Particle size and mineralogical composition of inorganic colloids in waters draining the adit of an abandoned mine,Goesdorf, Luxembourg

Particle size distributions and the mineralogy of inorganic colloids in waters draining the adit of an abandoned mine (Goesdorf, Luxembourg) were quantified by single particle counting based on light scattering (100 nm–2 μm) combined with transmission electronic microscopy coupled with energy dispersive spectroscopy and selected area electron diffraction. This water system was chosen as a surrogate for groundwaters. The dependence of the colloid number concentration on colloid diameters can be described by a power-law distribution in all cases. Power-law slopes ranged from −3.30 to −4.44, depending on water ionic strength and flow conditions. The same main mineral types were found in the different samples: 2:1 phyllosilicates (illite and mica), chlorite, feldspars (albite and orthoclase), calcite and quartz; with a variable number of Fe oxide particles. The colloid mineralogical composition closely resembles the composition of the parent rock. Spatial variations in the structure and composition of the rock in contact with the waters, i.e. fissured rock versus shear joints, are reflected in the colloid composition. The properties of the study colloids, as well as the processes influencing them, can be considered as representative of the colloids present in groundwaters.     

Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.     

An iodine mass-balance for Lake Constance, Germany: Insights into iodine speciation changes and fluxes

Lake Constance is one of Europe’s largest oligotrophic lakes and provides a water source for more than 4.5 million people in Germany and Switzerland. We present here a 12 month study on iodine concentrations, speciation and fluxes to and from the lake to gain a quantitative understanding of the limnic iodine cycle. Monthly water samples were obtained from all major tributaries (14) and the outflow to construct a mass-balance model. Sediment traps were also deployed in the lake for two years at two different stations. Total soluble iodine (TSI) in aqueous samples were analysed by ICP-MS and speciation (iodide, iodate and soluble organically bound iodine, SOI) by ion chromatography-ICP-MS. Iodine concentrations in the Alpine tributaries (1-2 μg l⁻¹) decreased over the summer months due to increasing proportions of snow and glacial melt water from the Alps, while iodine levels in the lowland rivers (∼2-10 μg l⁻¹) increased over the summer. Deposition of TSI to the catchment (16,340 kg I yr⁻¹) was similar to the TSI out-flux by rivers (16,000 kg I yr⁻¹). By also including the particulate riverine iodine flux out of the catchment (∼12,350 kg I yr⁻¹) it is shown that the catchment is a net source of iodine, with the highest particulate fluxes coming from the Alpine rivers. The total TSI flux to the lake was 16,770 kg I yr⁻¹, the largest proportion coming from the Alpenrhein (43%), followed by the Schussen (8%) and Bregenzer Ach (7.7%). Overall the mass-balance for TSI in the lake was negative, with more iodine flowing out of the lake than in (−2050 kg I yr⁻¹; 12% of TSI in-flux). To maintain mass-balance, 8.8 μg I m⁻² d⁻¹ from the Obersee and 23 μg I m⁻² d⁻¹ from the Untersee must be released from the sediments into the water column. Thus, in comparison with the total iodine flux to the sediments measured by the sediment traps (4762-8075 kg I yr⁻¹), up to 39% of the deposited iodine may be mobilised back into the lake. SOI was the dominant iodine fraction entering the lake, with a total flux of 10,290 kg I yr⁻¹ (64% of TSI input), followed by iodate (3120 kg I yr⁻¹) and iodide (2760 kg I yr⁻¹). Net formation of SOI from iodide and iodate was also noted within the lake, with an estimated production of 6560 kg I yr⁻¹, suggesting a strong role for biology in iodine cycling. In conclusion, organically bound iodine was the dominant iodine species in aqueous and solid phases in Lake Constance, despite low DOC concentrations (<2 mg l⁻¹), and thus is expected to play an important role in iodine cycling in most freshwater environments.     

