Uranium fate in wetland mesocosms: Effects of plants at two iron loadings with different pH values.

Small-scale continuous flow wetland mesocosms (∼0.8 L) were used to evaluate how plant roots under different iron loadings affect uranium (U) mobility. When significant concentrations of ferrous iron (Fe) were present at circumneutral pH values, U concentrations in root exposed sediments were an order of magnitude greater than concentrations in root excluded sediments. Micro X-ray absorption near-edge structure (µ-XANES) spectroscopy indicated that U was associated with the plant roots primarily as U(VI) or U(V), with limited evidence of U(IV). Micro X-ray fluorescence (µ-XRF) of plant roots suggested that for high iron loading at circumneutral pH, U was co-located with Fe, perhaps co-precipitated with root Fe plaques, while for low iron loading at a pH of ∼4 the correlation between U and Fe was not significant, consistent with previous observations of U associated with organic matter. Quantitative PCR analyses indicated that the root exposed sediments also contained elevated numbers of Geobacter spp., which are likely associated with enhanced iron cycling, but may also reduce mobile U(VI) to less mobile U(IV) species.

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots.

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ∼2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland processes, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.

Uranium immobilization in an iron-rich rhizosphere of a native wetland plant from the Savannah River Site under reducing conditions.

The hypothesis of this study was that iron plaques formed on the roots of wetland plants and their rhizospheres create environmental conditions favorable for iron reducing bacteria that promote the in situ immobilization of uranium. Greenhouse microcosm studies were conducted using native plants (Sparganium americanum) from a wetland located on the Savannah River Site, Aiken, SC. After iron plaques were established during a 73-day period by using an anoxic Fe(II)-rich nutrient solution, a U(VI) amended nutrient solution was added to the system for an additional two months. Compared to plant-free control microcosms, microcosms containing iron plaques successfully stimulated the growth of targeted iron reducing bacteria, Geobacter spp. Their population continuously increased after the introduction of the U(VI) nutrient solution. The reduction of some of the U(VI) to U(IV) by iron reducing bacteria was deduced based on the observations that the aqueous Fe(II) concentrations increased while the U(VI) concentrations decreased. The Fe(II) produced by the iron reducing bacteria was assumed to be reoxidized by the oxygen released from the roots. Advanced spectroscopic analyses revealed that a significant fraction of the U(VI) had been reduced to U(IV) and they were commonly deposited in association with phosphorus on the iron plaque.

Plutonium immobilization and remobilization by soil mineral and organic matter in the far-field of the Savannah River Site, U.S.

To study the effects of natural organic matter (NOM) on Pu sorption, Pu(IV) and (V) were amended at environmentally relevant concentrations (10(-14) M) to two soils of contrasting particulate NOM concentrations collected from the F-Area of the Savannah River Site. More Pu(IV) than (V) was bound to soil colloidal organic matter (COM). A de-ashed humic acid (i.e., metals being removed) scavenged more Pu(IV,V) into its colloidal fraction than the original HA incorporated into its colloidal fraction, and an inverse trend was thus observed for the particulate-fraction-bound Pu for these two types of HAs. However, the overall Pu binding capacity of HA (particulate + colloidal-Pu) decreased after de-ashing. The presence of NOM in the F-Area soil did not enhance Pu fixation to the organic-rich soil when compared to the organic-poor soil or the mineral phase from the same soil source, due to the formation of COM-bound Pu. Most importantly, Pu uptake by organic-rich soil decreased with increasing pH because more NOM in the colloidal size desorbed from the particulate fraction in the elevated pH systems, resulting in greater amounts of Pu associated with the COM fraction. This is in contrast to previous observations with low-NOM sediments or minerals, which showed increased Pu uptake with increasing pH levels. This demonstrates that despite Pu immobilization by NOM, COM can convert Pu into a more mobile form.

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and µ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding.

Examination of disinfection by-product (DBP) formation in source waters: a study using log-transformed differential spectra.

