Impact of uranium mines closure and abandonment on groundwater quality

The aim of the study is to assess the evolving mine water quality of closed uranium mines (abandoned between 1958 and 1992) in the Czech Republic. This paper focuses on the changes in mine water quality over time and spatial variability. In 2010, systematic monitoring of mine water quality was performed at all available locations of previous uranium exploitation. Gravity flow discharges (mine adits, uncontrolled discharges) or shafts (in dynamic state or stagnating) were sampled. Since the quality of mine water results from multiple conditions—geology, type of sample, sampling depth, time since mine flooding, an assessment of mine water quality evolution was done taking into account all these conditions. Multivariate analyses were applied in order to identify the groups of samples based on their similarity. Evaluation of hydrogeochemical equilibrium and evolution of mine waters was done using the Geochemist’s Workbench and PHREEQC software. The sampling proved that uranium concentrations in mine waters did not predominantly exceed 0.45 mg/L. In case of discharges from old adits abandoned more than 40 years ago, uranium concentrations were below the MCL of US Environmental Protection Agency for uranium in drinking water (0.03 mg/L). Higher concentrations, up to 1.23 mg/L of U, were found only at active dewatered mines. Activity concentration of ²²⁶Ra varied from 0.03 up to 1.85 Bq/L except for two sites with increased background values due to rock formation (granites). Radium has a typically increasing trend after mine abandonment with a large variability. Concerning metals in mine water, Al, Co and Ni exceeded legislative limits on two sites with low pH waters. The mine water quality changes with a focus on uranium mobility were described from recently dewatered mines to shafts with water level maintained in order to prevent outflows to surface water and finally to stagnating shafts and discharges of mine water from old adits. The results were in good agreement with published experience on mine water stratification, its disturbance by pumping or natural water decant and the “first flush” phenomenon after mine flooding.     

Use of blood parameters in fish to assess acidic stress and chloride pollution in French running waters

The study investigated whether plasmatic parameters in fish such as Cl- content could serve as physiological indicators to evaluate water quality. The variations of plasma Cl- content in two fish species caught in a wide range of rivers representative of the hydrographic system of Lorraine (N-E France) were investigated. First, we studied autochthonous populations of chub (Leuciscus cephalus) which is a widespread species in the rivers of Lorraine. Organisms living in highly mineralised rivers (>1500 microScm(-1))--either naturally or due to salt mine contamination--showed plasma Cl- content significantly greater than organisms living in river with a lower mineralisation. Second, we investigated plasma Cl- content of brown trout (Salmo trutta fario) in poorly mineralised streams (<80 microS cm(-1)) with different degrees of acidification, both on autochthonous and transferred organisms. While indigenous trout maintained their Cl- content even in the acidic streams, transferred trout exhibited an important decrease of Cl- content after 48 h of exposure under acidic conditions.     

Wintertime vertical variations in particulate matter (PM) and precursor concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Air quality monitoring was conducted at a rural site with a tower in the middle of California's San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM10/ PM2.5 Air Quality Study. Measurements at the surface and n a tower at 90 m were collected in Angiola, CA, from December 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO2 appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.     

Wintertime Vertical Variations in Particulate Matter (PM) and Precursor Concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Abstract

Air quality monitoring was conducted at a rural site with a tower in the middle of California’s San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM₁₀/M_2.5 Air Quality Study. Measurements at the surface and on a tower at 90 m were collected in Angiola, CA, from ecember 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO₂ appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM_2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.     

Two modelling approaches to water-quality simulation in a flooded iron-ore mine (Saizerais, Lorraine, France): a semi-distributed chemical reactor model and a physically based distributed reactive transport pipe network model

