Solute geochemical mass-balances and mineral weathering rates in small watersheds: Methodology,recent advances,and future directions

Solute-based geochemical mass balance methods are commonly used in small-watershed studies to estimate rates of a variety of geochemical processes at the Earth’s surface, including primary-mineral weathering and soil formation, and the quantitative contribution of these elemental transfer processes to cation budgets, nutrient cycling, and landscape susceptibility to acid deposition. Weathering rates of individual minerals in watershed mass-balance studies are determined by solving a system of simultaneous linear geochemical mass-balance equations with constant (stoichiometric) coefficients. These equations relate the measured net fluxes to the (known) stoichiometries and (unknown) rates of weathering reactions for multiple minerals in the weathering profiles. Solving the system of equations requires petrologic, mineralogic, hydrologic, botanical, and aqueous geochemical data. The number of mineral-weathering rates that can be determined is limited by the number of elements for which solute mass-balance equations can be written. In addition to calculating mineral weathering rates, elemental transfer into or out of the biomass may also be calculated. Elemental uptake by aggrading forest vegetation can act as an intrawatershed sink for at least some mineral-derived cations, producing mineral weathering rates higher than would be estimated from solute fluxes alone; similarly, element release from decaying forest biomass can result in higher solute fluxes than are produced by weathering alone. The mathematics of, significant contributions from, role of biomass in, and recent advances in, watershed geochemical mass-balance methods are discussed using examples from the Appalachian headwaters watersheds of the Coweeta Hydrologic Laboratory in the southern Blue Ridge Physiographic Province of North Carolina, USA.     

87Sr/86Sr as an indicator of flowpaths and weathering rates in the Plynlimon experimental catchments,Wales, U.K.

A knowledge of the processes involved in streamflow generation are critical to an understanding of solute transport and weathering rates in upland catchments. The determination of specific flow pathways and the formulation of process-based models have proved difficult in such terrains, largely due to the heterogeneous nature of catchments and the necessary limitations of bulked parameter models. Natural geochemical tracers have proved invaluable in developing conceptual models of catchment functioning and for constraining weathering processes and geochemical cycling. Strontium isotopes have been used as a natural tracer to calculate weathering rates for Sr and Ca, and to constrain the dominant flow pathways in two upland forested sub-catchments (Afon Hafren and Afon Hore) of the River Severn at Plynlimon in Central Wales. The dominant source of Sr in the catchments is considered to be from the weathering of silicate minerals. Weathering rates for Sr and Ca in the Afon Hafren, calculated using Sr isotopes, were similar to those derived from mass balance studies. The rates for the Afon Hore were similar for Ca, but significantly different for Sr. The reason for the difference is unclear, but may be due to additional sources (calcite) in the catchment. Strontium isotope ratios for different input sources and compartments within the catchment were characterised and helped to identify potential flow pathways. The data suggest an important role for groundwater inputs in contrast to previous models which indicated a dominant role for soil waters.     

The role of disseminated calcite in the chemical weathering of granitoid rocks

Accessory calcite, present at concentrations between 300 and 3000 mg kg⁻¹, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO₂, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57–98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering.The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.     

Mineralogical sources of the buffer capacity in a granite catchment determined by strontium isotopes

The role of different minerals in base cation release and thus the increase of buffering capacity of groundwater against acid deposition is controversially discussed in the literature. The ⁸⁷Sr/⁸⁶Sr ratios and base cation concentration were investigated in whole rock leachates, mineral separates, precipitation, soil solution, groundwater and stream water samples in the Lehstenbach catchment (Germany) to identify the weathering sequence of the granite bedrock. Three different approaches were followed in parallel. It was assumed that the contribution of different minerals to base cation supply of the groundwater with increasing weathering intensity would be observed by investigating (1) unweathered rock leachates, deep groundwater and shallow groundwater, (2) groundwater samples from new groundwater wells, reflecting the initial weathering of the drilled bedrock, and groundwater from wells that were drilled in 1988, (3) stream water during baseflow, dominated by deep groundwater, and stream water during high flow, being predominantly shallow groundwater. Whereas the first approach yielded consistent patterns, there was some evidence that groundwater from the new wells initially reflected contamination by the filter gravel rather than cation release in an initial stage of weathering. Time series samples of stream water and groundwater solute concentrations and isotope ratios turned out to reflect varying fractions of soil water and precipitation water at baseflow and high flow conditions rather than varying contributions of different minerals that prevail at different stages of granite weathering.     

