The evolution of alkaline, saline ground- and surface waters in the southern Siberian steppes

Groundwaters, river and lake waters have been sampled from the semi-arid Siberian Republic of Khakassia. Despite the relatively sparse data set, from a diversity of hydrological environments, clear salinity-related trends emerge that indicate the main hydrochemical evolutionary processes active in the region. Furthermore, the major ion chemistry of the evolution of groundwater baseflow, via rivers, to terminal saline lake water, can be adequately and simply modelled (using PHREEQCI) by invoking: (i) degassing of CO₂ from groundwater as it emerges as baseflow in rivers (rise in pH); (ii) progressive evapoconcentration of waters (parallel accumulation of Cl⁻, Na⁺, SO₄²⁻, and increase in pH due to common ion effect); and (iii) precipitation of calcite (depletion of Ca from waters, reduced rate of accumulation of alkalinity). Dolomite precipitation is ineffective at constraining Mg accumulation, due to kinetic factors. Silica saturation appears to control dissolved Si in low salinity waters and groundwaters, while sepiolite saturation and precipitation depletes Si from the more saline surface waters. Gypsum and sodium sulphate saturation are only approached in the most saline environments. Halite remains unsaturated in all waters. Sulphate reduction processes are important in the lower part of lakes.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Eutrophication and salinization of urban and rural kettle lakes in Kalamazoo and Barry Counties,Michigan, USA

Salinization and eutrophication caused by runoff of road salt and nutrients was assessed in three kettle lakes, two (Woods and Asylum Lakes) located in urban Kalamazoo, MI, and one (Brewster Lake) in rural Hastings, MI. Profiles of dissolved O₂, conductivity, pH, and temperature were measured in situ, at half meter intervals. Water samples were collected at discrete depth intervals of 1 m and analyzed for Fe(II), Mn(II), ammonium, alkalinity, Cl^?, Na, Mg, K and Ca. Results of this study indicate that all three lakes are eutrophic with anoxic bottom waters. Conductivity was much greater, and Cl^? levels were more than 100 times greater, in the two urban lakes compared to the rural lake, demonstrating the significant impact of road salt deicers on urban lake water chemistry.     

Rare earth elements (REE) of dissolved and suspended loads in the Xijiang River, South China

The Xijiang River is the main channel of the Zhujiang (Pearl River), the second largest river in China in terms of water discharge, and flows through one of the largest carbonate provinces in the world. The rare earth element (REE) concentrations of the dissolved load and the suspended particulate matter (SPM) load were measured in the Xijiang River system during the high-flow season. The low dissolved REE concentration in the Xijiang River is attributed to the interaction of high pH and low DOC concentration. The PAAS-normalized REE patterns for the dissolved load show some common features: negative Ce anomaly, progressively heavy REE (HREE) enrichment relative to light REE (LREE). Similar to the world’s major rivers the absolute concentration of the dissolved REE in the Xijiang River are mainly pH controlled. The degree of REE partitioning between the dissolved load and SPM load is also strongly pH dependent. The negative Ce anomaly is progressively developed with increasing pH, being consistent with the oxidation of Ce (III) to Ce (IV) in the alkaline river waters, and the lack of Ce anomalies in several DOC-rich waters is presumably due to both Ce (III) and Ce (IV) being strongly bound by organic matter. The PAAS-normalized REE patterns for the dissolved load and the SPM load in rivers draining the carbonate rock area exhibit middle REE (MREE) enrichment and a distinct maximum at Eu, indicating the preferential dissolution of phosphatic minerals during weathering of host lithologies. Compared to the Xijiang River waters, the MREE enrichment with a maximum at Eu disappeared and light REE were more depleted in the South China Sea (SCS) waters, suggesting that the REE sourced from the Xijiang River must be further fractionated and modified on entering the SCS. The river fluxes of individual dissolved REE introduced by the Xijiang River into the SCS vary from 0.04 to 4.36 × 10⁴ mol a⁻¹.     

The aquatic chemistry of rare earth elements in rivers and estuaries

Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions.     

