Uranium and thorium isotopes in the rivers of the Amazonian basin: hydrology and weathering processes

Two expeditions (October 1989 and May 1992) were carried out to two points of the main Amazon River channel and four tributaries. The Solimões and Madeira rivers, taking their origin in the Andes, are whitewater rivers. The Negro River is a typical acid, blackwater river. The Trombetas River flows through bauxite‐rich areas, and is characterized by low concentrations of dissolved humic substances. The ²³⁸U, ²³⁴U, ²³²Th and ²³⁰Th activities were recorded from dissolved, suspended particulate phases and river bank sediments. The latter were analysed for their ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb contents, and also subjected to leaching with 0·2 M hydroxylamine–hydrochloride solution to determine the concentrations of radionuclides bound to amorphous Fe hydroxides and Mn oxides and hydroxides. The dissolved U average concentration in the Amazon system is ten times lower than the mean world river concentration. The uranium concentration observed at Óbidos in the lower Amazon (0·095 µg L^?1), where the U content in the river bank sediments and suspended matter is lowest, suggests U release from the solid phase during river transport. About 485 t of U are transported annually to the Amazon delta area in dissolved form, and 1943 t bound to suspended particulate matter. Total U and Th concentrations in the river bank sediments ranged from 1·59 to 7·14 µg g^?1 and from 6·74 to 32 µg g^?1, respectively. The highest concentrations were observed in the Trombetas River. The proportion extracted by means of the hydroxylamine solution (HL) was relatively high for U in the Trombetas river bank sediment (31%) and for Th in the Solimões sediment (30%). According to the alpha recoil effects, the ²³⁴U/²³⁸U activity ratios of the Andean river waters and downstream Amazon water (Óbidos) were >1, but were <1 in the Negro River (at Manaus). The activity ratios of dissolved U correlate with pH and also with the U activity ratios in the river bank sediment hydroxylamine extracts. As expected, the ²³⁴U/²³⁸U activity ratios in river bank sediments were <1 in the Andean rivers and in the downstream Amazon, but they were >1 in the Trombetas and Negro rivers. Such ratios probably result from the binding of dissolved uranium to solid sediment. The ²²⁸Th/²³²Th ratios of river bank sediments were close to unity (except for the Negro River, where it is lower), suggesting no significant Th exchanges between the river water and the sediment. The ²²⁶Ra/²³²Th activity ratios were <1, and the ²²⁶Ra/²²⁸Ra activity ratios generally were significantly higher than the activity ratios of their respective parents. This perhaps is the result of easier leaching of the ²²⁶Ra parent, ²³⁰Th, from solid material (owing to the alpha recoil effect) than of the ²²⁸Ra parent. Uranium and thorium isotopes were used as tools to evaluate the chemical weathering rate of rocks in the Amazon system, which was estimated to be 2·7 cm 1000 year^?1 s^?1. Copyright © 2002 John Wiley & Sons, Ltd.     

Migration of Lead-210 and Stable Load in Surface Waters Impacted by Uranium Mine Wastes

Water and sediment samples from two surface water systems were analysed for ²¹⁰Pb and stable lead in order to elucidate the environmental importance and fate of ²¹⁰Pb released from uranium mining. In one system mine drainage waters treated by precipitation of barium sulfate contained a considerable activity of ²¹⁰Pb in particulate form. Spoil piles were the main source of ²¹⁰Pb in the second system, with the dissolved ²¹⁰Pb being the predominant migration form. In both systems the concentration of ²¹⁰Pb rapidly decreased with distance from the source indicating that waterborne ²¹⁰Pb did not represent an environmental problem. Uranium mining did not add significant amounts of stable lead into the surface water systems. It has been found that bottom sediments are a sensitive indicator of the pollution of surface waters with ²¹⁰Pb.     

Assessment of Water Quality in the Elbe River at Flood Water Conditions Based on Cluster Analysis,Principle Components Analysis,and Source Apportionment

An assessment of water quality measurements during a spring flood in the Elbe River is presented. Daily samples were taken at a site in the middle Elbe, which is part of the network of the International Commission for the Protection of the Elbe River (IKSE/MKOL). Cluster analysis (CA), principal components analysis (PCA), and source apportionment (APCS apportioning) were used to assess the flood‐dependent matter transport. As a result, three main components could be extracted as important to the matter transport in the Elbe River basin during flood events: (i) re‐suspended contaminated sediments, which led to temporarily increased concentrations of suspended matter and of most of the investigated heavy metals; (ii) water discharge related concentrations of pedogenic dissolved organic matter (DOM) as well as preliminary diluted concentrations of uranium and chloride, parameters with stable pollution background in the river basin; and (iii) abandoned mines, i.e., their dewatering systems, with particular influence on nickel, manganese, and zinc concentrations.     