Present weathering rates in a humid tropical watershed: Nsimi, South Cameroon

The study of biogeochemical and hydrological cycles in small experimental watersheds on silicate rocks, common for the Temperate Zone, has not yet been widely applied to the tropics, especially humid areas. This paper presents an updated database for a six-year period for the small experimental watershed of the Mengong brook in the humid tropics (Nsimi, South Cameroon). This watershed is developed on Precambrian granitoids (North Congo shield) and consists of two convexo-concave lateritic hills surrounding a large flat swamp covered by hydromorphic soils rich in upward organic matter. Mineralogical and geochemical investigations were carried out in the protolith, the saprolite, the hillside lateritic soils, and the swamp hydromorphic soils. Biomass chemical analyses were done for the representative species of the swamp vegetation. The groundwater was analysed from the parent rock/saprolite weathering front to the upper fringe in the hillside and swamp system. The chemistry of the wet atmospheric and throughfall deposits and the Mengong waters was monitored.In the Nsimi watershed the carbon transfer occurs primarily in an organic form and essentially as colloids produced by the slow biodegradation of the swamp organic matter. These organic colloids contribute significantly to the mobilization and transfer of Fe, Al, Zr, Ti, and Th in the uppermost first meter of the swamp regolith. When the organic colloid content is low (i.e., in the hillside groundwater), Th and Zr concentrations are extremely low (<3 pmol/L, ICP-MS detection limits). Strongly insoluble secondary thorianite (ThO₂) and primary zircon (ZrSiO₄) crystals control their mobilization, respectively. This finding thus justifies the potential use of both these elements as inert elements for isoelement mass balance calculations pertaining to the hillside regolith.Chloride can not be used as a conservative tracer of hydrological processes and chemical weathering in this watershed. Biogenic recycling significantly influences the low-Cl input fluxes. Sodium is a good tracer of chemical weathering in the watershed. The sodium solute flux corrected from cyclic salt input was used to assess the chemical weathering rate. Even though low (2.8 mm/kyr), the chemical weathering rate predominates over the mechanical weathering rate (1.9 mm/kyr). Compared to the Rio Icacos watershed, the most studied tropical site, the chemical weathering fluxes of silica and sodium in the Mengong are 16 and 40 times lower, respectively. This is not only related to the protective role of the regolith, thick in both cases, but also to differences in the hydrological functioning. This is to be taken into account in the calculations of the carbon cycle balance for large surfaces like that of the tropical forest ecosystems on a stable shield at the global level.     

Dolomite Versus Calcite Weathering in Hydrogeochemically Diverse Watersheds Established on Bedded Carbonates (Sava and So?a Rivers, Slovenia)

The relative contributions of dolomite to calcite weathering related to riverine fluxes are investigated on a highly resolved spatial scale in the diverse watersheds of Slovenia, which previous work has shown have some of the highest carbonate-weathering intensities in the world and suggests that dolomite weathering is favored over limestone weathering in mixed carbonate watersheds. The forested Sava and So?a River watersheds of Slovenia with their headwaters in the Julian Alps drain alpine regions with thin soils (<30 cm) and dinaric karst regions with thicker soils (0 to greater than 70 cm) all developed over bedded Mesozoic carbonates (limestone and dolomite), and siliclastic sediments is the ideal location for examining temperate zone carbonate weathering. This study extends previous work, presenting geochemical data on source springs and documenting downstream geochemical fluctuations within tributaries of the Sava and So?a Rivers. More refined sampling strategies of springs and discrete drainages permit directly linking the stream Mg²⁺/Ca²⁺ ratios to the local bedrock lithology and the HCO₃ ^? concentrations to the relative soil depths of the tributary drainages. Due to differences in carbonate source lithologies of springs and tributary streams, calcite and dolomite weathering end members can be identified. The Mg²⁺/Ca²⁺ ratio of the main channel of the Sava River indicates that the HCO₃ ^? concentration can be attributed to nearly equal proportions by mass of dolomite relative to calcite mineral weathering (e.g., Mg²⁺/Ca²⁺ mole ratio of 0.33). The HCO₃ ^? concentration and pCO₂ values increase as soil thickness and alluvium increase for discrete spring samples, which are near equilibrium with respect to calcite. Typically, this results in approximately 1.5 meq/l increase in HCO₃ ^? from the alpine to the dinaric karst regions. Streams in general do not change in HCO₃ ^?, Mg²⁺/Ca²⁺, or Mg²⁺/HCO₃ ^? concentrations down course, but warming and degassing of CO₂ produce high degrees of supersaturation with respect to calcite. Carbonate-weathering intensity (mmol/km²-s) is highest within the alpine regions where stream discharge values range widely to extreme values during spring snowmelt. Overall, the elemental fluxes of HCO₃ ^?, Ca²⁺, and Mg²⁺ from the tributary watersheds are proportional to the total water flux because carbonates dissolve rapidly to near equilibrium. Importantly, dolomite weathers preferentially over calcite except for pure limestone catchments.     