The hydrogeochemistry of the Lake Waco drainage basin,Texas

The origin of surface water chemistry in highly impacted drainage basins must be investigated on a drainage-basin scale if the causes of the pollution are to be elucidated. This study characterizes and deciphers the surface water chemistry of a nutrient polluted river system in central Texas. Four tributaries of the Lake Waco reservoir were chemically characterized temporally and spatially in order to gain a complete understanding of the nature and origin of dissolved solids being transported into the lake. Temporal chemical variations measured at the base of each of the drainage basins are repetitive and seasonal. The most periodic and well-defined variation is exhibited by nitrate concentrations although many of the other solutes show seasonal changes as well. These temporal chemical changes are controlled by seasonal precipitation. During rainy seasons, the shallow aquifer is recharged resulting in stream discharge that is high in nitrate, calcium, and bicarbonate. When the shallow flow system is depleted in the summer, stream waters are dominated by deeper groundwater and become rich in sodium. Spatial variations in the chemistry of South Bosque surface waters were characterized using the snapshot technique. The spatial distribution of nitrate in surface waters is controlled by fertilizer application to row crops and the location of a munitions factory. The concentrations of naturally derived solutes such as Ca⁺, Na⁺, Cl^–, and SO₄^–2are controlled by underlying lithologies.     

Evaluating the influence of road salt on water quality of Ohio rivers over time

Anthropogenic inputs have largely contributed to the increasing salinization of surface waters in central Ohio, USA. Major anthropogenic contributions to surface waters are chloride (Cl⁻) and sodium (Na⁺), derived primarily from inputs such as road salt. In 2012–2013, central Ohio rivers were sampled and waters analyzed for comparison with historical data. Higher Cl⁻ and Na⁺ concentrations and fluxes were observed in late winter as a result of increased road salt application during winter months. Increases in both chloride/bromide (Cl⁻/Br⁻) ratios and nitrate (N-NO₃⁻) concentrations and fluxes were observed in March 2013 relative to June 2012, suggesting a mixture of road salt and fertilizer runoff influencing the rivers in late winter. For some rivers, increased Cl⁻ and Na⁺ concentrations and fluxes were observed at downstream sites near more urban areas of influence. Concentrations of Na⁺ were slightly lower than respective Cl⁻ concentrations (in equivalents). High Cl⁻/Br⁻ mass ratios in the Ohio surface waters indicated the source of Cl⁻ was likely halite, or road salt. In addition, analysis of ³⁶Cl/Cl ratios revealed low values suggestive of a substantial dissolved halite component, implying the addition of “old” Cl⁻ into the water system. Temporal trend analysis via the Mann–Kendall test identified increasing trends in Cl⁻ and Na⁺ concentration beginning in the 1960s at river locations with more complete historical datasets. An increasing trend in Cl⁻ flux through the 1960s was also identified in the Hocking River at Athens, Ohio. Our results were similar to other studies that examined road salt impacts in the northern US, but a lack of consistent long-term data hindered historical analysis for some rivers.     

Dissolved rare earth elements in river waters draining karst terrains in Guizhou Province,China

Winter seasonal concentrations of dissolved rare earth elements (REE) of two major river systems (the Wujiang River system and the Yuanjiang River system) in karst-dominated regions in winter were measured by using a method involving solvent extraction and back-extraction and subsequent ICP-MS measurements. The dissolved REE concentrations in the rivers and their tributaries are lower than those in most of the large rivers in the world. High pH and high cation (i.e., Na⁺ + Ca²⁺) concentrations of the rivers are the most important factors controlling the concentrations of dissolved REE in the river water. The dissolved load (<0.22 μm) REE distribution patterns of high-pH river waters are very different from those of low-pH river waters. The shale (PAAS)-normalized REE patterns for the dissolved loads are characterized by light REE-enrichment and heavy REE-enrichment. Water in the upper reaches of the Wujiang River generally shows light REE-enriched patterns, while that in the middle and lower reaches generally shows heavy REE-enriched patterns. The Yuanjiang River is heavy REE enriched with respect to the light REE in the same samples. Water of the Wuyanghe River draining dolomite-dominated terrains has the highest heavy REE-enrichment. Most river water samples show the shale-normalized REE patterns with negative Ce and Eu anomalies, especially water from Wuyanghe River. Y/Ho ratios show that the water/particle interaction might have played an important role in fractionation between HREE and LREE.     

