Primary Attenuation Mechanism Research Articles

Insights into biogeochemistry and hot spots distribution characteristics of redox-sensitive elements in the hyporheic zone: Transformation mechanisms and contributing factors

Biogeochemical hot spots play a crucial role in the cycling and transport of redox-sensitive elements (RSEs) in the hyporheic zone (HZ). However, the transformation mechanisms of RSEs and patterns of RSEs hot spots in the HZ remain poorly understood. In this study, hydrochemistry and multi-isotope (N/C/S/O) datasets were collected to investigate the transformation mechanisms of RSEs, and explore the distribution characteristics of RSEs transformation hot spots. The results showed that spatial variability in key drivers was evident, while temporal change in RSEs concentration was not significant, except for dissolved organic carbon. Bacterial sulfate reduction (BSR) was the primary biogeochemical process for sulfate and occurred throughout the area. Ammonium enrichment was mainly caused by the mineralization of nitrogenous organic matter and anthropogenic inputs, with adsorption serving as the primary attenuation mechanism. Carbon dynamics were influenced by various biogeochemical processes, with dissolved organic carbon mainly derived from C3 plants and dissolved inorganic carbon from weathering of carbonate rocks and decomposition of organic matter. The peak contribution of dissolved organic carbon decomposition to the DIC pool was 46.44 %. The concentration thresholds for the ammonium enrichment and BSR hot spots were identified as 1.5 mg/L and 8.84 mg/L, respectively. The distribution pattern of RSEs hot spots was closely related to the hydrogeological conditions. Our findings reveal the complex evolution mechanisms and hot spots distribution characteristics of RSEs in the HZ, providing a basis for the safe utilization and protection of groundwater resources.

Understanding seismic path biases and magmatic activity at Mount St Helens volcano before its 2004 eruption

SUMMARY In volcanoes, topography, shallow heterogeneity and even shallow morphology can substantially modify seismic coda signals. Coda waves are an essential tool to monitor eruption dynamics and model volcanic structures jointly and independently from velocity anomalies: it is thus fundamental to test their spatial sensitivity to seismic path effects. Here, we apply the Multiple Lapse Time Window Analysis (MLTWA) to measure the relative importance of scattering attenuation vs absorption at Mount St Helens volcano before its 2004 eruption. The results show the characteristic dominance of scattering attenuation in volcanoes at lower frequencies (3–6 Hz), while absorption is the primary attenuation mechanism at 12 and 18 Hz. Scattering attenuation is similar but seismic absorption is one order of magnitude lower than at open-conduit volcanoes, like Etna and Kilauea, a typical behaviour of a (relatively) cool magmatic plumbing system. Still, the seismic albedo (measuring the ratio between seismic energy emitted and received from the area) is anomalously high (0.95) at 3 Hz. A radiative-transfer forward model of far- and near-field envelopes confirms this is due to strong near-receiver scattering enhancing anomalous phases in the intermediate and late coda across the 1980 debris avalanche and central crater. Only above this frequency and in the far-field diffusion onsets at late lapse times. The scattering and absorption parameters derived from MLTWA are used as inputs to construct 2-D frequency-dependent bulk sensitivity kernels for the S-wave coda in the multiple-scattering (using the Energy Transport Equations—ETE) and diffusive (AD, independent of MLTWA results) regimes. At 12 Hz, high coda-attenuation anomalies characterize the eastern side of the volcano using both kernels, in spatial correlation with low-velocity anomalies from literature. At 3 Hz, the anomalous albedo, the forward modelling, and the results of the tomographic imaging confirm that shallow heterogeneity beneath the extended 1980 debris-avalanche and crater enhance anomalous intermediate and late coda phases, mapping shallow geological contrasts. We remark the effect this may have on coda-dependent source inversion and tomography, currently used across the world to image and monitor volcanoes. At Mount St Helens, higher frequencies and deep borehole data are necessary to reconstruct deep volcanic structures with coda waves.