Bromine species fluxes from Lake Constance’s catchment, and a preliminary lake mass balance

Bromine was historically termed a cyclic salt in terrestrial freshwater environments due to its perceived conservative cycling between the oceans and the continents. This basic assumption has been challenged recently, with evidence that bromine is involved in dynamic chemical cycles in soils and freshwaters. We present here a study on dissolved bromine species (bromide, organically bound bromine, DOBr) concentrations and fluxes as well as sediment trap bromine levels and fluxes in Lake Constance, a large lake in southern Germany. Water samples were obtained from all major and some minor inflows and outflows over one year, where-after dissolved bromine species were measured by a combination of ICP-MS and ion chromatography coupled to an ICP-MS (IC-ICP-MS). Sediment traps were deployed at two locations for two years with Br, Ti and Zr levels being measured by μ-XRF.190 t yr⁻¹ of total dissolved bromine (TDBr) was delivered to the lake via 14 rivers and precipitation, with the rivers Alpenrhein (84 t TDBr yr⁻¹) and the Schussen (50 t TDBr yr⁻¹) providing the largest sources. The estimated particulate bromine flux contributed an extra 24-26 t Br yr⁻¹. In comparison, only 40 t TDBr yr⁻¹ was deposited to the lake’s catchment by precipitation, and thus ∼80% of the riverine TDBr flux came from soils and rocks. Bromide was the dominant species accounting for, on average, 78% of TDBr concentrations and 93% of TDBr flux to the lake. Despite some high concentrations in the smaller lowland rivers, DOBr was only a minor component of the total riverine bromine flux (∼12 t yr⁻¹, 7%), most of which came from the rivers Schussen, Bregenzer Ach and Argen. In contrast, most of the bromine in the sediment traps was bound to organic matter, and showed a clear seasonal pattern in concentrations, with a maximum in winter and minimum in summer. The summer minimum is thought to be due to dilution of a high Br autochthonous component by low bromine mineral and organic material from the catchment, which is supported by Ti, Zr and Br/C_org data. In the lake bromine was irreversibly lost to the sediments, with best flux estimates based on mass-balance and sediment trap data of +50-90 μg Br m⁻² d⁻¹. Overall, it appears that bromine is not simply a cyclic salt in the case of Lake Constance, with a clear geological component and dynamic lacustrine biogeochemistry.     

Monomethylmercury sources in a tropical artificial reservoir

The distribution and speciation of mercury (Hg) in the water column, the inputs (wet deposition and tributaries) and the outputs (atmospheric evasion and outlet) of an artificial partially anoxic tropical lake (Petit-Saut reservoir, French Guiana) were investigated on a seasonal basis in order to appraise the cycling and transformations of this metal. The total mercury (HgT) concentrations in the oxygenated epilimnetic waters averaged 5 ± 3 pmol L⁻¹ in the unfiltered samples (HgT_UNF) and 4 ± 2 pmol L⁻¹ in the dissolved (HgT_D) phase (<0.45 μm). On average, the monomethylmercury (MMHg) constituted 8%, 40% and 18% of the HgT in the dissolved phase, the particulate suspended matter and in the unfiltered samples, respectively. Covariant elevated concentrations of particulate MMHg and chlorophyll a in the epilimnion suggest that phytoplankton is an active component for the MMHg transfer in the lake. In the anoxic hypolimnion the HgT_UNF averages 13 ± 6 pmol L⁻¹ and the HgT_D 8 ± 4 pmol L⁻¹. The averages of MMHg_P and MMHg_D in hypolimnetic waters were two and three times the corresponding values of the epilimnion, 170 ± 90 pmol g⁻¹ and 0.9 ± 0.5 pmol L⁻¹, respectively. In the long dry and wet seasons, at the flooded forest and upstream dam sampling stations, the vertical profiles of MMHg_D concentrations accounted for two distinct maxima: one just below the oxycline and the other near the benthic interface. Direct wet atmospheric deposition accounted for 14 moles yr⁻¹ HgT_UNF, with 0.7 moles yr⁻¹ as MMHg_UNF, while circa 76 moles yr⁻¹ of HgT_UNF, with 4.7 moles yr⁻¹ as MMHg_UNF, coming from tributaries. Circa 78 moles (∼17% as MMHg) are annually exported through the dam, while 23 moles yr⁻¹ of Hg⁰ evolve in the atmosphere. A mass balance calculation suggests that the endogenic production of MMHg_UNF attained 8.1 moles yr⁻¹, corresponding to a methylation rate of 0.06% d⁻¹. As a result, the Petit-Saut reservoir is a large man-made reactor that has extensively altered mercury speciation in favor of methylated species.     

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.     