The solubility control of rare earth elements in natural terrestrial waters and the significance of PO 4 3− and CO 3 2− in limiting dissolved rare earth concentrations: A review of recent information

Rare earth element (REE) concentrations in alkaline lakes, circumneutral pH groundwaters, and an acidic freshwater lake were determined along with the free carbonate, free phosphate, and free sulfate ion concentrations. These parameters were used to evaluate the saturation state of these waters with respect to REE phosphate and carbonate precipitates. Our activity product estimates indicate that the alkaline lake waters and groundwaters are approximately saturated with respect to the REE phosphate precipitates but are significantly undersaturated with respect to REE carbonate and sulfate precipitates. On the other hand, the acidic lake waters are undersaturated with respect to REE sulfate, carbonate, and phosphate precipitates. Although carbonate complexes tend to dominate the speciation of the REEs in neutral and alkaline waters, our results indicate that REE phosphate precipitates are also important in controlling REE behavior. More specifically, elevated carbonate ion concentrations in neutral to alkaline natural waters tend to enhance dissolved REE concentrations through the formation of stable REE-carbonate complexes whereas phosphate ions tend to lead to the removal of the REEs from solution in these waters by the formation of REE-phosphate salts. Removal of REEs by precipitation as phosphate phases in the acid lake (pH=3.6) is inconsequential, however, due to extremely low [PO ₄ ^3– ] _F concentrations (i.e., 10^–23 mol/kg).     

A Comparison of Water Quality Between Low- and High-Flow River Conditions in a Tropical Estuary, Hilo Bay, Hawaii

Effects of storms on the water quality of Hilo Bay, Hawaii, were examined by sampling surface waters at 6 stations 10 times during low-flow and 18 times during high-flow (storms) river conditions. The direction of a storm’s impact on water quality parameters was consistent among storms and most stations; however, direction of the impact varied with the parameter. High river flow conditions increased concentrations of nitrate and decreased those of dissolved organic nitrogen (N); effects on ammonium and particulate N were station specific. Storms also increased dissolved organic and particulate carbon (C) concentrations. Dissolved phosphorus (P) concentrations were not affected by high river flow events. Dissolved organic forms dominated the N, C, and P pools under both low- and high-flow river conditions. Soil-derived particles and fecal indicator bacteria increased during storms, while chlorophyll a concentrations and bacterial cell abundances decreased. Our results suggest that an increase in storms with global warming could impact water quality of tropical estuaries.     

Arsenic in surface- and up to 90°C ground waters in a basalt area,N-Iceland: processes controlling its mobility

The concentrations of As in surface- and up to 90 °C ground waters in a tholeiite flood basalt area in N-Iceland lie in the range <0.03–10 μg/kg. With few exceptions surface waters contain <0.5 μg/kg As whereas ground waters generally contain >0.5 μg/kg As. The As content of ground waters increases on the whole with rising temperature. Arsenic is highly mobile in the basalt-water environment of the study area. An insignificant fraction of the As dissolved from the rock is taken up into secondary minerals. Arsenic is less mobile than B but considerably more mobile than Na which has the highest mobility among the major aqueous components. A significant fraction of the As in the basalt occurs in an easily soluble form. The As hosted in the primary minerals is expected to be concentrated in the titano-magnetite. This mineral is stable in contact with both surface- and ground waters and does not, therefore, supply As to the water, explaining the difference in mobility between As and B. Aqueous As concentrations are a reflection of water/rock ratios, i.e. how much rock a given quantity of water has dissolved. This ratio increases with increasing temperature and increasing residence time of the water in contact with the rock. The distribution of As species has been calculated on the assumption of equilibrium at the redox potential retrieved from measurement of aqueous Fe(II) and Fe(III) concentrations. These calculations indicate that pentavalent As is stable in surface waters and in ground waters with an in situ pH of <10 and would occur mostly as H₂AsO₄⁻ and HAsO₄⁻². In higher pH ground waters the concentrations of the arsenite species H₂AsO₃⁻ is significant at equilibrium, up to 65% of the total dissolved As.     

Transport of trace elements under different seasonal conditions: Effects on the quality of river water in a Mediterranean area

