A comparative overview of weathering intensity and HCO3 flux in the world's major rivers with emphasis on the Changjiang,Huanghe, Zhujiang (Pearl) and Mississippi Rivers

In this paper, general relationships of riverine bicarbonate concentrations and fluxes as a function of drainage basin mineral content and runoff are examined using a database of the 25 largest rivers in the world. Specific HCO₃⁻ flux normalized to unit basin area, which peaks in the mid latitudes, was found to be strongly correlated with the carbonate mineral content of river basins, while river HCO₃⁻ concentration was related to the balance of precipitation and evaporation. Within this global context, the weathering patterns of CO₂ in a few large rivers (Changjiang, Huanghe, Pearl, and Mississippi rivers) were examined in further detail. The Zhujiang (Pearl River), especially its largest branch (Xijiang), was characterized by the highest specific weathering rate among all the world's large rivers due to an exceptionally high carbonate mineral content (over 80%) in its drainage basin and its warm and wet environment. It has a moderate level of HCO₃⁻ concentration, however, due to dilution by relatively high precipitation in the watershed. In stark contrast, the Huanghe (Yellow River) has one of the lowest specific weathering rates because of low carbonate mineral content and a dry climate. However, it has a high HCO₃⁻ concentration due largely to the concentrating effects of high evaporative water loss, as a result of arid weather and the agricultural use of water through irrigation systems, as well as carbonate-containing surficial deposits (i.e., loess). The strong correlation between specific HCO₃⁻ fluxes and discharge in all four rivers with different discharge seasonality suggests that higher precipitation in drainage basins promotes higher weathering rates.     

Switch in chemical weathering caused by the mass balance variability in a Himalayan glacierized basin: a case of Chhota Shigri Glacier

Long-term data (2003–2015) on meltwater chemistry, mass balance and discharge of a benchmark glacier (Chhota Shigri Glacier, India) were studied to determine any association between these variables. To infer the factors governing the alteration of chemical weathering processes in glacierized basins, multi-annual records of the hydrochemical indices (Ca²⁺+Mg²⁺/Na⁺+K⁺) and the C-ratio were also examined. A succession of negative mass balance years has resulted in a decline in solute concentrations in the runoff, as discharge has increased. The (Ca²⁺+Mg²⁺/Na⁺+K⁺) and C-ratio are highest during periods of negative annual mass balance, when the spatial extent of the channelized drainage system increases. Conversely, these ratios are lowest in positive mass balance years, when the spatial extent of the channelized drainage system decreases, and chemical weathering in the distributed drainage system becomes more dominant. This paper is the first to show the inter-annual linkages between meltwater chemistry, mass balance and discharge for a valley glacier.     

Hydrochemical appraisal of ice‐ and rock‐glacier meltwater in the hyperarid Agua Negra drainage basin,Andes of Argentina

The Agua Negra drainage system (30 12′S, 69 50′ W), in the Argentine Andes holds several ice‐ and rock‐glaciers, which are distributed from 4200 up to 6300 m a.s.l. The geochemical study of meltwaters reveals that ice‐glaciers deliver a HCO₃^?? Ca²⁺ solution and rock‐glaciers a SO₄^2?? HCO₃^?? Ca²⁺ solution. The site is presumably strongly influenced by sublimation and dry deposition. The main processes supplying solutes to meltwater are sulphide oxidation (i.e. abundant hydrothermal manifestations), and hydrolysis and dissolution of carbonates and silicates. Marine aerosols are the main source of NaCl. The fine‐grained products of glacial comminution play a significant role in the control of dissolved minor and trace elements: transition metals (e.g. Mn, Zr, Cu, and Co) appear to be selectively removed from solution, whereas some LIL (large ion lithophile) elements, such as Sr, Cs, and major cations, are more concentrated in the lowermost reach. Daily concentration variation of dissolved rare earth elements (REE) tends to increase with discharge. Through PHREEQC inverse modelling, it is shown that gypsum dissolution (i.e. sulphide oxidation) is the most important geochemical mechanism delivering solutes to the Agua Negra drainage system, particularly in rock‐glaciers. At the lowermost reach, the chemical signature appears to change depending on the relative significance of different meltwater sources: silicate weathering seems to be more important when meltwater has a longer residence time, and calcite and gypsum dissolution is more conspicuous in recently melted waters. A comparison with a non‐glacierized semiarid drainage of comparable size shows that the glacierized basin has a higher specific denudation, but it is mostly accounted for by relatively soluble phases (i.e. gypsum and calcite). Meltwater chemistry in glacierized arid areas appears strongly influenced by sublimation/evaporation, in contrast with its humid counterparts. Copyright © 2007 John Wiley & Sons, Ltd.     