黑河上游高寒山区降雨-径流形成过程的同位素示踪

为揭示中、低纬度高寒山区降雨-径流的形成过程,指导水资源的合理开发利用,选择黑河上游红泥沟小流域为研究区,基于河道径流量及雨水和河水稳定同位素的观测数据,构建二元混合模型,计算了2013年7月23日及8月21日两次典型降雨-径流事件中事件水（降雨）和事件前水（流域前期储水）对河道径流的贡献及其动态变化.结果显示:两次降雨事件中事件前水的贡献比例分别为68.69%和54.46%;事件前水的贡献比例在涨水阶段减小,在退水阶段增大.结合河水电导率的观测结果,进一步分析了降雨-径流的形成过程:河道径流的形成主要受饱和区蓄满产流、河岸带地下径流和山坡地下径流3种产流机制控制;事件水主要源于蓄满产流,事件前水主要源于河岸带和山坡地下径流;事件初期和末期以河岸带地下水补给为主,涨水阶段后期和退水阶段前期转为以蓄满产流和山坡地下水补给为主,洪峰期间蓄满产流的贡献达到最大.两次事件的对比表明,事件前的湿度条件和降雨强度对降雨-径流的形成过程有着重要影响:前期越湿润,流域储水能力越弱,导水能力越强,事件水的贡献越大,河道径流对降雨的响应越迅速;降雨强度越大,蓄满产流及其中的事件水比例越高,河道径流中事件水的比例也越高.      

Cosmogenic nuclide methods for measuring long-term rates of physical erosion and chemical weathering

Understanding the evolution of geochemical and geomorphic systems requires measurements of long-term rates of physical erosion and chemical weathering. Erosion and weathering rates have traditionally been estimated from measurements of sediment and solute fluxes in streams. However, modern sediment and solute fluxes are often decoupled from long-term rates of erosion and weathering, due to storage or re-mobilization of sediment and solutes upstream from the sampling point. Recently, cosmogenic nuclides such as ¹⁰Be and ²⁶Al have become important new tools for measuring long-term rates of physical erosion and chemical weathering. Cosmogenic nuclides can be used to infer the total denudation flux (the sum of the rates of physical erosion and chemical weathering) in actively eroding terrain. Here we review recent work showing how this total denudation flux can be partitioned into its physical and chemical components, using the enrichment of insoluble tracers (such as Zr) in regolith relative to parent rock. By combining cosmogenic nuclide measurements with the bulk elemental composition of rock and soil, geochemists can measure rates of physical erosion and chemical weathering over 1000- to 10,000-year time scales.     

Effects of temperature on silicate weathering: Solute fluxes and chemical weathering in a temperate rain forest watershed,Jamieson Creek,British Columbia

