica in the Amazon estuary. 75 to 88% of the silica removed from surface waters by diatoms dissolves prior to accumulation in the seabed. Based on the mean biogenic silica content of shelf sediment (0.25%) and estimates of rates of sediment accumulation, the biogenic silica accumulation rate on the shelf is 2 × 10¹² g/yr, which represents only 4% of the dissolved silica supplied by the Amazon River. Biological uptake of silica in estuarine surface waters may not accurately reflect permanent removal of biogenic silica to the seabed because of dissolution which occurs in bottom waters and near the sediment-water interface.     

Nutrient dynamics in the Pomeranian Bay (southern Baltic): Impact of the Oder River outflow

The Pomeranian Bay is a coastal region fed by the Oder River, one of the seven largest Baltic rivers, whose waters flow through a large and complex estuarine system before entering the bay. Nutrients (NO₃ ⁻, NO₂ ⁻, NH₄ ⁺, Ntot, PO₄ ³⁻, P_tot, DSi), chlorophylla concentrations, oxygen content, salinity, and temperature were measured in the Pomeranian Bay in nine seasonally distributed cruises during 1993–1997. Strong spatial and temporal patterns were observed and they were governed by: the seasonally variable riverine water-nutrient discharges, the seasonally variable uptake of nutrients and their cycling in the river estuary and the Bay, the character of water exchange between the Pomeranian Bay and the Szczecin Lagoon, and the water flow patterns in the Bay that are dominated by wind-driven circulation. Easterly winds resulted in water and nutrient transport along the German coastline, while westerly winds confined the nutrient rich riverine waters to the Polish coast and transported them eastward beyond the study area. Two water masses, coastal and open, characterized by different chemical and physical parameters and chla content were found in the Bay independently of the season. The role of the Oder estuary in nutrient transformation, as well as the role of temperature in transformation processes is stressed in the paper. The DIN:DIP:DSi ratio indicated that phosphorus most probably played a limiting role in phytoplankton production in the Bay in spring, while nitrogen did the same in summer. During the spring bloom, predominated by diatoms, the DSi:DIN ratio dropped to 0.1 in the coastal waters and to 0.6 in the open bay waters, pointing to silicon limitation of diatom growth, similar to what is being observed in other Baltic regions.     

Dynamics of nutrient elements in three estuaries of North China: The Luanhe, Shuangtaizihe, and Yalujiang

Concentrations of nutrients (NO₃ ^?, NO₂ ^?, NH₄ ⁺, PO₄ ^3?, and dissolved SiO₂) were examined in three North China estuaries—the Luanhe, Shuangtaizihe, and Yalujiang. These riverine-estuarine systems provide distinct geographic and hydrodynamic conditions, that is, a shallow water zone embraced by shoals and sandbars (Luanhe), the confluence of two streams in the upper estuary with different water and sediment loads, and a turbidity maximum in the upper estuarine mixing zone (Yalujiang). Nutrient element concentrations in these rivers are high in comparison with large, less disturbed systems but similar to those from polluted and/or eutrophic European and North American rivers. This is attributed to intensive weathering and erosion and extensive use of chemical fertilizers. In the fresh-marine waters mixing zone, nutrient species can behave either conservatively or nonconservatively, or both. Wherever nonconservative behaviours of nutrient elements are observed, remobilization from solid phases is probably the predominant mechanism. The extrapolation of dilution curves to the fresh water end-members gives estimated riverine concentrations, which can be between two and ten times higher than those from field observations. Taking into account the high N:P ratios (10²–10⁴) from North China rivers and very low concentrations of nitrogen species in the Northwest Pacific coastal oceans (e.g., Yellow Sea), the estuaries in this study may act as regions in which production is limited by phosphorus to regions in which production is limited by nitrogen.     

Seasonally chemical weathering and CO<Subscript>2</Subscript> consumption flux of Lake Qinghai river system in the northeastern Tibetan Plateau

The major cation and anion compositions of waters from the Lake Qinghai river system (LQRS) in the northeastern Tibetan Plateau were measured. The waters were collected seasonally from five main rivers during pre-monsoon (late May), monsoon (late July), and post-monsoon (middle October). The LQRS waters are all very alkaline and have high concentrations of TDS (total dissolved solids) compared to rivers draining the Himalayas and the southeastern Tibetan Plateau. Seasonal variations in the water chemistry show that, except the Daotang River, the TDS concentration is high in October and low in July in the LQRS waters. The forward models were used to quantify the input of three main rivers (Buha River, Shaliu River, and Hargai River) from rain, halite, carbonates, and silicates. The results suggest that (1) atmospheric input is the first important source for the waters of the Buha River and the Shaliu River, contributing 36–57% of the total dissolved cations, (2) carbonate weathering input and atmospheric input have equal contribution to the Hargai River water, (3) carbonate weathering has higher contribution to these rivers than silicate weathering, and (4) halite is also important source for the Buha River. The Daotang River water is dominated by halite input owing to its underlying old lacustrine sediments. The water compositions of the Heima River are controlled by carbonate weathering and rainfall input in monsoon season, and groundwater input may be important in pre-monsoon and post-monsoon seasons. After being corrected the atmospheric input, average CO₂ drawdown via silicate weathering in the LQRS is 35 × 10³ mol/km² per year, with highest in monsoon season, lower than Himalayas and periphery of Tibetan Plateau rivers but higher than some rivers draining shields.     

Aquatic hydrocarbon distributions in the Seine estuary: Biogenic polyaromatics and n-alkanes

Dissolved and particulate hydrocarbons of biogenic origin were investigated for the first time in surface waters along the Seine River and its estuary. They comprise n-alkanes (n-ALKs) and diagenetic polycyclic aromatic hydrocarbons (PAHs). Samples were collected in three different sections of the estuary: the riverine zone, the mixing zone, and the marine zone. At the river mouth, two mooring stations were used for the collection of samples over tidal cycles. Total particulate n-ALK concentrations ranged from 31 ng 1^?1 to 2,918 ng 1^?1, or 5 μg g^?1 dry ng 1^?1, or 2 μg g^?1 of SM. Concentrations varied with the SM load and could be related to sedimentation and estuarine mixing. The sources of the n-ALKs were different in each zone of the estuary. The dissolved n-ALKs displayed lower concentrations than the particulate phase, varying from 136 ng 1^?1 to 344 ng 1^?1, while biogenic dissolved PAHs were almost absent.