Identification of persistent oil residues in Prince William Sound, Alaska using rapid spectroscopic techniques.

Spectroscopic techniques including X-ray fluorescence (XRF) and attenuated total reflectance - Fourier transform infrared spectroscopy (ATR-FTIR) are used to examine oil residues persisting on shorelines in Prince William Sound that originate from the 1989 Exxon Valdez oil spill and oil released as a consequence of the 1964 Great Alaska earthquake. When coupled to classification models, ATR-FTIR and XRF spectral data can be used to distinguish between the two sources of oil with 92% and 86% success rates for the two techniques respectively. Models indicate that the ATR-FTIR data used to determine oil source includes the CO stretch, the twisting-scissoring of the CH2 group, and the CC stretch. For XRF data, decision tree models primarily utilize the abundance of nickel and zinc present in the oil as a means to classify source. This approach highlights the utility of rapid, field-based spectroscopic techniques to distinguish different inputs of oil to coastal environments.

Gas chromatography - Mass spectrometry as a preferred method for quantification of insect hemolymph sugars.

Insects, due to their small size, have limited energy storage space, but they also have high metabolic rate, so their hemolymph sugars are incredibly dynamic and play a number of important physiological functional roles in maintaining energetic homeostasis. In contrast to vertebrates, trehalose is generally the primary sugar found in insect hemolymph, which is followed by glucose and fructose. Many analytical chemistry methods exist to measure sugars, yet a direct comparison of methods that can measure all three simultaneously, and trehalose in particular, from low sample volumes, are sparse. Using the honey bee as a model, we directly compare the leading current methods of using High Performance Liquid Chromatography (HPLC) with an evaporative light-scattering detector and Gas Chromatography coupled with Mass Spectrometry (GC-MS) to determine which method would be better for measuring trehalose, glucose, and fructose in terms of reproducibility, accuracy, and sensitivity. Furthermore, we injected the enzyme inhibitors trehalozin (a trehalase inhibitor) and sorbose (a trehalase p-synthase inhibitor) to manipulate the trehalose levels in honey bee foragers as a proof of concept that this sugar can be altered independently of hemolymph glucose and fructose levels. Overall the HPLC method was less reproducible for measuring fructose and glucose, and it also had lower sensitivity for measuring trehalose. Consequently, significant differences in trehalose levels within the forager class were only detected with the GC-MS and not the HPLC method. Lastly, using the GC-MS method in the follow up study we found that trehalozin and sorbose causes a significant increase and decrease of trehalose levels respectively, in forager honey bees, independent of the glucose and fructose levels, ten minutes after injection. Taken together, these methods will provide useful tools for future studies exploring the many different physiological functional roles that trehalose can play in maintaining insect energetic homeostasis.

Quantum cascade laser-based reflectance spectroscopy: a robust approach for the classification of plastic type.

The identification of plastic type is important for environmental applications ranging from recycling to understanding the fate of plastics in marine, atmospheric, and terrestrial environments. Infrared reflectance spectroscopy is a powerful approach for plastics identification, requiring only optical access to a sample. The use of visible and near-infrared wavelengths for plastics identification are limiting as dark colored plastics absorb at these wavelengths, producing no reflectance spectra. The use of mid-infrared wavelengths instead enables dark plastics to be identified. Here we demonstrate the capability to utilize a pulsed, widely-tunable (5.59 - 7.41 µm) mid-infrared quantum cascade laser, as the source for reflectance spectroscopy, for the rapid and robust identification of plastics. Through the application of linear discriminant analysis to the resulting spectral data set, we demonstrate that we can correctly classify five plastic types: polyethylene terephthalate (PET), high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), and polystyrene (PS), with a 97% accuracy rate.

Silicone Wristbands as Passive Samplers in Honey Bee Hives.

The recent decline of European honey bees (Apis mellifera) has prompted a surge in research into their chemical environment, including chemicals produced by bees, as well as chemicals produced by plants and derived from human activity that bees also interact with. This study sought to develop a novel approach to passively sampling honey bee hives using silicone wristbands. Wristbands placed in hives for 24 h captured various compounds, including long-chain hydrocarbons, fatty acids, fatty alcohols, sugars, and sterols with wide ranging octanol-water partition coefficients (Kow) that varied by up to 19 orders of magnitude. Most of the compounds identified from the wristbands are known to be produced by bees or plants. This study indicates that silicone wristbands provide a simple, affordable, and passive method for sampling the chemical environment of honey bees.

