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.     

The hydrochemistry of meltwaters draining a polythermal-based,high Arctic glacier,south Svalbard: I. The ablation season

Solute and runoff time-series at Finsterwalderbreen, Svalbard, provide evidence for considerable basal routing of water and the existence of at least two contrasting subglacial chemical weathering environments. The hydrochemistry of a subglacial upwelling provides evidence for a snowmelt-fed subglacial reservoir that dominates bulk runoff during recession flow. High concentrations of Cl⁻ and crustal ions, high pCO₂ and ratios of [*SO²⁻₄/(*SO²⁻₄+HCO⁻₃)] close to 0·5 indicate the passage of snowmelt through a subglacial weathering environment characterized by high rock:water ratios, prolonged residence times and restricted access to the atmosphere. At higher discharges, bulk runoff becomes dominated by icemelt from the lower part of the glacier that is conveyed through a chemical weathering environment characterized by low rock:water ratios, short residence times and free contact with atmospheric gases. These observations suggest that icemelt is routed via a hydrological system composed of basal/ice-marginal, englacial and supraglacial components and is directed to the glacier margins by the ice surface slope. Upwelling water flows relatively independently of icemelt to the terminus via a subglacial drainage system, possibly constituting flow through a sediment layer. Cold basal ice at the terminus forces it to take a subterranean routing in its latter stages. The existence of spatially discrete flow paths conveying icemelt and subglacial snowmelt to the terminus may be the norm for polythermal-based glaciers on Svalbard. Proglacial mixing of these components to form the bulk meltwaters gives rise to hydrochemical trends that resemble those of warm-based glaciers. These hydrochemical characteristics of bulk runoff have not been documented on any other glacier on Svalbard to date and have significance for understanding interactions between thermal regime and glacier hydrology. © 1998 John Wiley & Sons, Ltd.     

Seasonal evolution of meltwater generation,storage and discharge at a non‐temperate glacier in Svalbard

In glacierized catchments, meteorological inputs driving surface melting are translated into runoff outputs mediated by the glacier hydrological system: analysis of the relationship between meteorology and diurnal and seasonal patterns of runoff should reflect the functioning of that system, with the role of meltwater storage likely to be of particular importance. Daily meltwater storage is determined for a glacier at 78 °N in the Svalbard archipelago, by comparing inputs calculated from a surface energy balance model with measured outputs (proglacial discharge). Solar radiation, air temperature, wind speed and proglacial discharge are then analysed by regression and time‐series methods, in order to assess the meteorology–discharge relationship and its variation at diurnal and seasonal time‐scales. The recorded discharge time‐series can be divided into two contrasting intervals: up to early August, proglacial discharge was high and variable, mean hydrographs showed little indication of diurnal cycling, ARIMA models of discharge indicated a non‐seasonal, moving‐average generating process, and there was a net loss of meltwater from storage; from early August, proglacial discharge was low and relatively invariable, but with clearer diurnal cycles, regression models of discharge showed substantially improved correlations with air temperature and solar radiation, ARIMA models indicated a non‐seasonal, autoregressive generating process, and eventually a seasonal component, and there was a net gain in meltwater storage. The transition between the two periods is brief compared with the duration of the melt season. The runoff response to meteorology therefore lacks the strongly progressive element previously identified in mid‐latitude glacierized catchments. In particular, the glacier hydrological system only appears responsive to diurnal forcing following the depletion of the seasonal snowpack meltwater store. Copyright © 2001 John Wiley & Sons, Ltd.     