Attenuation limit of silica-based hollow-core fiber at mid-IR wavelengths

We study the mid-infrared attenuation of antiresonant hollow-core fiber made of fused silica glass. The role of absorptive losses increases with wavelength but can be minimized by reducing the overlap of the trapped light with the silica. We show that this overlap is least at the lowest-order antiresonance condition, corresponding to the thinnest core wall, and for higher resonances scales with the core wall thickness. A record-low minimum attenuation of 18 dB/km measured in our fiber at 3.1 µm wavelength is not limited by silica absorption. We measured 40 dB/km attenuation at 4 µm wavelength, where the attenuation of bulk silica is 860 dB/m. We show that this corresponds to a modal overlap of 2.81 × 10−5 which is in good agreement with simulations, suggesting that at this wavelength, attenuation is limited by silica absorption. This enables us to predict the achievable attenuation at longer wavelengths as well. Extrinsic losses due to gaseous molecular absorption may make demonstration of such losses difficult in some spectral bands. In contrast to shorter wavelengths, where leakage loss is the primary attenuation mechanism, introducing additional elements into the cladding design is unlikely to reduce the attenuation further, and further loss reduction would require a larger core size.

Experimental and computer simulation validation of ultrasound phase interference created by lateral inhomogeneity of transit time in replica bone: marrow composite models

The measurement of broadband ultrasound attenuation in cancellous bone for the assessment of osteoporosis follows a parabolic-type dependence with bone volume fraction, having minima values corresponding to both entire bone and entire marrow. Langton has recently proposed that the primary attenuation mechanism is phase interference due to variations in propagation transit time through the test sample as detected over the phase-sensitive surface of the receive ultrasound transducer. This fundamentally simple concept assumes that the propagation may be considered as an array of parallel 'sonic rays'. The transit time of each ray is defined by the proportion of bone and marrow propagated, being a minimum (t(min)) solely through bone and a maximum (t(max)) solely through marrow, from which a transit time spectrum, may be defined describing the proportion of sonic rays having a particular transit time. The aim of this study was to test the hypothesis that there is a dependence of phase interference upon the lateral inhomogeneity of transit time by comparing experimental measurements and computer simulation predictions of ultrasound propagation through a range of relatively simplistic solid:liquid models. From qualitative and quantitative comparison of the experimental and computer simulation results, there is an extremely high degree of agreement of 94.2%-99.0% between the two approaches. This combined experimental and computer simulation study has successfully demonstrated that lateral inhomogeneity of transit time has significant potential for phase interference to occur if a phase-sensitive receive ultrasound transducer is implemented as in most commercial ultrasound bone analysis devices.

Adsorptive attenuation of ferrocyanide from seepage water in landfill clay liners

The spent potliner (SPL) landfill liner system provides the primary attenuation mechanism that blocks the leaching of ferrocyanide. If the seepage occurs, however, the off-site leaching potential of ferrocyanide will be enhanced, resulting in contaminant dispersion. In this study, the adsorptive attenuation of ferrocyanide by two common lining materials (kaolinite and montmorillonite) was investigated under various seepage settings, such as influent concentration, liner thickness, and seepage velocity. The attenuation of ferrocyanide through both lining materials was obvious by lowering the maximum concentration and retarding the peak arrival time and was greater than that expected from batch data, likely due to the high mass-volume ratio under seepage condition. In comparison, seepage of ferrocyanide through lining material layer was retarded when (1) influent concentration was halved, (2) liner thickness was 1.5-fold, and (3) seepage velocity was halved. These experimental results strongly support the concentration-specific and rate-limited adsorptive attenuation of ferrocyanide by lining materials during the seepage process. An extended desorption front was observed for all seepage conditions; it was particularly more apparent for montmorillonite with a slow seepage velocity, further supporting that the release of adsorbed ferrocyanide from adsorbent is energetically hysteretic. Among the factors investigated in this study, the greatest retardation of ferrocyanide movement from seepage water was achieved upon doubling liner thickness. Therefore, for the design of a SPL landfill liner to minimize the leaching potential and thus the environmental risk of ferrocyanide, optimization of the liner thickness should be considered foremost.