Rapid Identification of Marine Plastic Debris via Spectroscopic Techniques and Machine Learning Classifiers.

To advance our understanding of the environmental fate and transport of macro- and micro-plastic debris, robust and reproducible methods, technologies, and analytical approaches are necessary for in situ plastic-type identification and characterization. This investigation compares four spectroscopic techniques: attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), near-infrared (NIR) reflectance spectroscopy, laser-induced breakdown spectroscopy (LIBS), and X-ray fluorescence (XRF) spectroscopy, coupled to seven classification methods, including machine learning classifiers, to determine accuracy for identifying type of both consumer plastics and marine plastic debris (MPD). With machine learning classifiers, consumer plastic types were identified with 99, 91, 97, and 70% success rates for ATR-FTIR, NIR reflectance spectroscopy, LIBS, and XRF, respectively. The classification of MPD had similar or lower success rates, likely arising from alterations to the plastic from environmental weathering processes with success rates of 99, 81, 76, and 66% for ATR-FTIR, NIR reflectance spectroscopy, LIBS, and XRF, respectively. Success rates indicate that ATR-FTIR, NIR reflectance spectroscopy, and LIBS coupled with machine learning classifiers can be used to identify both consumer and environmental plastic samples.

Appetite is correlated with octopamine and hemolymph sugar levels in forager honeybees.

Insects have rapidly changing energy demands, so they primarily rely on hemolymph and other carbohydrates to carry out life activities. However, how gustatory responsiveness and hemolymph sugar levels coordinate with one another to maintain energetic homeostasis in insects remains largely unknown for the highly social honeybee that goes through large physiological and behavioral changes. The potential role of biogenic amines and neuropeptides in the connection between the regulation of appetite and fluctuating sugar levels in the hemolymph, due to starvation, as the bee ages, was investigated. The largest appetite increase due to the starvation treatment was within the forager age class and this corresponded with an increase in octopamine levels in the brain along with a decline in hemolymph sugar levels. Adipokinetic hormone (AKH) was found in very small quantities in the brain and there were no significant changes in response to starvation treatment. Our findings suggest that the particularly dynamic levels of hemolymph sugar levels may serve as a monitor of the forager honeybee energetic state. Therefore, there may be a pathway in forager bees via octopamine responsible for their precise precipitous regulation of appetite, but to determine cause and effect relationships further investigation is needed.

Correction: Honey bee (Apis mellifera) exposomes and dysregulated metabolic pathways associated with Nosema ceranae infection.

[This corrects the article DOI: 10.1371/journal.pone.0213249.].

Honey bee (Apis mellifera) exposomes and dysregulated metabolic pathways associated with Nosema ceranae infection.

Honey bee (Apis mellifera) health has been severely impacted by multiple environmental stressors including parasitic infection, pesticide exposure, and poor nutrition. The decline in bee health is therefore a complex multifactorial problem which requires a holistic investigative approach. Within the exposome paradigm, the combined exposure to the environment, drugs, food, and individuals' internal biochemistry affects health in positive and negative ways. In the context of the exposome, honey bee hive infection with parasites such as Nosema ceranae is also a form of environmental exposure. In this study, we hypothesized that exposure to xenobiotic pesticides and other environmental chemicals increases susceptibility to N. ceranae infection upon incidental exposure to the parasite. We further queried whether these exposures could be linked to changes in conserved metabolic biological pathways. From 30 hives sampled across 10 sites, a total of 2,352 chemical features were found via gas chromatography-time of flight mass spectrometry (GC-TOF) in extracts of honey bees collected from each hive. Of these, 20 pesticides were identified and annotated, and found to be significantly associated with N. ceranae infection. We further determined that infected hives were linked to a greater number of xenobiotic exposures, and the relative concentration of the exposures were not linked to the presence of a N. ceranae infection. In the exposome profiles of the bees, we also found chemicals inherent to known biological metabolic pathways of Apis mellifera and identified 9 dysregulated pathways. These findings have led us to posit that for hives exposed to similar chemicals, those that incur multiple, simultaneous xenobiotic stressors have a greater incidence of infection with N. ceranae. Mechanistically, our results suggests the overwhelming nature of these exposures negatively affects the biological functioning of the bee, and could explain how the decline in bee populations is associated with pesticide exposures.