HYDROCHEMISTRY AS AN INDICATOR OF SUBGLACIAL DRAINAGE SYSTEM STRUCTURE: A COMPARISON OF ALPINE AND SUB-POLAR ENVIRONMENTS

The anion compositions (SO²₄, HCO⁻₃ and Cl⁻) of runoff from the Haut Glacier d'Arolla, Switzerland and Austre Brøggerbreen, Svalbard are compared to assess whether or not variations in water chemistry with discharge are consistent with current understanding of the subglacial drainage structure of warm- and polythermal-based glaciers. These glacial catchments have very different bedrocks and the subglacial drainage structures are also believed to be different, yet the range of anion concentrations show considerable overlap for SO²⁻₄ and HCO⁻₃. Concentrations of Cl⁻ are higher at Austre Brøggerbreen because of the maritime location of the glacier. Correcting SO²⁻₄ for the snowpack component reveals that the variation in non-snowpack SO²⁻₄ with discharge and with HCO⁻₃ is similar to that observed at the Haut Glacier d'Arolla. Hence, if we assume that the provenance of the non-snowpack SO²⁻₄ is the same in both glacial drainage systems, a distributed drainage system also contributes to runoff at Austre Brøggerbreen. We have no independent means of testing the assumption at present. The lower concentrations of non-snowpack SO²⁻₄ at Austre Brøggerbreen may suggest that a smaller proportion of runoff originates from a distributed drainage system than at the Haut Glacier d'Arolla.     

Aluminium in glacial meltwater demonstrates an association with nutrient export (Werenskiöldbreen,Svalbard)

The aluminium (Al) cycle in glacierised basins has not received a great deal of attention in studies of biogeochemical cycles. As Al may be toxic for biota, it is important to investigate the processes leading to its release into the environment. It has not yet been ascertained whether filterable Al (passing through a pore size of 0.45 μm) is incorporated into biogeochemical cycles in glacierised basins. Our study aims to determine the relationship between the processes bringing filterable Al and glacier‐derived filterable nutrients (particularly Fe and Si) into glacierised basins. We investigated the Werenskiöldbreen basin (44.1 km², 60% glacierised) situated in SW Spitsbergen, Svalbard. In 2011, we collected meltwater from a subglacial portal at the glacier front and at a downstream hydrometric station throughout the ablation season. The Al concentration, unchanged between the subglacial system and proglacial zone, reveals that aluminosilicate weathering is a dominant source of filterable Al under subglacial conditions. By examining the Al:Fe ratio compared with pH and the sulphate mass fraction index, we found that the proton source for subglacial aluminosilicate weathering is mainly associated with sulphide oxidation and, to a lesser degree, with hydrolysis and carbonation. In subglacial outflows and in the glacial river, Al and Fe are primarily in the forms of Al(OH)₄^‐ and Fe(OH)₃. The annual filterable Al yield (2.7 mmol m^‐2) was of a magnitude similar to that of nutrients such as filterable Fe (3.0 mmol m^‐2) and lower than that of dissolved Si (18.5 mmol m^‐2). Our results show that filterable Al concentrations in meltwater are significantly correlated to filterable and dissolved glacier‐derived nutrients (Fe and Si, respectively) concentrations in glaciers worldwide. We conclude that a potential bioavailable Al pool derived from glacierised basins may be incorporated in biogeochemical cycles, as it is strongly related to the concentrations and yields of glacier‐derived nutrients.     

The hydrochemistry of runoff from a ‘cold-based’ glacier in the High Arctic (Scott Turnerbreen,Svalbard)