The relationship of uranium isotopes to oxidation/reduction in the Edwards carbonate aquifer of Texas

The concentration of dissolved uranium and²³⁴U/²³⁸U alpha activity ratio (“A.R.”) were determined in water samples from 23 locations in the Edwards carbonate aquifer of south central Texas by isotope dilution methods and alpha spectrometry. This aquifer consists of two parts, an updip oxidized portion and a downdip reduced portion. At some places the boundary is associated with faulting and at others it is not. The boundary between the two portions of the aquifer can be located by an abrupt change in chemical properties of the water such as a large increase in concentration of Cl^?, SO₄^2? and total dissolved solids, the presence of H₂S and a decrease in Eh in moving from updip to downdip. Compared with the oxidized samples, the uranium concentration is much lower and the A.R. higher in the reduced samples so that the uranium from each portion falls in a distinct field. The oxidized aquifer samples show very little variation in the measured uranium parameters even though, in some cases, there is evidence that the water has flowed through some tens of kilometers of aquifer. Samples collected near the boundary at those places not associated with faulting yield dissolved uranium values which fall in neither field and which, for the most part, cannot result from mixing of the oxidized and reduced waters. These samples probably result from changes in location of the oxidation-reduction boundary.     

Radon and remediation measures near Băiţa-Ştei old uranium mine (Romania)

B?i?a-?tei mine is an open pit mine in NW Romania (West Carpathian Mountains). It was the largest surface uranium deposit in the world. Two means of uranium transport and dissemination were used over time. The first was the natural way, represented by transportation of geological sediments by Cri?ul-B?i?a River that crosses the B?i?a surface deposit. These sediments were used as building materials (stone, gravel, sand). The second way was related to the people living in this valley, who used also the uranium waste as building material. The preliminary indoor radon concentrations measured in the buildings ranged from 40 to 4000 Bq m^?3 with a mean value of 241 Bq m^?3. A focused radon survey facilitated the selection of 20 houses with the highest indoor radon that were therefore proposed for remediation. To find the radon sources of these houses, systematic investigations on radon were performed. The remedial measures for these 20 houses were tested on a chosen pilot house.     

Floodplain storage of mine tailings in the belle fourche river system: A sediment budget approach

Arsenic-contaminated mine tailings that were discharged into Whitewood Creek at Lead, South Dakota, from 1876 to 1978, were deposited along the floodplains of Whitewood Creek and the Belle Fourche River. The resulting arsenic-contaminated floodplain deposit consists mostly of overbank sediments and filled abandoned meanders along White-wood Creek, and overbank and point-bar sediments along the Belle Fourche River. Arsenic concentrations of the contaminated sediments indicate the degree of dilution of mine tailings by uncontaminated alluvium. About 13 per cent of the 110 × 10⁶ Mg of mine tailings that were discharged at Lead were deposited along the Whitewood Creek floodplain. Deposition of mine tailings near the mouth of Whitewood Creek was augmented by an engineered structure. About 29 per cent of the mine tailings delivered by Whitewood Creek were deposited along the Belle Fourche River floodplain. About 60 per cent of that sediment is contained in overbank deposits. Deposition along a segment of the Belle Fourche River was augmented by rapid channel migration. The proportions of contaminated sediment stored along Whitewood Creek and the Belle Fourche River are consistent with sediment storage along the floodplains of perennial streams in other, similar sized watersheds.     

The estuarine chemistry and isotope systematics of U in the Amazon and Fly Rivers

