Distribution of legacy and emerging per- and polyfluoroalkyl substances in riverine and coastal sediments of Southeastern North Carolina, USA.

The sediment distribution of per- and polyfluoroalkyl substances (PFAS) along a river to ocean transect was investigated. Samples were collected between September 2017 and October 2019 with targeted quantification of six legacy and replacement PFAS by LC-MS/MS. Total PFAS concentrations ranged from below the LOQ to 7.47 ng per g dry weight with PFOA, PFOS, HFPO-DA and PFMOAA the most frequently detected. Significant correlations (p < 0.05) were found between PFOS and HFPO-DA sedimentary concentration and percent organic carbon (% OC); however, PFOA and PFMOAA were not correlated with sediment % OC. This study highlights the occurrence of the replacement PFAS in sediments for the first time. Sediment extracts were screened for 18 additional PFAS compounds by high resolution mass spectrometry. A series of perfluorinated ether carboxylic acid and perfluorinated ether sulfonic acid with either one or two acidic functional groups were detected at various locations in the upper portion of the Cape Fear River. A series of chromatographically resolved isomers (C7F13O5S1; M-1) were detected and may be Nafion™ degradation products.

Isomers of emerging per- and polyfluoroalkyl substances in water and sediment from the Cape Fear River, North Carolina, USA.

Per- and polyfluoroalkyl substances (PFAS) have become ubiquitous environmental contaminants found in many parts of the globe and in all environmental compartments. The phase out of legacy C8 PFAS has led to an increase in functionality of the carbon backbone chain to include ether linkages and branching points. With the increased production of functionalized PFAS, there remains a paucity of information regarding the occurrence of constitutional isomers in the environment. In this study, a series of novel PFAS constitutional isomers were detected by high resolution mass spectrometry and characterized by MS/MS in river water collected weekly over 40 weeks. Constitutional isomers of C4H2F8O4S1 (-1.8 ± 2.5 ppm) were detected for the first time in 83% of the samples analyzed and the MS/MS fragmentation patterns clearly indicated there were two coeluting isomers present. Two chromatographically resolved peaks with deprotonated molecular formula C7H1F14O5S1 (1.9 ± 2.7 and 2.2 ± 3.1 ppm) were detected in 85% of the samples measured. MS/MS fragmentation patterns and a standard provided by a fluorochemical manufacturer confirmed the two isomers. A series of novel chlorinated PFAS were detected (M-1: C11H1Cl1F20O5 0.9 ± 2.7 ppm and C14H1Cl1F26O6 2.1 ± 2.6 ppm) in 34% of the water samples analyzed. The exact structure is not confirmed. River sediment collected below the water sample location contained several of the compounds detected in the water column illustrating the connectivity between the environmental compartments. Results highlight the need for further studies on the occurrence of isomers and authentic standards to confirm structures.

Compound-Specific Carbon Isotopic Composition of Ethanol in Brazil and US Vehicle Emissions and Wet Deposition.

Global atmospheric ethanol budget models include large uncertainties in the magnitude of ethanol emission sources and sinks. To apply stable isotope techniques to constrain ethanol emission sources, a headspace solid phase microextraction gas chromatograph-combustion-isotope ratio mass spectrometry method (HS-SPME-GC-C-IRMS) was developed to measure the carbon isotopic composition of aqueous phase ethanol at natural abundance levels (1-30 µM) with a precision of 0.4‰. The method was applied to determine the carbon isotope signatures (δ13C) of vehicle ethanol emission sources in Brazil (-12.8 ± 2.4‰) and the US (-9.8 ± 2.5‰), and to measure the carbon isotope composition of ethanol in wet deposition (-22.6 to -12.7‰). A two end-member isotope mixing model was developed using anthropogenic and biogenic end members and fractionation scenarios to estimate ethanol source contributions to wet deposition collected in Brazil and US. Mixing model results indicate anthropogenic sources contribute two and a half to four times more ethanol to the atmosphere than previously predicted in modeled global ethanol inventories. As established and developing countries continue to rapidly increase ethanol fuel consumption and subsequent emissions, understanding the magnitude of all ethanol sources and sinks will be essential for modeling future atmospheric chemistry and air quality impacts.