Sr and Nd isotopes as tracers of clastic sources in Lake Le Bourget sediment (NW Alps, France) during the Little Ice Age: Palaeohydrology implications

Geochemical methods (major elements and Sr, Nd isotopes) have been used to (1) characterize Lake Le Bourget sediments in the French Alps, (2) identify the current sources of the clastic sediments and estimate the source variability over the last 600 years. Major element results indicate that Lake Le Bourget sediments consist of 45% clastic component and 55% endogenic calcite. In addition, several individual flood levels have been identified during the Little Ice Age (LIA) on the basis of their higher clastic content (> 70%).Potential sources of Lake Le Bourget clastic sediments have been investigated from Sr and Nd isotope compositions. The sediments from the Sierroz River and Leysse River which are mainly derived from the Mesozoic Calcareous Massifs are characterised by lower ⁸⁷Sr/⁸⁶Sr ratios and slightly lower ?_Nd(0) ratios than the Arve River sediments which are derived from the Palaeozoic Mont-Blanc External Crystalline Massifs. The Rhône River appears to have been the main source of clastic sediments into the lake for the last 600 years, as evidenced by a similar Sr and Nd isotopic compositions analyzed in core B16 sediments (⁸⁷Sr/⁸⁶Sr = 0.719, ?_Nd(0) = − 10) and in the sediments of the Rhône River (⁸⁷Sr/⁸⁶Sr = 0.719, ?_Nd(0) = − 9.6).The isotopic signatures of flood events and background samples from core B16 in Lake Le Bourget are also similar. This indicates that prior to ∼ 1800, the inputs into the lake have remained relatively homogeneous with the proportion of clastic component mainly being a function of the palaeohydrology of the Rhone River. Early human modification (deforestation and agriculture) of the lake catchment before the 1800s appears to have had little influence on the source of clastic sediments.     

Seasonal variations of physical and chemical erosion: A three-year survey of the Rhone River (France)

Numerous studies of weathering fluxes have been carried out on major world rivers during the last decade, to estimate CO₂ consumption rates, landscape evolution and global erosion rates. For obvious logistical reasons, most of these studies were based on large scale investigations carried out on short timescales. By comparison, much less effort has been devoted to long term monitoring, as a means to verify the temporal variability of the average characteristics, their trends, and the representativeness of short-term investigations. Here we report the results of a three-year survey (November 2000 to December 2003) of the major and trace element composition of dissolved and suspended matter in the lower Rhone River (France), the largest river of the Mediterranean area. Subsurface water samples were collected in Arles, about 48 km upstream of the estuary, twice a month routinely, and at higher frequency during flood events.During each flood event, the suspended particulate matter (SPM) show the usual trend of clockwise hysteresis with higher SPM concentrations on the rising limb of the flood than at the same discharge on the falling limb. We show that the annual average SPM flux of the Rhone River to the Mediterranean Sea (7.3 ± 0.6 × 10⁶ tons yr⁻¹) was largely controlled by the flood events (83% of the solid discharge occurred in less than 12% of the time), and that the precision on the total output flux depends strongly on the precise monitoring of SPM variations during the floods.The chemical composition of water and SPM are characterized by the predominance of Ca²⁺ due to the abundance of carbonate rocks in the Rhone watershed. Chemical budgets have been calculated to derive the contributions of atmospheric deposition, carbonate, silicate and evaporite weathering, and anthropogenic inputs. The chemical weathering rate of carbonates is estimated to be 89 ± 5 t km⁻² yr⁻¹ compared to 14.4 ± 3 t km⁻² yr⁻¹ from silicates. By contrast, the physical erosion rate of silicates is about 51 t km⁻² yr⁻¹ against 19 t km⁻² yr⁻¹ for carbonates.The steady-state model of Gaillardet et al. (1995) has been applied to the chemical composition of dissolved and solid products. The results show that the Rhone River currently exports much less material than produced at steady-state by weathering in its watershed. The sediment flux inferred from the steady-state calculation (21-56 × 10⁶ t yr⁻¹) is on the same order as that estimated in literature for the 19th and the beginning of the 20th centuries. This imbalance may suggest that the Rhone is under a transient erosion regime following climate change (i.e. significant decrease of the flooding frequency since the beginning of the 19th century). On the other hand, the imbalance may also be due to the trapping of alluvion by the numerous dams on the river and its tributaries.Our data corroborate with previous studies that suggest a strong coupling between chemical and physical erosion fluxes, during the hydrological seasonal cycle of the Rhone River. The correlation between physical and chemical transport rates is, however, clearly different from that reported for global annual averages in large world rivers.     

