Influence of hydrological and geochemical processes on the transport of chelated metals and chromate in fractured shale bedrock

Field-scale processes governing the transport of chelated radionuclides in groundwater remain conceptually unclear for highly structured, heterogeneous environments. The objectives of this research were to provide an improved understanding and predictive capability of the hydrological and geochemical mechanisms that control the transport behavior of chelated radionuclides and metals in anoxic subsurface environments that are complicated by fracture flow and matrix diffusion. Our approach involved a long-term, steady-state natural gradient field experiment where nonreactive Br- and reactive 57Co(II)EDTA2- 109CdEDTA2-, and 51Cr(VI) were injected into a fracture zone of a contaminated fractured shale bedrock. The spatial and temporal distribution of the tracer and solutes was monitored for 500 days using an array of groundwater sampling wells instrumented within the fast-flowing fracture regime and a slower flowing matrix regime. The tracers were preferentially transported along strike-parallel fractures coupled with the slow diffusion of significant tracer mass into the bedrock matrix. The chelated radionuclides and metals were significantly retarded by the solid phase with the mechanisms of retardation largely due to redox reactions and sorption coupled with mineral-induced chelate-radionuclide dissociation. The formation of significant Fe(III)EDTA byproduct that accompanied the dissociation of the radionuclide-chelate complexes was believed to be the result of surface interactions with biotite which was the only Fe(III)-bearing mineral phase present in these Fe-reducing environments. These results counter current conceptual models that suggest chelated contaminants move conservatively through Fe-reducing environments since they are devoid of Fe-oxyhydroxides that are known to aggressively compete for chelates in oxic regimes. Modeling results further demonstrated that chelate-radionuclide dissociation reactions were most prevalent along fractures where accelerated weathering processes are expected to expose more primary minerals than the surrounding rock matrix. The findings of this study suggest that physical retardation mechanisms (i.e. diffusion) are dominant within the matrix regime, whereas geochemical retardation mechanisms are dominant within the fracture regime.     

Distribution of feminizing compounds in the aquatic environment and bioaccumulation in wild tilapia tissues

This study sampled six times of river water, sediment, and tilapia (Oreochromis niloticus) in the Dan-Shui River, Taipei, Taiwan; 10 feminizing compounds were analyzed using ultra-performance liquid chromatography-tandem mass spectrometry. Bisphenol A (508?±?634 ng/L, geometric mean (GM) 303 ng/L) and nonylphenol (491?±?570 ng/L, GM 328 ng/L) were the most abundant among analytes in the river water. Nonylphenol (770?±?602 ng/g wet weight, GM 617 ng/g wet weight) was also the highest in sediment. Fish may uptake nonylphenol and nonylphenol ethoxylates from river water and sediment because there were significant correlations between the concentrations in these matrixes and those in fish tissues (r _s ranged from 0.21 to 0.49, p?相似文献   

Evaluation of the impacts of mine drainage from a coal waste pile on the surrounding environment at Smolnica, southern Poland

Mine drainage impacts from a coal waste pile at Smolnica, Poland have been monitored. Groundwater in an unconfined aquifer downgradient from the pile has near-neutral pH, but high concentrations of sulfate (up to 3,827 mg/l), chloride (up to 903 mg/l), and sodium (up to 2,606 mg/l). Concentrations of iron and manganese are elevated only locally, and concentrations of other metals are low. The behavior of sulfate seems to be conservative in the downgradient aquifer, and gypsum may only be precipitating locally. Concentrations of iron and manganese seem to be controlled by the precipitation of ferric oxide and hydroxides and rhodochrosite, respectively. Complete neutralization of mine drainage by carbonates is consistent with high concentrations of calcium (up to 470 mg/l) and magnesium (up to 563 mg/l) and also with high strontium concentrations of up to 3.08 mg/l, observed in groundwater downgradient from the pile. Hydraulic head profiles at two sites within the river bottom sediments indicate upward flow toward the river with large local differences in groundwater recharge. Water chemistry profiles in the river bottom sediments and geochemical modeling suggest conservative behavior of Na, Cl, and SO₄ and precipitation of Fe and Mn at the groundwater/river water interface. Mine drainage enters the Bierawka River and causes increasing sulfate concentrations. In contrast, concentrations of sodium and chloride in the Bierawka River decrease downgradient from the pile because water in the river upgradient from the pile is already highly contaminated by these species from the discharge of mining waters. Concentrations of Fe and Mn in the river water are low, as a consequence of the precipitation of Fe and Mn oxide and hydroxides. Direct geochemical modeling was able to reproduce measured concentrations of conservative species (e.g., Na, Cl, and SO₄), but errors for metals and Ba were relatively large. In addition, calculated P_CO2 values in the river water are very high, suggesting that equilibrium with atmospheric P_CO2 and P_O2 has not been reached, and at least some reactions should be modeled as kinetic processes. High concentrations of Na, Cl, and SO₄ contribute to the contamination of the Odra River, which is joined by the Bierawka River farther downgradient, thus limiting the use of river water for recreation and other purposes.     