Formation of disinfection by-products (DBPs) in ten drinking source waters located in the United States was examined in this study. DBP generation was interpreted in the context of halogenation-induced changes of log-transformed absorbance spectra of dissolved organic matter (DOM) present in the waters. This approach allows probing the behavior of relatively minor structures that can be highly sensitive towards any process of interest, notably DOM halogenation. This concept was applied to examine effects of chlorination time on the kinetics of chlorine consumption and release of several DBP groups such as total trihalomethanes (THM4, including CHCl3, CHCl2Br, CHClBr2 and CHBr3), haloacetic acids (HAA9, including MCAA, MBAA, DCAA, TCAA, BCAA, DBAA, BDCAA, DBCAA and TBAA), haloacetonitriles (THAN4, including TCAN, DCAN, BCAN and DBAN), haloketones (HK2, including DCP and TCP), chloral hydrate (CH) and chloropicrin (CPN). Two alternative parameters, namely the differential logarithm of DOM absorbance at 350 nm (DLnA350) and change of the spectral slope in the range of wavelengths 325-375 nm (DSlope325-375) were introduced to quantify individual DBP species formed and Cl2 consumption. DLnA350 and DSlope325-375, especially DLnA350 were determined to be more reliable than differential absorbance at 272 nm that was utilized in prior applications of differential spectroscopy to characterize DBP formation. Strong linear relationships between DLnA350 values and concentrations of major groups of and individual DBP species (e.g. THM4, HAA9, HAN4 and CPN were found to exist (mostly, R(2) > 0.95) and the intercept of these correlations with the y-axis was near zero for the examined water sources. Correlations between DLnA350 values and concentrations of CH and HK2 were also strong but they were nonlinear. The slope of the correlations between the concentrations of major groups of DBP species vs -DLnA350 were also well correlated with SUVA254 and LnA350 for all the examined source waters. It indicates that log-transformations of the absorbance spectra of surface water and parameters based on such transformations (e.g., DLnA350 and DSlope325-375) have a potential to provide an alternative reliable approach to monitor the halogenation of DOM and attendant formation of individual DBP species.

Modeling bromide effects on yields and speciation of dihaloacetonitriles formed in chlorinated drinking water.

This study examined effects of bromide on yields and speciation of dihaloacetonitrile (DHAN) species that included dichloro-, bromochloro- and dibromoacetonitriles generated in chlorinated water. Experimental data obtained using two water sources, varying concentrations and characters of Natural Organic Matter (NOM), bromide concentrations, reaction times, chlorine doses, temperatures and pHs were interpreted using a semi-phenomenological model that assumed the presence of three kinetically distinct sites in NOM (denoted as sites S1, S2 and S3) and the occurrence of sequential incorporation of bromine and chlorine into them. One site was found to react very fast with the chlorine and bromine but its contribution in the DHAN generation was very low. The site with the highest contribution to the yield of DHAN (>70%) has the lowest reaction rates. The model introduced dimensionless coefficients (denoted as φ1(DHAN), φ2(DHAN) and φ3(DHAN)) applicable to the initial DHAN generation sites and their monochlorinated and monobrominated products, respectively. These parameters were used to quantify the kinetic preference to bromine incorporation over that of chlorine. Values of these coefficients optimized for DHAN formation were indicative of the strongly preferential incorporation of bromine into the engaged NOM sites. The same set of φ(i)(DHAN) coefficients could be used to model the speciation of DHAN released from their kinetically different precursors. The dimensionless speciation coefficients φ(i)(DHAN) were determined to be site specific and dependent on the NOM content and character as well as pH. The presented model of DHAN formation and speciation can help quantify in more detail the generation of DHAN and provide more insight necessary for further assessment of their potential health effects.

Interaction of bisphenol A with dissolved organic matter in extractive and adsorptive removal processes.