The distribution of total mercury and methyl mercury in a shallow hypereutrophic lake (Lake Taihu) in two seasons

To understand the geochemical cycle of Hg in hypereutrophic freshwater lake, two sampling campaigns were conducted in Lake Taihu in China during May and September of 2009. The concentrations of unfiltered total Hg (unfTHg) were in the range of 6.8–83 ng L⁻¹ (28 ± 18 ng L⁻¹) in the lake water and total Hg in the sediment was 12–470 ng g⁻¹, both of which are higher than in other background lakes. The concentration of unfTHg in ∼11% of the lake water samples exceeded the second class of the Chinese environmental standards for surface water of 50 ng L⁻¹ (GB 3838-2002), indicating that a high ecological risk is posed by the Hg in Lake Taihu. However, the concentrations of unfiltered total MeHg (unfMeHg) were relatively low in the lake water (0.14 ± 0.05 ng L⁻¹, excluding two samples with 0.81 and 1.0 ng L⁻¹). Lake sediment MeHg varied from 0.2–0.96 ng g⁻¹, with generally low ratios of MeHg/THg of <1%. The low concentrations of TMeHg in the lake water may have resulted from a strong uptake by the high primary productivity and the demethylation of MeHg in oxic conditions. In addition, contrary to the results of previous research conducted in deep-water lakes and reservoirs, the low concentrations of MeHg and low ratio of MeHg/THg in the lake sediment indicates that the net methylation of Hg was not accelerated by the elevated organic matter load created by the eutrophication of Lake Taihu. The results also showed that sediments were a source of THg and MeHg in the water. Higher diffusion fluxes of THg and MeHg may be partly responsible for the higher concentrations of THg in the lake water in May, 2009.     

Re-assessing the surface cycling of molybdenum and rhenium

We re-evaluate the cycling of molybdenum (Mo) and rhenium (Re) in the near-surface environment. World river average Mo and Re concentrations, initially based on a handful of rivers, are calculated using 38 rivers representing five continents, and 11 of 19 large-scale drainage regions. Our new river concentration estimates are 8.0 nmol kg⁻¹ (Mo), and 16.5 pmol kg⁻¹ (Re, natural + anthropogenic). The linear relationship of dissolved Re and in global rivers (R² = 0.76) indicates labile continental Re is predominantly hosted within sulfide minerals and reduced sediments; it also provides a means of correcting for the anthropogenic contribution of Re to world rivers using independent estimates of anthropogenic sulfate. Approximately 30% of Re in global rivers is anthropogenic, yielding a pre-anthropogenic world river average of 11.2 pmol Re kg⁻¹. The potential for anthropogenic contribution is also seen in the non-negligible Re concentrations in precipitation (0.03-5.9 pmol kg⁻¹), and the nmol kg⁻¹ level Re concentrations of mine waters. The linear Mo- relationship (R² = 0.69) indicates that the predominant source of Mo to rivers is the weathering of pyrite. An anthropogenic Mo correction was not done as anthropogenically-influenced samples do not display the unambiguous metal enrichment observed for Re. Metal concentrations in high temperature hydrothermal fluids from the Manus Basin indicate that calculated end-member fluids (i.e. Mg-free) yield negative Mo and Re concentrations, showing that Mo and Re can be removed more quickly than Mg during recharge. High temperature hydrothermal fluids are unimportant sinks relative to their river sources 0.4% (Mo), and 0.1% (pre-anthropogenic Re). We calculate new seawater response times of 4.4 × 10⁵ yr (τ_Mo) and 1.3 × 10⁵ yr (τ_Re, pre-anthropogenic).     

Holocene lake development and glacial-isostatic uplift at Lake Skallen and Lake Oyako,Lützow-Holm Bay,East Antarctica: Based on biogeochemical facies and molecular signatures

The paleolimnology of two lakes which were isolated as a result of the crustal uplift during the late Holocene along the Soya Coast, Lützow-Holm Bay, East Antarctica were studied. The focus was on temporal variations in the biogeochemical composition of sediment cores recovered from Lake Skallen at Skallen and Lake Oyako at Skarvsnes. Both sets of lake sediments record environmental changes associated with a transition from marine to lacustrine settings, as indicated by analyses of C and N contents, nitrogen isotopic compositions (δ¹⁵N), and major element concentrations. Changes in the dominant primary producers during the marine–lacustrine transition (marine diatom to cyanobacteria) at L. Skallen was clearly revealed by biogenic opal-A, diatom assemblages, and molecular signature from denaturing gradient gel electrophoresis (DGGE) with 16S ribosomal RNA (rRNA) gene analysis. Radiocarbon dating of acid-insoluble organic C suggested that the environmental transition from marine to fresh water occurred at 2940 ± 100 cal yr BP at L. Skallen and 1060 ± 90 cal yr BP at L. Oyako. Based on these data, a mean crustal uplift rate of 3.2 mm yr⁻¹ is inferred for the history of marine–lacustrine transition via brackish conditions. The geological setting causing glacio-isostatic uplift was the primary factor in controlling the transition event in sedimentary and biological facies.     