Modeling field-scale multiple tracer injection at a low-level waste disposal site in fractured rocks: effect of multiscale heterogeneity and source term uncertainty on conceptual understanding of mass transfer processes

Multiple factors may affect the scale-up of laboratory multi-tracer injection into structured porous media to the field. Under transient flow conditions and with multiscale heterogeneities in the field, previous attempts to scale-up laboratory experiments have not answered definitely the questions about the governing mechanisms and the spatial extent of the influence of small-scale mass transfer processes such as matrix diffusion. The objective of this research is to investigate the effects of multiscale heterogeneity, mechanistic and site model conceptualization, and source term density effect on elucidating and interpreting tracer movement in the field. Tracer release and monitoring information previously obtained in a field campaign of multiple, conservative tracer injection under natural hydraulic gradients at a low-level waste disposal site in eastern Tennessee, United States, is used for the research. A suite of two-pore-domain, or fracture-matrix, groundwater flow and transport models are calibrated and used to conduct model parameter and prediction uncertainty analyses. These efforts are facilitated by a novel nested Latin-hypercube sampling technique. Our results verify, at field scale, a multiple-pore-domain, multiscale mechanistic conceptual model that was used previously to interpret only laboratory observations. The results also suggest that, integrated over the entire field site, mass flux rates attributable to small-scale mass transfer are comparable to that of field-scale solute transport. The uncertainty analyses show that fracture spacing is the most important model parameter and model prediction uncertainty is relatively higher at the interface between the preferred flow path and its parent bedrock. The comparisons of site conceptual models indicate that the effect of matrix diffusion may be confined to the immediate neighborhood of the preferential flow path. Finally, because the relatively large amount of tracer needed for field studies, it is likely that source term density effect may exaggerate or obscure the effect of matrix diffusion on the movement of tracers from the preferred flow path into the bedrock.     

Quantifying the physical and chemical mass transfer processes for the fate and transport of Co(II)EDTA in a partially-weathered limestone-shale saprolite

The objective of the research is to quantify the relative contributions of physical and chemical mass transfer to the movement of Co(II/III)EDTA (chelates of Cobalt and Ethylene Diamine Tetraacetic Acid or EDTA) through a limestone-shale saprolite soil. Saprolite is a collective term referring to partially-weathered bedrock. It exists extensively in the subsurface. Because the parent bedding structures are maintained during the weathering process, saprolite soils are characterized by intensive fractures and secondary deposits of minerals such as Al-, Fe- and Mn-oxides on the fracture surfaces. Movement of reactive species through the soils may be influenced by diffusion into the rock matrix, a physical mass transfer (PMT) process, and interfacial chemical reactions, a chemical mass transfer (CMT) process. The PMT and CMT processes are phenomenologically similar but mechanistically different. In this research, previous laboratory observations from a Br and Co(II)EDTA tracer injection into an undisturbed saprolite soil column were used. Mechanistic reactive transport models were formulated to quantify the PMT and CMT processes. The PMT process was independently characterized by using the non-reactive tracer Br. Model parameters thus obtained were subsequently used as constraints to quantify the CMT processes involving Co(II)EDTA and its oxidation product Co(III)EDTA. Our calculations indicated that the PMT rates of the less reactive Co(III)EDTA were comparable with their theoretical CMT rates. In contrast, for the more reactive species Co(II)EDTA, CMT rates are higher than PMT rates. Evaluations of alternative CMT process models further confirmed one of our hypotheses on the basis of previous experimental understandings. The hypothesis suggested that competition from Fe-oxide for Co(II)EDTA may account for the majority of the decrease of Co(III)EDTA effluent concentrations that resulted in the separation of total Co and Co(III)EDTA breakthrough curves. Because Co(III)EDTA is more mobile than Co(II)EDTA in the subsurface, the results of this research suggest independent quantifications of CoEDTA PMT and CMT processes if laboratory results are to be interpreted correctly and scaled up for field and predictive uses.