Anthropogenic components of heavy metal (Cd,Zn, Cu,Pb) budgets in the Lot-Garonne fluvial system (France)     

《Applied Geochemistry》2004,19(5):769-786

Heavy metal (Zn, Cd, Cu and Pb) mass balances in the Lot-Garonne fluvial system have been established for 1999 and 2000. The mean annual discharges of these years are close to the mean discharge of the previous decade. The estimated annual dissolved and particulate fluxes in this model watershed integrate daily input from diffuse and point sources, diffusive fluxes at the water/sediment interface, changes in the dissolved-particulate partition and changes in sediment stock. Cadmium, Zn, Cu and Pb entering the Gironde estuary via the Garonne River (11–14 t a⁻¹ of Cd; 1330–1450 t a⁻¹ of Zn; 126–214 t a⁻¹ of Cu and 127–155 t a⁻¹ of Pb) are mainly transported in the particulate phase and the major part (i.e. ∼74 to 96% for Cd, ∼60% for Zn, ∼50 to 60% for Cu and ∼80% for Pb) is transported by the Lot River. The main anthropogenic heavy metal point source is located in a small upstream watershed (Riou-Mort River) accounting for at least 47% (Cd), ∼20% (Zn), ∼4% (Cu) and ∼7 to 9% (Pb) of the total heavy metal inputs into the Garonne River, although it contributes only 1% of the discharge. Mass balances for 1999 suggest that under mean annual hydrologic conditions on the basin scale, the heavy metal budget of the Lot-Garonne fluvial system is balanced and that the stocks of Cd [200 t; Environ. Tech. 16 (1995) 1145] and Zn in the Lot River sediment are constant under mean discharge conditions. Heavy metal input by molecular diffusion at the sediment surface represents an important component of dissolved metal inputs into the system (e.g. 30% for Cu). Except for Cu, these dissolved inputs are totally removed from solution by SPM. Based on the generally constant Zn/Cd (∼50) concentration ratio in sediment cores from the polluted Lot River reaches and the sediment stock of Cd [200 t; Environ. Tech. 16 (1995) 1145], the present day Zn stock in the Lot River sediments has been estimated at about 10,000 t. In addition to the mobilization of river-bed sediment and associated heavy metals by intense floods, local human activities, including river-bed dredging, may strongly modify the heavy metal budget of the river system. In 2000, the dredging-related remobilization of polluted Lot River sediment released 2–6 t Cd. This additional Cd point source was estimated to account for 15–43% of the gross inputs into the Gironde Estuary.  相似文献   

Behavior of arsenic and antimony in the surface freshwater reaches of a highly turbid estuary, the Gironde Estuary, France   总被引：1，自引：0，他引：1  

Matthieu Masson  Jrg Schfer  Grard Blanc  Aymeric Dabrin  Sabine Castelle  Gilbert Lavaux 《Applied Geochemistry》2009,24(9):1747-1756

