The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate–sulphate karst system

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO₂) downstream of karstic springs. However, in most karstic springs CO₂ degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re‐emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common‐ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO₄^2? composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common‐ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization. Copyright © 2016 John Wiley & Sons, Ltd.     

Seasonal controls of meltwater runoff chemistry and chemical weathering at Urumqi Glacier No.1 in central Asia

Temporal variation of runoff chemistry and its seasonal controls relating to chemical weathering processes and drainage system evolution were examined at Urumqi Glacier No.1 in Xinjiang, China, over a full melt season. The dominant ions in meltwater runoff are HCO₃^?, Ca²⁺, and SO₄^2?; and Fe, Sr, and Al are dominant elements. Concentrations of major ions and some elements show periodic variations with seasons and negatively correlate with discharge, whereas other elements (e.g., Al, Ni, Cu, Zn, Cd, and Pb) show a random change, providing insights into the hydrological and physicochemical controls. HCO₃^? and Ca²⁺ are primarily derived from calcite, SO₄^2? and Fe mainly come from pyrite, and Sr and Al principally originate from silicate. Hydrochemical fluxes of solutes exhibit strong seasonality but are positively related to discharge, suggesting an increasing release of solutes during higher flow conditions. Solute yields, cation denudation rate, and chemical weathering intensity observed at Urumqi Glacier No.1 are higher than those at most basins worldwide. This suggests that chemical weathering in central Asia may be stronger than at other glacial basins with similar specific discharge. Concentrations of some elements (e.g., Fe, Al, As, Pb, and Zn) are close to or exceed the guidelines for drinking water standards in meltwater‐fed rivers. These rivers may face future challenges of water quality degradation, and relationships between changing flow and water quality conditions should be established soon, given that development of channelized flow is expected to be earlier over a melt season in a warming climate.     

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.     

Hydrogeochemistry of seepage water collected within the Youngcheon diversion tunnel,Korea: source and evolution of SO4‐rich groundwater in sedimentary terrain

In the Youngcheon Diversion Tunnel area, South Korea, 46 samples of tunnel seepage water (TSW) and borehole groundwater were collected from areas with sedimentary rocks (mainly sandstone and shale) and were examined for hydrogeochemical characteristics. The measured SO₄ concentrations range widely from 7·7 to 942·0 mg/l, and exceed the Korean Drinking Water Standard (200 mg/l) in about half the samples. The TDS (total dissolved solid) content generally is high (171–1461 mg/l) from more shale‐rich formations and also reflects varying degrees of water–rock interaction. The water is classified into three groups: Ca? SO₄ type (61% of the samples collected), Ca? SO₄? HCO₃ type (15%) and Ca? HCO₃ type (24%). The Ca? HCO₃ type water (mean concentrations=369 mg/l Ca, 148 mg/l HCO₃ and 23 mg/l SO₄) reflected the simple reaction between CO₂‐recharged water and calcite, whereas the more SO₄‐rich nature of Ca? SO₄ type water (mean concentrations=153 mg/l Ca, 66 mg/l HCO₃ and 416 mg/l SO₄) reflected the oxidation of pyrite in sedimentary rocks and fracture zones. Pyrite oxidation resulted in precipitation of amorphous iron hydroxide locally within the tunnel as well as in high concentrations of Ca (mean 153 mg/l) and Na (mean 49 mg/l) for TSW, and is associated with calcite dissolution resulting in pH buffering. The pyrite oxidation required for the formation of Ca? SO₄ type water was enhanced by the diffusion of oxygenated air through the fractures related to the tunnel's construction. The subsequent outgassing of CO₂ into the tunnel resulted in precipitation of iron‐bearing carbonate. Copyright © 2001 John Wiley & Sons, Ltd.     

Hydrochemistry of meltwaters draining a polythermal‐based,high‐Arctic glacier,south Svalbard: II. Winter and early Spring

