Biosensor applications in contaminated estuaries: Implications for disaster research response.

BACKGROUND: Given the time and monetary costs associated with traditional analytical chemistry, there remains a need to rapidly characterize environmental samples for priority analysis, especially within disaster research response (DR2). As PAHs are both ubiquitous and occur as complex mixtures at many National Priority List sites, these compounds are of interest for post-disaster exposures. OBJECTIVE: This study tests the field application of the KinExA Inline Biosensor in Galveston Bay and the Houston Ship Channel (GB/HSC) and in the Elizabeth River, characterizing the PAH profiles of these region's soils and sediments. To our knowledge, this is the first application of the biosensor to include soils. METHODS: The biosensor enables calculation of total free PAHs in porewater (C free), which is confirmed through gas chromatography-mass spectrometry (GC-MS) analysis. To determine potential risk of the collected soils the United States Environmental Protection (USEPA) Agency's Regional Screening Level (RSL) Calculator is used along with the USEPA Region 4 Ecological Screening Values (R4-ESV) and Refined Screening Values (R4-RSV). RESULTS: Based on GC-MS results, all samples had PAH-related hazard indices below 1, indicating low noncarcinogenic risks, but some samples exceeded screening levels for PAH-associated cancer risks. Combining biosensor-based C free with Total Organic Carbon yields predictions highly correlated (r > 0.5) both with total PAH concentrations as well as with hazard indices and cancer risks. Additionally, several individual parent PAH concentrations in both the GB/HSC and Elizabeth River sediments exceeded the R4- ESV and R4-RSV values, indicating a need for follow-up sediment studies. CONCLUSIONS: The resulting data support the utility of the biosensor for future DR2 efforts to characterize PAH contamination, enabling preliminary PAH exposure risk screening to aid in prioritization of environmental sample analysis.

Volatile organic compounds in variably aged carrion impacted by the presence of the primary colonizer, Cochliomyia macellaria (Diptera: Calliphoridae).

The attraction and colonization of vertebrate remains by carrion-associated arthropods are processes largely governed by olfaction. As remains decompose, they emit a bouquet of volatile organic compounds (VOCs), which in part originate from endogenous and exogenous microbes surrounding the carcass or from the carcass itself. The composition and concentration of VOCs are influenced by the presence and abundance of microbial species and arthropods. Blowfly species, such as Cochliomyia macellaria, play a critical role in nutrient recycling and the decomposition process of carrion. Gas chromatography-mass spectroscopy analysis was used to identify and classify volatile emissions from insect-colonized (with C. macellaria) and uncolonized rat carcasses, as well as a standard Gainesville diet, over a 10-day period. There were significant differences in composition and abundance of compounds present in each treatment, with significant effects of time, and different compound composition between treatments. Notable indicator compounds included, but were not limited to, indole, dimethyl disulfide, and dimethyl trisulfide. A high compound richness, and a low compound diversity, was detected over the 10-day period. The indicator compounds detected across all treatments were found to be of microbial origin, highlighting the importance of microbes in decomposition processes and arthropod attraction to carrion. This study also discusses the significant impact of necrophagous arthropods to the VOC profile of carrion. The results of this study provide insight into the changes in decomposition VOCs over time, with an explanation of compounds in high concentration known to be attractive to carrion-colonizing arthropods.

Spatial distribution and ecological risk assessment of trace metals in surface sediments of Lake Qaroun, Egypt.

A suite of trace metals was determined in twenty surface sediments collected from Lake Qaroun, which is designated as a natural reserve in 1989 to examine their spatial distribution and their potential environmental impact on the lake. Contamination factor (Cf), enrichment factor (EF), geoaccumulation index (Igeo), and pollution load index (PLI) are applied to evaluate the quality of the lake. The highest concentrations were detected in the eastern portion of the lake near Al-Bats drain. The levels of Ba exceeded the toxicity reference value (TRV) (20 ng/g dw) set by US EPA for all sediments, while sediments collected from Al-Bats region exceeded the TRV for Zn (68 ng/g dw). Arsenic, Ba, Sn, Co, Cu, and Hg are poorly correlated with background value of Fe suggesting anthropogenic activities over the entire lake. The values of Cf and Igeo confirmed that the eastern portion of the lake has been found moderately to considerably contaminated by As, Sn, and Zn. Sediments collected from the eastern location (S1) were very highly enriched of Sn (22.47); however, the other eastern locations were highly enriched of Sn, As, Cd, Co, and Ba. It is clear that sites near Al-Bats and El-Wadi drains are hot spots, which got immense amounts of domestic, agricultural, and industrial wastes. Behind the influence of these discharges, concentrations are decreased. The PLI over the entire lake ranged from 0.247 to 0.801 for all sites, which reflect unpolluted status.