There are still relatively few hydrochemical studies of glacial runoff and meltwater routing from the high latitudes, where non-temperate glacier ice is frequently encountered. Representative samples of glacier meltwater were obtained from Scott Turnerbreen, a ‘cold-based’ glacier at 78° N in the Norwegian high Arctic archipelago of Svalbard, during the 1993 melt season and analysed for major ion chemistry. Laboratory dissolution experiments were also conducted, using suspended sediment from the runoff. Significant concentrations of crustal weathering derived SO²⁻₄ are present in the runoff, which is characterized by high ratios of SO²⁻₄: (SO²⁻₄+HCO⁻₃) and high p(CO₂). Meltwater is not routed subglacially, but flows to the glacier terminus through subaerial, ice marginal channels, and partly flows through a proglacial icing, containing highly concentrated interstitial waters, immediately afront the terminus. The hydrochemistry of the runoff is controlled by: (1) seasonal variations in the input of solutes from snow- and icemelt; (2) proglacial solute acquisition from the icing; and (3) subaerial chemical weathering within saturated, ice-cored lateral moraine adjoining drainage channels at the glacier margins, sediment and concentrated pore water from which is entrained by flowing meltwater. Diurnal variations in solute concentration arise from the net effects of variable sediment pore water entrainment and dilution in the ice marginal streams. Explanation of the hydrochemistry of Scott Turnerbreen requires only one major subaerial flow path, the ice marginal channel system, in which seasonally varying inputs of concentrated snowmelt and dilute icemelt are modified by seepage or entrainment of concentrated pore waters from sediment in lateral moraine, and by concentrated interstitial waters from the proglacial icing, supplied by leaching, slow drainage at grain intersections or simple melting of the icing itself. The ice marginal channels are analogous neither to dilute supra/englacial nor to concentrated subglacial flow components. © 1998 John Wiley & Sons, Ltd.     

VARIABILITY IN THE CHEMICAL COMPOSITION OF IN SITU SUBGLACIAL MELTWATERS

Meltwaters collected from boreholes drilled to the base of the Haut Glacier d'Arolla, Switzerland have chemical compositions that can be classified into three main groups. The first group is dilute, whereas the second group is similar to, though generally less concentrated in major ions, than contemporaneous bulk glacial runoff. The third group is more concentrated than any observed bulk runoff, including periods of flow recession. Waters of the first group are believed to represent supraglacial meltwater and ice melted during drilling. Limited solutes may be derived from interactions with debris in the borehole. The spatial pattern of borehole water levels and borehole water column stratification, combined with the chemical composition of the different groups, suggest that the second group represent samples of subglacial waters that exchange with channel water on a diurnal basis, and that the third group represent samples of water draining through a ‘distributed’ subglacial hydraulic system. High NO⁻₃ concentrations in the third group suggest that snowmelt may provide a significant proportion of the waters and that the residence time of the waters at the bed in this particular section of the distributed system is of the order of a few months. The high NO⁻₃ concentrations also suggest that some snowmelt is routed along different subglacial flowpaths to those used by icemelt. The average SO²⁻₄: (HCO⁻₃ + SO²⁻₄) ratio of the third group of meltwaters is 0.3, suggesting that sulphide oxidation and carbonate dissolution (which gives rise to a ratio of 0.5) cannot provide all the HCO⁻₃ to solution. Hence, carbonate hydrolysis may be occurring before sulphide oxidation, or there may be subglacial sources of CO₂, perhaps arising from microbial oxidation of organic C in bedrock, air bubbles in glacier ice or pockets of air trapped in subglacial cavities. The channel marginal zone is identified as an area that may influence the composition of bulk meltwater during periods of recession flow and low diurnal discharge regimes. © 1997 by John Wiley & Sons, Ltd.     

Trace element and major ion concentrations and dynamics in glacier snow and melt: Eliot Glacier,Oregon Cascades

We present concentrations of environmentally available (unfiltered acidified 2% v/v HNO₃) As, Cu, Cd, Pb, V, Sr, and major ions including Ca²⁺, Cl^?, and SO₄^2? in a July 2005 and a March 2006 shallow snow profile from the lower Eliot Glacier, Mount Hood, Oregon, and its proglacial stream, Eliot Creek. Low enrichment factors (EF) with respect to crustal averages suggests that in fresh March 2006 snow environmentally available elements are derived primarily from lithogenic sources. Soluble salts occurred in lower and less variable concentrations in July 2005 snow than March 2006. Conversely, environmentally available trace elements occurred in greater and more variable concentrations in July 2005 than March 2006 snow. Unlike major solutes, particulate‐associated trace elements are not readily eluted during the melt season. Additionally, elevated surface concentrations suggest that they are likely added throughout the year via dry deposition. In a 1‐h stream sampling, ratios of dissolved (<0·45 µm) V:Cl^?, Sr:Cl^?, and Cu:Cl^? are enriched in the Eliot Stream with respect to their environmentally available trace element to Cl^? ratios in Eliot Glacier snow, suggesting chemical weathering additions in the stream waters. Dissolved Pb:Cl^? is depleted in the Eliot Stream with respect to the ratio of environmentally available Pb to Cl^? in snow, corresponding to greater adsorption onto particles at greater pH values. Copyright © 2009 John Wiley & Sons, Ltd.     

