Joshua D. Landis

Geomorphic controls on groundwater arsenic distribution in the Mekong River Delta, Cambodia

Natural arsenic contamination of groundwater is a severe public health crisis affecting nearly 60 million people in South Asia and Southeast Asia alone. Contamination is spatially heterogeneous and results from the coupled microbial decomposition of organic matter and reductive dissolution of arsenic-bearing iron minerals. Here we demonstrate that elevated arsenic concentrations arise in regions of recent organic matter deposition and thus are controlled by fluvial geomorphic processes. Arsenic contamination is best expressed within recent geomorphic features such as docked islands, scroll bars, and avulsions. Within these features, the deposition of rapidly buried reactive organic matter facilitates microbial iron reduction and arsenic release. Ultimately, the organic matter supply is exhausted and the conditions necessary for soluble arsenic to persist diminish.

Origin and provenance of spherules and magnetic grains at the Younger Dryas boundary

Significance This study ties the spherules recovered in Pennsylvania and New Jersey to an impact in Quebec about 12,900 y ago at the onset of Younger Dryas. Our discovery resulted from an exhaustive search that examined the question of whether there is any evidence of extraterrestrial platinum group metals present in the bulk sediments, magnetic grains, and spherules recovered from the Younger Dryas boundary (YDB). We find that the spherules are likely quenched silicate melts produced following the impact at the YDB. The source of spherule osmium, however, is likely terrestrial and not meteorite derived. One or more bolide impacts are hypothesized to have triggered the Younger Dryas cooling at ∼12.9 ka. In support of this hypothesis, varying peak abundances of magnetic grains with iridium and magnetic microspherules have been reported at the Younger Dryas boundary (YDB). We show that bulk sediment and/or magnetic grains/microspherules collected from the YDB sites in Arizona, Michigan, New Mexico, New Jersey, and Ohio have 187Os/188Os ratios ≥1.0, similar to average upper continental crust (= 1.3), indicating a terrestrial origin of osmium (Os) in these samples. In contrast, bulk sediments from YDB sites in Belgium and Pennsylvania exhibit 187Os/188Os ratios <<1.0 and at face value suggest mixing with extraterrestrial Os with 187Os/188Os of ∼0.13. However, the Os concentration in bulk sample and magnetic grains from Belgium is 2.8 pg/g and 15 pg/g, respectively, much lower than that in average upper continental crust (=31 pg/g), indicating no meteoritic contribution. The YDB site in Pennsylvania is remarkable in yielding 2- to 5-mm diameter spherules containing minerals such as suessite (Fe-Ni silicide) that form at temperatures in excess of 2000 °C. Gross texture, mineralogy, and age of the spherules appear consistent with their formation as ejecta from an impact 12.9 ka ago. The 187Os/188Os ratios of the spherules and their leachates are often low, but Os in these objects is likely terrestrially derived. The rare earth element patterns and Sr and Nd isotopes of the spherules indicate that their source lies in 1.5-Ga Quebecia terrain in the Grenville Province of northeastern North America.

Effects of historical and modern mining on mercury deposition in southeastern Peru.

Both modern anthropogenic emissions of mercury (Hg), primarily from artisanal and small-scale gold mining (ASGM), and preindustrial anthropogenic emissions from mining are thought to have a large impact on present-day atmospheric Hg deposition. We study the spatial distribution of Hg and its depositional history over the past ∼400 years in sediment cores from lakes located regionally proximal (∼90-150 km) to the largest ASGM in Peru and distal (>400 km) to major preindustrial mining centers. Total Hg concentrations in surface sediments from fourteen lakes are typical of remote regions (10-115 ng g(-1)). Hg fluxes in cores from four lakes demonstrate preindustrial Hg deposition in southeastern Peru was spatially variable and at least an order of magnitude lower than previously reported fluxes in lakes located closer to mining centers. Average modern (A.D. 2000-2011) Hg fluxes in these cores are 3.4-6.9 μg m(-2) a(-1), compared to average preindustrial (A.D. 1800-1850) fluxes of 0.8-2.5 μg m(-2) a(-1). Modern Hg fluxes determined from the four lakes are on average 3.3 (±1.5) times greater than their preindustrial fluxes, similar to those determined in other remote lakes around the world. This agreement suggests that Hg emissions from ASGM are likely not significantly deposited in nearby down-wind regions.