Temporal variation of chemical and mechanical weathering in NE Iceland: Evaluation of a steady-state model of erosion

This study critically assesses the temporal sensitivity of the steady-state model of erosion that has been applied to chemical and mechanical weathering studies of volcanic islands and the continents, using only one sample from each catchment. The model assumes a geochemical mass balance between the initially unweathered rock of a drainage basin and the dissolved and solid loads of the river.Chemical composition of 178 samples of suspended and dissolved inorganic river constituents, collected in 1998–2002, were studied from five basaltic river catchments in NE Iceland. The Hydrological Service in Iceland has monitored the discharge and the total suspended inorganic matter concentration (SIM) of the glacial rivers for ~ four decades, making it possible to compare modelled and measured SIM fluxes.Concentration of SIM and grain size increased with discharge. As proportion of clay size particles in the SIM samples increased, concentrations of insoluble elements increased and of soluble decreased. The highest proportion of altered basaltic glass was in the clay size particles.The concentration ratio of insoluble elements in the SIM was used along with data on chemical composition of unweathered rocks (high-Mg basalts, tholeiites, rhyolites) to calculate the pristine composition of the original catchment rocks. The calculated rhyolite proportions compare nicely with area-weighted average proportions, from geological maps of these catchments.The calculated composition of the unweathered bedrock was used in the steady-state model, together with the chemical composition of the suspended and dissolved constituents of the river. Seasonal changes in dissolved constituent concentrations resulted in too low modelled concentrations of SIM_mod at high discharge (and too high SIM_mod at low discharge). Samples collected at annual average river dissolved load yielded SIM_mod concentrations close to the measured ones. According to the model, the studied rivers had specific mechanical denudation rates of 1.3–3.0 kg/m²/yr whereas the average measured rates were 0.8–3.5 kg/m²/yr which are among the highest on Earth.This study validates the use of a steady-state model of erosion to estimate mechanical weathering rates at the scale of a river catchment when the collected riverine dissolved load represents the average chemical composition over a mean hydrological year.     

Denudation rates on cratonic landscapes: comparison between suspended and dissolved fluxes,and 10Be analysis in the Nyong and Sanaga River basins,south Cameroon

South Cameroon is located in a tropical and tectonically quiescent region, with landscapes characterized by thick highly weathered regolith, indicative of the long‐term predominance of chemical weathering over erosion. Currently this region undergoes huge changes due to accelerated mutations related to a growing population and economical developments with associated needs and increasing pressures on land and natural resources. We analysed two of the main south Cameroon rivers: the Nyong River and Sanaga River. The Sanaga catchment undergoes a contrasted tropical climate from sub‐humid mountainous and humid climate and is impacted by deforestation, agriculture, damming, mining and urbanization, especially in the Mbam sub‐basin, draining the highly populated volcanic highlands. By contrast, the Nyong catchment, only under humid tropical climate, is preserved from anthropogenic disturbance with low population except in the region of Yaoundé (Méfou sub‐basin). Moreover the Nyong basin is dam‐free and less impacted by agriculture and logging. We explore both denudation temporal variability and the ratio between chemical and physical denudation through two catchment‐averaged erosion and denudation datasets. The first one consists of an 11‐year long gauging dataset, while the second one comes from cosmogenic radionuclides [CRNs, here beryllium‐10 (¹⁰Be)] from sand sampled in the river mainstreams (timescale of tens to hundreds of thousands of years). Modern fluxes estimated from gauging data range from 5 to 100 m/Ma (10 to 200 t/km²/yr); our calculations indicate that the usual relative contribution of chemical versus physical denudation is 60% and 40%, respectively, of the total denudation. Beryllium‐10 denudation rates and sediment fluxes range from 4.8 to 40.3 m/Ma or 13 to 109 t/km²/yr, respectively, after correction for quartz enrichment. These fluxes are slightly less than the modern fluxes observed in Cameroon and other stable tropical areas. The highest ¹⁰Be‐derived fluxes and the highest physical versus chemical denudation ratios are attributed to anthropogenic impact. Copyright © 2016 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.     