Effects of N-Methyl-D-aspartate (NMDA) antagonists ketamine, methoxetamine, and phencyclidine on the odor span test of working memory in rats.

The glutamate hypothesis proposes that N-Methyl-D-aspartate (NMDA) receptor hypofunction underlies cognitive and perhaps other schizophrenic symptoms. The present study used the odor span task to assess the effects of NMDA antagonists on remembering multiple stimuli in rodents. This task uses an incrementing nonmatching-to-sample procedure in which responses to a new olfactory stimulus are reinforced on each trial, whereas responses to previously presented stimuli are not. NMDA antagonists have been associated with memory impairments in a variety of animal models; however, there are inconsistencies across different NMDA antagonists and tasks used. The current study compared the acute effects of phencyclidine (PCP), ketamine (KET), and the novel NMDA antagonist methoxetamine (MXE) on responding in the odor span task and a simple discrimination control task. PCP and MXE impaired odor span accuracy at doses that did not impair simple discrimination in most rats; however, the effects of KET were less selective. Within-session analyses indicated that the effects of PCP and MXE depended on the number of stimuli to remember, that is, impairment only occurred when the memory load was relatively high. These effects of PCP and MXE were consistent with the hypothesis that NMDA antagonists may interfere with working memory, but the basis for less selective results with KET are unclear. (PsycINFO Database Record

Variability of ethanol concentration in rainwater driven by origin versus season in coastal and inland North Carolina, USA.

Rainwater ethanol concentrations were measured for one year (June 2013-May 2014) in central (Elon, NC) and coastal (Wilmington, NC) North Carolina, allowing for a comparison of the effects of coastal and marine rain on ethanol concentration and deposition both at the coast and 250 km inland. Rain samples were collected on an event basis and analyzed using enzyme oxidation and headspace solid-phase microextraction (HS-SPME). The volume-weighted average ethanol concentration at Elon (609 ±â€¯116 nM) was higher than at Wilmington (208 ±â€¯21 nM). Rainfall influenced by air masses originating over the Atlantic Ocean has previously been observed to be lower in ethanol concentration than terrestrial rain at the Wilmington location, and this was true during this study as well. Lower-ethanol marine and coastal air masses did not affect the concentration of ethanol in Elon rain, 250 km from the coast. This is likely due to the rapid supply of locally emitted ethanol to air masses moving over the land. No difference in rainwater ethanol concentrations was observed for Elon rain based on air mass back trajectories, most likely because all the rain was impacted by both anthropogenic and biogenic terrestrial sources typical of most inland areas. Seasonal variation in ethanol concentrations was significant in the inland location with elevated ethanol concentrations observed in fall; no seasonal variation was observed in coastal location rain. This study presents for the first time the different drivers for ethanol concentrations in rainwater from a coastal and a proximal inland location.

Use of experimentally determined Henry's Law and salting-out constants for ethanol in seawater for determination of the saturation state of ethanol in coastal waters.

The Henry's law constant for ethanol in seawater was experimentally determined to be 221 ± 4 M/atm at 22 °C compared with 247 ± 6 M/atm in pure water. The salting out coefficient for ethanol was 0.13 M-1. In seawater ln(KH) = -(12.8 ± 0.7) + (5310 ± 197)/T where KH is in M atm-1 and temperature is in K. This plus the salting out coefficient allow calculation of KH for any estuarine or sea water between 1 and 35 °C. High concentrations of dissolved organic carbon do not affect KH values in fresh or seawater. Nearshore surface waters were usually undersaturated with respect to gas phase ethanol except when air concentrations decreased, whereas surface seawater 40 km from shore was supersaturated. The percent saturation in surface waters is driven primarily by changes in air concentrations because these change quickly (hours) and more extensively than surface water. This study allows calculation of ethanol saturation states from air and surface water concentrations which is a necessary step to define the role of surface oceans in the global biogeochemical cycling of ethanol both now and in the future as use of ethanol biofuel continues to grow.

Photorelease of microcystin-LR from resuspended sediments.