Surficial redistribution of fallout 131iodine in a small temperate catchment

Isotopes of iodine play significant environmental roles, including a limiting micronutrient (127I), an acute radiotoxin (131I), and a geochemical tracer (129I). But the cycling of iodine through terrestrial ecosystems is poorly understood, due to its complex environmental chemistry and low natural abundance. To better understand iodine transport and fate in a terrestrial ecosystem, we traced fallout 131iodine throughout a small temperate catchment following contamination by the 11 March 2011 failure of the Fukushima Daiichi nuclear power facility. We find that radioiodine fallout is actively and efficiently scavenged by the soil system, where it is continuously focused to surface soils over a period of weeks following deposition. Mobilization of historic (pre-Fukushima) 137cesium observed concurrently in these soils suggests that the focusing of iodine to surface soils may be biologically mediated. Atmospherically deposited iodine is subsequently redistributed from the soil system via fluvial processes in a manner analogous to that of the particle-reactive tracer 7beryllium, a consequence of the radionuclides’ shared sorption affinity for fine, particulate organic matter. These processes of surficial redistribution create iodine hotspots in the terrestrial environment where fine, particulate organic matter accumulates, and in this manner regulate the delivery of iodine nutrients and toxins alike from small catchments to larger river systems, lakes and estuaries.

Watershed-Scale Impacts from Surface Water Disposal of Oil and Gas Wastewater in Western Pennsylvania

Combining horizontal drilling with high volume hydraulic fracturing has increased extraction of hydrocarbons from low-permeability oil and gas (O&G) formations across the United States; accompanied by increased wastewater production. Surface water discharges of O&G wastewater by centralized waste treatment (CWT) plants pose risks to aquatic and human health. We evaluated the impact of surface water disposal of O&G wastewater from CWT plants upstream of the Conemaugh River Lake (dam controlled reservoir) in western Pennsylvania. Regulatory compliance data were collected to calculate annual contaminant loads (Ba, Cl, total dissolved solids (TDS)) to document historical industrial activity. In this study, two CWT plants 10 and 19 km upstream of a reservoir left geochemical signatures in sediments and porewaters corresponding to peak industrial activity that occurred 5 to 10 years earlier. Sediment cores were sectioned for the collection of paired samples of sediment and porewater, and analyzed for analytes to identify unconventional O&G wastewater disposal. Sediment layers corresponding to the years of maximum O&G wastewater disposal contained higher concentrations of salts, alkaline earth metals, and organic chemicals. Isotopic ratios of 226Ra/228Ra and 87Sr/86Sr identified that peak concentrations of Ra and Sr were likely sourced from wastewaters that originated from the Marcellus Shale formation.

Tungsten Speciation and Solubility in Munitions-Impacted Soils

Considerable questions persist regarding tungsten geochemistry in natural systems, including which forms of tungsten are found in soils and how adsorption regulates dissolved tungsten concentrations. In this study, we examine tungsten speciation and solubility in a series of soils at firing ranges in which tungsten rounds were used. The metallic, mineral, and adsorbed forms of tungsten were characterized using X-ray absorption spectroscopy and X-ray microprobe, and desorption isotherms for tungsten in these soils were used to characterize its solid-solution partitioning behavior. Data revealed the complete and rapid oxidation of tungsten metal to hexavalent tungsten(VI) and the prevalence of adsorbed polymeric tungstates in the soils rather than discrete mineral phases. These polymeric complexes were only weakly retained in the soils, and porewaters in equilibrium with contaminated soils had 850 mg L-1 tungsten, considerably in excess of predicted solubility. We attribute the high solubility and limited adsorption of tungsten to the formation of polyoxometalates such as W12SiO404-, an α-Keggin cluster, in soil solutions. Although more research is needed to confirm which of such polyoxometalates are present in soils, their formation may not only increase the solubility of tungsten but also facilitate its transport and influence its toxicity.