Hurricane Isaac brings more than oil ashore: Characteristics of beach deposits following the Deepwater Horizon spill.

Prior to Hurricane Isaac making landfall along the Gulf of Mexico coast in August 2012, local and state officials were concerned that the hurricane would mobilize submerged oiled-materials from the Deepwater Horizon (DWH) spill. In this study, we investigated materials washed ashore following the hurricane to determine if it affected the chemical composition or density of oil-containing sand patties regularly found on Gulf Coast beaches. While small changes in sand patty density were observed in samples collected before and after the hurricane, these variations appear to have been driven by differences in sampling location and not linked to the passing of Hurricane Isaac. Visual and chemical analysis of sand patties confirmed that the contents was consistent with oil from the Macondo well. Petroleum hydrocarbon signatures of samples collected before and after the hurricane showed no notable changes. In the days following Hurricane Isaac, dark-colored mats were also found on the beach in Fort Morgan, AL, and community reports speculated that these mats contained oil from the DWH spill. Chemical analysis of these mat samples identified n-alkanes but no other petroleum hydrocarbons. Bulk and δ13C organic carbon analyses indicated mat samples were comprised of marshland peat and not related to the DWH spill. This research indicates that Hurricane Isaac did not result in a notable change the composition of oil delivered to beaches at the investigated field sites. This study underscores the need for improved communications with interested stakeholders regarding how to differentiate oiled from non-oiled materials. This is especially important given the high cost of removing oiled debris and the increasing likelihood of false positives as oiled-materials washing ashore from a spill become less abundant over time.

Pelagic tar balls collected in the North Atlantic Ocean and Caribbean Sea from 1988 to 2016 have natural and anthropogenic origins.

Tar balls are prevalent in oceans and the coastal environment; however, their origins are not well constrained on a global scale. To address this, we used gas chromatography to analyze the molecular composition of a unique set of 100 pelagic tar balls collected in the Western North Atlantic and Caribbean Sea between 1988 and 2016. Hierarchal cluster analysis (HCA) was employed to classify the samples into groups based on the relative proportions of resolved and unresolved hydrocarbon distributions. Additional analysis of polycyclic aromatic hydrocarbons revealed that 28% of samples originated from heavy fuel oils and therefore had anthropogenic origins consistent with the classifications based on HCA. Other samples examined could originate from anthropogenic or natural origins, such as natural seeps. This study provides a preliminary record of 100 classified pelagic tar ball samples and demonstrates an approach to determine their origin to the environment.

Chemical characterization of natural and anthropogenic-derived oil residues on Gulf of Mexico beaches.

Oil residues originating from the Deepwater Horizon (DWH) incident persist on Gulf of Mexico beaches alongside oil from offshore industrial activity, natural seepage, and asphalt from parking lots and roads. To determine the primary differences in the chemical composition of these oil residues, a variety of samples were collected from beaches from Florida to Alabama over a two-year period from 2015 to 2017. Bulk chemical characteristics of the oil residues were examined via gas chromatography with flame ionization detection (GC-FID) and mass spectrometry (GC-MS), as well as thin layer chromatography with flame ionization detection (TLC-FID), and attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR). These bulk chemical analyses revealed features unique to the different sample types, expanding our understanding of the chemical composition and variability of persistent oil residues, and providing a means to detect and monitor their long-term fate in the coastal environment.

Partial Photochemical Oxidation Was a Dominant Fate of Deepwater Horizon Surface Oil.