Adsorptive removal of aqueous fluoride and ferrocyanide by liner minerals from SPL landfill leachate: Effect of pH and adsorptive competition

Soil and water near a spent potliner (SPL) landfill are often found to be highly contaminated with fluoride and ferrocyanide. The liner system, composed of kaolinite and montmorillonite, provides the primary attenuation mechanism for the risk of soluble ferrocyanide and fluoride in the leachate from a SPL landfill. The adsorption of ferrocyanide and fluoride by montmorillonite and kaolinite was investigated in both a single and a binary solute system as a function of the aqueous pH. The adsorption of both solutes was highly pH-dependent, and competed with each of the two liner minerals. In the single solute–montmorillonite system, the adsorption was higher under acidic pH conditions and lower under alkaline pH conditions. For the single solute–kaolinite system, the maximum adsorption appeared near p K a value of the edge functional group. In the binary solute system, the adsorption of solute appeared to be suppressed by the presence of a counterpart, and the competitive adsorption becomes less significant with increasing pH where both adsorptions were minimal. As a result, increasing aqueous pH and the presence of a competitor in SPL-induced leachate can mitigate the attenuation capacity provided by the liner system, thereby, enhancing the leachability of ferrocyanide and fluoride from SPL landfill sites.

Speciation and natural attenuation of arsenic and iron in a tidally influenced shallow aquifer

The mobility of subsurface arsenic is controlled by sorption, precipitation, and dissolution processes that are tied directly to coupled redox reactions with more abundant, but spatially and temporally variable, iron and sulfur species. Adjacent to the site of a former pesticide manufacturing facility near San Francisco Bay (California, USA), soil and groundwater arsenic concentrations are elevated in sediments near the prior source, but decrease to background levels downgradient where shallow groundwater mixes with infiltrating tidal waters at the plume periphery, which has not migrated appreciably in over two decades of monitoring. We used synchrotron X-ray absorption spectroscopy, together with supporting characterizations and sequential chemical extractions, to directly determine the oxidation state of arsenic and iron as a function of depth in sediments from cores recovered from the unsaturated and saturated zones of a shallow aquifer (to 3.5 m below the surface). Arsenic oxidation state and local bonding in sediments, as As-sulfide, As(III)-oxide, or As(V)-oxide, were related to lithologic redox horizons and depth to groundwater. Based on arsenic and iron speciation, three subsurface zones were identified: (i) a shallow reduced zone in which sulfide phases were found in either the arsenic spectra (realgar-like or orpiment-like local structure), the iron spectra (presence of pyrite), or both, with and without As(III) or As(V) coordinated by oxygen; (ii) a middle transitional zone with mixed arsenic oxidation states (As(III)–O and As(V)–O) but no evidence for sulfide phases in either the arsenic or iron spectra; and (iii) a lower oxidized zone in the saturated freshwater aquifer in which sediments contained only oxidized As(V) and Fe(III) in labile (non-detrital) phases. The zone of transition between the presence and absence of sulfide phases corresponded to the approximate seasonal fluctuation in water level associated with shallow groundwater in the sand-dominated, lower oxic zone. Total sediment arsenic concentrations showed a minimum in the transition zone and an increase in the oxic zone, particularly in core samples nearest the former source. Equilibrium and reaction progress modeling of aqueous-sediment reactions in response to decreasing oxidation potential were used to illustrate the dynamics of arsenic uptake and release in the shallow subsurface. Arsenic attenuation was controlled by two mechanisms, precipitation as sulfide phases under sulfate-reducing conditions in the unsaturated zone, and adsorption of oxidized arsenic to iron hydroxide phases under oxidizing conditions in saturated groundwaters. This study demonstrates that both realgar-type and orpiment-type phases can form in sulfate-reducing sediments at ambient temperatures, with realgar predicted as the thermodynamically stable phase in the presence of pyrite and As(III) under more reduced conditions than orpiment. Field and modeling results indicate that the potential for release of arsenite to solution is maximized in the transition between sulfate-reduced and iron-oxidized conditions when concentrations of labile iron are low relative to arsenic, pH-controlled arsenic sorption is the primary attenuation mechanism, and mixed Fe(II,III)-oxide phases do not form and generate new sorption sites.