The hydrochemistry of naled and upwelling water sampled from the forefields of Finsterwalderbreen, Svalbard, during spring are used for the first time to infer the hydrology of overwinter meltwaters at a polythermal‐based glacier. Hydrochemical variations in naled are explained in terms of different water sources and their chemical alteration during freezing. Two water sources to naled are identified: surficially routed snowmelt and subglacial water. Naled that results from the freezing of the former is enriched in atmospherically derived ions such as Na⁺ and Cl⁻, and is believed to be formed during winter warm periods. Naled of subglacial origin contains relatively high proportions of crustally derived solute. It reflects the freezing of subglacial meltwaters that continue to issue from a subterranean upwellling during winter. An increasing dominance of SO²⁻₄ Mg²⁺, Na⁺ and Cl⁻ in subglacial naled with increasing distance from the upwelling reflects the progressive freezing of this water body and the associated removal of Ca²⁺ and HCO by calcite precipitation. These spatial trends are accentuated by the leaching of soluble ions from the naled close to its source by subsequent upwelling waters. The chemistry of spring upwelling waters, also of subglacial origin, strongly reflects this process. Meltwater produced by geothermal heating of glacier basal ice is believed to be the principal source of water to the subglacial drainage system during winter. Solute acquisition by this meltwater is limited by a scarcity of proton suppliers. Evolution of this dilute meltwater carries an imprint of ion exchange processes. Some stored subglacial water from the end of the previous ablation season may supplement the basal meltwater component in early winter. Copyright © 2000 John Wiley & Sons, Ltd.     

Hydrogeochemical evolution of Ordovician limestone groundwater in Yanzhou,North China

Major‐ion compositions of groundwater are employed in this study of the water–rock interactions and hydrogeochemical evolution within a carbonate aquifer system. The groundwater samples were collected from boreholes or underground tunnels in the Ordovician limestone of Yanzhou Coalfield where catastrophic groundwater inflows can be hazardous to mining and impact use of the groundwater as a water supply. The concentration of total dissolved solid (TDS) ranged from 961 to 3555 mg/l and indicates moderately to highly mineralized water. The main water‐type of the middle Ordovician limestone groundwater is Ca‐Mg‐SO₄, with SO₄^2‐ ranging from 537 to 2297 mg/l, and average values of Ca²⁺ and Mg²⁺ of 455.7 and 116.6 mg/l, respectively. The water samples were supersaturated with respect to calcite and dolomite and undersaturated or saturated with respect to gypsum. Along the general flow direction, deduced from increases of TDS and Cl^‐, the main water–rock interactions that caused hydrogeochemical evolution of the groundwater within the aquifer were the dissolution of gypsum, the precipitation of calcite, the dissolution or precipitation of dolomite, and ion exchange. Ion exchange is the major cause for the lower mole concentration of Ca²⁺ than that of SO₄^2‐. The groundwater level of Ordovician aquifer is much higher than that of C‐P coal‐bearing aquifers, so the potential flow direction is upward, and the pyrite in coal is not a possible source of sulfate; additional data on the stable sulfur and oxygen isotopic composition of the sulfate may be helpful to identify its origin. Although ion exchange probably accounts for the higher mole concentration of Na⁺ than that of Cl^‐, the dissolution of aluminosilicate cannot be ruled out. The data evaluation methods and results of this study could be useful in other areas to understand flow paths in aquifers and to provide information needed to identify the origin of groundwater. Copyright © 2012 John Wiley & Sons, Ltd.     

Groundwater mineralisation processes in Mediterranean semi‐arid systems (Cap‐Bon,North east of Tunisia): hydrogeological and geochemical approaches

The groundwater of the Korba plain represents major water resources in Tunisia. The Plio‐Quaternary unconfined aquifer of the Cap‐Bon (north‐east Tunisia) is subject to the intensive agricultural activities and high groundwater pumping rates due to the increasing of the groundwater extraction. The degradation of the groundwater quality is characterized by the salinization phenomena. Groundwater were sampled and analysed for physic‐chemical parameters: Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^‐, SO₄^2‐, HCO₃^‐, NO₃^‐, pH, electrical conductivity (EC), and the temperature (T°). The hydrochemical analysis is coupled with the calculation of the saturation indexes (SI gypsum, SI halite, SI calcite and SI dolomite), ionic derivation and with the ion correlations compared to chloride concentrations: Na⁺/ Cl^‐, Ca²⁺/ Cl^‐ and Mg²⁺/ Cl^‐ ratios. Seawater fractions in the groundwater were calculated using the chloride concentration. Those processes can be used as indicators of seawater intrusion progression. EC methods were also conducted to obtain new informations on the spatial scales and dynamics of the fresh water–seawater interface of coastal groundwater exchange. The mixing zone between freshwater and saltwater was clearly observed from the EC profile in the investigated area where a strong increase in EC with depth was observed, corresponding to the freshwater and saltwater interface. Results of hydrochemical study revealed the presence of direct cation exchange linked to seawater intrusion and dissolution processes associated with cations exchange. These results, together with EC investigation, indicated that the groundwater is affected by seawater intrusion and is still major actor as a source of salinization of the groundwater in Korba coastal plain. Further isotopic and hydrological investigations will be necessary to identify and more understood the underlying mechanisms. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Lithological and hydrological controls on water composition: evaporite dissolution and glacial weathering in the south central Andes of Argentina (33°–34°S)