Evaluating debris-flow and anthropogenic disturbance on 10Be concentration in mountain drainage basins: implications for functional connectivity and denudation rates across time scales

We examine the sensitivity of ¹⁰Be concentrations (and derived denudation rates), to debris-flow and anthropogenic perturbations in steep settings of the Eastern Alps, and explore possible relations with structural geomorphic connectivity. Using cosmogenic ¹⁰Be as a tracer for functional geomorphic connectivity, we conduct sampling replications across four seasons in Gadria, Strimm and Allitz Creek. Sampling sites encompass a range of structural connectivity configurations, including the conditioning of a sackung, all assessed through a geomorphometric index (IC). By combining information on contemporary depth of erosion and sediment yield, disturbance history and post-LGM (Last Glacial Maximum) sedimentation rates, we constrain the effects of debris-flow disturbance on ¹⁰Be concentrations at the Gadria sites. Here, we argue that bedrock weakening imparted by the sackung promotes high depth of erosion. Consequently, debris flows recruit sediment beyond the critical depth of spallogenic production (e.g., >3 m), which in turn, episodically, due to predominantly muogenic production pathways, lowers ¹⁰Be concentration by a factor of 4, for at least 2 years. In contrast, steady erosion in Strimm Creek yields very stable ¹⁰Be concentrations through time. In Allitz Creek, we observe two- to fourfold seasonal fluctuations in ¹⁰Be concentrations, which we explain as the combined effects of water diversion and hydraulic structures on sediment mixing. We further show that ¹⁰Be concentration correlates inversely with the IC index, where sub-basins characterized by high concentrations (long residence times) exhibit low IC values (structurally disconnected) and vice versa, implying that, over millennial time scales a direct relation exists between functional and structural connectivity, and that the IC index performed as a suitable metric for structural connectivity. The index performs comparably better than other metrics (i.e., mean slope and mean normalized channel steepness index) previously used to assess topographic controls on denudation rates in active unglaciated ranges. In terms of landscape evolution, we argue that the sackung, by favouring intense debris-flow activity across the Holocene, has aided rapid postglacial reshaping of the Gadria basin, which currently exhibits a topographic signature characteristic of unglaciated debris-flow systems. © 2020 John Wiley & Sons, Ltd.     

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.     

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.     

Coast formation in an Arctic area due to glacier surge and retreat: The Hornbreen–Hambergbreen case from Spistbergen

Glacierised coasts undergo faster geomorphic processes than unglaciated ones. We have studied changes of the coastal area in southern Svalbard with the glacier bridge between Torell Land and Sørkapp Land since the beginning of the 20th century. The existence of a continuous subglacial depression beneath the Hornbreen–Hambergbreen glacier system has been debated since the 1960s, with inconclusive results. In this study we assess both the subglacial topography and the bathymetry of Hornsund Fjord and Hambergbukta bay. This included ~40 km of radar surveys over the glacial system and sea depth sounding. The extent of the glaciers from maps and satellite images together with digital terrain models and surface elevation data based on GPS profiling were used to analyse geometry changes of the glacier surfaces. The results confirm the existence of a continuous subglacial depression below sea level (c. 40 m deep) between Hornsund and the Barents Sea. The Hornbreen‐Hambergbreen system has changed in shape over the past century, reflecting its dynamic origin and activity, also exemplified by the sequential surges identified since 1899. There was a pre‐surge build‐up event of Flatbreen causing a surge and subsequent lowering of the Hornbreen‐Hambergbreen frontal parts by the 1960s. After, the entire surface lowered, albeit with a delay in the Hornbreen terminal zone. Since the year 2000, Hornbreen terminus has retreated at an average rate of 106 m a^?1; ~50% faster than that of Hambergbreen. If the retreat continues at the 2000–2015 average rate, the ice bridge between Hornsund and Hambergbukta will be broken sometime between 2055 and 2065 and the Hornsund strait will separate Sørkapp Land from the Spitsbergen island. The processes and events described in this study, particularly the effects of the glacier surge, may provide a model for changes likely to occur in other coastal glaciated regions experiencing rapid change. Copyright © 2017 John Wiley & Sons, Ltd.     