Natural concentrations of ²³⁸U and δ²³⁴U values were determined in estuarine surface waters and pore waters of the Amazon and Fly (Papua New Guinea) Rivers to investigate U transport phenomena across river-dominated land–sea margins. Discharge from large, tropical rivers is a major source of dissolved and solid materials transported to the oceans, and are important in defining not only oceanic mass budgets, but also terrestrial weathering rates.On the Amazon shelf, salinity-property plots of dissolved organic carbon, pH and total suspended matter revealed two vastly contrasting water masses that were energetically mixed. In this mixing zone, the distribution of uranium was highly non-conservative and exhibited extensive removal from the water column. Uranium removal was most pronounced within a salinity range of 0–16.6, and likely the result of scavenging and flocculation reactions with inorganic (i.e., Fe/Mn oxides) and organic colloids/particles. Removal of uranium may also be closely coupled to exchange and resuspension processes at the sediment/water interface. An inner-shelf pore water profile indicated the following diagenetic processes: extensive (1 m) zones of Fe(III)—and, to a lesser degree, Mn(IV)—reduction in the absence of significant S(II) concentrations appeared to facilitate the formation of various authigenic minerals (e.g., siderite, rhodocrosite and uraninite). The pore water dissolved ²³⁸U profile co-varied closely with Mn(II). Isotopic variations as evidenced in δ²³⁴U pore waters values from this site revealed information on the origin and history of particulate uranium. Only after a depth of about 1 m did the δ²³⁴U value approach unity (secular equilibrium), denoting a residual lattice bound uranium complex that is likely an upper-drainage basin weathering product. This suggests that the enriched δ²³⁴U values represent a riverine surface complexation product that is actively involved in Mn–Fe diagenetic cycles and surface complexation reactions.In the Fly River estuary, ²³⁸U appears to exhibit a reasonably conservative distribution as a function of salinity. The absence of observed U removal does not necessarily imply non-reactivity, but instead may record an integration of concurrent U removal and release processes. There is not a linear correlation between δ²³⁴U vs. 1/²³⁸U that would imply simple two component mixing. It is likely that resuspension of bottom sediments, prolonged residence times in the lower reaches of the Fly River, and energetic particle–colloid interactions contribute to the observed estuarine U distribution. The supply of uranium discharged from humid, tropical river systems to the sea appears to be foremost influenced by particle/water interactions that are ultimately governed by the particular physiographic and hydrologic characteristics of an estuary.     

Application of inverse geochemical modelling for predicting surface water chemistry in Ekbatan watershed,Hamedan, western Iran

ABSTRACT

A study of surface water chemistry evolution was conducted by multivariate statistical analysis and inverse geochemical modelling using the PHREEQC computer program. Using hierarchical cluster analysis the 14 sampling sites were classified into three groups (recharge, transition and discharge areas). Water chemistry changed along a flow path so that waters with Ca–HCO₃ and Mg–Cl composition changed to Mg–Cl–HCO₃ waters. The order of abundance of the major cations was Mg > Ca > Na > K. Their average concentrations were 21, 19, 3.6 and 2.5 mg L^-1, respectively. Inverse geochemical modelling along flow paths indicated that the dissolution of sylvite and kaolinite, and precipitation of feldspars and andalusite, happened with Na entering the solution and Ca, Mg and K leaving the solution.

Editor D. Koutsoyiannis; Associate editor not assigned     

Uranium pollution in an estuary affected by pyrite acid mine drainage and releases of naturally occurring radioactive materials

After the termination of phosphogypsum discharges to the Huelva estuary (SW Spain), a unique opportunity was presented to study the response of a contaminated environmental compartment after the cessation of its main source of pollution. The evolution over time of uranium concentrations in the estuary is presented to supply new insights into the decontamination of a scenario affected by Naturally Occurring Radioactive Material (NORM) discharges. The cleaning of uranium isotopes from the area has not taken place as rapidly as expected due to leaching from phosphogypsum stacks.An in-depth study using various techniques of analysis, including ²³⁴U/²³⁸U and ²³⁰Th/²³²Th ratios and the decreasing rates of the uranium concentration, enabled a second source of uranium contamination to be discovered. Increased uranium levels due to acid mine drainage from pyrite mines located in the Iberian Pyrite Belt (SW Spain) prevent complete uranium decontamination and, therefore, result in levels nearly twice those of natural background levels.     

Clinopyroxene composition as a method of identification of the magmatic affinities of paleo-volcanic series