Concentrations of total and dissolved elements were determined in 35 water samples collected from rivers in Sardinia, a Mediterranean island in Italy. The overall composition did not change for waters sampled in both winter and summer (i.e., January at high-flow condition and June at low-flow condition), but the salinity and concentrations of the major ions increased in summer. Concentrations of elements such as Li, B, Mn, Rb, Sr, Mo, Ba and U were higher in summer with only small differences between total and dissolved (i.e., in the fraction <0.4 μm) concentrations. The fact that these elements are mostly dissolved during low flow periods appears to be related to the intensity of water–rock interaction processes that are enhanced when the contribution of rainwater to the rivers is low, that is during low-flow conditions. In contrast, the concentrations of Al and Fe were higher in winter during high flow with total concentrations significantly higher than dissolved concentrations, indicating that the total amount depends on the amount of suspended matter. In waters filtered through 0.015 μm pore-size filters, the concentrations of Al and Fe were much lower than in waters filtered through 0.4 μm pore-size filters, indicating that the dissolved fraction comprises very fine particles or colloids. Also, Co, Ni, Cu, Zn, Cd and Pb were generally higher in waters collected during the high-flow condition, with much lower concentrations in 0.015 μm pore-size filtered waters; this suggests aqueous transport via adsorption onto very fine particles. The rare earth elements (REE) and Th dissolved in the river waters display a wide range in concentrations (∑REE: 0.1–23 μg/L; Th: <0.005–0.58 μg/L). Higher REE and Th concentrations occurred at high flow. The positive correlation between ∑REE and Fe suggests that the REE are associated with very fine particles (>0.015 and <0.4 μm); the abundance of these particles in the river controls the partitioning of REE between solution and solid phases.Twenty percent of the water samples had dissolved Pb and total Hg concentrations that exceeded the Italian guidelines for drinking water (>10 μg/L Pb and >1 μg/L Hg). The highest concentrations of these heavy metals were observed at high-flow conditions and they were likely due to the weathering of mine wastes and to uncontrolled urban wastes discharged into the rivers.     

Speciation and behavior of arsenic in evaporation basins,California, USA

Disposal of saline subsurface drainage waters from croplands into evaporation basins (or ponds) in the San Joaquin Valley of California causes excessive accumulation of salts and elevated concentrations of arsenic (As), a potentially high risk element with little information about its fate, in the agricultural evaporation ponds. We examined dissolved As concentration, speciation, and distribution in waters as well as As fractionation in sediments in the 10-cell South Evaporation Basin for better understanding of processes and conditions affecting As transformations and fate in a specific drainage disposal facility. The increase of total dissolved As concentrations were observed with higher Cl⁻ and electric conductivity along flow path indicating that evaporation was an important factor regulating total dissolved As concentration. The increases of reduced As species such as arsenite [As(III)] and organic As (monomethylarsonic acid and dimethylarsinic acid) were found towards the terminal flow pathway. However, arsenate [As(V)], the oxidized species remained greater than 67% of total dissolved As in all cell waters. Sequential extractions of sediments indicated that reducing conditions may influence As behavior in sediments to be more soluble and exchangeable. Arsenic association with oxides was appreciable only under oxidizing condition. Carbonate minerals played an important role in immobilizing As into the sediments under alkaline condition and a broad range of redox conditions. However, these sink mechanisms did not significantly reduce As concentrations in the cell waters. The reducing condition facilitated by high concentration of organic matter might be a major factor for the increase in As mobility.     

Silica in Lake Superior: mass balance considerations and a model for dynamic response to eutrophication

The dissolved silica concentration in waters of Lake Superior probably is in a steady state because it is not influenced significantly by man, and the climate, topography and vegetation in the drainage area of the lake have been stable for the past 4000 years. Therefore the rate at which dissolved silica is introduced to the lake should equal the output rate.The primary inputs are: tributaries (4.1–4.6 × 10⁸kgSiO₂/yr), diffusion from sediment pore waters (0.21?0.78 × 10⁸kgSiO₂/yr) and atmospheric loading (0.26 × 10⁸kgSiO₂/yr). Silica is lost from the lake waters by: outflow through the St. Marys River, diatom deposition, adsorption onto particulates in the sediments, and authigenic formation of new silicate minerals. Tributary outflow accounts for less than one half the annual input of silica, and diatom deposition and silica adsorption withdraw less than 10% of the annual input. Therefore the formation of new silicate phases must be the dominant sink for dissolved silica in Lake Superior. The specific phases formed are not identified in the bottom sediments. X-ray diffraction studies suggest that smectite is one product, and amorphous ferroaluminum silicates may be another product.Mathematical modeling of the dissolved silica response to lake eutrophication suggests that the phosphate loading to Lake Superior would have to increase by about 250-fold to cause a silica depletion rate equal to that reported for Lake Michigan, assuming no change in the rate of upwelling of deep waters.     