Investigations on distributions and fluxes of sea-air CO_2 of the expedition areas in the Arctic Ocean

揋reenhouse effect?causing global warming has been an important issue of studying climate change. In the latest 100 years, the earth surface temperature has been increased by about 0.4℃—0.8℃[1,2]. And this has been becoming a hotspot of the world[3,4]     

Hydrologic impact of regional climate change for the snowfed and glacierfed river basins in the Republic of Tajikistan: hydrological response of flow to climate change

The warming of the Earth's atmosphere system is likely to change temperature and precipitation, which may affect the climate, hydrology and water resources at the river basins over the world. The importance of temperature change becomes even greater in snow or glacier dominated basins where it controls the snowmelt processes during the late‐winter, spring and summer months. In this study hydrologic responses of streamflow in the Pyanj and Vaksh River basins to climate change are analysed with a watershed hydrology model, based on the downscaled atmospheric data as input, in order to assess the regional climate change impact for the snowfed and glacierfed river basins in the Republic of Tajikistan. As a result of this analysis, it was found that the annual mean river discharge is increasing in the future at snow and glacier dominated areas due to the air temperature increase and the consequent increase in snow/ice melt rates until about 2060. Then the annual mean flow discharge starts to decrease from about 2080 onward because the small glaciers start to disappear in the glacier areas. It was also found that there is a gradual change in the hydrologic flow regime throughout a year, with the high flows occuring earlier in the hydrologic year, due to the warmer climate in the future. Furthermore, significant increases in annual maximum daily flows, including the 100‐year return period flows, at the Pyanj and Vaksh River basins toward the end of the 21st century can be inferred from flood frequency analysis results. Copyright © 2012 John Wiley & Sons, Ltd.     

Mass‐balance modeling of mineral weathering rates and CO2 consumption in the forested,metabasaltic Hauver Branch watershed,Catoctin Mountain,Maryland, USA

Mineral weathering rates and a forest macronutrient uptake stoichiometry were determined for the forested, metabasaltic Hauver Branch watershed in north‐central Maryland, USA. Previous studies of Hauver Branch have had an insufficient number of analytes to permit determination of rates of all the minerals involved in chemical weathering, including biomass. More equations in the mass‐balance matrix were added using existing mineralogic information. The stoichiometry of a deciduous biomass term was determined using multi‐year weekly to biweekly stream‐water chemistry for a nearby watershed, which drains relatively unreactive quartzite bedrock. At Hauver Branch, calcite hosts ~38 mol% of the calcium ion (Ca²⁺) contained in weathering minerals, but its weathering provides ~90% of the stream water Ca²⁺. This occurs in a landscape with a regolith residence time of more than several Ka (kiloannum). Previous studies indicate that such old regolith does not typically contain dissolving calcite that affects stream Ca²⁺/Na⁺ ratios. The relatively high calcite dissolution rate likely reflects dissolution of calcite in fractures of the deep critical zone. Of the carbon dioxide (CO₂) consumed by mineral weathering, calcite is responsible for approximately 27%, with the silicate weathering consumption rate far exceeding that of the global average. The chemical weathering of mafic terrains in decaying orogens thus may be capable of influencing global geochemical cycles, and therefore, climate, on geological timescales. Based on carbon‐balance calculations, atmospheric‐derived sulfuric acid is responsible for approximately 22% of the mineral weathering occurring in the watershed. Our results suggest that rising air temperatures, driven by global warming and resulting in higher precipitation, will cause the rate of chemical weathering in the Hauver Branch watershed to increase until a threshold temperature is reached. Beyond the threshold temperature, increased recharge would produce a shallower groundwater table and reduced chemical weathering rates. Copyright © 2013 John Wiley & Sons, Ltd.     

Oxygen isotope measurements of mammoth and reindeer skeletal remains: an archive of Late Pleistocene environmental conditions in Eurasian Arctic

58 samples of fossil mammoth and reindeer teeth and bones of various ages and coming from different locations were studied for the oxygen isotopic composition of their phosphate. Samples from Siberia have interstadial (Marine Isotope Stage 3), stadial (MIS 2), late-glacial and post-glacial ages. Russian and Ukrainian samples refer to the late-glacial and transitional (between the interstadial and glacial stages) time. The δ¹⁸O of palaeoenvironmental waters were calculated from the δ¹⁸O_p obtained from fossil samples by means of the isotope equations calibrated on modern specimens of elephants and deer respectively. The δ¹⁸O_w obtained are generally lighter than those measured nowadays in the same areas and not far from those measured on ice cores of Holocene age, the isotopic differences being not greater than a few δ units. The calculated values are also in fairly good agreement with some isotopic values obtained from Siberian permafrost samples. According to the results obtained it seems that the elephant and deer equations can be reasonably used respectively in the case of fossil mammoth and deer skeletons to evaluate environmental palaeowaters.     