Effect of groundwater pH and ionic strength on strontium sorption in aquifer sediments: Implications for Sr mobility at contaminated nuclear sites

Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of ⁹⁰Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of ⁹⁰Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L⁻¹), pH variation is the main control on sorption. The sorption edge for ⁹⁰Sr was observed between pH 4 and 6 with maximum sorption occurring (K_d ∼ 10³ L kg⁻¹) at pH 6–8. At ionic strengths above 10 mmol L⁻¹, and at pH values between 6 and 8, cation exchange processes reduced ⁹⁰Sr uptake to the sediment. This exchange process explains the lower ⁹⁰Sr sorption (K_d ∼ 40 L kg⁻¹) in the presence of artificial Magnox tank liquor (IS = 29 mmol L⁻¹). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr²⁺ in either HCO₃-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr²⁺ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated ⁹⁰Sr was exchangeable with 1 M MgCl₂ in all experiments. These results suggest that over long periods, ⁹⁰Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of ⁹⁰Sr is to be expected.     

Direct detection of ultra-trace vanadium (V) in natural waters by flow-injection chemiluminescence with controlled-reagent-release technology

A new simple, rapid, selective and sensitive analytical procedure based on chemiluminescence (CL) detection is described for the determination of vanadium (V) at sub-nanogram levels in natural waters by use of controlled-reagent- release technology in a flow injection system. The analytical reagents involved in the CL reaction, including luminal and periodate, were both immobilized on anion-exchange resins in a flow injection system. Through water injection, luminol and periodate were eluted from the anion exchange column to generate the chemiluminescence, which was enhanced in the presence of V(V). The increased CL intensity was linear with V(V) concentration in the range from 0.2 to 100 ng mL^− 1. The limit of detection was 60 pg mL^− 1 (3σ) and the relative standard deviation (RSD) was 1.45% (n = 5) for a 0.5 ng mL^− 1 V(V). At a flow rate of 2.0 mL min− ¹, including sampling and washing, a typical analytical procedure could be performed in 0.5 min with a RSD of less than 3.0%. The proposed method was successfully applied to determine vanadium in natural waters, and the results were in good agreement with those obtained by ion chromatography.     

Sr fluxes and Sr/Sr characterization of river waters from a karstic versus granitic watershed in the Yangtze River

The watershed in the southern Jiangxi Province (Jiangxi Province is called simply Gan) (SGW) and the watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) are two subtropical watersheds of the Yangtze River in China. Both watersheds have similar latitudes and climate, but distinct differences in basin lithology. These similarities and differences provide a good natural laboratory in which to investigate weathering processes and Sr end-members in river waters. This work aims to identify and contrast the sources, fluxes and controls on Sr isotopic composition in the river waters of these two areas. Results showed that the ⁸⁷Sr/⁸⁶Sr in the SGW waters ranged from 0.716501 to 0.724931, with dissolved Sr averaging 27 μg l^− 1. Rhyolites and granites are two major sources for the dissolved Sr. The SGW waters receive 42% of their Sr from silicates weathering, 32% from carbonates and 3.2% from evaporites. ⁸⁷Sr/⁸⁶Sr in the CQW waters has a lesser variation from 0.707694 to 0.710039, but higher Sr contents (average of 208 μg l^− 1). Dolomite, limestone and dolomitic limestone are major sources of Sr in the waters. The CQW waters receive 69% of their Sr from carbonates, 1.7% from silicates and 0.9% from evaporites. The chemical erosion rate and Sr flux in the CQW are 122 t km^− 2 a^− 1 and 0.079 t km^− 2 a^− 1, respectively, which are higher than those of the SGW (56 t km^− 2 a^− 1 and 0.021 t km^− 2 a^− 1, respectively). These data suggest that the intensive carbonates weathering occurred in the karstic area in the upper-reach of the Yangtze River exert great influence on the high Sr concentration and low Sr isotopic ratios in the River.     