Chemical weathering of silicate minerals has long been known as a sink for atmospheric CO₂, and feedbacks between weathering and climate are believed to affect global climate. While warmer temperatures are believed to increase rates of weathering, weathering in cool climates can be accelerated by increased mineral exposure due to mechanical weathering by ice. In this study, chemical weathering of silicate minerals is investigated in a small temperate watershed. The Jamieson Creek watershed is covered by mature coniferous forest and receives high annual precipitation (4000 mm), mostly in the form of rainfall, and is underlain by quartz diorite bedrock and glacial till. Analysis of pore water concentration gradients indicates that weathering in hydraulically unsaturated ablation till is dominated by dissolution of plagioclase and hornblende. However, a watershed scale solute mass balance indicates high relative fluxes of K and Ca, indicating preferential leaching of these solutes possibly from the relatively unweathered lodgement till. Weathering rates for plagioclase and hornblende calculated from a watershed scale solute mass balance are similar in magnitude to rates determined using pore water concentration gradients.When compared to the Rio Icacos basin in Puerto Rico, a pristine tropical watershed with similar annual precipitation and bedrock, but with dissimilar regolith properties, fluxes of weathering products in stream discharge from the warmer site are 1.8 to 16.2-fold higher, respectively, and regolith profile-averaged plagioclase weathering rates are 3.8 to 9.0-fold higher. This suggests that the Arrhenius effect, which predicts a 3.5- to 9-fold increase in the dissolution rate of plagioclase as temperature is increased from 3.4° to 22 °C, may explain the greater weathering fluxes and rates at the Rio Icacos site. However, more modest differences in K and Ca fluxes between the two sites are attributed to accelerated leaching of those solutes from glacial till at Jamieson Creek. Our findings suggest that under conditions of high rainfall and favorable topography, weathering rates of silicate minerals in warm tropical systems will tend to be higher than in cool temperate systems, even if the temperate system is has been perturbed by an episode of glaciation that deposits regolith high in fresh mineral surface area.     

Desalination of a sedimentary rock aquifer system invaded by Pleistocene Champlain Sea water and processes controlling groundwater geochemistry

The objective of this study was to identify geochemical processes and Quaternary geological events responsible for the variations in groundwater geochemistry observed in a sedimentary rock aquifer system, including brackish to saline groundwater. Inorganic constituents and environmental isotopes were analyzed for 146 groundwater samples. Dissolution of carbonates dominates in recharge areas, resulting in Ca-, Mg-HCO₃ groundwater. Further along flow paths, under confined conditions, Ca²⁺–Na⁺ ion exchange causes groundwater evolution to Na-HCO₃ type. Na-Cl groundwater is also found and it falls on a seawater mixing line. Using conservative tracers, Cl⁻ and Br⁻, the original Champlain Sea water is shown to have been, in the region, a mixture of about 34% seawater and 66% freshwater, a composition still retained by some groundwater. Na-Cl groundwater thus results from mixing with former Champlain Sea water and also from solute diffusion from overlying marine clay. The system is thus found to be at different stages of desalinization, from the original Champlain Sea water still present in hydraulically stagnant areas of the aquifer to fully flushed conditions in parts, where more flow occurs, especially in recharge zones. The geochemical processes are integrated within the hydrogeological context to produce a conceptual geochemical evolution model for groundwater of the aquifer system.     

穿透曲线反演管壁溶质通量的实验研究

泉口穿透曲线提供了一个便捷有效的方法来研究岩溶含水层中污染物的运移。在旱季,滞留在石灰岩中的污染物通 过岩壁释放入管道,与管道水相混合并运输到下游泉口,因此,泉口穿透曲线能够反演出污染物释放时的管壁溶质通量。 笔者利用一个基于运移稀释模型的解析解,由40条实验室测量的穿透曲线来反演出相应的管壁溶质通量。结果表明,其基 本形状与穿透曲线相似,管壁透水的非均匀性在穿透曲线上明显表现出来,而在管壁溶质通量上表现为强振荡。因此,管 壁溶质通量比泉口穿透曲线对管壁透水的非均匀性有更高的分辨率。该通量是一个连接泉口穿透曲线和污染物在岩石中早 期分布的中间量,本文提供了一种研究管壁污染物释放过程的新方法。     

Sr isotopes as a tracer of weathering processes and dust inputs in a tropical granitoid watershed, Luquillo Mountains, Puerto Rico

Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. ⁸⁷Sr/⁸⁶Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm⁻² ka⁻¹. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater ⁸⁷Sr/⁸⁶Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.     