Lithological and hydrological influence on fluvial physical and chemical erosion was studied in a glacierized sedimentary basin with high evaporite presence. Suspended particulate matter (SPM), total dissolved solids (TDS) and major ion concentrations were analysed for 2 years of different hydrologic condition: (i) 2009–2010, Q = 100% average; and (ii) 2010–2011, Q = 60% average. Annual hydrograph was simple regime‐type with one peak in summer related to snow melting. The intra‐annual SPM and TDS variations were directly and inversely associated to Q, respectively. Snow chemistry showed continental influence (Na⁺/Ca²⁺ = 0.17), and atmospheric input of TDS was <1% of the total exported flux. River water was highly concentrated in Ca²⁺ and SO₄²⁻ (~4 mmol l⁻¹) and in Na⁺ and Cl⁻ (~3 mmol l⁻¹). Ca²⁺/SO₄²⁻ and Na⁺/Cl⁻ molar ratios were ~1 and related to Q, directly and inversely, respectively. Major ion relationships suggest that river chemistry is controlled by evaporite (gypsum and halite) dissolution having a summer input from sulfide oxidation and carbonate dissolution, and a winter input from subsurface flow loaded with silicate weathering products. This variation pattern resulted in nearly chemostatic behaviour for Ca⁺, Mg²⁺ and SO₄²⁻, whereas Na⁺, Cl⁻ and SiO₂ concentrations showed to be controlled by dilution/concentration processes. During the 2009–2010 hydrological year, the fluxes of water, SPM and TDS registered in the snow melting–high Q season were, respectively, 71%, 92% and 67% of the annual total, whereas for equal period in 2010–2011, 56% of water, 86% of SPM and 54% of TDS annual fluxes were registered. The SPM fluxes for 2009–2010 and 2010–2011 were 1.19 × 10⁶ and 0.79 × 10⁶ t year⁻¹, whereas TDS fluxes were 0.68 × 10⁶ and 0.55 × 10⁶ t year⁻¹, respectively. Export rates for 2009–2010 were 484 t km² year⁻¹ for SPM and 275 t km² year⁻¹ for TDS. These rates are higher than those observed in glacierized granite basins and in non‐glacierized evaporite basins, suggesting a synergistic effect of lithology and glaciers on physical and chemical erosion. Copyright © 2014 John Wiley & Sons, Ltd.     

Suspended sediment and phosphorus in proglacial rivers: bioavailability and potential impacts upon the P status of ice‐marginal receiving waters

This paper adopts standard tests developed in temperate catchment research to determine the total phosphorus (TP) and the algal available (base‐extractable) phosphorus (NaOH–P) content of a wide range of glaciofluvial sediments from the Northern Hemisphere. We find that the TP content of these sediments is broadly similar to the P content of major rock types in Earth's crust (230–670 µgP/g) and so the TP yields of glacier basins may be high owing to the efficacy of suspended sediment evacuation by glacial meltwaters. We show that this is best achieved where subglacial drainage systems are present. The NaOH–P pool of the sediments is found to be low (1–23 µgP/g) relative to the TP pool and also to the NaOH–P pool of suspended sediments in temperate, non‐glacierized catchments. This most probably reflects the restricted duration of intimate contact between dilute meltwaters and glacial suspended sediments during the ablation season. Thus, despite the high surface‐area:volume ratio of glacial suspended sediments, the potential for P adsorption to mineral surfaces following release by dissolution is also low. Further, sorption experiments and sequential extraction tests conducted using glacial suspended sediments from two Svalbard catchments indicate that the generation of reactive secondary minerals (e.g. Fe‐ and other hydroxides) with a strong capacity to scavenge P from solution (and thereby promote the continued dissolution of P) may also be limited by the short residence times. Most P is therefore associated with poorly weathered, calcite/apatite‐rich mineral phases. However, we use examples from the Svalbard glacier basins (Austre Brøggerbreen and Midre Lovénbreen) to show that the high sediment yields of glaciers may result in appreciable NaOH–P loading of ice‐marginal receiving waters. Again, the importance of subglacial drainage is highlighted, as it produces a major, episodic release of NaOH–P at Midre Lovénbreen that results in a yield (8·2 kg NaOH–P/km²/year) more than one order of magnitude greater than that at Austre Brøggerbreen (where subglacial drainage is absent and the yield is 0·48 kg NaOH‐P/km²/year). Therefore, as since both detrimental and beneficial effects of sediment‐bound P loading in ice marginal receiving waters are possible (i.e. either reduced primary productivity owing to increased turbidity or P fertilization following desorption) there is a pressing need to assess the ambient P status of such environments and also the capacity for ice‐marginal ecosystems to adapt to such inputs. Copyright © 2004 John Wiley & Sons, Ltd.     

