Dynamic Inhibition of Calcite Dissolution in Flowing Acidic Pb2+ Solutions.

Reactions of mineral surfaces with dissolved metal ions at far-from-equilibrium conditions can deviate significantly from those in near-equilibrium systems due to steep concentration gradients, ion-surface interactions, and reactant transport effects that can lead to emergent behavior. We explored the effect of dissolved Pb2+ on the dissolution rate and topographic evolution of calcite (104) surfaces under far-from-equilibrium acidic conditions (pH 3.7) in a confined single-pass laminar-flow geometry. Operando measurements by digital holographic microscopy were conducted over a range of Pb2+ concentrations ([Pb2+] = 0 to 5 × 10-2 M) and flow velocities (v = 1.67-53.3 mm s-1). Calcite (104) surface dissolution rates decreased with increasing [Pb2+]. The inhibition of dissolution and the emergence of unique topographic features, including micropyramids, variable etch pit shapes, and larger scale topographic patterns, became increasingly apparent at [Pb2+] ≥ 5 × 10-3 M. A better understanding of such dynamic reactivity could be crucial for constructing accurate models of geochemical transport in aqueous carbonate systems.

Carbon and Nitrogen Isotope Fractionations During Biotic and Abiotic Transformations of 2,4-Dinitroanisole (DNAN).

2,4-Dinitroanisole (DNAN) is a main constituent in various new insensitive munition formulations. Although DNAN is susceptible to biotic and abiotic transformations, in many environmental instances, transformation mechanisms are difficult to resolve, distinguish, or apportion on the basis solely of analysis of concentrations. We used compound-specific isotope analysis (CSIA) to investigate the characteristic isotope fractionations of the biotic (by three microbial consortia and three pure cultures) and abiotic (by 9,10-anthrahydroquinone-2-sulfonic acid [AHQS]) transformations of DNAN. The correlations of isotope enrichment factors (ΛN/C) for biotic transformations had a range of values from 4.93 ± 0.53 to 12.19 ± 1.23, which is entirely distinct from ΛN/C values reported previously for alkaline hydrolysis, enzymatic hydrolysis, reduction by Fe2+-bearing minerals and iron-oxide-bound Fe2+, and UV-driven phototransformations. The ΛN/C value associated with the abiotic reduction by AHQS was 38.76 ± 2.23, within the range of previously reported values for DNAN reduction by Fe2+-bearing minerals and iron-oxide-bound Fe2+, albeit the mean ΛN/C was lower. These results enhance the database of isotope effects accompanying DNAN transformations under environmentally relevant conditions, allowing better evaluation of the extents of biotic and abiotic transformations of DNAN that occur in soils, groundwaters, surface waters, and the marine environment.

Aqueous Geochemical Controls on the Sestonic Microbial Community in Lakes Michigan and Superior.

Despite being the largest freshwater lake system in the world, relatively little is known about the sestonic microbial community structure in the Laurentian Great Lakes. The goal of this research was to better understand this ecosystem using high-throughput sequencing of microbial communities as a function of water depth at six locations in the westernmost Great Lakes of Superior and Michigan. The water column was characterized by gradients in temperature, dissolved oxygen (DO), pH, and other physicochemical parameters with depth. Mean nitrate concentrations were 32 µmol/L, with only slight variation within and between the lakes, and with depth. Mean available phosphorus was 0.07 µmol/L, resulting in relatively large N:P ratios (97:1) indicative of P limitation. Abundances of the phyla Actinobacteria, Bacteroidetes, Cyanobacteria, Thaumarchaeota, and Verrucomicrobia differed significantly among the Lakes. Candidatus Nitrosopumilus was present in greater abundance in Lake Superior compared to Lake Michigan, suggesting the importance of ammonia-oxidating archaea in water column N cycling in Lake Superior. The Shannon diversity index was negatively correlated with pH, temperature, and salinity, and positively correlated with DO, latitude, and N2 saturation. Results of this study suggest that DO, pH, temperature, and salinity were major drivers shaping the community composition in the Great Lakes.