Correlations between discharge and meteorological parameters and runoff forecasting from a highly glacierized Himalayan basin

Abstract

To assess the predictive significance of meteorological parameters for forecasting discharge from the Dokriani Glacier basin in the Himalayan region, discharge autocorrelation and correlations between discharge and meteorological factors were investigated on a monthly and a seasonal basis. Changes in correlations between discharge and meteorological variables, lagged by 0–3 days, were determined. Discharge autocorrelation was found to be very high for each individual summer month and for the melt season as a whole. This suggests that a substantial meltwater storage in the glacier, which results in a delayed response of runoff, and therefore discharge, from the highly glacierized basins is very much dependent on the previous day's discharge. A comparison of correlations between discharge and temperature, and discharge and precipitation shows that temperature has a better correlation with discharge during June and September, while precipitation has good correlation with discharge in July and August. Variations in the physical features of the glacier, weather conditions, and precipitation and its distribution with time over the basin account for changes in correlations. To forecast the runoff from the Dokriani Glacier basin, multiple linear regression equations were developed separately for each month and for the whole melt season. A better forecast was obtained using the seasonal regression equation. A comparison of correlations for the Dokriani Glacier with those for the Z'mutt Glacier basin, Switzerland, illustrates that, for both basins, the previous day's discharge (Q_i-1) shows maximum autocorrelation throughout the melt period. Whereas a good correlation between discharge and temperature was observed for the Z'mutt Glacier basin for the whole melt period, for the Dokriani Glacier basin it was strong at the beginning and end of the ablation season. Runoff delaying behaviour in the Dokriani Glacier basin is found more prominent than in the Z'mutt Glacier basin early in the melt season. Water storage appears to be less significant in the Dokriani Glacier than in the Z'mutt Glacier towards the end of the ablation season. The strength of correlation between discharge and precipitation is higher for the Dokriani Glacier basin than for the Z'mutt Glacier basin. This is due to higher rainfall in the Dokriani Glacier basin. In general, for both glacier basins, maximum correlation is found between discharge and precipitation on the same day.     

Solute provenance,transport and denudation in a high arctic glacierized catchment

Recent understanding of chemical weathering in glacierized catchments has been focused on mid-latitude, Alpine catchments; comparable studies from the high latitudes are currently lacking. This paper attempts to address this deficiency by examining solute provenance, transport and denudation in a glacierized catchment at 78°N in the Svalbard High Arctic archipelago. Representative samples of snow, glacier ice, winter proglacial icing and glacier meltwater were obtained from the catchment during spring and summer 1993 and analysed for major ion chemistry. Seasonal variations in the composition of glacier meltwater occur and are influenced by proglacial solute acquisition from the icing at the very start of the melt season, and subsequently by a period of discharge of concentrated snowmelt caused by snowpack elution; weathering within the ice-marginal channels that drain the glacier, particularly carbonation reactions, continues to furnish solute to meltwater when suspended sediment concentrations increase later in the melt season. Partitioning the solute flux into its various components (sea-salt, crustal, aerosol and atmospheric sources) shows that c. 25% of the total flux is sea salt derived, consistent with the maritime location of the glacier, and c. 71% is crustally derived. Estimated chemical denudation, 160 meq m⁻² a⁻¹ sea salt-corrected cation equivalent weathering rate, is somewhat low compared with other studied glacierized catchments (estimates in the range 450–1000 meq m⁻² a⁻¹), which is probably attributable to the relatively short melt season and low specific runoff in the High Arctic. A positive relationship was identified between discharge and CO₂ drawdown owing to carbonation reactions in turbid meltwater. © 1997 John Wiley & Sons, Ltd.     

Geochemical weathering at the bed of Haut Glacier d'Arolla,Switzerland—a new model