The flooding of abandoned mines in the Lorraine Iron Basin (LIB) over the past 25 years has degraded the quality of the groundwater tapped for drinking water. High concentrations of dissolved sulphate have made the water unsuitable for human consumption. This problematic issue has led to the development of numerical tools to support water-resource management in mining contexts. Here we examine two modelling approaches using different numerical tools that we tested on the Saizerais flooded iron-ore mine (Lorraine, France). A first approach considers the Saizerais Mine as a network of two chemical reactors (NCR). The second approach is based on a physically distributed pipe network model (PNM) built with EPANET 2 software. This approach considers the mine as a network of pipes defined by their geometric and chemical parameters. Each reactor in the NCR model includes a detailed chemical model built to simulate quality evolution in the flooded mine water. However, in order to obtain a robust PNM, we simplified the detailed chemical model into a specific sulphate dissolution-precipitation model that is included as sulphate source/sink in both a NCR model and a pipe network model. Both the NCR model and the PNM, based on different numerical techniques, give good post-calibration agreement between the simulated and measured sulphate concentrations in the drinking-water well and overflow drift. The NCR model incorporating the detailed chemical model is useful when a detailed chemical behaviour at the overflow is needed. The PNM incorporating the simplified sulphate dissolution-precipitation model provides better information of the physics controlling the effect of flow and low flow zones, and the time of solid sulphate removal whereas the NCR model will underestimate clean-up time due to the complete mixing assumption. In conclusion, the detailed NCR model will give a first assessment of chemical processes at overflow, and in a second time, the PNM model will provide more detailed information on flow and chemical behaviour (dissolved sulphate concentrations, remaining mass of solid sulphate) in the network. Nevertheless, both modelling methods require hydrological and chemical parameters (recharge flow rate, outflows, volume of mine voids, mass of solids, kinetic constants of the dissolution-precipitation reactions), which are commonly not available for a mine and therefore call for calibration data.     

Impacts on effluent contaminants from mine sites: risk assessment,fate, and distribution of pollution at basin scale

The environmental implications of mining activities are of worldwide concern. An environmental evaluation at the basin level was conducted because of widespread mining in Cajamarca in Northern Peru. A sediment monitoring program was developed at the Jequetepeque basin, located in Cajamarca. A total of 16 sites were monitored at three different times between June 2009 and July 2010, and a total of 42 samples were collected. All samples were analyzed by microwave digestion and by a sequential extraction scheme following the three-stage European Community Bureau of Reference (three-stage BCR) protocol. Trace element mobilization from the sediments to the water column was assessed by the risk assessment code (RAC). Spatial and temporal distribution of trace elements was evaluated by principal component analysis and hierarchical cluster analysis. Cd, Zn, As, and Pb showed the highest concentrations independent of season. Notably, Cu concentration and mobility increased during the wet season for all samples. Additionally, Hg concentration and mobility increased during the wet season near the mine sites. According to the enrichment factor, the highest enrichments of Cd, Zn, Pb, and As were related to mine runoff. The effect of trace elements near the mine sites at the Jequetepeque basin was considered a significant threat to the environment due to Cd, Zn, Pb, and As, and the concentrations of Cu and Hg were also considered a concern. This work establishes a baseline for the environmental quality status of the Jequetepeque basin that may support water quality management in Peru.     

Mercury levels in surface waters of the Carson River-Lahontan Reservoir system, Nevada: Influence of historic mining activities

Total mercury (HgT), methylmercury (MeHg), and other operationally defined Hg species were determined on water samples collected from a river-reservoir system impacted by historic mine wastes. Simultaneously, a comprehensive study was undertaken to determine the influence of some major physico-chemical parameters on the fate of Hg within the system. Total Hg levels showed an increase from background concentrations of 4 ng liter(-1) upstream of mining activity, to peak values of 1500-2100 ng liter(-1) downstream of Hg contaminated mine tailings piles. MeHg concentrations varied from 0.1 to 7 ng liter(-1) in surface waters. In both cases, peak values were associated with the highest concentrations of total suspended solids (TSS). Particulate Hg (HgP) was typically >50% of HgT and increased downstream. The dissolved fraction of MeHg (MeHgD) always constituted a large portion of total methylmercury (MeHgT). The [MeHgT]/[HgT] ratio decreased downstream suggesting either a high percentage of inorganic Hg input from point sources, or low specific rates of MeHg production within the aquatic system. The latter could be due to the combined effects on microbial populations of both high levels of Hg concentrations found in water and sediments, and other factors related to the aqueous geochemistry of the system. Concentrations of HgT in the water column appeared to be enhanced by inputs of contaminated particles from the watershed during spring snow melt. In the reservoir, significant losses of Hg from the water column were observed. In addition to losses of Hg bound to particles by sedimentation, the removal through volatilization of dissolved gaseous Hg could be an important pathway.     