Quality and quantity of pre-drainage methane and responding strategies in Chinese outburst coal mines

The potential sources of recharge of both water and solutes to the Quaternary aquifer in the area between Ismailia and El Kassara canals in northeastern Egypt include seepage from the irrigation canals and conduits, return flow after irrigation in the cultivated fields, local precipitation, and the upward flow of groundwater from the underlying Miocene aquifer system. Water isotopes, solute concentrations, and sulfate isotopes were used to investigate the geochemical sources, reactions, and the impacts of the hydraulic connections among recharge sources. The obtained results indicate a minimal influence of the underlying Miocene aquifer as a water and solute source while old and new contributions from the irrigation canals represent the main sources of recharge. The chemical reactions responsible for the chemical constituents and salinity in the aquifer include silicate weathering, evaporite dissolution, and carbonate precipitation. Most of groundwater samples appear to lie at/or close to equilibrium with montmorillonite, kaolinite, and illite where clay minerals are quite common in the local soils of the Quaternary aquifer.

     

Sources of Sr and implications for weathering of limestone under tallgrass prairie, northeastern Kansas

Grasslands of north-central Kansas are underlain by carbonate aquifers and shale aquitards. Chemical weathering rates in carbonates are poorly known, and, because large areas are underlain by these rocks, solute fluxes are important to estimating global weathering rates. Grasslands exist where the amount of precipitation is extremely variable, both within and between years, so studies in grasslands must account for changes in weathering that accompany changes in precipitation. This study: (1) identifies phases that dominate chemical fluxes at Konza Prairie Biological Station (KPBS) and Long-Term Ecological Research Site, and (2) addresses the impact of variable precipitation on mineral weathering. The study site is a remnant tallgrass prairie in the central USA, representing baseline weathering in a mid-temperate climate grassland.Groundwater chemistry and hydrology in the 1.2 km² watershed used for this study suggest close connections between groundwater and surface water. Water levels fluctuate seasonally. High water levels coincide with periods of precipitation plus low evapotranspiration rather than during precipitation peaks during the growing season. Precipitation is concentrated before recharging aquifers, suggesting an as yet unquantified residence time in the thin soils.Groundwater and surface water are oversaturated with respect to calcite within limitations of available data. Water is more dilute in more permeable aquifers, and water from one aquifer (Morrill) is indistinguishable from surface water. Cations other than Ca co-vary with each other, especially Sr and Mg. Potassium and Si co-vary in all aquifers and surface water, and increases in concentrations of these elements are the best indicators of silicate weathering at this study site. Silicate-weathering indices correlate inversely to aquifer hydraulic conductivity.⁸⁷Sr/⁸⁶Sr in water ranges from 0.70838 to 0.70901, and it decreases with increasing Sr concentration and with increasing silicate-weathering index. Carbonate extracted from aquifer materials, shales, soil, and tufa has Sr ranging from about 240 (soil) to 880 ppm (Paleozoic limestone). ⁸⁷Sr/⁸⁶Sr ranges from 0.70834 ± 0.00006 (limestone) to 0.70904 ± 0.00019 (soil). In all cases, ⁸⁷Sr/⁸⁶Sr of aquifer limestone is lower than ⁸⁷Sr/⁸⁶Sr of groundwater, indicating a phase in addition to aquifer carbonate is contributing solutes to water.Aquifer recharge controls weathering: during periods of reduced recharge, increased residence time increases the total amount of all phases dissolved. Mixing analysis using ⁸⁷Sr/⁸⁶Sr shows that two end members are sufficient to explain sources of dissolved Sr. It is proposed that the less radiogenic end member is a solution derived from dissolving aquifer material; longer residence time increases its contribution. The more radiogenic end member solution probably results from reaction with soil carbonate or eolian dust. This solution dominates solute flux in all but the least permeable aquifer and demonstrates the importance that land-surface and soil-zone reactions have on groundwater chemistry in a carbonate terrain.     