Stormwater drives seasonal geochemical processes beneath an infiltration basin.

Deicing salt is an important component of road safety during winter storms. Stormwater infiltration best management practices aim to prevent the salt from polluting streams and waterways, but this may shift pollutants to groundwater resources. In response to limited field studies investigating groundwater quality impacts caused by input of salt from stormwater infiltration best management practices, we monitored water levels and quality of groundwater at various depths in an unconfined aquifer around a stormwater infiltration basin using in situ sensors coupled with grab sampling. Our observations revealed differences in groundwater chemistry with depth in the aquifer and processes that were driven by the seasonal changes in the chemistry of stormwater (salt-impacted in winter and fresh in non-winter) recharging the aquifer. Water-matrix interactions in the vadose zone beneath the basin affected the transport of sodium (Na) into groundwater following non-winter recharge. Sodium movement through the aquifer was delayed relative to chloride (Cl), indicating a longer residence time of Na in the vadose zone. Radium (Ra) concentrations were correlated with Cl concentrations, suggesting salt-impacted recharge caused desorption of Ra into groundwater because of increased salinity. Stormwater-influenced groundwater followed a preferential flow path due to heterogeneity of the aquifer materials, and water chemistry varied with time and location along the flow path. These results highlight the importance of well screen length, placement and depth, and frequency of observations when designing a monitoring network.

Position-specific isotope effects during alkaline hydrolysis of 2,4-dinitroanisole resolved by compound-specific isotope analysis, 13C NMR, and density-functional theory.

Compound-specific isotope analysis (CSIA), position-specific isotope analysis (PSIA), and computational modeling (e.g., quantum mechanical models; reactive-transport models) are increasingly being used to monitor and predict biotic and abiotic transformations of organic contaminants in the field. However, identifying the isotope effect(s) associated with a specific transformation remains challenging in many cases. Here, we describe and interpret the position-specific isotope effects of C and N associated with a SN2Ar reaction mechanism by a combination of CSIA and PSIA using quantitative 13C nuclear magnetic resonance spectrometry, and density-functional theory, using 2,4-dinitroanisole (DNAN) as a model compound. The position-specific 13C enrichment factor of O-C1 bond at the methoxy group attachment site (εC1) was found to be approximately -41‰, a diagnostic value for transformation of DNAN to its reaction products 2,4-dinitrophenol and methanol. Theoretical kinetic isotope effects calculated for DNAN isotopologues agreed well with the position-specific isotope effects measured by CSIA and PSIA. This combination of measurements and theoretical predictions demonstrates a useful tool for evaluating degradation efficiencies and/or mechanisms of organic contaminants and may promote new and improved applications of isotope analysis in laboratory and field investigations.

Photocatalytic mechanisms of 2,4-dinitroanisole degradation in water deciphered by C and N dual-element isotope fractionation.

In surface water environments, photodegradation may be an important process for the natural attenuation of 2,4-dinitroanisole (DNAN). Understanding the photolysis and photocatalysis mechanisms of DNAN is difficult because the photosensitivity of nitro groups and the behavior of DNAN as a potential photosensitizer are unclear in aqueous solutions. Here, we investigate the degradation mechanisms of DNAN under UV-A (λ ~ 350 nm) and UV-C (λ ~ 254 nm) irradiation in a photolysis reactor where aqueous solution was continuously recycled through a UV-irradiated volume from a non-irradiated external reservoir. By tracking C and N isotopic fractionation in DNAN and its reaction products, we observed normal 13C fractionation (εC = -3.34‰) and inverse 15N fractionation (εN = +12.30‰) under UV-A (λ ~ 350 nm) irradiation, in contrast to inverse 13C fractionation (εC = +1.45‰) and normal 15N fractionation (εN = -3.79‰) under UV-C (λ ~ 254 nm) irradiation. These results indicate that DNAN can act as a photosensitizer and may follow a product-to-parent reversion mechanism in surface water environments. The data also indicate that photocatalytic degradation of DNAN in aqueous systems can be monitored via C and N stable isotope analysis.