Hydrochemical characteristics of mine waters from abandoned mining sites in Serbia and their impact on surface water quality

Upon completion of exploration and extraction of mineral resources, many mining sites have been abandoned without previously putting environmental protection measures in place. As a consequence, mine waters originating from such sites are discharged freely into surface water. Regional scale analyses were conducted to determine the hydrochemical characteristics of mine waters from abandoned sites featuring metal (Cu, Pb–Zn, Au, Fe, Sb, Mo, Bi, Hg) deposits, non-metallic minerals (coal, Mg, F, B) and uranium. The study included 80 mine water samples from 59 abandoned mining sites. Their cation composition was dominated by Ca²⁺, while the most common anions were found to be SO₄ ^2? and HCO₃ ^?. Strong correlations were established between the pH level and metal (Fe, Mn, Zn, Cu) concentrations in the mine waters. Hierarchical cluster analysis was applied to parameters generally indicative of pollution, such as pH, TDS, SO₄ ^2?, Fe total, and As total. Following this approach, mine water samples were grouped into three main clusters and six subclusters, depending on their potential environmental impact. Principal component analysis was used to group together variables that share the same variance. The extracted principal components indicated that sulfide oxidation and weathering of silicate and carbonate rocks were the primary processes, while pH buffering, adsorption and ion exchange were secondary drivers of the chemical composition of the analyzed mine waters. Surface waters, which received the mine waters, were examined. Analysis showed increases of sulfate and metal concentrations and general degradation of surface water quality.     

Improvement of water-quality environment in reservoir models using flow networks

It is known that thermal stratification and environmental problems such as water quality deterioration occur in water reservoirs. One principle cause is the stagnation of water in the reservoirs, which leads to the problems of density stratification, nutrient enrichment of algae and others. Various methods such as deep-layer mixing and forced-air injection have been utilised to counter these problems. In this paper, a new method is developed to resolve water quality environment problems in water reservoirs utilising flow characteristics of flow networks, defined as a system of mutually intersecting flow passages. It emphasises the investigation of flow characteristics in flow networks consisting of multiple pairs of intersecting passages. Self-induced flow oscillations from the exit of flow networks are disclosed, which can be utilised to enhance mixing in water reservoirs. It will lead to the improvement of water quality environment.     

Gram-negative bacteria responsible for insoluble technetium formation and the fate of insoluble Tc in the water column above flooded paddy soil

We studied the characteristic gram-stain of Tc insolubilizing bacteria using various antibiotics, and the fate of insoluble Tc in a water column above flooded paddy soil to clarify Tc behavior in paddy fields. The formation of insoluble Tc in water column samples was inhibited by the addition of antibiotics, especially reagents against gram-negative bacteria. For a sample without antibiotics, insoluble Tc formation increased with time, and the maximum amount of insoluble Tc was observed on day 4 of incubation with (95m)Tc. In contrast, concentrations of ferrous ion decreased with time. These results suggested that gram-negative bacteria were mainly responsible for insoluble Tc formation, and that these bacteria were able to transform soluble Tc to insoluble forms under oxidizing conditions.     

From wetland to farm and back again: phosphorus dynamics of a proposed restoration project

We studied the phosphorus dynamics in a former wetland, which had been converted to a celery farm, and now consists of two shallow, flooded ponds that are being proposed for aquatic habitat restoration. However, like many agricultural areas, this site is plagued by phosphorus legacy issues. Proposed restoration includes hydrologic reconnection of these ponds to its adjacent stream, which are now isolated from one another by an earthen berm, to create a wetland complex. One of the two flooded ponds was partially dredged, whereas the other one has remained undredged. Water column, sediment pore water, and sediment total phosphorus concentrations were significantly greater in the undredged pond compared to the dredged pond, but in both cases phosphorus levels in the water columns (mean TP 929 vs. 133 μg/L in undredged vs. dredged ponds, respectively) would exacerbate downstream water quality issues if hydrologic reconnection occurred without first addressing the phosphorus issue. Sediment isotherm and maximum sorption data indicated that the sediments are close to phosphorus saturation in the undredged pond; simulated dredging of the cores revealed that exposure of deeper sediment layers would increase sorption capacity. Pore water SRP concentrations increased with sediment depth and were significantly greater in the undredged vs. dredged pond at both the 1–4-cm depth (2249 vs. 112 μg/L) and 14–17-cm depth (5506 vs. 222 μg/L). This study provides a framework for other projects that need to balance the competing demands of habitat restoration vs. water quality when restoring wetlands that have been converted to agricultural production.

