Sediment accumulation and mixing in the Penobscot River and estuary, Maine.

Mercury (Hg) was discharged in the late 1960s into the Penobscot River by the Holtra-Chem chlor-alkali production facility, which was in operation from 1967 to 2000. To assess the transport and distribution of total Hg, and recovery of the river and estuary system from Hg pollution, physical and radiochemical data were assembled from sediment cores collected from 58 of 72 coring stations sampled in 2009. These stations were located throughout the lower Penobscot River, and included four principal study regions, the Penobscot River (PBR), Mendall Marsh (MM), the Orland River (OR), and the Penobscot estuary (ES). To provide the geochronology required to evaluate sedimentary total Hg profiles, 58 of 72 sediment cores were dated using the atmospheric radionuclide tracers 137Cs, 210Pb, and 239,240Pu. Sediment cores were assessed for depths of mixing, and for the determination of sediment accumulation rates using both geochemical (total Hg) and radiochemical data. At most stations, evidence for significant vertical mixing, derived from profiles of 7Be (where possible) and porosity, was restricted to the upper ~1-3cm. Thus, historic profiles of both total Hg and radionuclides were only minimally distorted, allowing a reconstruction of their depositional history. The pulse input tracers 137Cs and 239,240Pu used to assess sediment accumulation rates agreed well, while the steady state tracer 210Pb exhibited weaker agreement, likely due to irregular lateral sediment inputs.

Mercury inputs and redistribution in the Penobscot River and estuary, Maine.

We examined total mercury (Hg) distributions in sediments from the Penobscot River and estuary, Maine, a site of extensive Hg releases from HoltraChem (1967-2000). Our objectives were to quantify: (1) bottom sediment Hg inventories (upper ~1m; 50-100 y); (2) sediment accumulation rates; and (3) contemporary Hg fluxes to bottom sediments; by sampling the Penobscot River (PBR), Mendall Marsh (MM), the Orland River (OR) and the Penobscot estuary (ES). Hg was rapidly distributed here, and the cumulative total (9.28 metric tons) associated with sediments system-wide was within the range released (6-12 metric tons). Evidence of sediment/Hg remobilization was observed in cores primarily from the PBR, and to a lesser extent the ES, whereas cores from MM, most of the OR, the ES, and half from the PBR exhibited sharp peaks in Hg concentrations at depth, followed by gradual decreases towards the surface. Based on background PBR sediment Hg concentrations (100ngg-1), "elevated" (300ngg-1), or "highly elevated" (600ngg-1) Hg concentrations in sediments, and resulting inventories, we assessed impact levels ("elevated"≥270, or "highly elevated"≥540mgm-2). 71% of PBR stations had "elevated", and 29% had "highly elevated" Hg inventories; 45% of MM stations had "elevated", and 27% had "highly elevated" inventories; 80% of OR stations had "elevated" inventories only; and 17% of ES stations had "elevated" inventories only. Most "highly elevated" stations were located within 8km of HoltraChem, in MM, in the PBR, and in the OR. Near-surface sediments in the OR, PBR and MM were all "highly elevated", while those in the ES were "elevated", on average. Mean Hg fluxes to bottom sediments were greatest in the OR (554), followed by the PBR (469), then MM (452), and finally the ES (204ngcm-2y-1).

Recent advances in the detection of specific natural organic compounds as carriers for radionuclides in soil and water environments, with examples of radioiodine and plutonium.