Assessment and ecological indicators of total and polycyclic aromatic hydrocarbons in the aquatic environment of lake Manzala, Egypt.

The study objective was to assess the profile of aliphatic and polycyclic aromatic hydrocarbons in the aquatic environment of Lake Manzala and to determine the potential sources and effects of these hydrocarbons. To reach these objectives 24 surface sediment and 24 tilapia fish were collected and analyzed using GC-FID and GC-MS. The highest concentrations for n-alkanes (∑n-C15-35) (19,625 ng g-1) and PAHs (∑45PAHs) (5,153 ng g-1) were found in sediments collected from Bahr Al-Baqar drain while Al-Temsah and Al-Hamra sites contained the lowest concentrations. Different diagnostic molecular ratios for hydrocarbons were used to evaluate sources of the hydrocarbons. The hydrocarbons were found to have differing proportions of petrogenic, pyrogenic, and biogenic sources. Comparison to sediment quality guidelines indicated PAHs were below the effect range low (ERL) with the exception of acenaphthene, fluorine, and ∑45PAHs in Bahr Al-Baqar drain sediments. Tissue samples had moderate PAH concentrations for ∑45PAHs ranging from 302.5 ng g-1 West of Bashteer (S3) to 596 ng g-1 in Legam (S5). Since fish metabolize PAH quickly, their detection suggest continual or very recent exposure. The PAH in sediment and fish from Lake Manzala are at a low or below level of environmental concern.

Ecological risk assessment of dissolved heavy metals in the Yangtze River Estuary and Zhejiang coastal waters, China.

The study applied a tiered ecological risk assessment method to evaluate the long-term status and trend of the ecological risks of dissolved heavy metals from 2011 to 2019 in the Yangtze River Estuary and Zhejiang coastal waters, China. The results for spring, summer, and autumn of 2019 indicated that Pb, Cd, and Zn posed no adverse ecological risk, Cu posed a potential ecological risk, and As posed an ecological risk. The annual results from 2011 to 2019 suggested that Pb, Cd, and Zn posed no adverse ecological risks, and As and Cu posed an ecological risk. The trend analysis in the nine years showed that the ecological risk of Cu is gradually decreasing, while that of As is still a concern. The overall trend is attributed to the environmental protection policies that reduced these contaminants' terrestrial sources and atmospheric sources.

Using L. minor and C. elegans to assess the ecotoxicity of real-life contaminated soil samples and their remediation by clay- and carbon-based sorbents.

Toxic substances, such as polycyclic aromatic hydrocarbons (PAHs) and heavy metals, can accumulate in soil, posing a risk to human health and the environment. To reduce the risk of exposure, rapid identification and remediation of potentially hazardous soils is necessary. Adsorption of contaminants by activated carbons and clay materials is commonly utilized to decrease the bioavailability of chemicals in soil and environmental toxicity in vitro, and this study aims to determine their efficacy in real-life soil samples. Two ecotoxicological models (Lemna minor and Caenorhabditis elegans) were used to test residential soil samples, known to contain an average of 5.3, 262, and 9.6 ppm of PAHs, lead, and mercury, for potential toxicity. Toxicity testing of these soils indicated that 86% and 58% of soils caused ≤50% inhibition of growth and survival of L. minor and C. elegans, respectively. Importantly, 3 soil samples caused ≥90% inhibition of growth in both models, and the toxicity was positively correlated with levels of heavy metals. These toxic soil samples were prioritized for remediation using activated carbon and SM-Tyrosine sorbents, which have been shown to immobilize PAHs and heavy metals, respectively. The inclusion of low levels of SM-Tyrosine protected the growth and survival of L. minor and C. elegans by 83% and 78%, respectively from the polluted soil samples while activated carbon offered no significant protection. These results also indicated that heavy metals were the driver of toxicity in the samples. Results from this study demonstrate that adsorption technologies are effective strategies for remediating complex, real-life soil samples contaminated with hazardous pollutants and protecting natural soil and groundwater resources and habitats. The results highlight the applicability of these ecotoxicological models as rapid screening tools for monitoring soil quality and verifying the efficacy of remediation practices.