Biogeochemistry at a wetland sediment–alluvial aquifer interface in a landfill leachate plume

The biogeochemistry at the interface between sediments in a seasonally ponded wetland (slough) and an alluvial aquifer contaminated with landfill leachate was investigated to evaluate factors that can effect natural attenuation of landfill leachate contaminants in areas of groundwater/surface-water interaction. The biogeochemistry at the wetland-alluvial aquifer interface differed greatly between dry and wet conditions. During dry conditions (low water table), vertically upward discharge was focused at the center of the slough from the fringe of a landfill-derived ammonium plume in the underlying aquifer, resulting in transport of relatively low concentrations of ammonium to the slough sediments with dilution and dispersion as the primary attenuation mechanism. In contrast, during wet conditions (high water table), leachate-contaminated groundwater discharged upward near the upgradient slough bank, where ammonium concentrations in the aquifer where high. Relatively high concentrations of ammonium and other leachate constituents also were transported laterally through the slough porewater to the downgradient bank in wet conditions. Concentrations of the leachate-associated constituents chloride, ammonium, non-volatile dissolved organic carbon, alkalinity, and ferrous iron more than doubled in the slough porewater on the upgradient bank during wet conditions. Chloride, non-volatile dissolved organic carbon (DOC), and bicarbonate acted conservatively during lateral transport in the aquifer and slough porewater, whereas ammonium and potassium were strongly attenuated. Nitrogen isotope variations in ammonium and the distribution of ammonium compared to other cations indicated that sorption was the primary attenuation mechanism for ammonium during lateral transport in the aquifer and the slough porewater. Ammonium attenuation was less efficient, however, in the slough porewater than in the aquifer and possibly occurred by a different sorption mechanism. A stoichiometrically balanced increase in magnesium concentration with decreasing ammonium and potassium concentrations indicated that cation exchange was the sorption mechanism in the slough porewater. Only a partial mass balance could be determined for cations exchanged for ammonium and potassium in the aquifer, indicating that some irreversible sorption may be occurring. Although wetlands commonly are expected to decrease fluxes of contaminants in riparian environments, enhanced attenuation of the leachate contaminants in the slough sediment porewater compared to the aquifer was not observed in this study. The lack of enhanced attenuation can be attributed to the fact that the anoxic plume, comprised largely of recalcitrant DOC and reduced inorganic constituents, interacted with anoxic slough sediments and porewaters, rather than encountering a change in redox conditions that could cause transformation reactions. Nevertheless, the attenuation processes in the narrow zone of groundwater/surface-water interaction were effective in reducing ammonium concentrations by a factor of about 3 during lateral transport across the slough and by a factor of 2 to 10 before release to the surface water. Slough porewater geochemistry also indicated that the slough could be a source of sulfate in dry conditions, potentially providing a terminal electron acceptor for natural attenuation of organic compounds in the leachate plume.

Anaerobic Biodegradation and Hydrogeochemical Controls on Natural Attenuation of Trichloroethene in an Inland Forested Wetland

ABSTRACT A field and laboratory investigation of natural attenuation, focusing on anaerobic biodegradation, was conducted in a forested wetland where a plume of trichloroethene discharges from a sand aquifer through organic-rich wetland and stream-bottom sediments. The rapid response of the wetland hydrology to precipitation events altered groundwater flow and geochemistry during wet conditions in the spring compared to the drier conditions in the summer and fall. During dry conditions, partial reductive dechlorination of trichloroethene to cis-1,2-dichloroethene occurred in methanogenic wetland porewater. Influx of oxygenated recharge during wet conditions resulted in a change from methanogenic to iron-reducing conditions and a lack of 1,2-dichloroethene production in the wet spring conditions. During these wet conditions, dilution was the primary attenuation mechanism evident for trichloroethene in the wetland porewater. Trichloroethene degradation was insignificant in anaerobic microcosms constructed with the shallow wetland sediment, and microbiological analyses showed a low microbial biomass and absence of known dehalorespiring microorganisms. Despite the typically organic-rich characteristic of wetland sediments, natural attenuation by anaerobic degradation may not be an effective groundwater remediation for chlorinated solvents at all sites.