Among the key environmental factors influencing the fate and transport of radionuclides in the environment is natural organic matter (NOM). While this has been known for decades, there still remains great uncertainty in predicting NOM-radionuclide interactions because of lack of understanding of radionuclide interactions with the specific organic moieties within NOM. Furthermore, radionuclide-NOM studies conducted using modelled organic compounds or elevated radionuclide concentrations provide compromised information related to true environmental conditions. Thus, sensitive techniques are required not only for the detection of radionuclides, and their different species, at ambient and/or far-field concentrations, but also for potential trace organic compounds that are chemically binding these radionuclides. GC-MS and AMS techniques developed in our lab are reviewed here that aim to assess how two radionuclides, iodine and plutonium, form strong bonds with NOM by entirely different mechanisms; iodine tends to bind to aromatic functionalities, whereas plutonium binds to N-containing hydroxamate siderophores at ambient concentrations. While low-level measurements are a prerequisite for assessing iodine and plutonium migration at nuclear waste sites and as environmental tracers, it is necessary to determine their in-situ speciation, which ultimately controls their mobility and transport in natural environments. More importantly, advanced molecular-level instrumentation (e.g., nuclear magnetic resonance (NMR) and Fourier-transform ion cyclotron resonance coupled with electrospray ionization (ESI-FTICRMS) were applied to resolve either directly or indirectly the molecular environments in which the radionuclides are associated with the NOM.

Radioiodine Biogeochemistry and Prevalence in Groundwater.

129I is commonly either the top or among the top risk drivers, along with 99Tc, at radiological waste disposal sites and contaminated groundwater sites where nuclear material fabrication or reprocessing has occurred. The risk stems largely from 129I having a high toxicity, a high bioaccumulation factor (90% of all the body's iodine concentrates in the thyroid), a high inventory at source terms (due to its high fission yield), an extremely long half-life (16M years), and rapid mobility in the subsurface environment. Another important reason that 129I is a key risk driver is that there is uncertainty regarding its biogeochemical fate and transport in the environment. We typically can define 129I mass balance and flux at sites, but cannot predict accurately its response to changes in the environment. As a consequence of some of these characteristics, 129I has a very low drinking water standard, which is set at 1 pCi/L, the lowest of all radionuclides in the Federal Register. Recently, significant advancements have been made in detecting iodine species at ambient groundwater concentrations, defining the nature of the organic matter and iodine bond, and quantifying the role of naturally occurring sediment microbes to promote iodine oxidation and reduction. These recent studies have led to a more mechanistic understanding of radioiodine biogeochemistry. The objective of this review is to describe these advances and to provide a state of the science of radioiodine biogeochemistry relevant to its fate and transport in the terrestrial environment and provide information useful for making decisions regarding the stewardship and remediation of 129I contaminated sites. As part of this review, knowledge gaps were identified that would significantly advance the goals of basic and applied research programs for accelerating 129I environmental remediation and reducing uncertainty associated with disposal of 129I waste. Together the information gained from addressing these knowledge gaps will not alter the observation that 129I is primarily mobile, but it will likely permit demonstration that the entire 129I pool in the source term is not moving at the same rate and some may be tightly bound to the sediment, thereby smearing the modeled 129I peak and reducing maximum calculated risk.

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.

A novel approach for the simultaneous determination of iodide, iodate and organo-iodide for 127I and 129I in environmental samples using gas chromatography-mass spectrometry.

In aquatic environments, iodine mainly exists as iodide, iodate, and organic iodine. The high mobility of iodine in aquatic systems has led to (129)I contamination problems at sites where nuclear fuel has been reprocessed, such as the F-area of Savannah River Site. In order to assess the distribution of (129)I and stable (127)I in environmental systems, a sensitive and rapid method was developed which enables determination of isotopic ratios of speciated iodine. Iodide concentrations were quantified using gas chromatography-mass spectrometry (GC-MS) after derivatization to 4-iodo-N,N-dimethylaniline. Iodate concentrations were quantified by measuring the difference of iodide concentrations in the solution before and after reduction by Na(2)S(2)O(5). Total iodine, including inorganic and organic iodine, was determined after conversion to iodate by combustion at 900 °C. Organo-iodine was calculated as the difference between the total iodine and total inorganic iodine (iodide and iodate). The detection limits of iodide-127 and iodate-127 were 0.34 nM and 1.11 nM, respectively, whereas the detection limits for both iodide-129 and iodate-129 was 0.08 nM (i.e., 2pCi (129)I/L). This method was successfully applied to water samples from the contaminated Savannah River Site, South Carolina, and more pristine Galveston Bay, Texas.