Advances in Chemical Analysis of Oil Spills Since the Deepwater Horizon Disaster.

Analytical techniques for chemical analysis of oil, oil photochemical and biological transformation products, and dispersants and their biodegradation products benefited significantly from research following the 2010 Deepwater Horizon (DWH) disaster. Crude oil and weathered-oil matrix reference materials were developed based on the Macondo well oil and characterized for polycyclic aromatic hydrocarbons, hopanes, and steranes for use to assure and improve the quality of analytical measurements in oil spill research. Advanced gas chromatography (GC) techniques such as comprehensive two-dimensional GC (GC × GC), pyrolysis GC with mass spectrometry (MS), and GC with tandem MS (GC-MS/MS) provide a greater understanding at the molecular level of composition and complexity of oil and weathering changes. The capabilities of high-resolution MS (HRMS) were utilized to extend the analytical characterization window beyond conventional GC-based methods to include polar and high molecular mass components (>400 Da) and to provide new opportunities for discovery, characterization, and investigation of photooxidation and biotransformation products. Novel separation approaches to reduce the complexity of the oil and weathered oil prior to high-resolution MS and advanced fluorescence spectrometry have increased the information available on spilled oil and transformation products. HRMS methods were developed to achieve the required precision and sensitivity for detection of dispersants and to provide molecular-level characterization of the complex surfactants. Overall, research funding following the DWH oil spill significantly advanced and expanded the use of analytical techniques for chemical analysis to support petroleum and dispersant characterization and investigations of fate and effects of not only the DWH oil spill but future spills.

Recommendations for the advancement of oil-in-water media and source oil characterization in aquatic toxicity test studies.

During toxicity testing, chemical analyses of oil and exposure media samples are needed to allow comparison of results between different tests as well as to assist with identification of the drivers and mechanisms for the toxic effects observed. However, to maximize the ability to compare results between different laboratories and biota, it has long been recognized that guidelines for standard protocols were needed. In 2005, the Chemical Response to Oil Spills: Ecological Effects Research Forum (CROSERF) protocol was developed with existing common analytical methods that described a standard method for reproducible preparation of exposure media as well as recommended specific analytical methods and analyte lists for comparative toxicity testing. At the time, the primary purpose for the data collected was to inform oil spill response and contingency planning. Since then, with improvements in both analytical equipment and methods, the use of toxicity data has expanded to include their integration into fate and effect models that aim to extend the applicability of lab-based study results to make predictions for field system-level impacts. This paper focuses on providing a summary of current chemical analyses for characterization of oil and exposure media used during aquatic toxicity testing and makes recommendations for the minimum analyses needed to allow for interpretation and modeling purposes.

Fire and Oil Led to Complex Mixtures of PAHs on Burnt and Unburnt Plastic during the M/V X-Press Pearl Disaster.