Waters were sampled from 17 boreholes at Haut Glacier d'Arolla during the 1993 and 1994 ablation seasons. Three types of concentrated subglacial water were identified, based on the relative proportions of Ca²⁺, HCO₃^? and SO₄^2? to Si. Type A waters are the most solute rich and have the lowest relative proportion of Si. They are believed to form in hydrologically inefficient areas of a distributed drainage system. Most solute is obtained from coupled sulphide oxidation and carbonate dissolution (SO–CD). It is possible that there is a subglacial source of O₂, perhaps from gas bubbles released during regelation, because the high SO₄^2? levels found (up to 1200 µeq/L) are greater than could be achieved if sulphides are oxidized by oxygen in saturated water at 0 °C (c.414 µeq/L). A more likely alternative is that sulphide is oxidized by Fe³⁺ in anoxic environments. If this is the case, exchange reactions involving Fe^III and Fe^II from silicates are possible. These have the potential to generate relatively high concentrations of HCO₃^? with respect to SO₄^2?. Formation of secondary weathering products, such as clays, may explain the low Si concentrations of Type A waters. Type B waters were the most frequently sampled subglacial water. They are believed to be representative of waters flowing in more efficient parts of a distributed drainage system. Residence time and reaction kinetics help determine the solute composition of these waters. The initial water–rock reactions are carbonate and silicate hydrolysis, and there is exchange of divalent cations from solution for monovalent cations held on surface exchange sites. Hydrolysis is followed by SO–CD. The SO₄^2? concentrations usually are <414 µeq/L, although some range up to 580 µeq/L, which suggests that elements of the distributed drainage system may become anoxic. Type C waters were the most dilute, yet they were very turbid. Their chemical composition is characterized by low SO₄^2? : HCO₃^? ratios and high pH. Type C waters were usually artefacts of the borehole chemical weathering environment. True Type C waters are believed to flow through sulphide‐poor basal debris, particularly in the channel marginal zone. The composition of bulk runoff was most similar to diluted Type B waters at high discharge, and was similar to a mixture of Type B and C waters at lower discharge. These observations suggest that some supraglacial meltwaters input to the bed are stored temporarily in the channel marginal zone during rising discharge and are released during declining flow. Little of the subglacial chemical weathering we infer is associated with the sequestration of atmospheric CO₂. The progression of reactions is from carbonate and silicate hydrolysis, through sulphide oxidation by first oxygen and then Fe^III, which drives further carbonate and silicate weathering. A crude estimate of the ratio of carbonate to silicate weathering following hydrolysis is 4 : 1. We speculate that microbial oxidation of organic carbon also may occur. Both sulphide oxidation and microbial oxidation of organic carbon are likely to drive the bed towards suboxic conditions. Hence, we believe that subglacial chemical weathering does not sequester significant quantities of atmospheric CO₂ and that one of the key controls on the rate and magnitude of solute acquisition is microbial activity, which catalyses the reduction of Fe^III and the oxidation of FeS₂. Copyright © 2002 John Wiley & Sons, Ltd.     

Dissolved major ions,Sr and 87Sr/86Sr of coastal lakes from Larsemann hills,East Antarctica: Solute sources and chemical weathering in a polar environment

Dissolved major ions, Sr concentrations and ⁸⁷Sr/⁸⁶Sr ratios of 10 coastal lakes from the Larsemann Hills, East Antarctica have been studied to constrain their solute sources, transport and glacial weathering patterns in their catchments. In absence of perennial river/streams, lakes serve as only reliable archive to study land surface processes in these low-temperature regions. The lake water chemistry is mostly Na-Cl type and it does not show any significant depth variations. Sr isotope compositions of these lakes vary from 0.7110 to 0.7211 with an average value of 0.7145, which is higher than modern seawater value. In addition to oceanic sources, major ions and Sr isotopic data show appreciable amount of solute supply from chemical weathering of silicate rocks in lake catchments and dissolution of Ca-Mg rich salts produced during the freezing of seawaters. The role of sulphide oxidation and carbonate weathering are found to be minimal on lake hydro-chemistry in this part of Antarctica. Inverse model calculations using this chemical dataset provide first-order estimates of dissolved cations and Sr; they are mostly derived from oceanic (seawater + snow) sources (cations approximately 76%) and (Sr approximately 92%) with minimal supplies from weathering of silicates (cations approximately 15%); (Sr approximately 2%) and Ca-rich minerals (cations approximately 9%); (Sr approximately 7%). The silicate weathering rate and its corresponding atmospheric CO₂ consumption rate estimates for Scandrett lake catchment (3.6 ± 0.3 tons/km²/year and 0.5 × 10⁵ moles/km²/year), are lower than that of reported values for the average global river basins (5.4 tons/km²/year and 0.9 × 10⁵ tons/km²/year) respectively. The present study provides a comprehensive report of chemical weathering intensity and its role in atmospheric CO₂ consumption in low-temperature pristine environment of Antarctica. These estimates underscore the importance of Antarctica weathering on atmospheric CO₂ budget, particularly during the past warmer periods when the large area was exposed and available for intense chemical weathering.     