This study reports on the behavior of two redox-sensitive elements, As and Sb, along the turbidity gradient in the freshwater reaches of the turbid Gironde Estuary. During a 17-month survey, surface water and suspended particulate matter (SPM) were sampled monthly at six sites representing both fluvial branches of the Gironde Estuary. Additionally, two longitudinal high resolution profiles were sampled along the fluvial estuary of the Garonne Branch during two contrasted seasons, i.e. with and without the presence of the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of dissolved (<0.2 μm; <0.02 μm) and particulate As, Sb and Fe were measured and combined with SPM data to understand metalloid behavior in the estuarine freshwater turbidity gradient.At the two main fluvial entries of the Gironde Estuary, dissolved As and Sb concentrations showed strong (by a factor of 2–4) seasonal variations, that were only partly controlled by discharge-related dilution. Seasonal addition of dissolved As and Sb was attributed to the degradation of particulate As and Sb carrier phases in bottom sediment and/or in the adjacent aquifers, rather than release from SPM. In the surface freshwater reaches of the Gironde Estuary, Sb behaved conservatively under all hydrological conditions. In contrast, As was strongly reactive in the presence of the MTZ, with opposite behaviors in the two fluvial branches of the estuary: in the Garonne Branch As was removed from the dissolved phase, whereas in the Dordogne Branch As was added. Redistribution of As between the dissolved and the particulate phases along the turbidity gradient in estuarine freshwater only affected the <0.02 μm fraction, as the 0.02–0.2 μm fraction remained constant (300 ng L⁻¹ in September 2005). Accordingly, As removal seemed to be decoupled from concomitant “colloidal” (0.02–0.2 μm) Fe flocculation in the turbidity gradient. The contrasting behavior of dissolved As in the fluvial estuaries of the Garonne and Dordogne Branches was attributed to sorption processes during equilibration of river-borne dissolved As with estuarine SPM forming the MTZ. This equilibrium, described by a distinct distribution coefficient K_d(As)  11,000 L kg⁻¹ in the MTZ, resulted in either As release (desorption; Dordogne Branch) or removal (adsorption; Garonne Branch) in the respective fluvial estuaries. A mixing experiment under controlled laboratory conditions tended to support that equilibration between the dissolved phase and MTZ particles may induce both As release and removal in the estuarine freshwater reaches, with As distribution evolving towards a distinct K_d value for increasing SPM concentrations. The long-term survey allowed estimating annual (2004) dissolved fluxes of As and, for the first time Sb, at the main fluvial entries of the Gironde Estuary at 30.7 t a⁻¹ and 3.2 t a⁻¹ (Garonne River) and at 8.0 t a⁻¹ and 2.3 t a⁻¹ (Dordogne River), respectively.  相似文献   

Mercury sources and transformations in a man-perturbed tidal estuary: The Sinnamary Estuary, French Guiana     

B. Muresan  M. Coquery 《Geochimica et cosmochimica acta》2008,72(22):5416-5430

The distribution, partition and speciation of mercury (Hg) were studied along the redox gradient of an anthropogenically perturbed tropical estuary, the Sinnamary Estuary in French Guiana. This system is a partially mixed estuary characterized by an anoxic freshwater end-member, while the marine end-member consists of the Amazon Plume.The set up of an artificial oxygenation system in the anoxic freshwater end-member generates sharp gradients of major chemical species (iron, sulfides, etc.) coupled with intense organic matter (OM) turnover. The coexistence of oxygenated waters and dissolved sulfides in an organic rich environment depicts the Upper Sinnamary Estuary (USE: part of Sinnamary Estuary under the tidal influence but upstream of the salt intrusion) as a potential site for Hg methylation. The concentrations of all mercury compounds (HgT) in the unfiltered samples (HgT_UNF), in the dissolved (HgT_D) and particulate (HgT_P) phases of the USE average 11 ± 3, 6 ± 2 and 5 ± 3 (i.e. 600 ± 200 pmol g⁻¹) pmol L⁻¹, respectively. Average concentrations of monomethylmercury (MMHg) in the unfiltered (MMHg_UNF), dissolved (MMHg_D) and particulate (MMHg_P) phases were 3.7 ± 1.0, 2.0 ± 0.9 and 1.8 ± 1.2 (i.e. 220 ± 130 pmol g⁻¹) pmol L⁻¹, respectively. Water oxygenation and sulfides concentrations emerged to play a critical role in controlling MMHg levels. Additionally, iron cycling, acid-base mechanisms, and redox-dependent processes were involved in the MMHg partitioning between phases.Overall, the USE constitutes a biogeochemical reactor that gathers partitioning and methylation processes. The permanent MMHg inputs from the anoxic freshwater end-member combined with the intense endogenous Hg methylation ensures high-MMHg levels in both dissolved and particulate phases. To illustrate, the USE exports 60 ± 20% more MMHg_UNF than it imports: 5.5 ± 0.7 vs. 3.5 ± 1.2 kg year⁻¹.  相似文献   

Detection of manure-derived organic compounds in rivers draining agricultural areas of intensive manure spreading     