In May 2021, the M/V X-Press Pearl container ship burned for 2 weeks, leading to the largest maritime spill of resin pellets (nurdles). The disaster was exacerbated by the leakage of other cargo and the ship's underway fuel. This disaster affords the unique opportunity to study a time-stamped, geolocated release of plastic under real-world conditions. Field samples collected from beaches in Sri Lanka nearest to the ship comprised nurdles exposed to heat and combustion, burnt plastic pieces (pyroplastic), and oil-plastic agglomerates (petroplastic). An unresolved question is whether the 1600+ tons of spilled and recovered plastic should be considered hazardous waste. Due to the known formation and toxicity of combustion-derived polycyclic aromatic hydrocarbons (PAHs), we measured 20 parent and 21 alkylated PAHs associated with several types of spilled plastic. The maximum PAH content of the sampled pyroplastic had the greatest amount of PAHs recorded for marine plastic debris (199,000 ng/g). In contrast, the sampled unburnt white nurdles had two orders of magnitude less PAH content. The PAH composition varied between the types of spilled plastic and presented features typical of and conflicting with petrogenic and pyrogenic sources. Nevertheless, specific markers and compositional changes for burning plastics were identified, revealing that the fire was the main source of PAHs. Eight months after the spill, the PAH contents of sampled stray nurdles and pyroplastic were reduced by more than 50%. Due to their PAH content exceeding levels allowable for plastic consumer goods, classifying burnt plastic as hazardous waste may be warranted. Following a largely successful cleanup, we recommend that the Sri Lankans re-evaluate the identification, handling, and disposal of the plastic debris collected from beaches and the potential exposure of responders and the public to PAHs from handling it. The maritime disaster underscores pyroplastic as a type of plastic pollution that has yet to be fully explored, despite the pervasiveness of intentional and unintentional burning of plastic globally.

Seasonal and body size-dependent variability in the bioaccumulation of PAHs and their alkyl homologues in pearl oysters in the central Arabian Gulf.

Spatiotemporal concentration patterns for 19 parents and their alkyl homologues were measured in Pinctada radiata from 7 locations in the central Arabian Gulf around Qatar in the winter, spring and summer (2014-2015). The concentrations of PAHs ranged from 20 to 2240 (262 ± 38.0 ng·g-1 dw) with the highest occurrence in the Doha harbor (738.4 ± 197.3 ng·g-1 dw) and the lowest in the west coast of Qatar (48.3 ± 5.8 ng·g-1 dw). Residual PAHs in the oysters were about two times higher in winter than in spring and summer (P < 0.05). PAHs in oysters are dominated by 2 and 3 rings PAHs and their alkyls. Alkylated PAHs (APAHs) comprised >55 % of the ΣPAHs. Statistically significant differences in PAHs profiles among oysters were due in part to differences in lipid contents and shell biometrics. Principal component analysis (PCA) and diagnostic ratios for sources identifications suggested that PAHs accumulations in oysters were due to petrogenic and fuel combustion.

Mesopelagic microbial community dynamics in response to increasing oil and Corexit 9500 concentrations.

Marine microbial communities play an important role in biodegradation of subsurface plumes of oil that form after oil is accidentally released from a seafloor wellhead. The response of these mesopelagic microbial communities to the application of chemical dispersants following oil spills remains a debated topic. While there is evidence that contrasting results in some previous work may be due to differences in dosage between studies, the impacts of these differences on mesopelagic microbial community composition remains unconstrained. To answer this open question, we exposed a mesopelagic microbial community from the Gulf of Mexico to oil alone, three concentrations of oil dispersed with Corexit 9500, and three concentrations of Corexit 9500 alone over long periods of time. We analyzed changes in hydrocarbon chemistry, cell abundance, and microbial community composition at zero, three and six weeks. The lowest concentration of dispersed oil yielded hydrocarbon concentrations lower than oil alone and microbial community composition more similar to control seawater than any other treatments with oil or dispersant. Higher concentrations of dispersed oil resulted in higher concentrations of microbe-oil microaggregates and similar microbial composition to the oil alone treatment. The genus Colwellia was more abundant when exposed to multiple concentrations of dispersed oil, but not when exposed to dispersant alone. Conversely, the most abundant Marinobacter amplicon sequence variant (ASV) was not influenced by dispersant when oil was present and showed an inverse relationship to the summed abundance of Alcanivorax ASVs. As a whole, the data presented here show that the concentration of oil strongly impacts microbial community response, more so than the presence of dispersant, confirming the importance of the concentrations of both oil and dispersant in considering the design and interpretation of results for oil spill simulation experiments.

Exposure methodologies for dissolved individual hydrocarbons, dissolved oil, water oil dispersions, water accommodated fraction and chemically enhanced water accommodated fraction of fresh and weathered oil.