The role of sulfate groups in controlling CaCO3 polymorphism

The nucleation and growth of CaCO₃ phases from aqueous solutions with SO₄²⁻:CO₃²⁻ ratios from 0 to 1.62 and a pH of ∼10.9 were studied experimentally in batch reactors at 25 °C. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and microanalyses. The solids recovered after short reaction times (5 min to 1 h) consisted of a mixture of calcite and vaterite, with a S content that linearly correlates with the SO₄²⁻:CO₃²⁻ ratio in the aqueous solution. The solvent-mediated transformation of vaterite to calcite subsequently occurred. After 24 h of equilibration, calcite was the only phase present in the precipitate for aqueous solutions with SO₄²⁻:CO₃²⁻ ? 1. For SO₄²⁻:CO₃²⁻ > 1, vaterite persisted as a major phase for a longer time (>250 h for SO₄²⁻:CO₃²⁻ = 1.62). To study the role of sulfate in stabilizing vaterite, we performed a molecular simulation of the substitution of sulfate for carbonate groups into the crystal structure of vaterite, aragonite and calcite. The results obtained show that the incorporation of small amounts (<3 mole%) of sulfate is energetically favorable in the vaterite structure, unfavorable in calcite and very unfavorable in aragonite. The computer modeling provided thermodynamic information, which, combined with kinetic arguments, allowed us to put forward a plausible explanation for the observed crystallization behavior.     

Temporal variability in terrestrially-derived sources of particulate organic carbon in the lower Mississippi River and its upper tributaries

In this study, we examined the temporal changes of terrestrially-derived particulate organic carbon (POC) in the lower Mississippi River (MR) and in a very limited account, the upper tributaries (Upper MR, Ohio River, and Missouri River). We used for the first time a combination of lignin-phenols, bulk stable carbon isotopes, and compound-specific isotope analyses (CSIA) to examine POC in the lower MR and upper tributaries.A lack of correlation between POC and lignin phenol abundances (Λ₈) was likely due to dilution effects from autochthonous production in the river, which has been shown to be considerably higher than previously expected. The range of δ¹³C values for p-hydroxycinnamic and ferulic acids in POC in the lower river do support that POM in the lower river does have a significant component of C₄ in addition to C₃ source materials. A strong correlation between δ¹³C values of p-hydroxycinnamic, ferulic, and vanillyl phenols suggests a consistent input of C₃ and C₄ carbon to POC lignin while a lack of correlation between these same phenols and POC bulk δ¹³C further indicates the considerable role of autochthonous carbon in the lower MR POC budget. Our estimates indicate an annual flux of POC of 9.3 × 10⁸ kg y⁻¹ to the Gulf of Mexico. Total lignin fluxes, based on Λ₈ values of POC, were estimated to be 1.2 × 10⁵ kg y⁻¹. If we include the total dissolved organic carbon (DOC) flux (3.1 × 10⁹ kg y⁻¹) reported by [Bianchi T. S., Filley T., Dria K. and Hatcher, P. (2004) Temporal variability in sources of dissolved organic carbon in the lower Mississippi River. Geochim. Cosmochim. Acta68, 959-967.], we get a total organic carbon flux of 4.0 × 10⁹ kg y⁻¹. This represents 0.82% of the annual total organic carbon supplied to the oceans by rivers (4.9 × 10¹¹ kg).     

Subaquatic slope instabilities: The aftermath of river correction and artificial dumps in Lake Biel (Switzerland)

River engineering projects are developing rapidly across the globe, drastically modifying water courses and sediment transfer. Investigation of the impact of engineering works focuses usually on short-term impacts, thus a longer-term perspective is still missing on the effects that such projects have. The ‘Jura Water Corrections’ – the largest river engineering project ever undertaken in Switzerland – radically modified the hydrological system of Lake Biel in the 19th and 20th Century. The deviation of the Aare River into Lake Biel more than 140 years ago, in 1878, thus represents an ideal case study to investigate the long-term sedimentological impacts of such large-scale river rerouting. Sediment cores, along with new high-resolution bathymetric and seismic reflection datasets were acquired in Lake Biel to document the consequences of the Jura Water Corrections on the sedimentation history of Lake Biel. Numerous subaquatic mass transport structures were detected on all of the slopes of the lake. Notably, a relatively large mass transport complex (0·86 km²) was observed on the eastern shore, along the path of the Aare River intrusion. The large amount of sediment delivered by the Aare River since its deviation into the lake likely caused sediment overloading resulting in subaquatic mass transport. Alternatively, the dumping since 1963 in a subaquatic landfill of material excavated during the second phase of river engineering, when the channels flowing into and out of Lake Biel were widened and deepened, might have triggered the largest mass transport, dated to 1964 or 1965. Additional potential triggers include two nearby small earthquakes in 1964 and 1965 (M_W 3·9 and 3·2, respectively). The data for this study indicate that relatively large mass transports have become recurrent in Lake Biel following the deviation of the Aare River, thus modifying hazard frequency for the neighbouring communities and infrastructure.     