Following the Deepwater Horizon (DWH) blowout in 2010, oil floated on the Gulf of Mexico for over 100 days. In the aftermath of the blowout, substantial accumulation of partially oxidized surface oil was reported, but the pathways that formed these oxidized residues are poorly constrained. Here we provide five quantitative lines of evidence demonstrating that oxidation by sunlight largely accounts for the partially oxidized surface oil. First, residence time on the sunlit sea surface, where photochemical reactions occur, was the strongest predictor of partial oxidation. Second, two-thirds of the partial oxidation from 2010 to 2016 occurred in less than 10 days on the sunlit sea surface, prior to coastal deposition. Third, multiple diagnostic biodegradation indices, including octadecane to phytane, suggest that partial oxidation of oil on the sunlit sea surface was largely driven by an abiotic process. Fourth, in the laboratory, the dominant photochemical oxidation pathway of DWH oil was partial oxidation to oxygenated residues rather than complete oxidation to CO2. Fifth, estimates of partial photo-oxidation calculated with photochemical rate modeling overlap with observed oxidation. We suggest that photo-oxidation of surface oil has fundamental implications for the response approach, damage assessment, and ecosystem restoration in the aftermath of an oil spill, and that oil fate models for the DWH spill should be modified to accurately reflect the role of sunlight.

Long-term weathering and continued oxidation of oil residues from the Deepwater Horizon spill.

To investigate the long-term weathering of oil from the Deepwater Horizon (DWH) incident, oil-soaked sand patties were collected from Gulf of Mexico beaches from Florida to Alabama over a three-year period from 2012 to 2014. Analysis of oil residues by gas chromatography with flame ionization detection (GC-FID), thin-layer chromatography with flame ionization detection (TLC-FID), and Fourier transform infrared spectroscopy (FT-IR) indicated uniformity in their chemical composition. Some variability within and between samples was observed, arising from differences in exposure to light and water, which increase the amount of weathering. Oxygenated hydrocarbons (OxHC) produced by weathering processes dominate the majority of oil residues. These OxHC have continued recalcitrance in the environment, and increase in relative abundance over time. Analyses of the bulk characteristics of oil residues via TLC-FID and FT-IR should be continued as these techniques provide important insight into the weathering state of oil residues.

Evaluating a Midwife-Led Model of Antenatal Care for Women with a Previous Cesarean Section: A Retrospective, Comparative Cohort Study.

BACKGROUND: Research is yet to identify effective and safe interventions to increase the vaginal birth after cesarean (VBAC) rate. This research aimed to compare intended and actual VBAC rates before and after implementation of midwife-led antenatal care for women with one previous cesarean birth and no other risk factors in a large, tertiary maternity hospital in England. METHODS: This was a retrospective, comparative cohort study. Data were collected from the medical records of women with one previous lower segment cesarean delivery and no other obstetric, medical, or psychological complications who gave birth at the hospital before (2008) and after (2011) the implementation of midwife-led antenatal care. Chi-squared analysis was used to calculate the odds ratio, and logistic regression to account for confounders. RESULTS: Intended and actual VBAC rates were higher in 2011 compared with 2008: 90 percent vs. 77 percent, adjusted odds ratio (aOR) 2.69 (1.48-4.87); and 61 percent vs. 47 percent, aOR 1.79 (1.17-2.75), respectively. Mean rates of unscheduled antenatal care sought via the delivery suite and inpatient admissions were lower in 2011 than 2008. Postnatal maternal and neonatal safety outcomes were similar between the two groups, except mean postnatal length of stay, which was shorter in 2011 compared with 2008 (2.67 vs. 3.15 days). CONCLUSIONS: Implementation of midwife-led antenatal care for women with one previous cesarean offers a safe and effective alternative to traditional obstetrician-led antenatal care, and is associated with increased rates of intended and actual VBAC.

Unresolved complex mixture (UCM) in coastal environments is derived from fossil sources.