     

Organics in the water colümn and air-water interface samples of Mississippi river water

Organic compounds in Mississippi river water were collected using a teflon disc to obtain surface film samples and a submerged bottle to collect water column samples. These organics were analyzed and characterized by high resolution gas chromatography-mass spectrometry. The presence of n-alkanes, polynuclear aromatics and chlorinated hydrocarbons was established, with the more hydrophobic compounds found in greater quantities at the air-water interface as compared to the sub-surface water column.     

Sorption, desorption and mineralisation of the herbicides glyphosate and MCPA in samples from two Danish soil and subsurface profiles

The vertical distribution of the sorption, desorption and mineralisation of glyphosate and MCPA was examined in samples from two contrasting soil and subsurface profiles, obtained from a sandy agricultural site and a non-agricultural clay rich site. The highest mineralisation of [14C-methylen]glyphosate, with 9.3-14.7% degraded to 14CO2 within 3 months was found in the deepest sample from the clay site. In the deeper parts of the sandy profile high sorption and low desorption of glyphosate coincided with no or minor mineralisation indicating a limited glyphosate bioavailability. MCPA was readily mineralised except in the deepest samples from both sites. The highest MCPA mineralisation was detected just below the surface layers with 72% or 44% degraded to 14CO2 at the sandy or the clay sites, respectively. MCPA sorped to a minor extent in all samples and no indications of sorption-controlled mineralisation was revealed. None of the herbicides were mineralised under anoxic conditions.     

Growth of Phragmites australis (Cav.) Trin ex. Steudel in mine water treatment wetlands: effects of metal and nutrient uptake

The abandoned mine of Shilbottle Colliery, Northumberland, UK is an example of acidic spoil heap discharge that contains elevated levels of many metals. Aerobic wetlands planted with the common reed, Phragmites australis, were constructed at the site to treat surface runoff from the spoil heap. The presence of a perched water table within the spoil heap resulted in the lower wetlands receiving acidic metal contaminated water from within the spoil heap while the upper wetland receives alkaline, uncontaminated surface runoff from the revegetated spoil. This unique situation enabled the comparison of metal uptake and growth of plants used in treatment schemes in two cognate wetlands. Results indicated a significant difference in plant growth between the two wetlands in terms of shoot height and seed production. Analyses of metal and nutrient concentrations within plant tissues provided the basis for three hypotheses to explain these differences: (i) the toxic effects of high levels of metals in shoot tissues, (ii) the inhibition of Ca (an essential nutrient) uptake by the presence of metals and H+ ions, and (iii) low concentrations of bioavailable nitrogen sources resulting in nitrogen deficiency. This has important implications for the engineering of constructed wetlands in terms of the potential success of plant establishment and vegetation development.     

Trace metal and metalloid levels in surface water of Marcal River before and after the Ajka red mud spill, Hungary

The aim of this study was to compare and assess the dissolved concentrations of trace elements (As, Zn, Hg, Cd, Cr, Ni, Pb and Cu) in surface water of Marcal River before and after the red mud spill that occurred in Ajka, western Hungary, in October 2010. The caustic sludge flooded the surrounding settlements and polluted the nearby Torna Creek, which flows through the Marcal and Raba rivers into the Danube. A total of 92 surface water samples were collected from the Marcal River in the period of 2007–2012 and analysed for dissolved trace metal(loid)s by atomic absorption spectroscopy method. After the spill, the water management authority initially focused on acid dosing of surface waters to lower pH and was effective in lowering both pH and metal(loid) concentrations. Among the dissolved trace metal(loid)s, arsenic and nickel levels were moderately higher in the Marcal River 2 years since the spill compared to that observed in the pre-disaster period. The concentrations of dissolved trace metal(loid)s did not exceed the European water quality standards and the US Environmental Protection Agency aquatic life criteria values (excluding one sample for cadmium).     