Effects of aridity and vegetation on plant-wax δD in modern lake sediments

We analyzed the deuterium composition of individual plant-waxes in lake sediments from 28 watersheds that span a range of precipitation D/H, vegetation types and climates. The apparent isotopic fractionation (ε_a) between plant-wax n-alkanes and precipitation differs with watershed ecosystem type and structure, and decreases with increasing regional aridity as measured by enrichment of ²H and ¹⁸O associated with evaporation of lake waters. The most negative ε_a values represent signatures least affected by aridity; these values were −125 ± 5‰ for tropical evergreen and dry forests, −130‰ for a temperate broadleaf forest, −120 ± 9‰ for the high-altitude tropical páramo (herbs, shrubs and grasses), and −98 ± 6‰ for North American montane gymnosperm forests. Minimum ε_a values reflect ecosystem-dependent differences in leaf water enrichment and soil evaporation. Slopes of lipid/lake water isotopic enrichments differ slightly with ecosystem structure (i.e. open shrublands versus forests) and overall are quite small (slopes = 0-2), indicating low sensitivity of lipid δD variations to aridity compared with coexisting lake waters. This finding provides an approach for reconstructing ancient precipitation signatures based on plant-wax δD measurements and independent proxies for lake water changes with regional aridity. To illustrate this approach, we employ paired plant-wax δD and carbonate-δ¹⁸O measurements on lake sediments to estimate the isotopic composition of Miocene precipitation on the Tibetan plateau.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Reduced sulfur species in a stratified seawater lake (Rogoznica Lake, Croatia); seasonal variations and argument for organic carriers of reactive sulfur

Over a period of a year, Hg⁰-reactive, total reduced sulfur species (RSS_T), as well as a non-volatile fraction that cannot be gas-stripped at pH ∼2 (RSS_NV), have been measured by voltammetry in a stratified, saline lake. In the hypolimnion, RSS_T is dominated by unusually high (up to 5 mM) dissolved divalent sulfur (S^−II), present as H₂S + HS⁻ and as inorganic polysulfides (H_xS_n^x−2). Less abundant RSS_NV is attributed to dissolved zero-valent sulfur (S⁰) in inorganic polysulfides. Assuming negligible contribution of organic S⁰ species in the hypolimnion, the equilibrium distribution of polysulfide ions is calculated; S₅²⁻ is found to predominate. In the epilimnion, all RSS_T consists of RSS_NV within analytical uncertainty. Through spring and summer, RSS_T and RSS_NV display little vertical or seasonal variation, but they increase dramatically when stratification breaks down in autumn. Based on decay rate, RSS during mixing events is attributed to dissolved S₈ from oxidation of sulfide and decomposition of inorganic polysulfides. This hypothesis quantitatively predicts precipitation of elemental sulfur in a year when colloidal sulfur was observed and predicts no precipitation in a year when it was not observed. Except during mixing events, the entire water column is undersaturated with respect to both rhombic sulfur and biologic sulfur, and the limited variations of RSS exclude hydrophobic and volatile aqueous S₈ as a major species. During such periods, RSS (typically 8 nM) may be associated with organic carbon, perhaps as adsorbed S₈ or as covalently bound polysulfanes or polysulfides. The hypolimnion is viewed as a zero-valent sulfur reactor that creates S⁰-containing, dissolved organic macromolecules during stable stratification periods. Some are sufficiently degradation-resistant and hydrophilic to be dispersed throughout the lake during mixing events, subsequently giving rise to ∼10⁻⁸ M RSS in the oxic water column. Voltammetrically determined RSS in oxic natural waters has often been described as “sulfide” or “metal complexed sulfide”, implying an oxidation state of S^−II; we argue that RSS in oxic Rogoznica Lake waters is mainly S⁰.