Isotopic composition of natural and synthetic chlorate (δ18O, Δ17O, δ37Cl, 36Cl/Cl): Methods and initial results.

Natural chlorate (ClO3-) is widely distributed in terrestrial and extraterrestrial environments. To improve understanding of the origins and distribution of ClO3-, we developed and tested methods to determine the multi-dimensional isotopic compositions (δ18O, Δ17O, δ37Cl, 36Cl/Cl) of ClO3- and then applied the methods to samples of natural nitrate-rich caliche-type salt deposits in the Atacama Desert, Chile, and Death Valley, USA. Tests with reagents and artificial mixed samples indicate stable-isotope ratios were minimally affected by the purification processes. Chlorate extracted from Atacama samples had δ18O = +7.0 to +11.1‰, Δ17O = +5.7 to +6.4‰, δ37Cl = -1.4 to +1.3‰, and 36Cl/Cl = 48 × 10-15 to 104 × 10-15. Chlorate from Death Valley samples had δ18O = -6.9 to +1.6‰, Δ17O = +0.4 to +2.6‰, δ37Cl = +0.8 to +1.0‰, and 36Cl/Cl = 14 × 10-15 to 44 × 10-15. Positive Δ17O values of natural ClO3- indicate that its production involved reaction with O3, while its Cl isotopic composition is consistent with a tropospheric or near-surface source of Cl. The Δ17O and δ18O values of natural ClO3- are positively correlated, as are those of ClO4- and NO3- from the same localities, possibly indicating variation in the relative contributions of O3 as a source of O in the formation of the oxyanions. Additional isotopic analyses of ClO3- could provide stronger constraints on its production mechanisms and/or post-formational alterations, with applications for environmental forensics, global biogeochemical cycling of Cl, and the origins of oxyanions detected on Mars.

Elevated radium levels in Nubian Aquifer groundwater of Northeastern Africa.

The Nubian Sandstone Aquifer System in Northeast Africa and the Middle East is a huge water resource of inestimable value to the population. However, natural radioactivity impairs groundwater quality throughout the aquifer posing a radiological health risk to millions of people. Here we present measurements of radium isotopes in Nubian Aquifer groundwater from population centers in the Western Desert of Egypt. Groundwater has 226Ra and 228Ra activities ranging from 0.01 to 2.11 and 0.03 to 2.31 Bq/L, respectively. Most activities (combined 226Ra + 228Ra) exceed U.S. EPA drinking water standards. The estimated annual radiation doses associated with ingestion of water having the highest measured Ra activities are up to 138 and 14 times the WHO-recommended maxima for infants and adults, respectively. Dissolved Ra activities are positively correlated with barium and negatively correlated with sulfate, while barite is approximately saturated. In contrast, Ra is uncorrelated with salinity. These observations indicate the dominant geochemical mechanisms controlling dissolved Ra activity may be barite precipitation and sulfate reduction, along with input from alpha-recoil and dissolution of aquifer minerals and loss by radioactive decay. Radium mitigation measures should be adopted for water quality management where Nubian Aquifer groundwater is produced for agricultural and domestic consumption.

Biotransformation of the insensitive munition constituents 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4-dinitroanisole (DNAN) by aerobic methane-oxidizing consortia and pure cultures.