Spatial characteristics and controlling factors of chemical weathering of loess in the dry season in the middle Loess Plateau,China

Hydrochemistry methods were used to decipher the weathering and geochemical processes controlling solute acquisition of river waters in the dry season in the middle Loess Plateau (MLP), one of the most severely eroded areas and turbid riverine systems in the world. River waters were neutral to slightly alkaline with pH varying from 7.6 to 9.6. The total dissolved solids decreased from northwest to southeast with a mean value of 804 mg/l, much higher than the global average and other large rivers in China. Ternary diagram showed that river waters were dominated by Na⁺, HCO₃^?, and Cl^? with the main water‐type of HCO₃^?–Cl^?–Na⁺. Saturation index values, Mg²⁺, Ca²⁺, and HCO₃^? analyses indicated the preferential Ca²⁺ removal by calcite precipitation. Gibbs plots and stoichiometry plots indicated that the dissolved solutes were mainly derived from rock weathering with minor anthropogenic and atmospheric inputs. Samples in the northwestern basin are also influenced by evaporation. A forward model of mass budget calculation showed that, owing to high soluble characteristics, evaporite dissolution was a major feature of river waters and contributed 41% to the total dissolved cations on average, while carbonate and silicate weathering contributed 28%,and 25% on average, respectively. Besides evaporite dissolution, cation exchange is also responsible for the high concentrations of Na⁺ in river water. Spatial variations showed that evaporite dissolution and silicate weathering were higher in the northern basin, whereas carbonate weathering was higher in the southern basin. Different from most rivers in the world, the physical erosion rates (varying from 117.7 to 4116.6 t/km²y) are much higher than the chemical weathering rates (varying from 3.54 to 6.76 t/km²y) in the MLP because of the loose structure of loess and poor vegetation in the basin. In the future, studies on comparison of water geochemistry in different seasons and on influence of different types of land use and soil salinization on water geochemistry, denudation rates, and water quality should be strengthened in the MLP. These results shed some lights on processes responsible for modern loess weathering and also indicate the importance of time‐series sampling strategy for river water chemistry. Copyright © 2016 John Wiley & Sons, Ltd.     

Sampling strategy to describe the temporal hydrochemical characteristics of an alpine proglacial stream

A hierarchical sampling programme (including continuous monitoring, twice-daily sampling and sampling at hourly intervals over selected 24 hour periods) was devised to support hydrochemical and hydrological research programmes on an alpine proglacial stream. The rationale for the research and for the sampling programme are explained and the hydrochemical time series generated over an ablation season are analysed to assess the degree to which they support the study aims. It appears that there is no satisfactory substitute for the chemical analysis of at least two water samples taken at approximately maximum and minimum discharge every day, if seasonal variations in meltwater chemistry are to be effectively characterized. Such time series data can be used to estimate Box-Jenkins transfer function-noise models between particular solutes (SO²⁻₄, Ca²⁺, Mg²⁺, Na⁺ and possibly K⁺) and either discharge or electrical conductivity, which can then be used to fill any short gaps in the data. This approach is not satisfactory even for filling short gaps in the twice-daily determinations of pH, HCO⁻₃ and NO⁻₃. At the diurnal time-scale (based on hourly determinations over 24 hour periods) electrical conductivity seems to provide a good surrogate for most of the solutes studied. HCO⁻₃, SO²⁻₄, Ca²⁺ and Mg²⁺ were found to be particularly strongly related to electrical conductivity and there was little if any significant serial autocorrelation in the residuals from all of the simple linear regression relationships that were estimated between individual species and conductivity. It is concluded that the hierarchical sampling design was suitable for the purposes of the study, and that the continuous monitoring of electrical conductivity provides excellent supporting information to the chemical analysis of water samples if it is used carefully as a means of short term calibration and interpolation of the solute record.     

The Apure River: geochemistry of major and selected trace elements in an Orinoco River tributary coming from the Andes,Venezuela

The analysis of physicochemical variables and selected dissolved elements was performed on the Apure River waters for 15 months. The variables pH, alkalinity, dissolved O₂, conductivity and Na, Ca, Mg and Cd concentrations showed maximum values during low water, whereas K, Si, Fe, Al, Mn, Zn, Cu, Cr and dissolved organic carbon (DOC) showed maximum concentrations during rising and high water. Five important factors were found to control the amount and temporal variability of the dissolved elements: lithology, hydrology, vegetation–floodplain processes, redox conditions and organic complexation. Weathering of silicates, carbonates and evaporites in the Andes provides most of the proportion of Na, Ca, Mg and HCO₃^? to waters. The temporal variability of these ions is controlled by a dilution process. Although Si can be taken up by the biomass, Si and K can be leached from the floodplain by weathering of clays. Microbial decay of the submerged plants in the floodplain during the inundation periods provides DOC and K to river waters and changes the redox conditions in water. The changing redox conditions control the solubility of Mn, Zn and Fe. Dissolved Mn is a function of pH‐dependent redox process, whereas Zn solubility is controlled by scavenging of Zn during the oxidation of Mn²⁺ to MnO₂. Positive relationships between Al, Fe, Cu, Cr and DOC suggest that these elements are complexed by organic colloids generated in the floodplain. Moreover, the binding capacity of Fe with DOC increases under reducing conditions. Although Cd seems to be provided by weathering in the Andes, several processes can affect the mobility of Cd during transport. Copyright © 2010 John Wiley & Sons, Ltd.     