Emilie Jardé  Gérard Gruau  Laurence Mansuy-Huault 《Applied Geochemistry》2007

It is essential to have suitable tools able to trace the fate of manure organic matter in the environment to assess whether manure disposal on the soils of catchments could affect the organic quality of rivers. Sterol compounds – mainly expressed as C_29 + 28/C₂₇ and 5β/C₂₇ ratios – have been shown to be specific molecular tracers of pig, dairy and poultry manures in soils. The objective of this study was to measure C_29 + 28/C₂₇ and 5β/C₂₇ ratios in five Brittany rivers (Elorn, Yar, Léguer, Min Ran and Couesnon) draining agricultural catchments receiving massive annual inputs of pig, poultry and dairy manures and compare these ratios with ratios published for enriched soils and manure samples. The particulate organic fractions from the studied rivers yielded steroid signatures typical of animal manures. More specifically, a stanol compound diagnostic of pig slurry – the 5β-stanol known as coprostanol – was found to be very widespread, with particularly high concentrations in one of the rivers (Elorn). The C_29 + 28/C₂₇ and 5β/C₂₇ ratios of the particulate fractions of the rivers were compared with ratios measured directly in pig, dairy and poultry manure samples, as well as with the breeding activities on river catchments. These comparisons show that the steroid profiles of the five investigated rivers correlate closely with the types of manure (i.e. pig, poultry or dairy) spread on soils in their catchments. For instance, the C_29 + 28/C₂₇ and 5β/C₂₇ ratios in the Elorn river are similar to the values typical of pig slurry (e.g. 5β/C₂₇ > 4); compared with other catchments, the soils in this area receive by far the largest amount of pig slurry. By contrast, the Yar river drains a catchment receiving only poultry and dairy manures, and its soils exhibit C_29 + 28/C₂₇ and 5β/C₂₇ ratios similar to those of dairy and poultry manures (e.g. 5β/C₂₇ ∼ 1). Thus, this study indicates that the organic quality of rivers is modified in catchments where there is intense manure spreading on soils. It also provides evidence that rivers draining areas receiving different manure types may exhibit differences in the long-term evolution of their OM content. Indeed, two of the investigated river catchments receive dominantly dairy and poultry manure, and exhibit clear long-term upward trends in OM. On the other hand, one catchment receiving high proportions of pig slurry clearly shows a long-term downward trend in OM contents. A survey of the literature shows that the relative amount of OM and N received by soils in agricultural catchments could be the key parameter in determining the direction of the long-term OM trend of the river, rather than the absolute amount and/or type of manure that is applied to the soil. In any case, the present study suggests that sterol/stanol compounds may be of diagnostic value in determining whether a stream or a river is undergoing contamination by manure-derived organic matter.  相似文献   

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

B.S. Gilfedder  M. Petri  H. Biester 《Geochimica et cosmochimica acta》2011,75(12):3385-3401

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.  相似文献   

Pb chronology and trace metal geochemistry at Los Tuxtlas, Mexico, as evidenced by a sedimentary record from the Lago Verde crater lake     

Ana Carolina Ruiz-Fernández  Claude Hillaire-Marcel  Federico Páez-Osuna  Bassam Ghaleb  Margarita Caballero 《Quaternary Research》2007,67(2):181-192

Lago Verde is a fresh-water maar found on the lower slopes of San Martin volcano, at the Sierra de Los Tuxtlas, Mexico, currently the northernmost remnant of the tropical rain forest in America. ²¹⁰Pb and ¹³⁷Cs analyzed in a sediment core were used to reconstruct the historical fluxes of Ag, Cd, Cu, Pb, Hg and Zn to the site during the last ∼ 150 yr. The ²¹⁰Pb_xs-derived sediment accumulation rates, the magnetic susceptibility, C/N ratios and δ¹³C data evidenced background conditions at the lake until 1960s, when enhanced erosion related to the clearing of large forested areas at Los Tuxtlas promoted higher accumulation rates of a heavier and more magnetic sedimentary material. Recent sediments from Lago Verde were found enriched by Pb (26-fold natural concentration level [NCLs]) and moderately enriched by Cd > Cu > Zn and Hg (6-, 5-, 4- and 4-fold corresponding NCLs, respectively). The fluxes of Cu, Hg, Pb and Zn have significantly increased since 1940s, with peak ratios of total modern to pre-industrial fluxes of 11, 11, 19 and 49, respectively. The lake occupies a relatively pristine, non-industrialized basin, and therefore the increased metal fluxes might be related to long-distance aeolian transport of trace metals.  相似文献   