Influence of trophic status on PCB distribution in lake sediments and biota

We investigated the relationship between trophic status and polychlorinated biphenyl (PCB) distribution in 19 Swedish lakes. We analyzed PCB in water, phytoplankton, zooplankton, fish and sediment during two sampling periods, in spring and summer. The mass of sigma PCB in the lake sediments was positively related to lake trophy, i.e. more PCBs were accumulated and buried in the sediment of eutrophic lakes than in oligotrophic lakes. In the oligotrophic lakes a greater fraction of the total PCB load was dissolved in water. We conclude that this is a result of higher sedimentation rates in eutrophic lakes and relatively lower turnover of organic carbon in the water column of the shallow, eutrophic lakes. In the stratified lakes, the amount of PCB per cubic meter in the epilimnion decreased from spring to summer. We suggest that sedimentation of plankton beneath the thermocline during stratification act as a sink process of PCBs from the epilimnion.     

Erratum

The influence of soil macro-porosity and manure on atrazine (6-chloro-N-ethyl-N′-(1-methylethyl)-1,3,5-triazine-2,4-diamine) transport was investigated under laboratory conditions using disturbed and undisturbed soil columns. The macro-porosity in the soil column was obtained with CT scanning technique. Liquid manure was applied at the surface of soil column, 19 cm long and 8 cm in diameter, at a rate of 60 m³/ha. Experimental results revealed that atrazine moves faster through the soils in the presence of manure compared to soil without application of manure. The average time for elusion and the relative peak concentration in the disturbed soil column without manure was 14.5 h and 3.1%, respectively compared to 11.0 h and 6.9% in the presence of manure, respectively. Similar behavior was observed in the case of disturbed soil columns. Soil macro-porosity has shown large impact on atrazine transport, especially in the presence of manure.     

Macroporosity and manure influence on atrazine transport through soil

The influence of soil macro-porosity and manure on atrazine (6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine) transport was investigated under laboratory conditions using disturbed and undisturbed soil columns. The macro-porosity in the soil column was obtained with CT scanning technique. Liquid manure was applied at the surface of soil column, 19 cm long and 8 cm in diameter, at a rate of 60 m3/ha. Experimental results revealed that atrazine moves faster through the soils in the presence of manure compared to soil without application of manure. The average time for elusion and the relative peak concentration in the disturbed soil column without manure was 14.5 h and 3.1%, respectively compared to 11.0 h and 6.9% in the presence of manure, respectively. Similar behavior was observed in the case of disturbed soil columns. Soil macro-porosity has shown large impact on atrazine transport, especially in the presence of manure.     

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.     

Database uncertainty as a limiting factor in reactive transport prognosis

The effect of uncertainties in thermodynamic databases on prediction performances of reactive transport modeling of uranium (VI) is investigated with a Monte Carlo approach using the transport code TReaC. TReaC couples the transport model to the speciation code PHREEQC by a particle tracking method. A speciation example is given to illustrate the effect of uncertainty in thermodynamic data on the predicted solution composition. The transport calculations consequently show the prediction uncertainty resulting from uncertainty in thermodynamic data. A conceptually simple scenario of elution of uranium from a sand column is used as an illustrating example. Two different cases are investigated: a carbonate-enriched drinking water and an acid mine water associated with uranium mine remediation problems. Due to the uncertainty in the relative amount of positively charged and neutral solution species, the uncertainty in the thermodynamic data also infers uncertainty in the retardation behavior. The carbonated water system shows the largest uncertainties in speciation calculation. Therefore, the model predictions of total uranium solubility have a broad range. The effect of data uncertainty in transport prediction is further illustrated by a prediction of the time when eluted uranium from the column exceeds a threshold value. All of these Monte Carlo transport calculations consume large amounts of computing time.