Hydrochemistry and source of high fluoride in groundwater of the Nairobi area,Kenya / Hydrochimie et origine des fortes concentrations en fluorure dans l'eau souterraine de la région de Nairobi,au Kenya

Abstract

This study aims to identify the hydrogeochemical processes influencing the high fluoride concentrations in groundwater of the Nairobi area, Kenya. For this purpose 16 groundwater samples were collected and analysed. Fluoride concentrations above the WHO standard are found in the downstream areas. The high F^? concentrations are correlated with high sodium and pH and low Ca²⁺ concentrations. Weathering of sodium-rich alkaline igneous rocks causes a pH increase resulting in an increase in HCO₃ ^? and CO₃ ^2- by dissolution of CO₂. Groundwater becomes oversaturated compared to calcite and calcite precipitation occurs, leading to a decrease in Ca²⁺. This causes a sub-saturation with respect to fluorite and dissolution of fluorite increases the F^? concentration. These reactions were modelled using the PHREEQC model and the results showed a good agreement with the measured groundwater quality, indicating that the proposed reactions are plausible for explaining the observed concentrations in groundwater.     

Hydrological and isotopic characterization of river water,groundwater, and groundwater recharge in the Heihe River basin,northwestern China

We used hydrochemistry and environmental isotope data (δ¹⁸O, δD, tritium, and ¹⁴C) to investigate the characteristics of river water, groundwater, and groundwater recharge in China's Heihe River basin. The river water and groundwater could be characterized as Ca²⁺? Mg²⁺? HCO₃^?? SO₄^2? and Na⁺? Mg²⁺? SO₄^2?? Cl^? types, respectively. Hydrogeochemical modelling using PHREEQC software revealed that the main hydrogeochemical processes are dissolution (except for gypsum and anhydrite) along groundwater flow paths from the upper to middle Heihe reaches. Towards the lower reaches, dolomite and calcite tend to precipitate. The isotopic data for most of the river water and groundwater lie on the global meteoric water line (GMWL) or between the GMWL and the meteoric water line in northwestern China, indicating weak evaporation. No direct relationship existed between recharge and discharge of groundwater in the middle and lower reaches based on the isotope ratios, d‐excess, and ¹⁴C values. On the basis of tritium in precipitation and by adopting an exponential piston‐flow model, we evaluated the mean residence time of shallow groundwater with high tritium activities, which was around 50 years (a). Furthermore, based on the several popular models, it is calculated that the deep groundwaters in piedmont alluvial fan zone of the middle reaches and in southern part of the lower reaches are modern water, whereas the deep groundwaters in the edge of the middle reaches and around Juyan Lake in the lower reaches of Heihe river basin are old water. Copyright © 2010 John Wiley & Sons, Ltd.     

Slope failures and erosion rates on a glacierized high‐mountain face under climatic changes

In this study, rapid topographic changes and increased erosion rates caused by massive slope failures in a glacierized and permafrost‐affected high‐mountain face were investigated with respect to the current climatic change. The study was conducted at one of the highest periglacial rock faces in the European Alps, the east face of Monte Rosa, Italy. Pronounced changes in ice cover and repeated rock and ice avalanche events have been documented in this rock wall since around 1990. The performed multi‐temporal comparison of high‐resolution digital terrain models (DTMs) complemented by detailed analyses of repeat photography represents a unique assessment of topographic changes and slope failures over half a century and reveals a total volume loss in bedrock and steep glaciers in the central part of the face of around 25 × 10⁶ m³ between 1988 and 2007. The high rock and ice avalanche activity translates into an increase in erosion rates of about one order of magnitude during recent decades. The study indicates that changes in atmospheric temperatures and connected changes in ice cover can induce slope destabilization in high‐mountain faces. Analyses of temperature data show that the start of the intense mass movement activity coincided with increased mean annual temperatures in the region around 1990. However, once triggered, mass movement activity seems to be able to proceed in a self‐reinforcing cycle, whereby single mass movement events might be strongly influenced by short‐term extreme temperature events. The investigations suggest a strong stability coupling between steep glaciers and underlying bedrock, as most bedrock instabilities are located in areas where surface ice has disappeared recently and the failure zones are frequently spatially correlated and often develop from lower altitudes progressively upwards. Copyright © 2013 John Wiley & Sons, Ltd.     