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes     

Aaron J. Beck  Yoko Tsukamoto  Antonio Tovar-Sanchez  Miguel Huerta-Diaz  Henry J. Bokuniewicz  Sergio A. Sañudo-Wilhelmy 《Applied Geochemistry》2007

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.  相似文献   

Diffusive reequilibration of quartz-hosted silicate melt and fluid inclusions: Are all metal concentrations unmodified?   总被引：1，自引：0，他引：1  

Zoltan Zajacz  Jacob J. Hanley  Werner E. Halter 《Geochimica et cosmochimica acta》2009,73(10):3013-2827

Experiments were conducted to determine the extent and mechanism by which the composition of quartz-hosted silicate melt inclusions (SMI) and aqueous fluid inclusions (FI) can undergo post-entrapment modification via diffusion. Quartz slabs containing assemblages of SMI and FI were reacted with synthetic HCl bearing and metalliferous aqueous fluids at T = 500-720 °C and P = 150-200 MPa. SMI from the single inclusion assemblages were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and electron probe microanalysis (EPMA) before and after the experiments. Analyses revealed that rapid diffusion of the univalent cations Na⁺, Li⁺, Ag⁺, Cu⁺ and H⁺ occurred through the quartz from the surroundings, resulting in significant changes in the concentrations of these elements in the inclusions. Concentrations of other elements with an effective ionic radius larger than that of Ag⁺, or multiple valence states were not modified in the inclusions during the experiments. Our results warn inclusion‘‘ researchers that the interpretation of Na, Li, Cu and Ag concentrations from quartz-hosted SMI and FI should be treated critically.  相似文献   

Hafnium isotopes in Arctic Ocean water   总被引：1，自引：0，他引：1  

Bettina Zimmermann  Martin Frank  M. Baskaran  Alex N. Halliday 《Geochimica et cosmochimica acta》2009,73(11):3218-5926

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.  相似文献   

Distribution and reactivity of oxyanions (Sb, As, V, Mo) in the surface freshwater reaches of the Gironde Estuary (France)     

Matthieu Masson  Laurent LanceleurMary-Lou Tercier-Waeber  Jörg SchäferTeddy Hezard  Aurélie LarroseCécile Bossy  Gérard Blanc 《Applied Geochemistry》2011,26(7):1222-1230

The present work reports on the temporal variations of Sb, As, V and Mo concentrations in the surface freshwater reaches of the Gironde Estuary (SW France). Dissolved (<0.2 and <0.02 μm) and particulate Sb, As, V and Mo concentrations were measured in samples collected with high temporal resolution (every 30 min) during two consecutive tides at a fixed station located upstream of the city of Bordeaux and the maximum turbidity zone (MTZ). In addition, measurements of suspended particulate matter concentration, physico-chemical parameters, Cl⁻ concentration, water depth, current velocity and particulate Th concentration were performed either at the same time resolution or continuously. The data obtained suggested that variations in particulate As, V and Mo concentrations were most probably related to tidal cycling near the sampling site of fine grained particles from the MTZ located downstream. Significant differences in the behavior of the dissolved target oxyanions, mostly present in the <0.02 μm fraction, occurred. The behavior of Sb was conservative. Variations of the dissolved As and V concentrations showed similar cycling trends, strongly related to tidal cycles. These As and V cycles were interpreted as a mixing between upstream freshwater and downstream water enriched in dissolved As and V by desorption from the MTZ particles. The observed trend in the variation of the dissolved Mo was more complex than that of As and Sb and attributed to the mixing of the water bodies mentioned above coupled to a point source input of dissolved Mo from an intra-estuarine source. The contribution of this suspected Mo source to the dissolved Mo concentrations measured at the sampling site was estimated from the ratio of dissolved Mo to dissolved As concentrations. The additional dissolved Mo signal, coupled to the monitored ebb and flood length and associated current velocities, suggested an anthropogenic input which may derive from industrial activity near the city of Bordeaux. Extrapolating these results to the annual scale suggested that this dissolved Mo may be equivalent to 45-90% of the annual dissolved Mo flux into the Garonne Branch, highlighting the importance to further investigate the origin and behavior of Mo in the fluvial estuary near Bordeaux.  相似文献   