We present the first report of biotransformation of 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4-dinitroanisole (DNAN), replacements for the explosives 1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT), respectively, by methane-oxidizing cultures under aerobic conditions. Two consortia, dominated by Methylosinus spp., degraded both compounds with transient production of reduced NTO products, and non-stoichiometric production of reduced DNAN products. No release of inorganic nitrogen was observed with either compound, indicating that NTO and DNAN may be utilized as nitrogen sources by these consortia. The pure culture Methylosinus trichosporium OB3b also degraded both compounds. Degradation was observed in the presence of acetylene (a known inhibitor of methane monooxygenase; MMO) when methanol was supplied, indicating that MMO was not involved. Furthermore, studies with purified soluble MMO (sMMO) from OB3b indicated that neither compound was a substrate for sMMO. Degradation was inhibited by 2-iodosobenzoic acid, but not by dicoumarol, suggesting involvement of an oxygen- and dicoumarol-insensitive (nitro)reductase. These results indicate methanotrophs can aerobically degrade NTO and DNAN via one or more (nitro)reductases, with sMMO serving a supporting role deriving reducing equivalents from methane. This finding is important because methanotrophic bacteria are widely dispersed, and may represent a previously unrecognized route of NTO and DNAN biotransformation in aerobic environments.

Sources and behavior of perchlorate in a shallow Chalk aquifer under military (World War I) and agricultural influences.

Perchlorate (ClO4ö) has been detected at concentrations of concern for human health on a large scale in groundwater used for drinking water supplies in NE France. Two sources are suspected: a military source related to World War I (WWI) and an agricultural source related to past use of Chilean nitrate fertilizers. The sources and behavior of ClO4ö have been studied in groundwater and rivers near the Reims city, by monitoring monthly the major ions and ClO4- concentrations for two years (2017-2019), and by measuring the isotopic composition of ClO4ö and NO3ö in water samples. ClO4ö was detected throughout the study area with high concentrations (> 4 µg⋅L-1) detected mainly downgradient of the Champagne Mounts, where large quantities of ammunition were used, stored and destroyed during and after WWI. A WWI military origin of ClO4- is inferred from isotopic analysis and groundwater ages. Different tendencies of ClO4- variation are observed and interpreted by a combination of ClO4- concentrations, aquifer functioning and historical investigations, revealing major sources of ClO4- (e.g., unexploded ordnance, ammunition destruction sites) and its transfer mechanisms in the aquifer. Finally, we show that concentrations of ClO4ö in groundwater seems unlikely to decrease in the short- to medium-term.

Nonclassical Behavior in Competitive Ion Adsorption at a Charged Solid-Water Interface.

Ion adsorption at solid-water interfaces is commonly described by interactions between specific surface sites and adsorbed ions in classical models. However, energetic contributions from non-site-specific ion-ion interactions have been less well understood. Here, we report nonclassical behaviors observed during competitive adsorption between Sr2+ and Na+/Rb+ at the negatively charged muscovite mica (001)-water interface, revealing apparent controls of adsorbed ion speciation over the interfacial reactivity. In the absence of competing cations, Sr2+ adsorbs in approximately equivalent proportions of inner-sphere and outer-sphere complexes, whereas it adsorbs predominantly as an outer-sphere complex in the presence of Na+/Rb+. This transformation of adsorbed Sr2+ speciation significantly decreases its adsorption strength, as indicated by the ∼15-fold shift in the Sr2+ adsorption edge concentration, compared to that calculated from a classical Langmuir isotherm model developed on the basis of site-specific interactions. These observations highlight the importance of non-site-specific interactions in controlling the energetics of chemical reactions at the charged interface.

Alkaline hydrolysis pathway of 2,4-dinitroanisole verified by 18O tracer experiment.

The environmental fate of insensitive munitions compounds, such as 2,4-dinitroanisole (DNAN), has drawn increasing attention because of their growing use in military activities. One of the main attenuation mechanisms of DNAN degradation in aqueous environments is alkaline hydrolysis. We investigated the pathway for alkaline hydrolysis of DNAN at pH 12 by a combined approach of experiment and theory. An experiment using 18O-labeled water was performed to verify the reaction pathway. Calculated free energies for two putative reaction pathways by density-functional theory optimized at the SMD(Pauling)/M06-2X/6-311++G(2d,2p) level including explicit solvation of DNAN by 10 H2O molecules and one OH- ion gave a prediction in agreement with the experimental result. The verified reaction pathway for alkaline hydrolysis of DNAN is a SN2Ar nucleophilic aromatic substitution with a methoxy leaving group (OCH3) at the C1 site.