A series of ten photolysis experiments was conducted with sediments exposed to Microcystis sp. blooms to determine if sunlight is capable of mobilizing the biotoxin microcystin-LR (MC-LR) into the water column. There was a net photorelease of MC-LR in irradiated suspensions in all cases relative to dark controls, ranging from 0.4 to 192µgL-1g-1 into the dissolved phase. This should be viewed as a minimum estimate of photorelease due to concurrent photodegradation of dissolved toxin. Dissolved MC-LR concentrations in a sediment suspension increased linearly in the aqueous phase during a six-hour irradiation with simulated sunlight suggesting that longer exposure times produce greater quantities of MC-LR. There was a significant positive correlation between photorelease of toxin and percent organic carbon of the resuspended material, implying that organic-rich sediments yield the greatest photorelease of MC-LR upon exposure to full spectrum sunlight. Samples exposed to photosynthetically active radiation (400nm-700nm) were responsible for less than 2% of the photorelease compared to full spectrum exposures. Model calculations indicate that photochemical processing of bloom impacted sediments could be responsible for as much as 100% of the average standing stock of MC-LR in a freshwater pond located in southeastern North Carolina, where surface water concentrations were also measured. Mass spectrometric analysis revealed a new peak in light exposed flasks that appears to be a photo-induced isomerized product of MC-LR. Photoproduction from resuspended sediments therefore represents a significant but previously unrecognized source of highly toxic MC-LR and photoproducts of unknown toxicity and fate to aquatic ecosystems.

Surface waters as a sink and source of atmospheric gas phase ethanol.

This study reports the first ethanol concentrations in fresh and estuarine waters and greatly expands the current data set for coastal ocean waters. Concentrations for 153 individual measurements of 11 freshwater sites ranged from 5 to 598 nM. Concentrations obtained for one estuarine transect ranged from 56 to 77 nM and levels in five coastal ocean depth profiles ranged from 81 to 334 nM. Variability in ethanol concentrations was high and appears to be driven primarily by photochemical and biological processes. 47 gas phase concentrations of ethanol were also obtained during this study to determine the surface water degree of saturation with respect to the atmosphere. Generally fresh and estuarine waters were undersaturated indicating they are not a source and may be a net sink for atmospheric ethanol in this region. Aqueous phase ethanol is likely converted rapidly to acetaldehyde in these aquatic ecosystems creating the undersaturated conditions resulting in this previously unrecognized sink for atmospheric ethanol. Coastal ocean waters may act as either a sink or source of atmospheric ethanol depending on the partial pressure of ethanol in the overlying air mass. Results from this study are significant because they suggest that surface waters may act as an important vector for the uptake of ethanol emitted into the atmosphere including ethanol from biofuel production and usage.

Temporal and spatial variability of trace volatile organic compounds in rainwater.

This study presents the first detailed concentration profile of trace VOCs in atmospheric waters. Analytes were detected and quantified in 111 unique rain events in Wilmington, NC, USA over a one-year period. Headspace solid phase microextraction was optimized for detection of these compounds at sub-nanomolar levels. Distinct seasonality in both the occurrence and concentration of compounds was observed with the lowest abundance occurring during low irradiance winter months. In contrast to other rainwater components studied at this location, VOCs did not show any correlation between rainfall amount and concentrations. There was significant spatial variation with regards to air-mass back-trajectory for methyfuran with higher concentrations observed in terrestrial events during the growing season. Air mass back trajectory also impacted CCl4 concentrations in rainwater with evidence of a possible oceanic input. However there was no significant impact of air-mass back-trajectory on the concentration of BTEX observed in rain indicating that storm origin is not the controlling factor driving concentrations of these analytes in precipitation. Members of the BTEX family did, however, have significant correlations with each other occurring in ratios aligned closely with ratios reported in the literature for gas-phase BTEX. Using available gas-phase data from locations with similar anthropogenic sources and Henry's Law constants, calculated concentrations agreed with VOC levels found in Wilmington rain. Results of this study indicate local gas-phase scavenging is the major source of VOCs in rain and wet deposition is not an efficient removal mechanism (<0.1%) of VOCs from the atmosphere.

Enhanced detection of the algal toxin PbTx-2 in marine waters by atmospheric pressure chemical ionization mass spectrometry.