Uranium contents and²³⁴U/²³⁸U activity ratios have been determined for groundwaters from the Lincolnshire Limestone artesian aquifer in eastern England. Changes in the quantitative and isotopic chemistry of the dissolved uranium are explained in terms of a mixing model involving the rapidly moving fissure water and much older water stored in the pore system of this oolitic limestone. The western part of the aquifer, closest to recharge, is dominated by oxidising groundwaters which then enter a reducing zone towards the east, where there is an abrupt decrease in Eh and the chlorinity of the groundwaters begins to increase. Uranium contents in the oxidising zone range from 0.7 to 3.4 μg kg^?1 and²³⁴U/²³⁸U activity ratio of this dissolved uranium is close to unity, the equilibrium value. The uranium content decreases abruptly when the grounwaaters enter the reducing zone, averaging 0.04 μg kg^?1 east of the oxidation/reduction barrier. Simultaneously with the decrease in uranium content, there is an increase in²³⁴U/²³⁸U activity ratio and this ratio increases to a maximum within 7 km of the oxidation/reduction barrier. This increase in activity ratio is attributed to enhanced²³⁴U solution due to²³⁴Th recoil from uraniferous fissure surfaces east of the oxidising zone. The activity ratio of dissolved uranium in the ancient pore waters could in principle reach high values due to²³⁴Th recoil from the oolith surfaces. However, the activity ratio actually declines further east and this can only be explained as a consequence of mixing with pore waters in which the uranium activity ratio is closer to equilibrium.²³⁴Th recoil from the oolith surfaces has probably been inhibited by sealing of the uranium-bearing surfaces in the process of oolith cementation.     

Solute concentrations in the lower niger river and the source rock contribution

Water quality analyses for the Niger River for the 1980/81 hydrological year are presented. The samples were collected from the main river at Lokoja, and from two main tributaries, the Kaduna and the Benue Rivers. Different water types were distinguished by the concentrations of major ions. The type Ca > Na > Mg > K - HCO₃ > SO₄ > Cl was represented at all stations during at least part of the year. Chloride was found to dominate the sulphate ion in the Kaduna and Niger, while the Benue maintained a higher concentration of sulphate relative to chloride all year round. Distinct patterns of seasonal variation in the ion concentrations were observed, particularly for the samples collected at Lokoja. Low ion concentrations were prominent during periods of high discharge, while low flow periods coincided with high dissolved ion concentrations. The contribution of rainwater to the total dissolved solids in the river waters was assessed indirectly using rainwater chemistry data from the Gulf of Guinea. The estimated rainwater contribution to the Lower Niger amounts to 5.15 mg 1^?1. Geochemical weathering calculations involving reactions of the four major minerals of granitic rocks - anorthite, biotite, albite, and K-feldspar - with carbon dioxide and water, can account for the average water composition of the Lower Niger. The proportion of the ionic components was also related to the occurrence of the respective element in the minerals.     

Arsenic speciation and distribution in the Carnon estuary following the acute discharge of contaminated water from a disused mine

In February 1991 Wheal Jane, a tin mine in S.W. England, was closed, the mine drainage pumps were removed and underground water levels were left to rise. By January 1992 the build up of water in the mine was sufficient to cause the Nangiles adit to burst, and contaminated mine water containing high levels of arsenic overflowed into the Carnon River. The river in turn drained into an estuary system which reaches the sea at Falmouth. A contingency plan was introduced, with water being pumped from the mine and treated before discharge through a tailings dam. This brought the discharge from Nangiles under control by late February 1992, although flow recommenced from mid-April until early July 1992.The immediate impact of the discharge and treatment operation on the distribution and speciation of arsenic in the river was the presence of high concentrations of dissolved arsenite, with a level of 240 μg As l⁻¹ being measured below the mine tailings dam. Elevated concentrations of arsenite, typically 9 μg As l⁻¹, persisted in the saline region of the Carnon estuary. By the following July the levels of arsenite had dropped significantly in the river but the levels in Restronguet Creek remained essentially unchanged. In comparison with the arsenite concentrations, the arsenate levels were comparatively low in the whole river/estuary system in the February following the initial discharge. A significant increase was however found in the saline region in the following July.Methylated arsenic species were absent from the river but were present in the biologically productive saline region during the warmer summer sampling period. The July concentrations of dimethylarsenic ranged from 1.0 to 2.1 μg As l⁻¹ and monomethylarsenic from 0.2 to 0.5 μg As l⁻¹.     

234U and238U concentration in brine from geopressured aquifers of the northern Gulf of Mexico basin

The²³⁴U and²³⁸U concentration in brine from six Gulf Coast geopressured aquifers has been determined. The results reveal very low uranium concentrations (from 0.003 to 0.03 μg/l) and uranium activity ratios slightly greater than unity (from 1.06 to 1.62). Reducing conditions within the aquifers are responsible for the low uranium concentrations. The uranium activity ratios observed are well below those calculated using theoretical considerations of alpha-particle recoil effects. This can be explained by interference with alpha-recoil nuclides entering the liquid phase as a result of quartz overgrowths on sand grains and high-temperature re-equilibration that tends to minimize the effects of the alpha-recoil process.The fact that the uranium activity ratios of the brines are slightly greater than unity instead of the equilibrium value of 1.000 indicates that either the alpha particle recoil blocking and re-equlibration effects are not complete or that another process is operative that enriches the fluid in excess²³⁴U by selectively removing uranium from radiation induced damage sites in the mineral (sand grain) matrix.     