Application of a multiple lines of evidence approach to document natural attenuation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in groundwater.

This study utilized innovative analyses to develop multiple lines of evidence for natural attenuation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in groundwater at the U.S. Department of Energy's Pantex Plant. RDX, as well as the degradation product 4-nitro-2,4-diazabutanal (NDAB; produced by aerobic biodegradation or alkaline hydrolysis) were detected in a large portion of the plume, with lower concentrations of the nitroso-containing metabolites produced during anaerobic biodegradation. 16S metagenomic sequencing detected the presence of bacteria known to aerobically degrade RDX (e.g., Gordonia, Rhodococcus) and NDAB (Methylobacterium), as well as the known anoxic RDX degrader Pseudomonas fluorescens I-C. Proteomic analysis detected both the aerobic RDX degradative enzyme XplA, and the anoxic RDX degradative enzyme XenB. Groundwater enrichment cultures supplied with low concentrations of labile carbon confirmed the potential of the extant groundwater community to aerobically degrade RDX and produce NDAB. Compound-specific isotope analysis (CSIA) of RDX collected at the site showed fractionation of nitrogen isotopes with δ15N values ranging from approximately -5‰ to +9‰, providing additional evidence of RDX degradation. Taken together, these results provide evidence of in situ RDX degradation in the Pantex Plant groundwater. Furthermore, they demonstrate the benefit of multiple lines of evidence in supporting natural attenuation assessments, especially with the application of innovative isotopic and -omic technologies.

Halogenated flame retardants in sediments from the Upper Laurentian Great Lakes: Implications to long-range transport and evidence of long-term transformation.

Most hydrophobic halogenated flame retardants (HFRs) are highly accumulative and persistent in aquatic sediments. The objective of this study was to reveal spatial distributions, temporal trends, and transformation of selected legacy and emerging HFRs in sediments of Lakes Superior, Michigan, and Huron. We collected Ponar grab samples at 112 locations and sediment cores at 28 sites in the three lakes, and measured concentrations of 19 brominated FRs and 12 chlorinated FRs. Based on grab samples, concentrations were higher at southeastern and sites near Sleeping Bear Dunes of Lake Michigan, and Saginaw Bay and the North Channel of Lake Huron. The annual loadings of polybrominated diphenyl either (PBDEs) and Dechlorane Plus (DPs) to sediment have leveled off or been declining since 2000, while loadings of DBDPE and Dec604 have increased since the 1960s in most cores. The concentration ratio of BB101 to BB153 increased with sediment depth, suggesting the occurrence of in situ debromination of BB153. The ratio of dechlorinated anti-Cl11DP over anti-DP increases with the increasing latitude of sampling locations, suggesting the occurrence of dechlorination of anti-DP to anti-Cl11DP during transport. This ratio also increases with increasing sediment age in most cores, implying in situ dechlorination over time.

Submarine groundwater discharge data at meter scale (223Ra, 224Ra, 226Ra, 228Ra and 222Rn) in Indian River Bay (Delaware, US).

Submarine groundwater discharge (SGD) was sampled at high-spatial resolution in Indian River Bay, DE, USA, in July 2016 to characterize the spatial variability of the activity of the radium and radon isotopes commonly used to estimate SGD. These data were part of an investigation into the methods and challenges of characterizing SGD rates and variability, especially in the coastal aquifer transition from freshwater to saltwater (Hydrogeological processes and near shore spatial variability of radium and radon isotopes for the characterization of submarine groundwater discharge (Duque et al., 2019)). Samples were collected with seepage meters and minipiezometers to obtain sufficient volumes for analytical characterization. Seepage meter samples (for 223Ra, 224Ra, 226Ra, and 228Ra) were collected at two-hour intervals over a semi-diurnal tidal cycle from 30 seepage meters. Samples for 222Rn characterization were collected with a minipiezometer from 25 cm below the bay bed at each seepage meter location. All samples were analyzed with standard and state of the art procedures.