Coupling between Pb_ex and organic matter in sediments of a nutrient-enriched lake: An example from Lake Chenghai, China     

G.J. Wan  J.A. Chen  S.Q. Xu  E.Y. Wan  R.G. Huang  P.H. Santschi 《Chemical Geology》2005,224(4):223-236

Sediment cores were collected from deep-water areas of Lake Chenghai, China in June 1997. The vertical profile of ¹³⁷Cs activity gives reliable geochronological results. The results also indicate that sediment accumulation rates in deep-water areas of Lake Chenghai were relatively constant in recent decades, averaging 0.43 g cm^− 2 y^− 1, despite a variable organic carbon influx. ²¹⁰Pb_eq (= ²²⁶Ra) activity was relatively constant also, with an average value of 54.3 ± 3.2 Bq kg^− 1. Vertical profiles of ²¹⁰Pb_ex (= ²¹⁰Pb_total − ²²⁶Ra) decreased exponentially, resulting in somewhat lower sediment accumulation rates (0.3 g cm^− 2 y^− 1). These lower rates are likely less reliable, as the relatively large fluctuations in ²¹⁰Pb_ex activities correlate closely to the organic carbon (C_org) content of the sediments. For example, the vertical profile of ²¹⁰Pb_ex activity displays peaks at mass depths of 3.7-4.7 g cm^− 2 (10-12 cm) and 10-11 g cm^− 2(25-28 cm), similar to the maxima in the vertical profile of C_org. This phenomenon must be related to the delivery of particulate organic matter (POM) from the water to the sediments, or to watershed soil erosion. Since the mean atomic ratios of H_org / C_org and C_org / N_org in Lake Chenghai sediments are 5.5 and 7.0, respectively, indicating that POM was predominantly derived from the remains of authigenic algae, this eliminates watershed erosion rates as a primary control on lake sedimentation rates as resolved by ²¹⁰Pb_ex. Sedimentation fluxes (F(C_org)) of particulate organic carbon since 1970 varied between 60 to 160 g m^− 2 y^− 1, and appeared to closely influence variations in ²¹⁰Pb_ex concentrations. For example, sedimentation fluxes of ²¹⁰Pb_ex (F(²¹⁰Pb_ex)) showed maxima in the years 1972-1974 and 1986-1989, likely reflecting historical variations of lake biological productivity or carbon preservation.  相似文献   

Geochemistry of volcanic and hydrothermal fluids and volatile budget of the Kamchatka-Kuril subduction zone     

Yuri A. Taran 《Geochimica et cosmochimica acta》2009,73(4):1067-1094

A data base for the composition and emission rates of more than 100 thermal manifestations including boiling geothermal systems and 23 volcanoes along the 1900 km long Kamchatka-Kuril (KK) arc is presented. These results were used to estimate mean fluxes of volatiles from the KK arc. The fluxes from the KK arc are compared with the fluxes from the best studied Central American (CA) arc and with the compiled literature data on global fluxes. The error ranges and the OUT/IN (in)balance calculations are also discussed. The estimated fluxes of volatiles from volcanic fumaroles and the observed, normalized to the Cl content, fluxes from hydrothermal systems are very close, with the higher hydrothermal flux from Kuril Islands due to a larger number of the acidic Cl-SO₄ springs on the Islands and their outflow rates. The total volcanic SO₂ flux from the whole KK arc is estimated to be higher than 3000 t/d. The measured S and C fluxes from hydrothermal systems are much lower than the volcanic output due to the loss of these components in the upper crust (mineral precipitation). The Cl/³He ratio is inferred to be a stable indicator of the arc setting for hydrothermal and volcanic fluids with a mean value of (2 ± 4) × 10⁹. Comparison of the obtained volcano-hydrothermal fluxes with fluxes calculated from the erupted solid volcanic products at Kamchatka and Kurils during Holocene time reveals that the total estimated volatile output from the KK arc is compatible with the total magmatic output if the intruded to erupted ratio is close to 7, i.e. almost the same as assumed for the Central American arc. Calculated fluxes as well as the ratios for OUT/IN fluxes (volcanic + hydrothermal output/slab + mantle input) for CO₂, S, H₂O, Cl, N₂, ⁴He and ³He from the KK arc normalized to the arc length are in general close to the global estimates. The fractions of CO₂ and S in the total volatile output at KK arc derived directly from the mantle wedge are 18% and 16% (mole basis), respectively. Fractions of mantle derived H₂O, N₂ and Cl are much lower, less that 5% of their output.  相似文献   