Applicability of isotopic hydrograph separation in a suburban basin during snowmelt

C. H. TAYLOR Methodological issues associated with isotopic hydrograph separations (IHSs) in built-up environments are explored using results from the 1990 spring melt in a suburban basin in Peterborough, Ontario, Canada. The hetrogeneous nature of suburban environments complicates the selection of appropriate isotopic signatures for event and pre-event waters. Near-stream groundwater δ¹⁸O sampled from wells was poorly mixed, such that the pre-event water signature was best characterized by δ¹⁸O in pre-melt baseflow or discharge from a headwater spring. The event water signature during snowmelt can be characterized using δ¹⁸O in the pre-melt snowpack, surface runoff samples or meltwater from lysimeters. However, the use of snowpack δ¹⁸O may be inappropriate in suburban basins where meltwater from thin snowcover may exhibit pronounced responses to δ¹⁸O in rainfall contributions. Intensive sampling of the spatial variability of runoff or meltwater δ¹⁸O may be required to characterize the average event water signature adequately. Rainfall δ¹⁸O provided an appropriate event water signal during a large rain on snow event, and differences between this IHS and one generated using an event water signature that included meltwater contributions from snow-covered surfaces were within the uncertainty attributable to the analytical error in δ¹⁸O values. Event water supplied 55-63% of the peak discharge and 48-58% of total runoff from the basin during the melt, which is consistent with the fraction of the basin that has been developed. These results contrast with IHSs conducted in forested basins that suggest that stormflow is dominated by pre-event water contributions.     

From on high: Geochemistry of alpine springs,Niwot Ridge,Colorado Front Range,USA

Snowmelt‐fed springs and small (0.5 km²) upland catchments in alpine areas of the western United States contribute significantly to the quantity and inorganic chemistry of water delivered to downstream basins but have not been studied extensively. Mineral weathering, transit time, and hydrologic mixing control the solute chemistry of waters that drain the upland zone of Niwot Ridge, Colorado Front Range, and adjacent areas in the granitic core of the Southern Rocky Mountains. Water in 37 springs sampled in this study flows in generally short steep paths (~0.3 km) through shallow regolith with mean transit times (MTT) of weeks to months, producing solutions dominated by Si, Ca²⁺, Na⁺, and HCO₃^?, locally SO₄^2?. Rock type is a significant control on spring, surface, and shallow groundwater chemistry, and plagioclase (oligoclase) is the major source of dissolved Na⁺ and Si. Concentrations of Ca²⁺ exceed stoichiometric predictions of oligoclase weathering by ~3.5×; excess Ca²⁺ likely represents weathering of aeolian material, vein calcite, or trace minerals. Concentrations of base cations and Si increase slowly with estimated MTT of 0.2 years for Niwot Ridge spring waters, and several years for shallow groundwater sampled by wells. Chemical weathering of silicate minerals is slow with estimated rates of ~2.0 and 0.2 pmol·m^?2·s^?1 for oligoclase and microcline, respectively; the most mineralized spring waters are saturated only with respect to kaolinite and montmorillonite. More than 50% of the dissolved base cations + Si measured in Boulder Creek at Orodell (~25 km downstream) accumulate before water emerges from alpine springs on Niwot Ridge. Warming global temperatures are shifting more high‐elevation precipitation to rain, potentially changing run‐off patterns, transit time, and solute loads. Acquisition of solutes by alpine waters thus has implications far beyond small upland catchments.     

Major ion chemistry of two cratonic rivers in the tropics: Weathering rates and their controlling factors