Organo-iodine formation in soils and aquifer sediments at ambient concentrations.

One of the key risk drivers at radioactive waste disposal facilities is radioiodine, especially 129I. As iodine mobility varies greatly with iodine speciation, experiments with 129I-contaminated aquifer sediments from the Savannah River Site located in Aiken, SC, were carried out to test iodine interactions with soils and aquifer sediments. Using tracer 125I- and stable 127I- additions, it was shown that such interactions were highly dependent on I- concentrations added to sediment suspensions, contact time with the sediment, and organic carbon (OC) content, resulting in an empirical particle-water partition coefficient (Kd) that was an inverse power function of the added I- concentration. However, Kd values of organically bound 127I were 3 orders of magnitude higher than those determined after 1-2 weeks of tracer equilibration, approaching those of OC. Under ambient conditions, organo-iodine (OI) was a major fraction (67%) of the total iodine in the dissolved phase and by implication of the particulate phase. As the total concentration of amended I- increased, the fraction of detectable dissolved OI decreased. This trend, attributed to OC becoming the limiting factor in the aquifer sediment explains why at elevated I-concentrations OI is often not detected.

Colloidal cutin-like substances cross-linked to siderophore decomposition products mobilizing plutonium from contaminated soils.

Relatively recently, inorganic colloids have been invoked to reconcile the apparent contradictions between expectations based on classical dissolved-phase Pu transport and field observations of "enhanced" Pu mobility (Kersting et al. Nature 1999, 397, 56-59). A new paradigm for Pu transport is mobilization and transport via biologically produced ligands. This study for the first time reports a new finding of Pu being transported, at sub-pM concentrations, by a cutin-like natural substance containing siderophore-like moieties and virtually all mobile Pu. Most likely, Pu is complexed by chelating groups derived from siderophores that are covalently bound to a backbone of cutin-derived soil degradation products, thus revealing the history of initial exposure to Pu. Features such as amphiphilicity and small size make this macromolecule an ideal collector for actinides and other metals and a vector for their dispersal. Cross-linking to the hydrophobic domains (e.g., by polysaccharides) gives this macromolecule high mobility and a means of enhancing Pu transport. This finding provides a new mechanism for Pu transport through environmental systems that would not have been predicted by Pu transport models.

Invariance of isotope ratios of lithogenic radionuclides: more evidence for their use as sediment source tracers.

Activities of radionuclides in the 238U (230Th, 226Ra, 210Pb) and 232Th (232Th, 228Th, 228Ra) decay series were determined in sediments from an east Texas watershed and examined with isotope ratios and compared to particulate organic carbon (POC), % fines (<63 microm) and total concentrations of Al, Fe and Mn. The objective was to elucidate the presence or absence of relationships affecting the effectiveness of these radionuclides in modeling sediment transport. Strong positive correlations were observed between radionuclides and Mn (Th) and % fines (Ra and Th). Isotope ratios effectively reduce these influences, supporting the contention that isotope ratios offset extrinsic variability in terrestrial sediments. Strong associations of 210Pbxs (excess 210Pb) and 226Ra/230Th with POC agree with data from marine and terrestrial settings, indicating that the role of POC in isotope fractionation, transport and sequestration merits further investigation.

Historical contamination of PAHs, PCBs, DDTs, and heavy metals in Mississippi River Delta, Galveston Bay and Tampa Bay sediment cores.