RATIONALE: Karenia brevis, a marine dinoflagellate, biosynthesizes a unique class of polyether toxins called brevetoxins that produce significant health, environmental and economic impacts in and along coastal waters. Previous application of liquid chromatography/mass spectrometry for detection of the most common brevetoxin, PbTx-2, has relied almost exclusively upon electrospray ionization (ESI). A different ionization source is proposed in this study with improved sensitivity ultimately leading to lower limit of detection compared to (+) ESI. METHODS: Brevetoxin standards and samples (PbTx-2) were analyzed by liquid chromatography/mass spectrometry using both (+) atmospheric pressure chemical ionization and (+) electrospray ionization sources. RESULTS: LC/MS with (+) APCI exhibited an order of magnitude improvement in the limit of detection (7.7 × 10(-4) pg mass on-column) compared to the same method using (+) ESI (7.5 × 10(-3) pg mass on-column). The calibration sensitivity of (+) APCI (1.3 × 10(3)) was also five times higher than positive mode (+) ESI (0.26 × 10(3)). CONCLUSIONS: Positive mode APCI represents a significant improvement in detection and quantification of PbTx-2 by LC/MS allowing for smaller sample sizes compared to previous studies using (+) ESI. This in turn leads to higher throughput of samples during and after bloom events giving stakeholders detailed information on the fate of this potent marine toxin.

Photodegradation of the antihistamine cetirizine in natural waters.

The photodegradation rate of the anti-histamine cetirizine (Zyrtec®) was investigated in various water matrices. The average observed first-order photodegradation rate coefficient (kobs ), obtained by linear regression of the logarithmic-transformed cetirizine concentrations versus irradiation time in simulated sunlight, was 0.024 h(-1) (n = 6; standard deviation ± 0.004) in deionized water corresponding to a half-life of approximately 30 h. There was no statistical difference in the kobs of cetirizine photodegradation in coastal seawater compared with deionized water or deionized water amended with dissolved chromophoric organic matter. The quantum yield of cetirizine photodegradation decreased dramatically with increasing wavelength and decreasing energy of incoming radiation, with the average value ranging from 5.28 × 10(-4) to 6.40 × 10(-3) in the ultraviolet wavelength range (280-366 nm). The activation energy of cetirizine photodegradation was 10.3 kJ mol(-1) with an observed increase in cetirizine photodegradation as temperature increased. This is a significant environmental factor influencing half-life and an important consideration, given that cetirizine has been detected in wastewater and receiving waters from different locations globally.

Characterization of carbohydrates in rainwater from the southeastern North Carolina.

Carbohydrates have been widely reported in atmospheric aerosols, but have not previously been quantified in rainwater. We have identified and quantified a series of 11 specific compounds including monosaccharides (glucose, fructose, arabinose, galactose and pinitol), disaccharides (sucrose and trehalose), sugar alcohols (arabitol, dulcitol and mannitol) and the anhydrosaccharide levoglucosan. Rainwater analyzed in this study includes 52 distinct precipitation events in Wilmington, NC between June 2011 and October 2012. Our analysis indicates carbohydrates typically contribute <1% of total dissolved organic carbon in rain, but can account for as much as 10-35% during periods of high pollen or local fires. Concentrations of individual carbohydrates reached as high as 5.8 µM, with glucose and sucrose typically being the predominant species. The distribution of carbohydrates exhibited a distinct seasonal pattern, with higher concentrations of most carbohydrates, especially sucrose, in spring and summer, driven primarily by increased biogenic inputs during the growing season. Concentrations of carbohydrates were an order of magnitude higher in storms of terrestrial origin compared to marine events, further supporting a terrestrial biogenic origin of most species. Sequential sampling of Hurricane Irene showed significant quantities of carbohydrates present at the end of the storm when air mass back trajectories traversed over land. The highest level of levoglucosan, a compound associated with biomass burning, was detected in rain with an air mass back trajectory that traveled over a region affected by wildfires. When compared to aerosol concentrations reported by others, the sugar concentrations in rain demonstrate wet deposition is an important removal mechanism of this water-soluble and bioavailable fraction of atmospheric particulate organic matter.

Controls on the redox potential of rainwater.

