Abstract: Permeable reactive barriers (PRBs) are used for groundwater remediation at contaminated sites worldwide. This technology has been efficient at appropriate sites for treating organic and inorganic contaminants using zero-valent iron (ZVI) as a reductant and as a reactive material. Continued development of the technology over the years suggests that a robust understanding of PRB performance and the mechanisms involved is still lacking. Conflicting information in the scientific literature downplays the critical role of ZVI corrosion in the remediation of various organic and inorganic pollutants. Additionally, there is a lack of information on how different mechanisms act in tandem to affect ZVI-groundwater systems through time. In this review paper, we describe the underlying mechanisms of PRB performance and remove isolated misconceptions. We discuss the primary mechanisms of ZVI transformation and aging in PRBs and the role of iron corrosion products. We review numerous sites to reinforce our understanding of the interactions between groundwater contaminants and ZVI and the authigenic minerals that form within PRBs. Our findings show that ZVI corrosion products and mineral precipitates play critical roles in the long-term performance of PRBs by influencing the reactivity of ZVI. Pore occlusion by mineral precipitates occurs at the influent side of PRBs and is enhanced by dissolved oxygen and groundwater rich in dissolved solids and high alkalinity, which negatively impacts hydraulic conductivity, allowing contaminants to potentially bypass the treatment zone. Further development of site characterization tools and models is needed to support effective PRB designs for groundwater remediation.

Abstract: 81Kr and 36Cl can both be used to date groundwater beyond the dating range of 14C. 81Kr usually provides reliable groundwater ages because it has uniform initial distribution and negligible subsurface generation, while 36Cl is commonly influenced by subsurface sources or “dead” chloride dissolution. Therefore, the combined use of 81Kr and 36Cl could provide clues on the evolution history of groundwater. In the present study, we performed 36Cl and 81Kr dating of geothermal water in Weihe Basin of China and interpreted the possible cause of disagreement. Two distinct water masses were identified with distinctive isotopic signals: groundwater with significant δ18O shifts (up to −2.0‰), dissolved dead Cl and ages < 1.0 Ma (Cluster A), and older water with little δ18O shifts, negligible dissolved Cl and ages >1.0 Ma (Cluster B). The results confirm the eastward flow path of Cluster B to the Ancient Sanmen Lake with an increasing trend of Cl concentration and age. Modern recharge from the mountains flows to the basin center with intense interaction between water and carbonate under respective reservoir temperatures (100 ∼ 130 °C). These waters flow through the saline stratum emerging from the spillover of the Ancient Sanmen Lake, resulting in higher dead Cl dissolution. A significant linear relationship is observed with the older end-member of ∼1.3Ma under the topographically-driven faster circulation effect. 81Kr ages seem to support the hypothesis that the birth of the modern Yellow River was at about 1.0–1.3 Ma. We inferred the drainage reorganization from the Ancient Sanmen Lake to the modern Yellow River since the Mid-Pleistocene Transition induced the change in groundwater dynamics as well as its chemical evolution. The excavation of the Ancient Sanmen Lake and the accentuated incision of the Weihe River induced groundwater gradient, and therefore the recharge from precipitation from both slopes of the Qinling Mountains in the south and the Beishan Mountains in the north. Our results highlight the effects of dead Cl on 36Cl dating and demonstrate the significant impact of catchment reorganization on groundwater dynamics and its chemistry.

Abstract: Due to its radiological and toxicological properties even at low concentration levels, uranium is increasingly recognized as relevant contaminant in drinking water from aquifers. Uranium originates from different sources, including natural or geogenic, mining and industrial activities, and fertilizers in agriculture. The goal of this study was to obtain insights into the origin of uranium in groundwater while differentiating between geogenic sources and fertilizers. A literature review concerning the sources and geochemical processes affecting the occurrence and distribution of uranium in the lithosphere, pedosphere and hydrosphere provided the background for the evaluation of data on uranium in groundwater at regional scale. The state of Baden-Württemberg, Germany, was selected for this study, because of its hydrogeological and land-use diversity, and for reasons of data availability. Uranium and other parameters from N=1935 groundwater monitoring sites were analyzed statistically and geospatially. Results show that (i) 1.6% of all water samples exceed the German legal limit for drinking water (10μg/L); (ii) The range and spatial distribution of uranium and occasional peak values seem to be related to geogenic sources; (iii) There is a clear relation between agricultural land-use and low-level uranium concentrations, indicating that fertilizers generate a measurable but low background of uranium in groundwater.

Abstract: This paper presents the first continuous pollen record from the southern Namib Desert spanning the last 50,000years. Obtained from rock hyrax middens found near the town of Pella, South Africa, these data are used to reconstruct vegetation change and quantitative estimates of temperature and aridity. Results indicate that the last glacial period was characterised by increased water availability at the site relative to the Holocene. Changes in temperature and potential evapotranspiration appear to have played a significant role in determining the hydrologic balance. The record can be considered in two sections: 1) the last glacial period, when low temperatures favoured the development of more mesic Nama-Karoo vegetation at the site, with periods of increased humidity concurrent with increased coastal upwelling, both responding to lower global/regional temperatures; and 2) the Holocene, during which time high temperatures and potential evapotranspiration resulted in increased aridity and an expansion of the Desert Biome. During this latter period, increases in upwelling intensity created drier conditions at the site. Considered in the context of discussions of forcing mechanisms of regional climate change and environmental dynamics, the results from Pella stand in clear contrast with many inferences of terrestrial environmental change derived from regional marine records. Observations of a strong precessional signal and interpretations of increased humidity during phases of high local summer insolation in the marine records are not consistent with the data from Pella. Similarly, while high percentages of Restionaceae pollen has been observed in marine sediments during the last glacial period, they do not exceed 1% of the assemblage from Pella, indicating that no significant expansion of the Fynbos Biome has occurred during the last 50,000years. These findings pose interesting questions regarding the nature of environmental change in southwestern Africa, and the significance of the diverse records that have been obtained from the region.

Abstract: Acid in situ leaching (AISL) is a subsurface mining approach suitable for low-grade ores which does not generate tailings, and has been adopted widely in uranium mining. However, this technique causes an extremely high concentration of contaminants at post-mining sites and in the surroundings soon after the mining ceases. As a potential AISL remediation strategy, natural attenuation has not been studied in detail. To address this problem, groundwater collected from 26 wells located within, adjacent, upgradient, and downgradient of a post-mining site were chosen to analyze the fate of U(VI), SO42−, δ34S, and δ238U, to reveal the main mechanisms governing the migration and attenuation of the dominant contaminants and the spatio-temporal evolutions of contaminants in the confined aquifer of the post-mining site. The δ238U values vary from −0.07 ‰ to 0.09 ‰ in the post-mining site and from −1.43 ‰ to 0.03 ‰ around the post-mining site. The δ34S values were found to vary from 3.3 ‰ to 6.2 ‰ in the post-mining site and from 6.0 ‰ to 11.0 ‰ around the post-mining site. Detailed analysis suggests that there are large differences between the range of isotopic composition variation and the range of pollutants concentration distribution, and the estimated Rayleigh isotope fractionation factor is 0.9994–0.9997 for uranium and 1.0032–1.0061 for sulfur. The isotope ratio of uranium and sulfur can be used to deduce the migration history of the contaminants and the irreversibility of the natural attenuation process in the anoxic confined aquifer. Combining the isotopic fractionation data for U and S with the concentrations of uranium and sulfate improved the accuracy of understanding of reducing conditions along the flow path. The study also indicated that as long as the geological conditions are favorable for redox reactions, natural attenuation could be used as a cost-effective remediation scheme.