210Po in Nevada Groundwater and Its Relation to Gross Alpha Radioactivity

Polonium‐210 (²¹⁰Po) is a highly toxic alpha emitter that is rarely found in groundwater at activities exceeding 1 pCi/L. ²¹⁰Po activities in 63 domestic and public‐supply wells in Lahontan Valley in Churchill County in northern Nevada, United States, ranged from 0.01 ± 0.005 to 178 ± 16 pCi/L with a median activity of 2.88 pCi/L. Wells with high ²¹⁰Po activities had low dissolved oxygen concentrations (less than 0.1 mg/L) and commonly had pH greater than 9. Lead‐210 activities are low and aqueous ²¹⁰Po is unsupported by ²¹⁰Pb, indicating that the ²¹⁰Po is mobilized from aquifer sediments. The only significant contributors to alpha particle activity in Lahontan Valley groundwater are ^234/238U, ²²²Rn, and ²¹⁰Po. Radon‐222 activities were below 1000 pCi/L and were uncorrelated with ²¹⁰Po activity. The only applicable drinking water standard for ²¹⁰Po in the United States is the adjusted gross alpha radioactivity (GAR) standard of 15 pCi/L. ²¹⁰Po was not volatile in a Nevada well, but volatile ²¹⁰Po has been reported in a Florida well. Additional information on the volatility of ²¹⁰Po is needed because GAR is an inappropriate method to screen for volatile radionuclides. About 25% of the samples had ²¹⁰Po activities that exceed the level associated with a lifetime total cancer risk of 1× 10^?4 (1.1 pCi/L) without exceeding the GAR standard. In cases where the 72‐h GAR exceeds the uranium activity by more than 5 to 10 pCi/L, an analysis to rule out the presence of ²¹⁰Po may be justified to protect human health even though the maximum contaminant level for adjusted GAR is not exceeded.     

Multiple injected and natural conservative tracers quantify mixing in a stream confluence affected by acid mine drainage near Silverton,Colorado

The acidic discharge from Cement Creek, containing elevated concentrations of dissolved metals and sulphate, mixed with the circumneutral‐pH Animas River over a several hundred metre reach (mixing zone) near Silverton, CO, during this study. Differences in concentrations of Ca, Mg, Si, Sr, and SO₄^2? between the creek and the river were sufficiently large for these analytes to be used as natural tracers in the mixing zone. In addition, a sodium chloride (NaCl) tracer was injected into Cement Creek, which provided a Cl^? ‘reference’ tracer in the mixing zone. Conservative transport of the dissolved metals and sulphate through the mixing zone was verified by mass balances and by linear mixing plots relative to the injected reference tracer. At each of seven sites in the mixing zone, five samples were collected at evenly spaced increments of the observed across‐channel gradients, as determined by specific conductance. This created sets of samples that adequately covered the ranges of mixtures (mixing ratios, in terms of the fraction of Animas River water, %AR). Concentratis measured in each mixing zone sample and in the upstream Animas River and Cement Creek were used to compute %AR for the reference and natural tracers. Values of %AR from natural tracers generally showed good agreement with values from the reference tracer, but variability in discharge and end‐member concentrations and analytical errors contributed to unexpected outlier values for both injected and natural tracers. The median value (MV) %AR (calculated from all of the tracers) reduced scatter in the mixing plots for the dissolved metals, indicating that the MV estimate reduced the effects of various potential errors that could affect any tracer. Copyright © 2006 John Wiley & Sons, Ltd.     

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

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

Environmental Emission of Mercury During Gold Mining by Amalgamation Process and its Impact on Soils of Gympie, Australia

— The aims of this study were to estimate the total amount of mercury released to the environment during 60 years of gold mining (1867–1926) at Gympie, Queensland, Australia and to measure the mercury levels in soil samples surrounding the mining activity. We estimated that 1902 tonnes of mercury was released to the environment and about 1236 tonnes of which was released to the air. The mean mercury in the soil samples in the vicinity of the Scottish battery varied from 1.07 to 99.26 μg g^?1 as compared to 0.075 μg g^?1 as background mercury concentrations. The maximum mercury concentration measured in sediments of the Langton Gully was 6.12 μg g^?1. These results show that large amount of mercury was used in this area during gold mining. Since mining is active in the area and Langton Gully flows into Mary River, we therefore, recommend that mercury concentration in air and fish should be monitored.     