Hydrogen peroxide acting as a reductant affects the redox potential of rainwater collected at the Bermuda Atlantic Time Series Station, the South Island of New Zealand, the contiguous USA, and the primary study site in Wilmington, NC. Analytical measurements of both halves of redox couples for dissolved iron, mercury, and the nitrate-nitrite-ammonium system can predict the rainwater redox potential measured directly by a platinum electrode. Measurements of these redox couples along with the pH in rain yields pe⁻ between 8 and 11; the half reaction for hydrogen peroxide acting as a reductant using typical rainwater conditions of 15 µM H2O2 at pH 4.7 gives pe⁻ = 9.12, where pe⁻ = negative log of the activity of hydrated electrons. Of the six rainwater redox systems investigated, only manganese speciation appeared to be controlled by molecular oxygen (pe⁻ = 15.90). Copper redox speciation was consistent with superoxide acting as a reductant (pe⁻ = 2.7). The concentration of H2O2 in precipitation has more than doubled over the preceding decade due to a decrease in SO2 emissions, which suggests the redox chemistry of rainwater is dynamic and changing, potentially altering the speciation of many organic compounds and trace metals in atmospheric waters.

Brevetoxin persistence in sediments and seagrass epiphytes of east Florida coastal waters.

A bloom of Karenia brevis Davis developed in September 2007 near Jacksonville, Florida and subsequently progressed south through east Florida coastal waters and the Atlantic Intracoastal Waterway (ICW). Maximum cell abundances exceeded 106 cells L-1 through October in the northern ICW between Jacksonville and the Indian River Lagoon. The bloom progressed further south during November, and terminated in December 2007 at densities of 104 cells L-1 in the ICW south of Jupiter Inlet, Florida. Brevetoxins were subsequently sampled in sediments and seagrass epiphytes in July and August 2008 in the ICW. Sediment brevetoxins occurred at concentrations of 11-15 ng PbTx-3 equivalents (g dry wt sediment)-1 in three of five basins in the northern ICW during summer 2008. Seagrass beds occur south of the Mosquito Lagoon in the ICW. Brevetoxins were detected in six of the nine seagrass beds sampled between the Mosquito Lagoon and Jupiter Inlet at concentrations of 6-18 ng (g dry wt epiphytes)-1. The highest brevetoxins concentrations were found in sediments near Patrick Air Force Base at 89 ng (g dry wt sediment)-1. In general, brevetoxins occurred in either seagrass epiphytes or sediments. Blades of the resident seagrass species have a maximum life span of less than six months, so it is postulated that brevetoxins could be transferred between epibenthic communities of individual blades in seagrass beds. The occurrence of brevetoxins in east Florida coast sediments and seagrass epiphytes up to eight months after bloom termination supports observations from the Florida west coast that brevetoxins can persist in marine ecosystems in the absence of sustained blooms. Furthermore, our observations show that brevetoxins can persist in sediments where seagrass communities are absent.

Determination of brevetoxin in recent marine sediments.

Harmful algal blooms (HAB) of Karenia brevis (K. brevis) produce a suite of lipid soluble polyether brevetoxins, known to cause environmental, health and economic ill effects. There is evidence that K. brevis has increased in abundance over the past 50 years, but the dataset is incomplete. The objective of this paper was to analyze sediment from an area where K. brevis blooms have occurred and investigate if these compounds are incorporated into the underlying sediment, thus potentially allowing the use of brevetoxins as an indicator of past K. Brevis blooms. The results from LC-ESI-MS-MS analyses of brevetoxin analogs detected in surficial sediments from three sites (Fort Meyers Beach [FMB], Big Hickory Pass [BHP] and Big Carlos Pass [BCP]) along the Southwest Florida coastline with prior HAB history are promising. The analogs detected from BHP sediments were PbTx-2 and PbTx-3 with values of 0.81 and 3.1 ng g(-1) dry sediment, respectively. The detected PbTx-2 from BCP was 3.6 ng g(-1) dry sediment, while the detected PbTx-3 from BCP was 9.7 ng g(-1) dry sediment. PbTx-3 was only detected at the FMB site (2.7 ng g(-1) dry sediment). The detection of brevetoxins in recent sediments where K. brevis have occurred indicates brevetoxin incorporation into marine sediments.