Chemical weathering and CO2 consumption rate in a multilayered‐aquifer dominated watershed under intensive farming: The Orgeval Critical Zone Observatory,France

The impact of intensive farming on chemical weathering in the Critical Zone is still an open question. Extensively instrumented and monitored over the last 50 years, the Orgeval Critical Zone Observatory (CZO) in France is an observation site impacted by intensive farming since the 1960s. The Orgeval observatory represents an ideal place to study the response and resilience capability of the Critical Zone under agricultural stress. This paper investigates the chemical composition of different water bodies in two nested catchments of the Orgeval CZO, including rainfall, springs, rivers, and rocks, over one and half hydrological year. We show that elemental and strontium isotopic ratios are powerful to constrain the origin of the elements. The results show that the river chemistry at the outlet of the two nested catchments is dominated by rain inputs (particularly atmospheric dust dissolution) and the chemical weathering of limestone and gypsum. Fertilizer input is clearly visible, although the distinction between gypsum dissolution and fertilizer inputs needs more investigation. The mixtures of water masses inferred from our data are in good agreement with the hydrological context of the watershed, that is, a multilayered aquifer structure. At the main outlet of the CZO, we estimate that the input of ocean‐derived solutes through rainfall represents 7 t km^?2 year^?1, on the same order of magnitude as the net fertilizer input (10 t km^?2 year^?1), and that rock weathering releases 50 t km^?2 year^?1. Including previously published physical erosion rates, we estimate that the total denudation rate (physical and chemical) of the Orgeval CZO is 20 mm (1,000 year)^?1, which, along with the entire Seine watershed, is among the lowest chemical denudation rates for carbonate terrains under temperate climate. Chemical denudation is about 10 times higher than physical erosion in the Orgeval CZO. The consumption of CO₂ by rock weathering is estimated to be between 265.10³ and 360.10³ molC km² year^?1, similar for the two nested catchments. Compared with the rivers, the springs show a higher CO₂ consumption rate that suggests, as pointed out earlier, a enhancement of carbonate dissolution linked to nitrification and thus fertilizer application. The hyporheic zone appears to be a hot spot in the carbon cycle at the Orgeval CZO. This study sheds light on the complex, anthropocenic, interplay between geology, climate, and human activities that characterize and that take place in intensive agriculture regions.     

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.     

Near‐surface hydraulic conductivity of northern hemisphere glaciers

The hydrology of near‐surface glacier ice remains a neglected aspect of glacier hydrology despite its role in modulating meltwater delivery to downstream environments. To elucidate the hydrological characteristics of this near‐surface glacial weathering crust, we describe the design and operation of a capacitance‐based piezometer that enables rapid, economical deployment across multiple sites and provides an accurate, high‐resolution record of near‐surface water‐level fluctuations. Piezometers were employed at 10 northern hemisphere glaciers, and through the application of standard bail–recharge techniques, we derive hydraulic conductivity (K) values from 0.003 to 3.519 m day^?1, with a mean of 0.185 ± 0.019 m day^?1. These results are comparable to those obtained in other discrete studies of glacier near‐surface ice, and for firn, and indicate that the weathering crust represents a hydrologically inefficient aquifer. Hydraulic conductivity correlated positively with water table height but negatively with altitude and cumulative short‐wave radiation since the last synoptic period of either negative air temperatures or turbulent energy flux dominance. The large range of K observed suggests complex interactions between meteorological influences and differences arising from variability in ice structure and crystallography. Our data demonstrate a greater complexity of near‐surface ice hydrology than hitherto appreciated and support the notion that the weathering crust can regulate the supraglacial discharge response to melt production. The conductivities reported here, coupled with typical supraglacial channel spacing, suggest that meltwater can be retained within the weathering crust for at least several days. Not only does this have implications for the accuracy of predictive meltwater run‐off models, but we also argue for biogeochemical processes and transfers that are strongly conditioned by water residence time and the efficacy of the cascade of sediments, impurities, microbes, and nutrients to downstream ecosystems. Because continued atmospheric warming will incur rising snowline elevations and glacier thinning, the supraglacial hydrological system may assume greater importance in many mountainous regions, and consequently, detailing weathering crust hydraulics represents a research priority because the flow path it represents remains poorly constrained.     

