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A combination of synchrotron-based elemental analysis and acute toxicity tests was used to investigate the biodistribution and adverse effects in Daphnia magna exposed to uranium nanoparticle (UNP, 3-5 nm) suspensions or to uranium reference (U ref ) solutions. Speciation analysis revealed similar size distributions between exposures, and toxicity tests showed comparable acute effects (UNP LC 50 : 402 μg L -1 [336-484], U ref LC 50 : 268 μg L -1 [229-315]). However, the uranium body burden was 3- to 5-fold greater in UNP-exposed daphnids, and analysis of survival as a function of body burden revealed a ∼5-fold higher specific toxicity from the U ref exposure. High-resolution X-ray fluorescence elemental maps of intact, whole daphnids from sublethal, acute exposures of both treatments revealed high uranium accumulation onto the gills (epipodites) as well as within the hepatic ceca and the intestinal lumen. Uranium uptake into the hemolymph circulatory system was inferred from signals observed in organs such as the heart and the maxillary gland. The substantial uptake in the maxillary gland and the associated nephridium suggests that these organs play a role in uranium removal from the hemolymph and subsequent excretion. Uranium was also observed associated with the embryos and the remnants of the chorion, suggesting uptake in the offspring. The identification of target organs and tissues is of major importance to the understanding of uranium and UNP toxicity and exposure characterization that should ultimately contribute to reducing uncertainties in related environmental impact and risk assessments.

Micro- and nanoscopic X-ray techniques were used to investigate the relationship between uranium (U) tissue distributions and adverse effects to the digestive tract of aquatic model organism Daphnia magna following uranium nanoparticle (UNP) exposure. X-ray absorption computed tomography measurements of intact daphnids exposed to sublethal concentrations of UNPs or a U reference solution (U Ref ) showed adverse morphological changes to the midgut and the hepatic ceca. Histological analyses of exposed organisms revealed a high proportion of abnormal and irregularly shaped intestinal epithelial cells. Disruption of the hepatic ceca and midgut epithelial tissues implied digestive functions and intestinal barriers were compromised. Synchrotron-based micro X-ray fluorescence (XRF) elemental mapping identified U co-localized with morphological changes, with substantial accumulation of U in the lumen as well as in the epithelial tissues. Utilizing high-resolution nano-XRF, 400-1000 nm sized U particulates could be identified throughout the midgut and within hepatic ceca cells, coinciding with tissue damages. The results highlight disruption of intestinal function as an important mode of action of acute U toxicity in D. magna and that midgut epithelial cells as well as the hepatic ceca are key target organs.

Uranyl phosphate minerals represent an important secondary source of uranium release at contaminated sites. In flow-through column experiments with background porewater (BPW) of typical freshwater aquifer composition (pH 7.0, ∼0.2 mM total carbonate (TC)), dissolution of K-ankoleite (KUO 2 PO 4 ·3H 2 O), Na-autunite (NaUO 2 PO 4 ·3H 2 O), and Ca-autunite (Ca(UO 2 ) 2 (PO 4 ) 2 ·6H 2 O) was controlled by mineral solubility at steady-state U release. Effluent concentrations indicated exchange with BPW cations, and postreaction characterization showed alteration of the initial mineral composition, changes in structure (decreased crystallinity, increased disorder, and distortion of U-P mineral sheets) and possible neoformation of phases of similar structure. Increasing the BPW pH and TC to 8.1-8.2 and 2.2-3.7 mM, respectively, resulted in mineral undersaturation and produced ca. 2 orders-of-magnitude higher U and P release without reaching steady state. Minerals incorporated less BPW cations into their structures compared to low carbonate BPW experiments but showed structural disorder and distortion. Faster dissolution rates were attributed to the formation of binary and ternary uranyl carbonate complexes that accelerate the rate-determining step of uranyl detachment from the uranyl-phosphate layered structure. Calculated dissolution rates (log R s between -8.95 and -10.32 mol m -2 s -1 ), accounting for reaction and transport in porous media, were similar to dissolution rates of other classes of uranyl minerals. In undersaturated solutions, dissolution rates for uranyl phosphate, oxyhydroxide, and silicate minerals can be predicted within 1-2 orders-of-magnitude from pH ∼5-10 on the basis of pH/carbonate concentration.

A method was developed for direct measurements of 226 Ra in water samples with triple quadrupole inductively coupled plasma mass spectrometry (ICP-QQQ). The limit of detection was 0.42 pg L -1 226 Ra (15 mBq L -1 , 0.42 pCi L -1 ), which is compliant with the specifications for methods used for routine analysis of drinking water quality according to European and U.S. regulations. The use of N 2 O as reaction gas ensured that no separation before analysis was necessary. Water samples with high total dissolved solids (conductivity >100 mS cm -1 ) were also successfully analyzed after a simple dilution, yet the associated detection limit was higher (17 pg L -1 , 0.61 Bq L -1 , 16 pCi L -1 ). 226 Ra content in soil and rock samples was determined with the same method after acid (HNO 3 + H 3 PO 4 ) digestion and dilution, resulting in a limit of detection of 0.75 ng kg -1 (27 Bq kg -1 , 0.74 nCi L -1 ). Analysis of water samples was achieved within 2 min on a running instrument, while the preparation and analysis of 15 geological samples can be completed in 3 h. The key advantages of this direct analysis method are short preparation time, low labor intensity, low sample input (2 mL for water samples, 0.2 g for geological material), high sample throughput (2 min sample to sample, >150 samples measured in 8 h), and use of standard ICP-QQQ hardware. Overall, the proposed method offers a new opportunity for measuring a large number of samples with minimal effort and, in turn, for improving emergency preparedness, environmental monitoring, and data collection for environmental modeling.

The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford's cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO 2 )(PO 4 )·3H 2 O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K 2 (UO 2 ) 6 O 4 (OH) 6 ·7H 2 O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10 -12 mol g -1 s -1 . In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10 -10 mol g -1 s -1 . The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.