The unresolved complex mixture (UCM) frequently dominates organic extracts isolated from estuarine and coastal sediments in the vicinity of industrial centers. Despite an obvious link to a petroleum source, speculation exists that biogenic sources also contribute to the UCM. To determine the source of the UCM to these environments, natural abundance radiocarbon (Δ(14)C) and stable carbon (δ(13)C) isotopic composition of the UCM solvent-extracted from coastal sediments, road dust, and urban atmospheric particulate in the United States was measured. Extracts of UCM and separate saturate and aromatic fractions from all samples are predominantly (>90%) fossil-derived and hence have a petroleum source. Even the polar fraction of the UCM, which has a Δ(14)C composition reflecting contributions from recently photosynthesized carbon (-665‰), is composed of ~66% fossil carbon indicating the presence of petroleum residues that have been transformed into more polar derivatives. The δ(13)C of the UCM had consistent values (-27.65 ± 0.51‰; n = 16) for all but one sample, indicating a common origin of the UCM. We conclude that in coastal areas dominated by human activities whole fractions of the UCM, as well as separate saturate, aromatic, and polar fractions, are principally derived from petroleum sources.

Impact of the Deepwater Horizon oil spill on a deep-water coral community in the Gulf of Mexico.

To assess the potential impact of the Deepwater Horizon oil spill on offshore ecosystems, 11 sites hosting deep-water coral communities were examined 3 to 4 mo after the well was capped. Healthy coral communities were observed at all sites >20 km from the Macondo well, including seven sites previously visited in September 2009, where the corals and communities appeared unchanged. However, at one site 11 km southwest of the Macondo well, coral colonies presented widespread signs of stress, including varying degrees of tissue loss, sclerite enlargement, excess mucous production, bleached commensal ophiuroids, and covering by brown flocculent material (floc). On the basis of these criteria the level of impact to individual colonies was ranked from 0 (least impact) to 4 (greatest impact). Of the 43 corals imaged at that site, 46% exhibited evidence of impact on more than half of the colony, whereas nearly a quarter of all of the corals showed impact to >90% of the colony. Additionally, 53% of these corals' ophiuroid associates displayed abnormal color and/or attachment posture. Analysis of hopanoid petroleum biomarkers isolated from the floc provides strong evidence that this material contained oil from the Macondo well. The presence of recently damaged and deceased corals beneath the path of a previously documented plume emanating from the Macondo well provides compelling evidence that the oil impacted deep-water ecosystems. Our findings underscore the unprecedented nature of the spill in terms of its magnitude, release at depth, and impact to deep-water ecosystems.

Quantitative population dynamics of microbial communities in plankton-fed microbial fuel cells.

This study examines changes in diversity and abundance of bacteria recovered from the anodes of microbial fuel cells (MFCs) in relation to anode potential, power production and geochemistry. MFCs were batch-fed with plankton, and two systems were maintained at different potentials whereas one was at open circuit for 56.8 days. Bacterial phylogenetic diversity during peak power was assessed from 16S rDNA clone libraries. Throughout the experiment, microbial community structure was examined using terminal restriction fragment length polymorphism. Changes in cell density of key phylotypes, including representatives of delta-, epsilon-, gamma-proteobacteria and Flavobacterium-Cytophaga-Bacteroides, were enumerated by quantitative PCR. Marked differences in phylogenetic diversity were observed during peak power versus the final time point, and changes in microbial community structure were strongly correlated to dissolved organic carbon and ammonium concentrations within the anode chambers. Community structure was notably different between the MFCs at different anode potentials during the onset of peak power. At the final time point, however, the anode-hosted communities in all MFCs were similar. These data demonstrate that differences in growth, succession and population dynamics of key phylotypes were due to anode potential, which may relate to their ability to exploit the anode as an electron acceptor. The geochemical milieu, however, governs overall community diversity and structure. These differences reflect the physiological capacity of specific phylotypes to catabolize plankton-derived organic matter and exploit the anode of an MFC for their metabolism directly or indirectly through syntrophy.

Radiocarbon-based assessment of fossil fuel-derived contaminant associations in sediments.