Characterizing the nature and effects of oil released into the marine environment is very challenging. It is generally recognized that "environmentally relevant" conditions for exposure involve a range of temporal and spatial conditions, a range of exposure pathways (e.g., dissolved, emulsions, sorbed onto particulates matter), and a multitude of organisms, populations, and ecosystems. Various exposure methodologies have been used to study the effects of oil on aquatic organisms, and uniform protocols and exposure methods have been developed for the purposes of regulatory toxicological assessments. Ultimately, all exposure methods have drawbacks, it is impossible to totally mimic field conditions, and the choice of exposure methodology depends on the specific regulatory, toxicological, or other research questions to be addressed. The aim of this paper is to provide a concise review of the state of knowledge to identify gaps in that knowledge and summarize challenges for the future.

Using epibenthic fauna as biomonitors of local marine contamination adjacent to McMurdo Station, Antarctica.

Ten benthic fauna taxa in a polluted marine area adjacent to McMurdo Station, Antarctica were deemed to be potential biomonitors because PCBs, DDTs, PAHs, copper, lead and/or zinc in their tissues were significantly higher than in tissues of taxa living in reference areas (p < 0.05). Concentrations of PCBs and DDT were highest in Trematomus (fish). Total PAH concentrations were highest in Alcyonium antarcticum (soft coral), Isotealia antarctica (anemone) and L. elliptica. Copper and lead concentrations were highest in Laternula elliptica (bivalve) and Flabegraviera mundata (polychaete), and lowest in Trematomus and Parbolasia corrugatus (nemertean). However, copper concentrations were even higher in the asteroids Perknaster fuscus antarcticus, Odontaster validus and Psilaster charcoti. Bioaccumulation factors for different species were highest for PCBs and DDT, and lowest for lead. Bioaccumulation of some contaminants are likely prevalent in benthic taxa at McMurdo Station, but concentrations are usually low relative to human consumption standards.

Tight sorption of arsenic, cadmium, mercury, and lead by edible activated carbon and acid-processed montmorillonite clay.

Heavy metal exposure in humans and animals commonly occurs through the consumption of metal-contaminated drinking water and food. Although many studies have focused on the remediation of metals by purification of water using sorbents, limited therapeutic sorbent strategies have been developed to minimize human and animal exposures to contaminated water and food. To address this need, a medical grade activated carbon (MAC) and an acid processed montmorillonite clay (APM) were characterized for their ability to bind heavy metals and mixtures. Results of screening and adsorption/desorption isotherms showed that binding plots for arsenic, cadmium, and mercury sorption on surfaces of MAC (and lead on APM) fit the Langmuir model. The highest binding percentage, capacity, and affinity were shown in a simulated stomach model, and the lowest percentage desorption (< 18%) was shown in a simulated intestine model. The safety and protective ability of MAC and APM were confirmed in a living organism (Hydra vulgaris) where 0.1% MAC significantly protected the hydra against As, Cd, Hg, and a mixture of metals by 30-70%. In other studies, APM showed significant reduction (75%) of Pd toxicity, compared with MAC and heat-collapsed APM, suggesting that the interlayer of APM was important for Pb sorption. This is the first report showing that edible sorbents can bind mixtures of heavy metals in a simulated gastrointestinal tract and prevent their toxicity in a living organism. Graphical abstract.

Spatial Distribution of Polycyclic Aromatic Hydrocarbon Contaminants after Hurricane Harvey in a Houston Neighborhood.

BACKGROUND: Hurricane Harvey made landfall along the Texas Gulf Coast as a Category 4 hurricane on August 25, 2017, producing unprecedented precipitation that devastated coastal areas. Catastrophic flooding in the City of Houston inundated industrial and residential properties resulting in the displacement and transfer of soil, sediment, and debris and heightening existing environmental justice (EJ) concerns. OBJECTIVES: The primary aim of this study was to evaluate the presence, distribution, and potential human health implications of polycyclic aromatic hydrocarbons (PAHs) in a residential neighborhood of Houston, Texas following a major hurricane. METHODS: Concentrations of PAHs in 40 soil samples collected from a residential neighborhood in Houston, Texas were measured. Spatial interpolation was applied to determine the distribution of PAHs. Potential human health risks were evaluated by calculating toxicity equivalency quotients (TEQs) and incremental excess lifetime cancer risk (IELCR). RESULTS: Total priority PAH concentrations varied across samples (range: 9.7 × 101 ng/g-1.6 × 104 ng/g; mean: 3.0 × 103 ng/g ± 3.6 × 103 standard deviation). Spatial analysis indicated a variable distribution of PAH constituents and concentrations. The IELCR analysis indicated that nine of the 40 samples were above minimum standards. CONCLUSIONS: Findings from this study highlight the need for fine scale soil testing in residential areas as well as the importance of site-specific risk assessment. COMPETING INTERESTS: The authors declare no competing financial interests.