Hydrochemistry and pollution probability of selected sites along the Euphrates River, Western Iraq

The hydrochemistry of Euphrates River in the study area which extended from Hit to Al-Saqlawia was studied in order to determine the physical, chemical, and biological properties in addition to the radiation level. Thirty-one stations along the Euphrates River were chosen, 17 of them represented the Euphrates River itself, whereas the other stations are considered as point pollution sources which all empty their load directly in the Euphrates River with an average total discharge of 32 m³/s. Twenty-eight samples of the Euphrates water of both high- and low-flow periods were analyzed for cations (Ca²⁺, Mg²⁺, Na⁺, and K⁺), anions (SO ₄ ⁼ , Cl^?, CO ₃ ⁼ , HCO ₃ ^? , NO ₃ ^? , PO ₄ ^?3 ), H₂S boron, dissolved oxygen, biological oxygen demand, bacteriological tests, radiation levels in addition to physical parameters such as hydrogen number (pH), total dissolved solid, electrical conductivity, total suspended solid, and temperature. This study showed that the cations and anions during periods of high and low flows are within acceptable limit with exceptional Cl^?. Hydrochemical formula during the high flow was Na-Ca-Mg-Cl-SO₄, then it changed into Na-Ca-Mg-HCO3-SO₄-Cl during the low-flow period. The average output cations and anions at downstream (Saqlawiya area) was relatively higher than those of input at upstream (Hit area); this attributed to the natural and anthropogenic activities originated mainly from agricultural activity and population communities around the river. Radiation level for ²¹²Pb, ²¹⁴Pb, ⁴⁰k, ²²⁰Ac, and ²¹⁴Bi showed that the higher level of radiation is concentrated within sediment rather than in water, but the radiation in both is within acceptable limit.     

Hydrogeochemistry in the Ngorongoro Crater,Tanzania, and implications for land use in a World Heritage Site

The chemistry of surface and ground waters in the Ngorongoro Crater, Tanzania, home to thousands of large mammals and a World Heritage Site, is controlled by the volcanic host rock lithology, evaporative concentration, mineral precipitation and redissoluton, and biological factors. Three groups of waters are informally differentiated based on their ranges of concentration: (1) dilute inflow (meteoric runoff and springs from short flowpaths: pH<8, Cl⁻<10 mg/l); (2) concentrated inflow (concentrated runoff and springs from long flowpaths: pH=8–9, Cl⁻=10–100 mg/l); and (3) brackish waters (pools and Lake Makat: pH>9, Cl⁻>100 mg/l). Evaporative concentration and biological activity in swamps commonly produce strong geochemical gradients between dilute sources and peripheral concentrated ephemeral wetlands. Dilute inflow is found in the Lerai, Munge, and Oljoro Nyuki streams, and several large springs near the Crater wall such as Ngoitokitok and Seneto. Concentrated inflow is found in downstream reaches of the Munge stream, discharging from springs away from the Crater wall such as Engitati and Mti Moja, and in dry-season pools. Brackish waters are found discharging from springs on the southern margin of Lake Makat, in mudflats surrounding marshes, in ephemeral pools, and in the lake itself. Although few hydrologic data are available, the persistence of relatively fresh water in vegetated wetlands is consistent with lower sedge-dominated wetland evapotranspiration rates compared with open water. This suggests that wetlands may play an important role in ensuring fresh water availability in the basin, and it demonstrates the need for future hydrologic study. Most of the Ngorongoro waters originate as rainfall outside the Crater, and travel into the basin as surface or ground water flow, emphasizing the need for a watershed-scale approach to land management.     

Seasonal uranium distributions in the coastal waters off the Amazon and Mississippi Rivers