Profiles of trace contaminant concentrations in sediment columns can be a natural archive from which pollutant inputs into coastal areas can be reconstructed. Reconstruction of historical inputs of anthropogenic chemicals is important for improving management strategies and evaluating the success of recent pollution controls measures. Here we report a reconstruction of historical contamination into three coastal sites along the US Gulf Coast: Mississippi River Delta, Galveston Bay and Tampa Bay. Within the watersheds of these areas are extensive agricultural lands as well as more than 50% of the chemical and refinery capacity of the USA. Despite this pollution potential, relatively low concentrations of trace metals and trace organic contaminants were found in one core from each of the three sites. Concentrations and fluxes of most trace metals found in surface sediments at these three sites, when normalized to Al, are typical for uncontaminated Gulf Coast sediments. Hydrophobic trace organic contaminants that are anthropogenic (polycyclic aromatic hydrocarbons, DDTs, and polychlorinated biphenyls) are found in sediments from all locations. The presence in surface sediments from the Mississippi River Delta of low level trace contaminants such as DDTs, which were banned in the early 1970's, indicate that they are still washed out from cultivated soils. It appears that the DDTs profile in that sediment core was produced by a combination of erosion processes of riverine and other sedimentary deposits during floods. Most of the pollutant profiles indicate that present-day conditions have improved from the more contaminated conditions in the 1950-1970's, before the advent of the Clean Water Act.

Effect of dissolved organic matter on the uptake of trace metals by American oysters.

To examine the effects of dissolved organic matter on metal bioavailability, uptake of trace metals (Cd, Co, Hg, Cr, Ag, Zn) by American oysters (Crassostrea virginica) was compared between treatments with different dissolved organic carbon (DOC) concentrations and contrasting low molecular weight (LMW, 1 kDa) and high molecular weight (HMW, 1 kDa-0.2 micron) DOC fractions, using radiotracer techniques and short-term exposure experiments. Uptake rate constants (mL g-1 h-1) of metals, in general, increased with increasing DOC concentrations, with an initial decrease at lower DOC concentrations. Oyster dry weight concentration factors (DCF, mL g-1), determined at the end of exposure experiments (8 h), also increased for Cd, Co, Cr, Ag, and Zn, but decreased for Hg, with increasing DOC concentrations. Changes of metal uptake rate constants and DCF values with DOC concentration suggest that metal uptake pathways by American oysters vary from predominantly uptake (by diffusion of neutral) of free ionic, inorganically complexed, and LMW organic ligand complexed metals at very low DOC concentration to direct ingestion and digestion of HMW or colloidally complexed metals at higher DOC concentrations. Measured partition coefficients (Kc) between dissolved and colloidal phases were comparable between metals, ranging from 10(5.12) to 10(5.75) mL g-1. However, DCF values and uptake rate constants differed considerably between metals, with the highest DCF values and uptake rate constants found for B-type metals, e.g., Ag, Hg, Zn, and Cd, and the lowest ones for several intermediate-type metals (e.g., Co, Cr). Metal types and thus the interaction of metals with organic ligands, such as strong complexation of B-type metals with S-containing organic ligands, may play an important role in the bioavailability and toxicity of metals to aquatic organisms. Differences in metal uptake in contrasting LMW and HMW DOC treatments suggest a generally depressed bioavailability of colloidally complexed metals at low DOC concentration (0.5 ppm) but a generally enhanced uptake at higher DOC concentrations.

Box coring artifacts in sediments affected by a waste water outfall.

Variations in porosity of surface sediments are often the major cause of sediment loss during gravity and box coring. Sediments with a high content of organic matter usually have higher porosity, and thus, lower resistance (strain) towards mechanical disturbance. Here, we demonstrate that box coring artifacts (i.e. sediment loss and core shortening) can be produced in sediments from the Palos Verdes (PV) shelf, which in the past had received relatively high loads of organic carbon (OC) enriched particulate matter originating from the Whites Point outfall that had created a high porosity layer at depth. This has been overlooked as a possibility for obtaining low estimates of sediment and pollutant accumulation rates. Since any such sediment loss during coring can lead to serious underestimates of sedimentation rates, our results here may have important implications for any attempts at reconstructing pollutant fluxes and histories in these coastal marine sediments.