Seasonal variations of physical and chemical erosion: A three-year survey of the Rhone River (France)   总被引：2，自引：0，他引：2  

P. Ollivier  B. Hamelin  O. Radakovitch 《Geochimica et cosmochimica acta》2010,74(3):907-230

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.  相似文献   

Predicting the impact of land use on the major element and nutrient fluxes in coastal Mediterranean rivers: The case of the Têt River (Southern France)     

Javier Garcia-Esteves  Wolfgang Ludwig  Philippe Kerhervé  Jean-Luc Probst  Franck Lespinas 《Applied Geochemistry》2007

This study presents a detailed discrimination between the natural and anthropogenic sources of dissolved major elements in the Têt River, a typical small coastal river in the south of France. The main objectives were to quantify the materials that were released by human activities in the basin, and to determine the specific element inputs for the major land use forms. The dissolved material fluxes were estimated by weekly monitoring over a hydrological year (2000–2001) along the major water gauging stations, and the flux relationships were examined in the context of anthropogenic and natural basin characteristics as determined by a Geographical Information System (GIS). Intensive agricultural land use in the form of fruit tree cultures and vineyards has a strong control on the dissolved element fluxes in the river. Area specific element releases for these cultures are greatest for SO₄, with an estimated average of about 430 ± 18 keq km⁻² a⁻¹. This is ?11 times the natural SO₄ release by rock weathering. Also for K, NO₃, PO₄ and Mg, the specific releases were ?6 times the natural weathering rates (respectively about 44, 60, 4 and 265 keq km⁻² a⁻¹). Waste-waters are the other major source of anthropogenic elements in the river. They have an important role for the fluxes of inorganic P and N, but they are also a considerable source of Cl and Na to the river. For example, the average annual release of Cl is around 150 moles/inhabitant in the rural basin parts. Further downstream, however, where population density strongly increases, industrial effluents can enhance this value (>300 moles/inhabitant). The waste-waters contribute more than 70% of the dissolved inorganic N export to the sea, although their contribution to the average DOC export is almost negligible (3%).  相似文献   

Preparation and characterization of antibacterial silver/vermiculites and silver/montmorillonites   总被引：1，自引：0，他引：1  

Marta Valášková  Marianna Hundáková  Jana Seidlerová  Erich Pazdziora  Martin He?mánek  David Rafaja 《Geochimica et cosmochimica acta》2010,74(22):6287-6300

The reason for the preparation and characterization of the novel antibacterial silver/vermiculites (Ag/V) together with the silver/montmorillonites (Ag/M) was that the information on the vermiculite structure change and stability of Ag/V in water as well as its effect on bacteria are sporadic. The vermiculite (V), (Si_3.02Al_0.98)^IV (Mg_2.27Al_0.12Ti_0.07)^VI O₁₀(OH)₂ Ca_0.09Na_0.21K_0.50 from West China and montmorillonite (M), (Si_3.96Al_0.04)^IV (Al_1.20Mg_0.42Ti_0.02)^VI O₁₀ (OH)₂Ca_0.15Na_0.14K_0.08 from Ivan?ice (Czech Republic), fraction <0.4 μm were the starting clay materials for sample preparation. The samples V1 and M1 were prepared via reaction of the V and M with the 0.01 mol L⁻¹ AgNO₃ aqueous solution. The samples V2 and M2 were treated with the aqueous solution of AgNO₃ for two times. The cation exchange and reduced metallic silver on M1 and V1 evoked the specific surface area (SSA) diminution, the mean particle-size diameter extension and appearance of micropores with radius (<0.4 nm). Repeated silver cation exchange in M2 and V2 reduced particle size, increased slightly SSA and micropores with radius of 0.4-0.5 nm. Samples Ag/V and Ag/M showed higher content of pores with radius 0.5-1.0 nm than original V and M. The Ag concentration was found higher in Ag/V than in Ag/M and higher in repeatedly treated samples: 0.9 wt.% Ag in V1, 1.4 wt.% Ag in V2, 0.6 wt.% Ag in M1 and 1.0 wt.% Ag in M2. Vermiculite structure consisting of the hydrated interstratified phases and the mica-like phase changed to the cation-one-zero layer hydrate interstratification structure in V1 and to the random of two-one layer hydrate interstratifications in V2. Infrared and Mössbauer spectroscopy revealed no changes in the structure of the clay minerals that could be related directly to the sorption and crystallization of silver. Transmission electron microscopy showed that the silver nanoparticles size distribution was much narrower for the samples Ag/M than for Ag/V. The mean size of the Ag particles was between 40 and 50 nm. Although the Ag nanoparticles did not adhere sufficiently at the clay minerals surface and migrated moderately into water, all samples under study were approved to be effective inhibitors of the bacterial growth persisting for the whole testing period of 6 days. Silver/vermiculite was antimicrobial more efficient against Klebsiella pneumoniae and Pseudomonas aeruginosa than silver/montmorillonite.  相似文献   