Long-term changes in contamination and macrobenthic communities adjacent to McMurdo Station, Antarctica.

Improved waste management at McMurdo Station, Antarctica beginning in the 1980s has been followed by decreases in polycyclic aromatic hydrocarbon (PAH) and metal contamination in the adjacent marine sediments. However, determining the effect of the decreased contamination on marine ecological indicators (macrobenthic fauna) is confounded by concurrent changes in climate cycles and other physical forces. Between 2000 and 2013, there was a decrease in concentrations of some contaminants including mercury, copper, organochlorines, and PAHs in marine sediments adjacent to McMurdo Station. PAH concentrations in Winter Quarters Bay decreased an order of magnitude from 2000/2003 to 2012/2013 and were within an order of magnitude of reference area concentrations by 2013. Macrobenthic communities did not indicate any sign of recovery and have not become more similar to reference communities over this same period of time. Temporal changes in macrobenthic community composition during the study period had higher correlations with climatic and sea ice dynamics than with changes in contaminant concentrations. The Interdecadal Pacific Oscillation climatic index had the highest correlation with macrobenthic community composition. The Antarctic Oscillation climatic index, maximum ice extent and other natural environmental factors also appear to influence macrobenthic community composition. Despite large improvements in environmental management at McMurdo Station, continuing environmental vigilance is necessary before any noticeable improvement in ecological systems is likely to occur. The effects of climate must be considered when determining temporal changes in anthropogenic effects in Antarctica. Maintaining long-term monitoring of both contaminants and ecological indicators is important for determining the localized and global influences of humans on Antarctica, which will have implications for the whole planet.

Environmental impacts of Hurricane Florence flooding in eastern North Carolina: temporal analysis of contaminant distribution and potential human health risks.

BACKGROUND: Hurricane Florence made landfall in North Carolina in September 2018 causing extensive flooding. Several potential point sources of hazardous substances and Superfund sites sustained water damage and contaminants may have been released into the environment. OBJECTIVE: This study conducted temporal analysis of contaminant distribution and potential human health risks from Hurricane Florence-associated flooding. METHODS: Soil samples were collected from 12 sites across four counties in North Carolina in September 2018, January and May 2019. Chemical analyses were performed for organics by gas chromatography-mass spectrometry. Metals were analyzed using inductively coupled plasma mass spectrometry. Hazard index and cancer risk were calculated using EPA Regional Screening Level Soil Screening Levels for residential soils. RESULTS: PAH and metals detected downstream from the coal ash storage pond that leaked were detected and were indicative of a pyrogenic source of contamination. PAH at these sites were of human health concern because cancer risk values exceeded 1 × 10-6 threshold. Other contaminants measured across sampling sites, or corresponding hazard index and cancer risk, did not exhibit spatial or temporal differences or were of concern. SIGNIFICANCE: This work shows the importance of rapid exposure assessment following natural disasters. It also establishes baseline levels of contaminants for future comparisons.

Polycyclic aromatic hydrocarbon status in post-hurricane Harvey sediments: Considerations for environmental sampling in the Galveston Bay/Houston Ship Channel region.

Hurricane Harvey led to a broad redistribution of sediment throughout Galveston Bay and the Houston Ship Channel (GB/HSC), but the resulting changes in chemical contaminant distributions have yet to be characterized. To address this question, we collected and analyzed post-Harvey sediment for concentrations of the EPA 16 Priority Pollutant polycyclic aromatic hydrocarbon (PAHs), determining the extent to which the spatial distribution and sourcing of contaminants may have changed in contrast to historical surface sediment data (<5 cm) from the National Oceanic Atmospheric Administration (NOAA) available for the years 1996-2011. We found a small, but detectable increase from pre- to post-Harvey in PAH concentrations, with PAH diagnostic sourcing indicating combustion origins. Of the detected PAHs, none exceeded Sediment Quality Guideline values. Overall, we have added to the understanding of PAH spatial trends within the GB/HSC region, and developed a reference PAH baseline to inform future studies.