Delineating volcanic aquifer recharge areas using geochemical and isotopic tools

Relative recharge areas are evaluated using geochemical and isotopic tools, and inverse modeling. Geochemistry and water quality in springs discharging from a volcanic aquifer system in Guatemala are related to relative recharge area elevations and land use. Plagioclase feldspar and olivine react with volcanically derived CO₂ to produce Ca-montmorillonite, chalcedony and goethite in the groundwater. Alkalinity, Mg, Ca, Na, and SiO_2(aq) are produced, along with minor increases in Cl and SO₄ concentrations. Variations in groundwater δD and δ¹⁸O values are attributed to recharge elevation and used in concert with geochemical evolution to distinguish local, intermediate, and regional flow systems. Springs with geochemically inferred short flow paths provided useful proxies to estimate an isotopic gradient for precipitation (??.67 δ¹⁸O/100?m). No correlation between spring discharge and relative flow-path length or interpreted recharge elevation was observed. The conceptual model was consistent with evidence of anthropogenic impacts (sewage and manure) in springs recharged in the lower watershed where livestock and humans reside. Spring sampling is a low-budget approach that can be used to develop a useful conceptual model of the relative scale of groundwater flow (and appropriate watershed protection areas), particularly in volcanic terrain where wells and boreholes are scarce.     

Seasonal variability of element fluxes in two Central Siberian rivers draining high latitude permafrost dominated areas

In order to constrain the origin and fluxes of elements carried by rivers of high latitude permafrost-dominated areas, major and trace element concentrations as well as Sr and U isotopic ratios were analyzed in the dissolved load of two Siberian rivers (Kochechum and Nizhnyaya Tunguska) regularly sampled over two hydrological cycles (2005-2007). Large water volumes of both rivers were also collected in spring 2008 in order to perform size separation through dialysis experiments. This study was completed by spatial sampling of the Kochechum watershed carried out during summer and by a detailed analysis of the main hydrological compartments of a small watershed. From element concentration variations along the hydrological cycle, different periods can be marked out, matching hydrological periods. During winter baseflow period (October to May) there is a concentration increase for major soluble cations and anions by an order of magnitude. The spring flood period (end of May-beginning of June) is marked by a sharp concentration decrease for soluble elements whereas dissolved organic carbon and insoluble element concentrations strongly increase.When the spring flood discharge occurs, the significant increase of aluminum and iron concentrations is related to the presence of organo-mineral colloids that mobilize insoluble elements. The study of colloidal REE reveals the occurrence of two colloid sources successively involved over time: spring colloids mainly originate from the uppermost organic-rich part of soils whereas summer colloids rather come from the deep mineral horizons. Furthermore, U and Sr isotopic ratios together with soluble cation budgets in the Kochechum river impose for soluble elements the existence of three distinct fluxes over the year: (a) at the spring flood a surface flux coming from the leaching of shallow organic soil levels and containing a significant colloidal component (b) a subsurface flux predominant during summer and fall mainly controlled by water-rock interactions within mineral soils and (c) a deep groundwater flux predominant during winter which enters large rivers through unfrozen permafrost-paths. Detailed study of the Kochechum watershed suggests that the contribution of this deep flux strongly depends on the depth and continuous nature of the permafrost.     

Stable-isotope and solute-chemistry approaches to flow characterization in a forested tropical watershed,Luquillo Mountains,Puerto Rico

The prospect of changing climate has led to uncertainty about the resilience of forested mountain watersheds in the tropics. In watersheds where frequent, high rainfall provides ample runoff, we often lack understanding of how the system will respond under conditions of decreased rainfall or drought. Factors that govern water supply, such as recharge rates and groundwater storage capacity, may be poorly quantified. This paper describes 8-year data sets of water stable isotope composition (δ²H and δ¹⁸O) of precipitation (4 sites) and a stream (1 site), and four contemporaneous stream sample sets of solute chemistry and isotopes, used to investigate watershed response to precipitation inputs in the 1780-ha Río Mameyes basin in the Luquillo Mountains of northeastern Puerto Rico. Extreme δ²H and δ¹⁸O values from low-pressure storm systems and the deuterium excess (d-excess) were useful tracers of watershed response in this tropical system. A hydrograph separation experiment performed in June 2011 yielded different but complementary information from stable isotope and solute chemistry data. The hydrograph separation results indicated that 36% of the storm rain that reached the soil surface left the watershed in a very short time as runoff. Weathering-derived solutes indicated near-stream groundwater was displaced into the stream at the beginning of the event, followed by significant dilution. The more biologically active solutes exhibited a net flushing behavior. The d-excess analysis suggested that streamflow typically has a recent rainfall component (∼25%) with transit time less than the sampling resolution of 7 days, and a more well-mixed groundwater component (∼75%). The contemporaneous stream sample sets showed an overall increase in dissolved solute concentrations with decreasing elevation that may be related to groundwater inputs, different geology, and slope position. A considerable amount of water from rain events runs off as quickflow and bypasses subsurface watershed flowpaths, and better understanding of shallow hillslope and deeper groundwater processes in the watershed will require sub-weekly data and detailed transit time modeling. A combined isotopic and solute chemistry approach can guide further studies to a more comprehensive model of the hydrology, and inform decisions for managing water supply with future changes in climate and land use.     