Hydrophobic organic contaminants (HOCs) are associated with natural organic matter (OM) in the environment via mechanisms such as sorption or chemical binding. The latter interactions are difficult to quantitatively constrain, as HOCs can reside in different OM pools outside of conventional analytical windows. Here, we exploited natural abundance variations in radiocarbon (14C) to trace various fossil fuel-derived HOCs (14C-free) within chemically defined fractions of contemporary OM (modern 14C content) in 13 samples including marine and freshwater sediments and one dust and one soil sample. Samples were sequentially treated by solvent extraction followed by saponification. Radiocarbon analysis of the bulk sample and resulting residues was then performed. Fossil fuel-derived HOCs released by these treatments were quantified from an isotope mass balance approach as well as by gas chromatography-mass spectrometry. For the majority of samples (n = 13), 98-100% of the total HOC pool was solvent extractable. Nonextracted HOCs are only significant (29% of total HOC pool)in one sample containing p,p-2,2-bis(chlorophenyl)-1,1,1-trichloroethane and its metabolites. The infrequency of significant incorporation of HOCs into nonextracted OM residues suggests that most HOCs are mobile and bioavailable in the environment and, as such, have a greater potential to exert adverse effects.

Substrate degradation kinetics, microbial diversity, and current efficiency of microbial fuel cells supplied with marine plankton.

The decomposition of marine plankton in two-chamber, seawater-filled microbial fuel cells (MFCs) has been investigated and related to resulting chemical changes, electrode potentials, current efficiencies, and microbial diversity. Six experiments were run at various discharge potentials, and a seventh served as an open-circuit control. The plankton consisted of a mixture of freshly captured phytoplankton and zooplankton (0.21 to 1 mm) added at an initial batch concentration of 27.5 mmol liter(-1) particulate organic carbon (OC). After 56.7 days, between 19.6 and 22.2% of the initial OC remained, sulfate reduction coupled to OC oxidation accounted for the majority of the OC that was degraded, and current efficiencies (of the active MFCs) were between 11.3 and 15.5%. In the open-circuit control cell, anaerobic plankton decomposition (as quantified by the decrease in total OC) could be modeled by three terms: two first-order reaction rate expressions (0.79 day(-1) and 0.037 day(-1), at 15 degrees C) and one constant, no-reaction term (representing 10.6% of the initial OC). However, in each active MFC, decomposition rates increased during the third week, lagging just behind periods of peak electricity generation. We interpret these decomposition rate changes to have been due primarily to the metabolic activity of sulfur-reducing microorganisms at the anode, a finding consistent with the electrochemical oxidization of sulfide to elemental sulfur and the elimination of inhibitory effects of dissolved sulfide. Representative phylotypes, found to be associated with anodes, were allied with Delta-, Epsilon-, and Gammaproteobacteria as well as the Flavobacterium-Cytophaga-Bacteroides and Fusobacteria. Based upon these results, we posit that higher current efficiencies can be achieved by optimizing plankton-fed MFCs for direct electron transfer from organic matter to electrodes, including microbial precolonization of high-surface-area electrodes and pulsed flowthrough additions of biomass.

Abundance, composition, and vertical transport of PAHs in marsh sediments.

Petroleum-derived hydrocarbons continue to persist in Wild Harbor, West Falmouth, MA, following a spill of No. 2 fuel oil in 1969 from the barge Florida. Recent analysis of marsh sediments revealed that residues of degraded oil are present with concentrations of total petroleum hydrocarbons as high as approximately 9 mg g(-1). Polycyclic aromatic hydrocarbons (PAHs) constitute only a minor fraction of these residues with maximum concentrations of 134 mirog g(-1), but their fate is of interest because of their potential toxicity to organisms. As compared to typical unweathered No. 2 fuel oil, the current distribution of PAHs in the sediments reflects substantial weathering by abiotic and biotic processes, specifically a preferential loss of naphthalenes relative to phenanthrenes, as well as isomer-specific biodegradation of alkylated PAHs. Based on comparison to results from an earlier study, it appears that little or no change has occurred to the distribution of PAHs since 1989, indicating that weathering at this site has stalled or is now proceeding at a significantly slower rate. To assess whether sediment-water partitioning and molecular diffusion in the interstitial medium are now the dominant processes controlling the vertical distribution of PAHs, downcore profiles were compared to a numerical model. While in some cases the model accurately reproduced the measured data, there were instances where the distribution of PAHs was slightly under or overestimated. Reasons for these discrepancies are discussed and are likely due to bioturbation, colloid-facilitated transport, or both. Assessment of the influence of these processes on the spilled oil expands our understanding of the overall fate of these compounds and their potential long-term effects on the environment.