High resolution profiles for arsenic in the Seine Estuary. Seasonal variations and net fluxes to the English Channel

Three sampling cruises were conducted in the Seine Estuary from 1993 to 1995 in varying hydrological and seasonal conditions. The site included all of the lower part of the river under the influence of tidal dynamics and the dilution plume in the Baie de Seine. Chemical speciation of arsenic showed high seasonal variations, especially in September when AsIII represented around 50% of dissolved arsenic. The inclusion of organoarsenic compounds not accessible to direct analysis by hydride generation required preliminary mineralisation of the samples. The ratio of dissolved to particulate arsenic distribution was controlled mainly by the iron content of particles. Biological activity had an influence on chemical speciation and thus on the partition coefficient (K_D 10⁻³=6±1 in September and 12±0.9 in February). The zone of conservative mixing used for Seine River flow calculations was limited to a salinity range of approximately 10–30. Dissolved arsenic concentrations extrapolated to null salinities were lower during the high-water period because of dilution (17.6±1.1 nM), and maximal during the low-water period in summer (35.7±0.9 nM). Mean arsenic export to the English Channel was estimated at 33.2±6 T yr⁻¹ for dissolved arsenic. Observation of an arsenic output greater than the upstream input, as well as a simultaneous increase in dissolved and particulate arsenic concentrations during the mixing of freshwater with seawater, strongly suggested the existence of an important intra-estuarine source of arsenic, either of industrial origin or related to the transport and diagenesis of marine sediments.     

Matrix Diffusion Effects on Contaminant Migration from an Injection Well in Fractured Sandstone

Deep-well injection into fractured sandstone is an option for the disposal of contaminated mine dewatering discharge from an open pit uranium mine. As part of the assessment of potential contaminant migration from deep-well injection, the effect of matrix diffusion was evaluated. An analytical mathematical model was developed for the simulation of the radial movement of a contaminant front away from an injection point under steady flow conditions in a planar fracture with uniform properties. The model includes the effects of advection in the fracture, diffusion of contaminants from the fracture into the rock matrix, and equilibrium adsorption on the fracture surface as well as in the rock matrix. Effective diffusion coefficients obtained from laboratory experiments on 11 intact core samples varied from 3.4 × 10⁻⁸ to 3.2 × 10⁻⁷ cm²/s. Model simulations were made with diffusion coefficient values in this range and with single-fracture injection rates estimated from fracture frequencies in boreholes, and from bulk hydraulic conductivity values obtained from field tests. Because of matrix diffusion, the rate of outward movement of the front of the nonreactive contaminants from the injection well is much slower than the rate of water flow in the fractures. Simulations of the movement of contaminants that undergo adsorption indicate that even a small distribution coefficient for the rock matrix causes the contaminants to remain very close to the injection well during the one-year period. The results of the simplified model demonstrate that matrix diffusion is an important process that cannot be neglected in the assessment of a waste disposal scheme located in fractured porous rock. However, in order to make a definitive assessment of the capability of matrix diffusion and associated matrix adsorption to significantly limit the extent of contaminant migration around injection wells, it would be necessary to conduct field tests such as a preliminary or experimental injection.     

The application of uranium series disequilibrium concepts to sediment yield determination

The determination of uranium series disequilibria in fluvial environments is proposed as a method of calculating catchment mass balances. The technique is based on two main principles. Firstly, ²³⁴U is more mobile than ²³⁸U, especially during the early stages of weathering. Secondly, uranium is far more mobile than either thorium or protactinium. Consequently, teaching during weathering results in the loss of the uranium found in the fresh rock, leaving the two immobile daughters behind. The ratio of uranium carried by sediment to that dissolved, U_S/U_W can, therefore, be determined from river water and sediment isotopic activity ratios. Fluxes of uranium can then be calculated from average concentrations in the water and the associated sediment, from which a sediment yield can be inferred. The Witham catchment in Lincolnshire has been used to test the proposed method. A U_S/U_W ratio of between 5 and 7 is determined and a sediment yield of 2.51 ± 2.12 tonnes yr^?1 km^?2 is proposed. Although some problems concerning environmental chemistry have arisen, the validity of the approach is confirmed by the close correspondence between the results obtained and those inferred by earlier workers using more conventional methods.