Assessment of natural attenuation of chlorinated aliphatics and BTEX in subarctic groundwater.

We examined biogeochemistry and microbiology associated with natural attenuation of trichloroethene (TCE), trichloroethane (TCA), and benzene in a subarctic aquifer. Identification of a predominant terminal electron-accepting process (TEAP) and characterization of typical natural attenuation footprints was difficult. Hydrogen and ferrous iron concentrations suggested that iron reduction was the predominant TEAP; calculated in situ Gibbs free energies for iron reduction were energetically feasible at all wells although a source of ferric iron has not been conclusively determined. The presence of dissolved sulfide and favorable free energies for sulfate reduction provided support of concurrent iron and sulfate reduction. Methanogenesis from H2/CO2 was generally not energetically favorable. The presence of TCE and TCA degradation intermediates suggested that biological reductive dechlorination occurred, although proportions of intermediates relative to parent compounds remained stable. By September 2000, contaminant concentrations were within regulatory standards at most sampling points. However, low rates of microbial activity and incomplete degradation imply that intrinsic bioremediation did not likely represent an important contribution to contaminant removal atthis site, where dilution appeared to be the primary attenuation mechanism.

An experimental study of heavy metal attenuation and mobility in sandy loam soils

Column flow-through experiments reacting wastewater solutions with sandy loam soil samples were performed to study heavy metal attenuation by two soils with different physical and chemical properties. Reacted soil columns were leached with synthetic acid rain to study the mobility of attenuated heavy metals under leaching conditions. This study demonstrates that cation exchange, surface adsorption, chelation with solid organic material, and precipitation were the important attenuation mechanisms for the heavy metals (Cd, Cr, Cu, Mo, Ph, and Zn). Adsorption on soil hydrous oxide surfaces was the primary attenuation mechanism for Cd and Zn in both soils, and for Cu in a soil with low organic matter content. Wastewater solution pH is also an important factor that influences the retention of heavy metals. Cadmium, Cu, Cr, and Zn became mobile after prolonged application of spiked wastewater solution, either through saturation of soil adsorption sites or due to decreasing pH. Only Cr, Pb, and Mo, which are attenuated primarily through precipitation, show significant net retention by soil. Acid rain water removed heavy metals left in the column residual pore solution and weakly sorbed heavy metals in the soils, and has the ability to mobilize some strongly attenuated heavy metals, especially when the soil organic matter content is high. The results have important applications in predicting heavy metal mobility in contaminated soil, the disposal of acid mine drainage, and assessing the risks of landfall leachate leakage.

Transport and transformation of hexavalent chromium through soils and into ground water

Abstract A detailed characterization of the underlying and adjacent soils of a chrome‐plating shop was performed to provide information on the extent of soil and aquifer contamination at the site and on the potential for off‐site migration and environmental impact. Intact, moist cores were obtained from more than 40 different locations, resulting in more than 200 discrete samples for total metal analysis, selective extraction tests, and adsorption‐reduction experiments, to assess the chemical speciation and distribution of chromium on the contaminated soils and its leaching potential. Surface analytical techniques were also used to determine chemical speciation and to further elucidate mineral fractions responsible for retention of the chromium on the soils and sediments. Adsorption and reduction capacities of the saturated aquifer sediments were variable and low, while the unsaturated soils’ reduction capacities were much greater and were correlated with depth (decreasing capacity with increasing depth). The soils’ adsorption and reduction capacities were eventually overwhelmed, however, and permitted the passage of Cr(VI) into the underlying ground water. Adsorption capacity differences were primarily related to clay content and pH, and less so to the presence of amorphous iron oxide coatings on matrix minerals as operationally defined by the selective extraction methods used in the study. Reduction of Cr(VI) to Cr(III) and subsequent precipitation as (Fe, Cr)(OH)3 is proposed as the primary attenuation mechanism in the unsaturated soils immediately beneath the shop, based on extraction and surface analyses results.