50-year record and solid state speciation of mercury in natural and contaminated reservoir sediment     

Sabine Castelle  Jörg SchäferGérard Blanc  Stéphane AudryHenri Etcheber  Jean-Pierre Lissalde 《Applied Geochemistry》2007

Contaminated fluvial sediments represent both temporary sinks for river-borne pollutants and potential sources in case of natural and/or anthropogenic resuspension. Reservoir lakes play a very important role in sediment dynamics of watersheds and may offer great opportunities to study historical records of river-borne particles and associated elements transported in the past. The fate and potential environmental impact of Hg depends on its abundance, its carrier phases and its chemical speciation. Historical Hg records and solid state Hg speciation were compared in sediments from two contrasting reservoirs of the Lot River (France) upstream and downstream from a major polymetallic pollution (e.g. Cd, Zn) source. Natural (geochemical background) and anthropogenic Hg concentrations and their relationships with predominant carrier phases were determined. The results reveal important historical Hg contamination (up to 35 mg kg⁻¹) of the downstream sediment, reflecting the historical evolution of industrial activity at the point source, i.e. former coal mining, Zn ore treatment and post-industrial remediation work. Single chemical extractions (ascorbate, H₂O₂, KOH) suggest that at both sites most (∼75%) of the Hg is bound to organic and/or reactive sulphide phases. Organo-chelated (KOH-extracted) Hg, representing an important fraction in the uncontaminated sediment, shows similar concentrations (∼0.02 mg kg⁻¹) at both sites and may be mainly attributed to natural inputs and/or processes. Although, total Hg concentrations in recent surface sediments at both sites are still very different, similar mono-methylmercury concentrations (up to 4 μg kg⁻¹) and vertical distributions were observed, suggesting comparable methylation-demethylation processes. High mono-methylmercury concentrations (4–15 μg kg⁻¹) in 10–40 a-old, sulphide-rich, contaminated sediment suggest long-term persistence of mono-methylmercury. Beyond historical records of total concentrations, the studied reservoir sediments provided new insights in solid state speciation and carrier phases of natural and anthropogenic Hg. In case of sediment resuspension, the major part of the Hg historically stored in the Lot River sediments will be accessible to biogeochemical recycling in the downstream fluvial-estuarine environment.  相似文献   

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates     

Art F. White  Marjorie S. Schulz  Davison V. Vivit  Tom D. Bullen  Alex E. Blum 《Geochimica et cosmochimica acta》2009,73(10):2769-58

The spatial and temporal changes in hydrology and pore water elemental and ⁸⁷Sr/⁸⁶Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q_h), based on Cl mass balances, vary from 0.06 to 0.22 m yr⁻¹, resulting in fluid residence times in the terraces of 10-24 yrs.As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO₃ > HCO₃ > SO₄ reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute ⁸⁷Sr/⁸⁶Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and ⁸⁷Sr/⁸⁶Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate.Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R_solute are estimated from linear Na and Si pore weathering gradients b_solute such that