The chemical reactivity of uranium was investigated across estuarine gradients from two of the world’s largest river systems: the Amazon and Mississippi. Concentrations of dissolved (<0.45 μm) uranium (U) were measured in surface waters of the Amazon shelf during rising (March 1990), flood (June 1990) and low (November 1991) discharge regimes. The dissolved U content was also examined in surface waters collected across estuarine gradients of the Mississippi outflow region during April 1992, August 1993, and November (1993). All water samples were analyzed for U by isotope dilution inductively coupled plasma mass spectrometry (ICP-MS). In Amazon shelf surface waters uranium increased nonconservatively from about 0.01 μg I^?1 at the river’s mouth to over 3 μg I^?1 at the distal site, irrespective of river discharge stage. Observed large-scale U removal at salinities generally less than 15 implies a) that riverine dissolved U was extensively adsorbed by freshly-precipitated hydrous metal oxides (e.g., FeOOH, MnO₂) as a result of flocculation and aggregation, and b) that energetic resuspension and reworking of shelf sediments and fluid muds on the Amazon shelf released a chemically reactive particle/colloid to the water column which can further scavenge dissolved U across much of the estuarine gradient. In contrast, the estuarine chemistry of U is inconclusive within surface waters of the Mississippi shelf-break region. U behavior is most likely controlled less by traditional sorption and/or desorption reactions involving metal oxides or colloids than by the river’s variable discharge regime (e.g., water parcel residence time during estuarine mixing, nature of particulates, sediment storage and resuspension in, the confined lower river), and plume dispersal. Mixing of the thin freshwater lens into ambient seawater is largely defined by wind-driven rather than physical processes. As a consequence, in the Mississippi outflow region uranium predominantly displays conservative behavior; removal is evident only during anomalous river discharge regimes. ‘Products-approach’ mixing experiments conducted during the Flood of 1993 suggest the importance of small particles and/or colloids in defining a depleted U versus salinity distribution.     

Geo-chemical Behavior of Uranium in the Sambhar Salt Lake, Rajasthan (India): Implications to "Source" of Salt and Uranium "Sink"

Among several salt lakes in the Thar Desert of western India, the Sambhar is the largest lake producing about 2 × 10⁵ tons of salt (NaCl) annually. The “lake system” (lake waters, inflowing river waters, and sub-surface brines) provides a unique setting to study the geo-chemical behavior of uranium isotopes (²³⁸U, ²³⁴U) in conjunction with the evolution of brines over the annual wetting and evaporation cycles. The concentration of ²³⁸U and the total dissolved solids (TDS) in lake water increase from ~8 μg L⁻¹ and ~8 g L⁻¹ in monsoon to ~1,400 μg L⁻¹ and 370 g L⁻¹, respectively, during summer time. The U/TDS ratio (~1 μg g⁻¹ salt) and the ²³⁴U/²³⁸U activity ratio (1.65 ± 0.05), however, remain almost unchanged throughout the year, except when U/TDS ratio approaches to 3.8 at/or beyond halite crystallization. These observations suggest that uranium behaves conservatively in the lake waters during the annual cycle of evaporation. Also, uranium and salt content (TDS) are intimately coupled, which has been used to infer the origin and source of salt in the lake basin. Furthermore, near uniform ratios in evaporating lake waters, when compared to the ratio in seawater (~0.1 μg g⁻¹ salt and 1.14 ± 0.02, respectively), imply that aeolian transport of marine salts is unlikely to be significant source of salt to the lake in the present-day hydrologic conditions. This inference is further consistent with the chemical composition of wet-precipitation occurring in and around the Sambhar lake. The seasonal streams feeding the lake and groundwaters (within the lake’s periphery) have distinctly different ratios of U/TDS (2–69 μg g⁻¹ salt) and ²³⁴U/²³⁸U (1.15–2.26) compared to those in the lake. The average U/TDS ratio of ~1 μg g⁻¹ salt in lake waters and ~19 μg g⁻¹ salt in river waters suggest dilution of the uranium content by the recycled salt and/or removal processes presently operating in the lake during the extraction of salt for commercial use. Based on mass-balance calculations, a conservative estimate of "uranium sink" (in the form of bittern crust) accounts for ~5 tons year⁻¹ from the lake basin, an estimate similar to its input flux from rivers, i.e., 4.4 tons year⁻¹.     

Assessment of variations in water quality using statistical techniques: a case study of Işıklı Lake, Çivril/Denizli,Turkey

A study of the hydrochemical evaluation of waters in the I??kl? Lake and surrounding area was carried out with the objective of identifying the geochemical processes and their relation with water quality in the region. The multivariate statistical techniques were used in the hydrochemical evaluation of waters. Statistical analysis of water quality parameters was made to seeing the interrelationship between different variables in order to explain the water quality and pollution status of study area. For this purpose, water samples were taken from lake, river, stream, and springs which are represented by investigated area and water qualities were evaluated. Generally, Ca²⁺, Mg²⁺, and Cl^?, HCO₃ ^? ions are dominant within surface water and water sources. Arsenic concentration increase is determined in I??kl? spring and Kufi stream water samples. Also, aluminum concentration is high level in the Kufi stream water samples. This increase was related to igneous rocks as geogenic origin. Also, geogenic contamination was identified in R-mode factor and cluster analyses. There is high correlation between electrical conductivity and major ions of waters.