The fate of endocrine disrupting chemicals (EDCs) in natural and engineered systems is complicated due to their interactions with various water constituents. This study investigated the interaction of bisphenol A (BPA) with dissolved organic matter (DOM) and colloids present in surface water and secondary effluent as well as its adsorptive removal by powdered activated carbons. The solid phase micro-extraction (SPME) method followed by thermal desorption and gas chromatography-mass spectrometry (GC-MS) was utilized for determining the distribution of BPA molecules in water. The BPA removal by SPME decreased with the increased DOM content, where the formation of BPA-DOM complexes in an aqueous matrix was responsible for the reduced extraction of BPA. Colloidal particles in water samples sorbed BPA leading to the marked reduction of liquid phase BPA. BPA-DOM complexes had a negative impact on the adsorptive removal of BPA by powered activated carbons. The complex formation was characterized based on Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, along with the calculation of molecular interactions between BPA and functional groups in DOM. It was found that the hydrogen bonding between DOM and BPA would be preferred over aromatic interactions. A pseudo-equilibrium molecular coordination model for the complexation between a BPA molecule and a hydroxyl group of the DOM was developed, which enabled estimation of the maximum sorption site and complex formation constant as well as prediction of organic complexes at various DOM levels.

Strontium and cesium release mechanisms during unsaturated flow through waste-weathered Hanford sediments.

Leaching behavior of Sr and Cs in the vadose zone of Hanford site (Washington) was studied with laboratory-weathered sediments mimicking realistic conditions beneath the leaking radioactive waste storage tanks. Unsaturated column leaching experiments were conducted using background Hanford pore water focused on first 200 pore volumes. The weathered sediments were prepared by 6 months reaction with a synthetic Hanford tank waste leachate containing Sr and Cs (10(-5) and 10(-3) molal representative of LO- and HI-sediment, respectively) as surrogates for (90)Sr and (137)Cs. The mineral composition of the weathered sediments showed that zeolite (chabazite-type) and feldspathoid (sodalite-type) were the major byproducts but different contents depending on the weathering conditions. Reactive transport modeling indicated that Cs leaching was controlled by ion-exchange, while Sr release was affected primarily by dissolution of the secondary minerals. The later release of K, Al, and Si from the HI-column indicated the additional dissolution of a more crystalline mineral (cancrinite-type). A two-site ion-exchange model successfully simulated the Cs release from the LO-column. However, a three-site ion-exchange model was needed for the HI-column. The study implied that the weathering conditions greatly impact the speciation of the secondary minerals and leaching behavior of sequestrated Sr and Cs.

Concentration-dependent mobility, retardation, and speciation of iodine in surface sediment from the Savannah River Site.

Iodine occurs in multiple oxidation states in aquatic systems in the form of organic and inorganic species. This feature leads to complex biogeochemical cycling of stable iodine and its long-lived isotope, (129)I. In this study, we investigated the sorption, transport, and interconversion of iodine species by comparing their mobility in groundwaters at ambient concentrations of iodine species (10(-8) to 10(-7) M) to those at artificially elevated concentrations (78.7 µM), which often are used in laboratory analyses. Results demonstrate that the mobility of iodine species greatly depends on, in addition to the type of species, the iodine concentration used, presumably limited by the number of surface organic carbon binding sites to form covalent bonds. At ambient concentrations, iodide and iodate were significantly retarded (K(d) values as high as 49 mL g(-1)), whereas at concentrations of 78.7 µM, iodide traveled along with the water without retardation. Appreciable amounts of iodide during transport were retained in soils due to iodination of organic carbon, specifically retained by aromatic carbon. At high input concentration of iodate (78.7 µM), iodate was found to be reduced to iodide and subsequently followed the transport behavior of iodide. These experiments underscore the importance of studying iodine geochemistry at ambient concentrations and demonstrate the dynamic nature of their speciation during transport conditions.

Immobilization of 99-technetium (VII) by Fe(II)-goethite and limited reoxidation.