降雨和地形地貌对水文模型模拟结果的影响分析

概念性水文模型数量众多,判断模型是否适合研究流域可以通过模拟结果来体现,但是熟悉流域的产汇流特性可以筛选模型,从根源上大量减少工作量,也可以解决相似流域无资料的问题。选取6种概念性水文模型,以马渡王、板桥和志丹这3个半湿润与半干旱流域为研究区域,探讨流域特性与模型结构之间的关系,并通过降雨和地形地貌分析其对模型模拟结果的影响。研究结果表明,流域地形及植被对产汇流过程有重要影响,由于局部产流现象严重,河道坡度影响大于流域平均坡度,当区域气候条件相差不大时,地形地貌比降雨对流域产汇流特性影响更大。因此对于水文模型的选择,可以在熟悉流域产汇流特性的基础上因地制宜,必要时可以增加适合研究流域的模块来获得更好的预报,在半干旱与半湿润流域,同时具有蓄满和超渗机制的模型能得到更好的应用。     

A simulation-based approach for estimating premining water quality: Red Mountain Creek,Colorado

Regulatory agencies are often charged with the task of setting site-specific numeric water quality standards for impaired streams. This task is particularly difficult for streams draining highly mineralized watersheds with past mining activity. Baseline water quality data obtained prior to mining are often non-existent and application of generic water quality standards developed for unmineralized watersheds is suspect given the geology of most watersheds affected by mining. Various approaches have been used to estimate premining conditions, but none of the existing approaches rigorously consider the physical and geochemical processes that ultimately determine instream water quality. An approach based on simulation modeling is therefore proposed herein. The approach utilizes synoptic data that provide spatially-detailed profiles of concentration, streamflow, and constituent load along the study reach. This field data set is used to calibrate a reactive stream transport model that considers the suite of physical and geochemical processes that affect constituent concentrations during instream transport. A key input to the model is the quality and quantity of waters entering the study reach. This input is based on chemical analyses available from synoptic sampling and observed increases in streamflow along the study reach. Given the calibrated model, additional simulations are conducted to estimate premining conditions. In these simulations, the chemistry of mining-affected sources is replaced with the chemistry of waters that are thought to be unaffected by mining (proximal, premining analogues). The resultant simulations provide estimates of premining water quality that reflect both the reduced loads that were present prior to mining and the processes that affect these loads as they are transported downstream. This simulation-based approach is demonstrated using data from Red Mountain Creek, Colorado, a small stream draining a heavily-mined watershed. Model application to the premining problem for Red Mountain Creek is based on limited field reconnaissance and chemical analyses; additional field work and analyses may be needed to develop definitive, quantitative estimates of premining water quality.     

Environmental applications of geophysical and geochemical methods to map groundwater quality at Tuticorin, Tamilnadu, India

Coastal aquifers can become polluted due to natural and human activities, such as intrusion of saline water, discharge of effluents in industrial areas and chemical weathering of natural geological deposits. The present study is aimed mainly at understanding the geophysical and chemical characteristics of groundwater near Tuticorin, Tamilnadu, India by studying the electrical resistivity distribution of the subsurface groundwater by applying the Schlumberger vertical electrical sounding (VES) technique followed by chemical analysis of water samples. A total of 20 VES soundings were carried out to understand the resistivity distribution of the area and 21 water samples were collected to analyze the chemical quality. The interpretation and analysis of the results have identified different hydrogeologic behaviors, a highly saline coastal aquifer and freshwater locations. The results obtained from geophysical and geochemical sampling are in good agreement with each other. The approach shows the efficacy of the combination of geophysical and geochemical methods to map groundwater contamination zones in the study area.