Continental weathering plays a dominant role in regulating the global carbon cycle, soil chemistry and nutrient supply to oceans. The CO₂-mediated silicate weathering acts as a major CO₂ sink, whereas sulphuric acid-mediated carbonate dissolution releases CO₂ to the atmosphere–ocean system. In this study, dissolved major ions and silica concentrations of two tropical (Damodar and Subarnarekha) river systems from India have been measured to constrain the type and rate of chemical weathering for these basins. The total dissolved solids (TDS) of these rivers, a measure of total solute supply from all possible sources, are about 2–3 times higher than that of the global average for rivers. Mass balance calculations involving inverse modelling estimate that 63 ± 11% of total cations are derived from rock weathering, of which 27 ± 7% of cations are supplied through silicate weathering. The sulphide-S concentrations are estimated by comparing the water chemistry of these two rivers with that of a nearby river (Brahmani) with similar lithology but no signatures of sulphide oxidation. The outflows of Damodar and Subarnarekha rivers receive 17% and 55% of SO₄ through sulphide oxidation, respectively. The sulphide oxidation fluxes from the ore mining areas, such as upper Damodar (0.52 × 10⁹ mol/yr) and lower Subarnarekha (0.66 × 10⁹ mol/yr) basins, are disproportionally (~9 times) higher compared to their fractional areal coverage to the global drainage area. The corresponding CO₂ release rate (2.84 × 10⁴ mol/km²/yr) for the Damodar basin is lower by five times than its CO₂ uptake rate (1.38 × 10⁵ mol/km²/yr). The outcomes of this study underscore the dominance of sulphide oxidation in controlling the dissolved chemical (cationic and sulphur) fluxes.     

Sr fluxes and isotopic compositions of the eleven rivers originating from the Qinghai-Tibet Plateau and their contributions to <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr evolution of seawater

To evaluate influence of chemical weathering of the Qinghai-Tibet Plateau (QTP) on seawater ⁸⁷Sr/⁸⁶Sr variation, river water and sediment samples were collected, and their Sr concentrations and isotopic compositions analyzed, from the seven large rivers that originated from the QTP. By combining these with the data of the Ganges, Brahmaputra, Indus and Irrawaddy originated in the southern QTP, the total Sr flux of the eleven rivers reaches 3.47×10⁹ mol·a⁻¹, which accounts for 10.2% of the total Sr flux transported by the global rivers. The weighted mean ⁸⁷Sr/⁸⁶Sr is 0.71694, higher than the average value of the global rivers. The ⁸⁷Sr_ex (⁸⁷Sr flux in excess of the seawater ⁸⁷Sr/⁸⁶Sr ratio) of the Chinese seven rivers is 1.55×10⁶ mol·a⁻¹, only accounting for about 6% of the value of the eleven rivers originated from QTP, and the Ganges-Brahmaputra system accounts for 86%. We assume that the QTP rivers have no strontium contributions to the oceans before ∼40 Ma and the Sr fluxes of the global rivers, except the QTP eleven rivers, are constant, then a maximum linear increase in Sr fluxes of the QTP rivers from zero to the modern value in response to tectonic uplift can explain ∼69% increase of seawater ⁸⁷Sr/⁸⁶Sr over the past ∼40 Ma and the remainder of 31% is perhaps provided from other factors. Supported by National Natural Science Foundation of China (Grant Nos. 40473009, 40331001, 40873001)     

Chemical weathering and CO2 consumption in the glaciated Karuxung River catchment,Tibetan Plateau

Climate factors play critical roles in controlling chemical weathering, while chemically weathered surface material can regulate climate change. To estimate global chemical weathering fluxes and CO₂ balance, it is important to identify the characteristics and driving factors of chemical weathering and CO₂ consumption on the Tibetan Plateau, especially in glaciated catchments. The analysis of the hydro-geochemical data indicated that silicate weathering in this area was inhibited by low temperatures, while carbonate weathering was promoted by the abundant clastic rocks with fresh surfaces produced by glacial action. Carbonate weathering dominated the riverine solute generation (with a contribution of 58%, 51%, and 43% at the QiangYong Glacier (QYG), the WengGuo Hydrological Station (WGHS), and the lake estuary (LE), respectively). The oxidation of pyrite contributed to 35%, 42%, and 30% of the riverine solutes, while silicate weathering contributed to 5%, 6%, and 26% of the riverine solutes at the QYG, WGHS, and LE, respectively. The alluvial deposit of easily weathering fine silicate minerals, the higher air temperature, plant density, and soil thickness at the downstream LE in comparison to upstream and midstream may lead to longer contact time between pore water and mineral materials, thus enhancing the silicate weathering. Because of the involvement of sulfuric acid produced by the oxidation of pyrite, carbonate weathering in the upstream and midstream did not consume atmospheric CO₂, resulting in the high rate of carbonate weathering (73.9 and 75.6 t km⁻² yr⁻¹, respectively, in maximum) and potential net release of CO₂ (with an upper constraint of 35.6 and 35.2 t km⁻² yr⁻¹, respectively) at the QYG and WGHS. The above results indicate the potential of the glaciated area of the Tibetan Plateau with pyrite deposits being a substantial natural carbon source, which deserves further investigation.