During the nuclear waste vitrification process volatilized (99)Tc will be trapped by melter off-gas scrubbers and then washed out into caustic solutions, and plans are currently being contemplated for the disposal of such secondary waste. Solutions containing pertechnetate [(99)Tc(VII)O(4)(-)] were mixed with precipitating goethite and dissolved Fe(II) to determine if an iron (oxy)hydroxide-based waste form can reduce Tc(VII) and isolate Tc(IV) from oxygen. The results of these experiments demonstrate that Fe(II) with goethite efficiently catalyzes the reduction of technetium in deionized water and complex solutions that mimic the chemical composition of caustic waste scrubber media. Identification of the phases, goethite + magnetite, was performed using XRD, SEM and TEM methods. Analyses of the Tc-bearing solid products by XAFS indicate that all of the Tc(VII) was reduced to Tc(IV) and that the latter is incorporated into goethite or magnetite as octahedral Tc(IV). Batch dissolution experiments, conducted under ambient oxidizing conditions for more than 180 days, demonstrated a very limited release of Tc to solution (2-7 µg Tc/g solid). Incorporation of Tc(IV) into the goethite lattice thus provides significant advantages for limiting reoxidation and curtailing release of Tc disposed in nuclear waste repositories.

The methods of identification, analysis, and removal of endocrine disrupting compounds (EDCs) in water.

The information regarding endocrine disrupting compounds (EDCs) was reviewed, including the definition and characteristics, the recent research trends concerning identification and analytical methods, and the applicable removal processes. EDCs include various types of natural and synthetic chemical compounds presenting the mimicking or inhibition of the reproductive action of the endocrine system in animals and humans. The ubiquitous presence with trace level concentrations and the wide diversity are the reported characteristics of EDCs. Biologically based assays seem to be a promising method for the identification of EDCs. On the other hand, mass-based analytical methods show excellent sensitivity and precision for their quantification. Several extraction techniques for the instrumental analysis have been developed since they are crucial in determining overall analytical performances. Conventional treatment techniques, including coagulation, precipitation, and activated sludge processes, may not be highly effective in removing EDCs, while the advanced treatment options, such as granular activated carbon (GAC), membrane, and advanced oxidation processes (AOPs), have shown satisfactory results. The oxidative degradation of some EDCs was associated with aromatic moieties in their structure. Further studies on EDCs need to be conducted, such as source reduction, limiting exposure to vulnerable populations, treatment or remediation of contaminated sites, and the detailed understanding of transport mechanisms in the environment.

Differential absorbance study of effects of temperature on chlorine consumption and formation of disinfection by-products in chlorinated water.

Effects of chlorine dose, reaction time and temperature on the formation of disinfection by-products (DBPs) and corresponding changes in the absorbance of natural organic matter (NOM) in chlorinated water were examined in this study. Although variations of chlorination parameters, notably those of temperature that was varied from 3 to 35 degrees C, influenced the kinetics of chlorine consumption and DBP release, correlations between chlorine consumption, concentrations of trihalomethanes (THMs), haloacetonitriles (HANs), other DBP species and, on the other hand, intensity of differential absorbance at 272nm remained unaffected. THM and HAN speciation was correlated with the differential absorbance, indicating preferential incorporation of bromine at the initial phases of halogenation that correspond to low DeltaA(272) values. Because the DeltaA(272) parameter is a strong indicator of the formation of DBP species and chlorine decay, optimization of chlorination operations and DBPs control based on this parameter can be beneficial for many water utilities, especially those with pronounced variability of water temperature and residence times.

Examination of NOM chlorination reactions by conventional and stop-flow differential absorbance spectroscopy.