Polycyclic aromatic hydrocarbons in soil of the Canadian river floodplain in Oklahoma.

The accumulation of polycyclic aromatic hydrocarbons (PAH) in soil, plants, and water may impart negative effects on ecosystem and human health. We quantified the concentration and distribution of 41 PAH (n = 32), organic C, total N, and S (n = 140) and investigated PAH sources using a chronosequence of floodplain soils under a natural vegetation succession. Soil samples were collected between 0- and 260-cm depth in bare land (the control), wetland, forest, and grassland areas near a closed municipal landfill and an active asphalt plant (the contaminant sources) in the north bank of the Canadian River near Norman, OK. Principal component, cluster, and correlation analyses were used to investigate the spatial distribution of PAH, in combination with diagnostic ratios to distinguish pyrogenic vs. petrogenic PAH suites. Total PAH concentration (SigmaPAH) had a mean of 1300 ng g(-1), minimum of 16 ng g(-1), and maximum of 12,000 ng g(-1). At 0- to 20-cm depth, SigmaPAH was 3500 +/- 1600 ng g(-1) (mean +/- 1 SE) near the contaminant sources. The most common compounds were nonalkylated, high molecular weight PAH of pyrogenic origin, i.e., fluoranthene (17%), pyrene (14%), phenanthrene (9%), benzo(b)fluoranthene (7%), chrysene (6%), and benzo(a)anthracene (5%). SigmaPAH in the control (130 +/- 23 ng g(-1)) was comparable to reported concentrations for the rural Great Plains. Perylene had a unique distribution pattern suggesting biological inputs. The main PAH contamination mechanisms were likely atmospheric deposition due to asphalt production at the 0- to 20-cm depth and past landfill operations at deeper depths.

Niche Partitioning between Coastal and Offshore Shelf Waters Results in Differential Expression of Alkane and Polycyclic Aromatic Hydrocarbon Catabolic Pathways.

Marine oil spills can impact both coastal and offshore marine environments, but little information is available on how the microbial response to oil and dispersants might differ between these biomes. Here, we describe the compositional and functional response of microbial communities to different concentrations of oil and chemically dispersed oil in coastal and offshore surface waters from the Texas-Louisiana continental shelf. Using a combination of analytical chemistry and 16S rRNA amplicon and metatranscriptomic sequencing, we provide a broad, comparative overview of the ecological response of hydrocarbon-degrading bacteria and their expression of hydrocarbon-degrading genes in marine surface waters over time between two oceanic biomes. We found evidence for the existence of different ecotypes of several commonly described hydrocarbon-degrading bacterial taxa which behaved differentially in coastal and offshore shelf waters despite being exposed to similar concentrations of oil, dispersants, and nutrients. This resulted in the differential expression of catabolic pathways for n-alkanes and polycyclic aromatic hydrocarbons (PAHs)-the two major categories of compounds found in crude oil-with preferential expression of n-alkane degradation genes in coastal waters while offshore microbial communities trended more toward the expression of PAH degradation genes. This was unexpected as it contrasts with the generally held view that n-alkanes, being more labile, are attacked before the more refractory PAHs. Collectively, our results provide new insights into the existence and potential consequences of niche partitioning of hydrocarbon-degrading taxa between neighboring marine environments.IMPORTANCE In the wake of the Deepwater Horizon oil spill, the taxonomic response of marine microbial communities to oil and dispersants has been extensively studied. However, relatively few studies on the functional response of these microbial communities have been reported, especially in a longitudinal fashion. Moreover, despite the fact that marine oil spills typically impact thousands of square kilometers of both coastal and offshore marine environments, little information is available on how the microbial response to oil and dispersants might differ between these biomes. The results of this study help fill this critical knowledge gap and provide valuable insight into how oil spill response efforts, such as chemically dispersing oil, may have differing effects in neighboring coastal and offshore marine environments.