Oxidation induced strain and defects in magnetite crystals.

Oxidation of magnetite (Fe3O4) has broad implications in geochemistry, environmental science and materials science. Spatially resolving strain fields and defect evolution during oxidation of magnetite provides further insight into its reaction mechanisms. Here we show that the morphology and internal strain distributions within individual nano-sized (~400 nm) magnetite crystals can be visualized using Bragg coherent diffractive imaging (BCDI). Oxidative dissolution in acidic solutions leads to increases in the magnitude and heterogeneity of internal strains. This heterogeneous strain likely results from lattice distortion caused by Fe(II) diffusion that leads to the observed domains of increasing compressive and tensile strains. In contrast, strain evolution is less pronounced during magnetite oxidation at elevated temperature in air. These results demonstrate that oxidative dissolution of magnetite can induce a rich array of strain and defect structures, which could be an important factor that contributes to the high reactivity observed on magnetite particles in aqueous environment.

Does elevated atmospheric CO2affect soil carbon burial and soil weathering in a forest ecosystem?

Most experimental studies measuring the effects of climate change on terrestrial C cycling have focused on processes that occur at relatively short time scales (up to a few years). However, climate-soil C interactions are influenced over much longer time scales by bioturbation and soil weathering affecting soil fertility, ecosystem productivity, and C storage. Elevated CO2can increase belowground C inputs and stimulate soil biota, potentially affecting bioturbation, and can decrease soil pH which could accelerate soil weathering rates. To determine whether we could resolve any changes in bioturbation or C storage, we investigated soil profiles collected from ambient and elevated-CO2plots at the Free-Air Carbon-Dioxide Enrichment (FACE) forest site at Oak Ridge National Laboratory after 11 years of 13C-depleted CO2 release. Profiles of organic carbon concentration, δ13C values, and activities of 137Cs, 210Pb, and 226Ra were measured to ∼30 cm depth in replicated soil cores to evaluate the effects of elevated CO2 on these parameters. Bioturbation models based on fitting advection-diffusion equations to 137Cs and 210Pb profiles showed that ambient and elevated-CO2 plots had indistinguishable ranges of apparent biodiffusion constants, advection rates, and soil mixing times, although apparent biodiffusion constants and advection rates were larger for 137Cs than for 210Pb as is generally observed in soils. Temporal changes in profiles of δ13C values of soil organic carbon (SOC) suggest that addition of new SOC at depth was occurring at a faster rate than that implied by the net advection term of the bioturbation model. Ratios of (210Pb/226Ra) may indicate apparent soil mixing cells that are consistent with biological mechanisms, possibly earthworms and root proliferation, driving C addition and the mixing of soil between ∼4 cm and ∼18 cm depth. Burial of SOC by soil mixing processes could substantially increase the net long-term storage of soil C and should be incorporated in soil-atmosphere interaction models.

Spatial and temporal trends in poly- and per-fluorinated compounds in the Laurentian Great Lakes Erie, Ontario and St. Clair.

The temporal and spatial trends in sediment of 22 poly- and perfluorinated (PFAS) compounds were investigated in the southern Great Lakes Erie and Ontario as well as Lake St. Clair. Surface concentrations measured by Ponar grab samples indicated a trend for greater concentrations near to urban sites. Mean concentrations ∑22PFAS were 15.6, 18.2 and 19 ng g-1 dm for Lakes St. Clair, Erie and Ontario, respectively. Perfluoro-n-butanoic acid (PFBA) and Perfluoro-n-hexanoic acid (PFHxA) were frequently determined in surface sediment and upper core samples indicating a shift in use patterns. Where PFBA was identified it was at relatively great concentrations typically >10 ng g-1 dm. However as PFBA and PFHxA are less likely to bind to sediment they may be indicative of pore water concentrations Sedimentation rates between Lake Erie and Lake Ontario differ greatly with greater rates observed in Lake Erie. In Lake Ontario, in general concentrations of PFAS observed in core samples closely follow the increase in use along with an observable change due to regulation implementation in the 1970s for water protection. However some of the more water soluble PFAS were observed in deeper core layers than the time of production could account for, indicating potential diffusion within the sediment. Given the greater sedimentation rates in Lake Erie, it was hoped to observe in greater resolution changes since the mid-1990s. However, though some decrease was observed at some locations the results are not clear. Many cores in Lake Erie had clearly observable gas voids, indicative of gas ebullition activity due to biogenic production, there were also observable mussel beds that could indicate mixing by bioturbation of core layers.

