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.

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.

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.

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.