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.     

Formation of phreatic caves in an eogenetic karst aquifer by CO2 enrichment at lower water tables and subsequent flooding by sea level rise

Formation of extensive phreatic caves in eogenetic karst aquifers is widely believed to require mixing of fresh and saltwater. Extensive phreatic caves also occur, however, in eogenetic karst aquifers where fresh and saltwater do not mix, for example in the upper Floridan aquifer. These caves are thought to have formed in their modern settings by dissolution from sinking streams or by convergence of groundwater flow paths on springs. Alternatively, these caves have been hypothesized to have formed at lower water tables during sea level low‐stands. These hypotheses have not previously been tested against one another. Analyzing morphological data and water chemistry from caves in the Suwannee River Basin in north‐central Florida and water chemistry from wells in the central Florida carbonate platform indicates that phreatic caves within the Suwannee River Basin most likely formed at lower water tables during lower sea levels. Consideration of the hydrological and geochemical constraints posed by the upper Floridan aquifer leads to the conclusion that cave formation was most likely driven by dissolution of vadose CO₂ gas into the groundwater. Sea level rise and a wetter climate during the mid‐Holocene lifted the water table above the elevation of the caves and placed the caves tens of meters below the modern water table. When rising water tables reached the land surface, surface streams formed. Incision of surface streams breached the pre‐existing caves to form modern springs, which provide access to the phreatic caves. Phreatic caves in the Suwannee River Basin are thus relict and have no causal relationship with modern surficial drainage systems. Neither mixing dissolution nor sinking streams are necessary to form laterally extensive phreatic caves in eogenetic karst aquifers. Dissolution at water tables, potentially driven by vadose CO₂ gas, offers an underappreciated mechanism to form cavernous porosity in eogenetic carbonate rocks. Copyright © 2012 John Wiley & Sons, Ltd.     

Variations in dissolved CO2 and CH4 in a first‐order stream and catchment: an investigation of soil–stream linkages

Spatial and seasonal variations in CO₂ and CH₄ concentrations in streamwater and adjacent soils were studied at three sites on Brocky Burn, a headwater stream draining a peatland catchment in upland Britain. Concentrations of both gases in the soil atmosphere were significantly higher in peat and riparian soils than in mineral soils. Peat and riparian soil CO₂ concentrations varied seasonally, showing a positive correlation with air and soil temperature. Streamwater CO₂ concentrations at the upper sampling site, which mostly drained deep peats, varied from 2·8 to 9·8 mg l^?1 (2·5 to 11·9 times atmospheric saturation) and decreased markedly downstream. Temperature‐related seasonal variations in peat and riparian soil CO₂ were reflected in the stream at the upper site, where 77% of biweekly variation was explained by an autoregressive model based on: (i) a negative log‐linear relationship with stream flow; (ii) a positive linear relationship with soil CO₂ concentrations in the shallow riparian wells; and (iii) a negative linear relationship with soil CO₂ concentrations in the shallow peat wells, with a significant 2‐week lag term. These relationships changed markedly downstream, with an apparent decrease in the soil–stream linkage and a switch to a positive relationship between stream flow and stream CO₂. Streamwater CH₄ concentrations also declined sharply downstream, but were much lower (<0·01 to 0·12 mg l^?1) than those of CO₂ and showed no seasonal variation, nor any relationship with soil atmospheric CH₄ concentrations. However, stream CH₄ was significantly correlated with stream flow at the upper site, which explained 57% of biweekly variations in dissolved concentrations. We conclude that stream CO₂ can be a useful integrative measure of whole catchment respiration, but only at sites where the soil–stream linkage is strong. Copyright © 2004 John Wiley & Sons, Ltd.