Mechanisms of chlorination of natural organic matter (NOM) in surface water (Lake Washington) were explored via differential spectroscopy. Two types of differential spectra (overall and incremental) were generated for this water chlorinated at pH 7 using varying chlorine doses and reaction times. The differential spectra contain two kinetically and spectroscopically distinct components. One of these components is attributable to functional groups that react rapidly with chlorine, while the other reflects transformations of slowly reacting chromophores that arise following the depletion of the fast chromophores. Small concentrations of disinfection byproducts (DBPs), exemplified in this study by dichloroacetic acid and chloral hydrate, were produced during the initial phase of chlorination, when the fast-reacting chromophores were being consumed. Rather, the release of those DBPs was correlated with the breakdown of the slowly reacting chromophores.

Structural study of the incorporation of heavy metals into solid phase formed during the oxidation of EDTA by permanganate at high pH.

Properties of solid phases formed during the oxidation of EDTA by permanganate in a high-pH, high-ionic strength solution, and the retention of Cu2+, Ni2+, and Zn2+ by them were examined. Morphologically, the solids were agglomerates of particles with sizes <100 nm. X-ray absorption spectroscopy (XAS) analysis indicated that these particles were birnessite. Its precipitation was accompanied by the removal of Zn2+ and Cu2+ released as a result of the breakdown of their complexes with EDTA. However, Ni2+ was not removed from the supernatant. Cu2+ was strongly bound by birnessite and exhibited little mobility in the pH range from 3 to 14. Zn2+ was more mobile, especially at pH > 12. XAS showed that Cu2+ binding sites were located within MnO6 octahedra-comprised sheets that constitute birnessite while Zn2+ was positioned between them.

Investigation of mechanisms of oxidation of EDTA and NTA by permanganate at high pH.

Permanganate has been used for oxidation of nuclear wastes containing chelating agents such as ethylenediaminetetraacetic and nitrilotriacetic acids (EDTA and NTA) to improve separation of radionuclides and heavy metals from the wastes, butthe mechanisms of degradation of these and related organic ligands at high pHs have not been studied. EDTA, NTA, and the model compound ethylenediamine (EN) were found to be readily oxidized by permanganate at pH 12-14. The reduction of permangante was accompanied by formation of unstable manganate and dispersed MnO2 particles, which constituted the final product of permanganate reduction. The yields and speciation of EDTA, NTA, and EN breakdown products were affected by the pH and permanganate dose. Iminodiacetic acid (IDA), oxalate, formate, and ammonia were the predominant EDTA and NTA oxidation products. Mineralization of EDTA, NTA, and EN to CO2 was more significant at pH 12. At pH 14 formation of oxalate and deamination to NH3 were the most important reactions. IDA was released upon the oxidation of both EDTA and NTA, but EDTA oxidation yielded no ethylenediaminediacetic acid (EDDA). The speciation of the reaction products indicated that the ethylene group in EDTA was the preferred attack site in oxidations by alkaline permanganate.

Adsorption of uranyl on gibbsite: A time-resolved laser-induced fluorescence spectroscopy study.

Uranyl adsorbed on gibbsite at pH 4.0-8.0 and ionic strengths (ISs) 0.001-0.4 M (NaClO4) in the absence of carbonate was studied using time-resolved laser-induced fluorescence spectroscopy (TRLIFS) under cryogenic conditions. TRLIFS data showed the presence of several distinct emission components. Their contributions were determined using the evolving factor analysis approach. Four components denoted as species A, B, C, and D were discerned. Each of them was characterized by a characteristic response to pH and IS changes and also by a unique combination of the values of the fundamental transition energy E0,0, vibronic spacing deltaE, and half-width of the vibronic lines deltaW. Species A and B were major contributors to the overall emission. They were mainly affected by the pH and predominated below and above pH 5.0, respectively. In contrast with that, the contribution of species C was noticeable only at IS = 0.001 M, while it was suppressed or absent at high IS values. It was concluded that species A and B are likely to correspond to inner-sphere surface aluminol complexes =AlO-(UO2)+ and =AlO-(UO2)OH degrees, while species C was hypothesized to correspond to electrostatically bound uranyl complexes (predominantly [UO2(OH)3]-).