Current and historical concentrations of poly and perfluorinated compounds in sediments of the northern Great Lakes - Superior, Huron, and Michigan.

Current and historical concentrations of 22 poly- and perfluorinated compounds (PFASs) in sediment collected from Lake Superior and northern Lake Michigan in 2011 and Lake Huron in 2012 are reported. The sampling was performed in two ways, Ponar grabs of surface sediments for current spatial distribution across the lake and dated cores for multi-decadal temporal trends. Mean concentrations of the sum of PFASs (∑PFASs) were 1.5, 4.6 and 3.1 ng g-1 dry mas (dm) in surface sediments for Lakes Superior, Michigan and Huron, respectively. Of the five Laurentian Lakes, the watersheds of Superior and Huron are the less densely populated by humans, and concentrations observed were typically less and from more diffuse sources, due to lesser urbanization and industrialization. However, some regions of greater concentrations were observed and might indicate more local, point sources. In core samples concentrations ranged from 7 that include perfluoro-n-octane sulfonate (PFOS) bind more strongly to sediment, which resulted in more accurate analyses of temporal trends. Shorter-chain PFASs, such as perfluoro-n-butanoic acid which is the primary replacement for C8 PFASs that have been phased out, are more soluble and were identified in some core layers at depths corresponding to pre-production periods. Thus, analyses of temporal trends of these more soluble compounds in cores of sediments were less accurate. Total elemental fluorine (TF) and extractable organic fluorine (EOF) indicated that identified PFASs were not a significant fraction of fluorine containing compounds in sediment (<0.01% in EOF).

Geological and hydrogeochemical controls on radium isotopes in groundwater of the Sinai Peninsula, Egypt.

Radium isotopes (226Ra and 228Ra) were analyzed in 18 groundwater samples from the Nubian Sandstone Aquifer System (NSAS) and the shallow alluvial aquifers overlying the basement complex of the Sinai Peninsula, Egypt. Groundwater samples from deep Nubian aquifer wells (total depths 747 to 1250m) have 226Ra and 228Ra activities ranging from 0.168 to 0.802 and 0.056 to 1.032Bq/L, respectively. The shallower Nubian aquifer wells (63 to 366m) have 226Ra and 228Ra activities ranging from 0.033 to 0.191 and 0.029 to 0.312Bq/L, respectively. The basement shallow alluvial aquifers have 226Ra and 228Ra activities ranging from 0.014 to 0.038 and 0.007 to 0.051Bq/L, respectively. Combined Ra activities in most wells were generally in excess of the US Environmental Protection Agency (EPA), the European Union (EU), and the World Health Organization (WHO) maximum contaminant levels (MCL) for drinking water. Radium in groundwater is produced mainly by decay of parent nuclides in the aquifer solids, and observed activities of dissolved Ra isotopes result from a combination of alpha-recoil, adsorption/desorption, co-precipitation/dissolution processes. The observed correlation between Ra activities and salinity indicates that adsorption/desorption processes may be the dominant factor controlling Ra mobility in Sinai groundwater. Radium activities in central and northern Sinai are generally higher than those in southern Sinai, consistent with a gradual increase in salinity and water-rock interaction with increasing groundwater age. Barite is approximately saturated in the groundwater and may limit maximum dissolved Ra concentration. The results of this study indicate that Sinai groundwater should be used with caution, possibly requiring Ra removal from water produced for domestic and agricultural consumption.