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.     

Determining long time‐scale hyporheic zone flow paths in Antarctic streams

In the McMurdo Dry Valleys of Antarctica, glaciers are the source of meltwater during the austral summer, and the streams and adjacent hyporheic zones constitute the entire physical watershed; there are no hillslope processes in these systems. Hyporheic zones can extend several metres from each side of the stream, and are up to 70 cm deep, corresponding to a lateral cross‐section as large as 12 m², and water resides in the subsurface year around. In this study, we differentiate between the near‐stream hyporheic zone, which can be characterized with stream tracer experiments, and the extended hyporheic zone, which has a longer time‐scale of exchange. We sampled stream water from Green Creek and from the adjacent saturated alluvium for stable isotopes of D and ¹⁸O to assess the significance and extent of stream‐water exchange between the streams and extended hyporheic zones over long time‐scales (days to weeks). Our results show that water residing in the extended hyporheic zone is much more isotopically enriched (up to 11‰ D and 2·2‰ ¹⁸O) than stream water. This result suggests a long residence time within the extended hyporheic zone, during which fractionation has occurred owing to summer evaporation and winter sublimation of hyporheic water. We found less enriched water in the extended hyporheic zone later in the flow season, suggesting that stream water may be exchanged into and out of this zone, on the time‐scale of weeks to months. The transient storage model OTIS was used to characterize the exchange of stream water with the extended hyporheic zone. Model results yield exchange rates (α) generally an order magnitude lower (10^?5 s^?1) than those determined using stream‐tracer techniques on the same stream. In light of previous studies in these streams, these results suggest that the hyporheic zones in Antarctic streams have near‐stream zones of rapid stream‐water exchange, where ‘fast’ biogeochemical reactions may influence water chemistry, and extended hyporheic zones, in which slower biogeochemical reaction rates may affect stream‐water chemistry at longer time‐scales. Copyright © 2003 John Wiley & Sons, Ltd.     

Hydrochemical evaluation of changing glacier meltwater contribution to stream discharge: Callejon de Huaylas,Peru / Evaluation hydrochimique de la contribution évolutive de la fonte glaciaire à l'écoulement fluvial: Callejon de Huaylas,Pérou

Abstract

Discharge measurements, precipitation observations and hydrochemical samples from catchments of the Callejon de Huaylas watershed draining the Cordillera Blanca to the Rio Santa, Peru, facilitate estimating the glacier meltwater contribution to streamflow over different spatial scales using water balance and end-member mixing computations. A monthly water balance of the Yanamarey Glacier catchment shows elevated annual discharge over December 2001–July 2004 compared to 1998–1999, with net glacier mass loss in all months. Glacial melt now accounts for an estimated 58% of annual mean discharge, 23% greater than 1998–1999. At Lake Querococha, below Yanamarey (3.4% glacierized), a hydrochemical end-member mixing model estimates that 50% of the streamflow is derived from the glacier catchment. Average concentrations from the Rio Santa leaving the Callejon de Huaylas (8% glacierized) are modelled as a mixture with 66% deriving from glacierized tributaries of the Cordillera Blanca as opposed to the non-glacierized Cordillera Negra end member.     

Estimating sublimation of intercepted and sub‐canopy snow using eddy covariance systems

Direct measurements of winter water loss due to sublimation were made in a sub‐alpine forest in the Rocky Mountains of Colorado. Above‐and below‐canopy eddy covariance systems indicated substantial losses of winter‐season snow accumulation in the form of snowpack (0·41 mm d^?1) and intercepted snow (0·71 mm d^?1) sublimation. The partitioning between these over and under story components of water loss was highly dependent on atmospheric conditions and near‐surface conditions at and below the snow/atmosphere interface. High above‐canopy sensible heat fluxes lead to strong temperature gradients between vegetation and the snow‐surface, driving substantial specific humidity gradients at the snow surface and high sublimation rates. Intercepted snowfall resulted in rapid response of above‐canopy latent heat fluxes, high within‐canopy sublimation rates (maximum = 3·7 mm d^?1), and diminished sub‐canopy snowpack sublimation. These results indicate that sublimation losses from the sub‐canopy snowpack are strongly dependent on the partitioning of sensible and latent heat fluxes in the canopy. This compels comprehensive studies of snow sublimation in forested regions that integrate sub‐canopy and over‐story processes. Copyright © 2007 John Wiley & Sons, Ltd.