Ultrafiltration behavior of major ions (Na, Ca, Mg, F, Cl, and SO4) in natural waters.

Aquatic colloids, including macromolecules and microparticles, with sizes ranging between 1 nm to 1 micron, play important roles in the mobility and bioavailability of heavy metals and other contaminants in natural waters. Cross-flow ultrafiltration has become one of the most commonly used techniques for isolating aquatic colloids. However, the ultrafiltration behavior of chemical species remains poorly understood. We report here the permeation behavior of major ions (Na, Ca, Mg, F, Cl, and SO4) in natural waters during ultrafiltration using an Amicon 1 kDa ultrafiltration membrane (S10N1). Water samples across a salinity gradient of 0-20@1000 were collected from the Trinity River and Galveston Bay. The permeation behavior of major ions was well predicted by a permeation model, resulting in a constant permeation coefficient for each ion. The value of the model-derived permeation coefficient (Pc) was 0.99 for Na, 0.97 for Cl, and 0.95 for F, respectively, in Trinity River waters. Values of Pc close to 1 indicate that retention of Na, Cl, and F by the 1 kDa membrane during ultrafiltration was indeed minimal (< 1-5%). In contrast, significant (14-36%) retention was observed for SO4, Ca, and Mg in Trinity River waters, with a Pc value of 0.64, 0.82, and 0.86 for SO4, Ca and Mg, respectively. However, these retained major ions can further permeate through the 1 kDa membrane during diafiltration with ultrapure water. The selective retention of major ions during ultrafiltration may have important implications for the measurement of chemical and physical speciation of trace elements when using cross-flow ultrafiltration membranes to separate colloidal species from natural waters. Our results also demonstrate that the percent retention of major ions during ultrafiltration decreases with increasing salinity or ionic strength. This retention is largely attributed to electrostatic repulsion by the negatively charged cartridge membrane.

129I and 127I transport in the Mississippi River.

The watershed processes which control 129I/127I ratios, 129I and 127I concentrations, and speciation of iodine isotopes were studied through an investigation into the variability of these parameters in the Mississippi River near New Orleans, undertaken in 1996-1998. Analyses of suspended particulate matter (SPM) revealed a greater percent association of 127I than of 129I, resulting in lower 129I/127I ratios in SPM than in surrounding water. Furthermore, crossflow ultrafiltration showed that organo-iodine was the dominant form for both isotopes, with 70-85% of these isotopes found in the 0.45 microm filter-passing fraction associated with colloidal macromolecular organic matter. 129I showed a weak correlation, 127I no correlation, and 129I/127I ratios a strong inverse correlation with river flow rate. Inverse correlations between 129I/127I ratios and river flow rates can be best explained by rainwater and evapotranspiration dominated ratios at base flow and a lowering of the isotope ratios during higher flow due to extra inputs of 127I from soil weathering. We postulate that different equilibration times for 127I and 129I as well as for bomb-produced 129I and reprocessing-produced 129I are responsible for these fractionation effects and the differential mobilities of these isotopes in the Mississippi River watershed.

Sensitive determination of dissolved sulfide in estuarine water by solid-phase extraction and high-performance liquid chromatography of methylene blue.

A sensitive method involving solid-phase extraction and HPLC analysis of methylene blue has been developed to measure nanomolar levels of dissolved sulfide in oxic surface waters. The procedure included 1) a preconcentration step, in which methylene blue generated from sulfide reaction with n,n-dimethyl-p-phenylenediamine in acidic conditions in the presence of ferric ion was absorbed onto Waters tC18 cartridge; and 2) a determination step, in which methylene blue was separated by HPLC in a gradient elution to minimize natural organic matter interference and detected by absorbance. The concentrations of the dissolved sulfide, quantified by standard addition, were about 2.1-4.7 nM in oxic surface waters from Galveston Bay, Texas.