Impacts of anthropogenic emissions and meteorology on spring ozone differences in San Antonio, Texas between 2017 and 2021.

San Antonio has been designated as ozone nonattainment under the current National Ambient Air Quality Standards (NAAQS). Ozone events in the city typically occur in two peaks, characterized by a pronounced spring peak followed by a late summer peak. Despite higher ozone levels, the spring peak has received less attention than the summer peak. To address this research gap, we used the Weather Research and Forecasting (WRF)-driven GEOS-Chem (WRF-GC) model to simulate San Antonio's ozone changes in the spring month of May from 2017 to 2021 and quantified the respective contributions from changes in anthropogenic emissions and meteorology. In addition to modeling, observations from the San Antonio Field Studies (SAFS), the Texas Commission on Environmental Quality (TCEQ) Continuous Ambient Monitoring Stations (CAMS), and the spaceborne TROPOspheric Monitoring Instrument (TROPOMI) are used to examine and validate changes in ozone and precursors. Results show that the simulated daytime mean surface ozone in May 2021 is 3.8 ± 0.6 ppbv lower than in May 2017, which is slightly less than the observed average differences of -5.3 ppbv at CAMS sites. The model predicted that the anthropogenic emission-induced changes contribute to a 1.4 ± 0.5 ppbv reduction in daytime ozone levels, while the meteorology-induced changes account for a 2.4 ± 0.6 ppbv reduction over 2017-2021. This suggests that meteorology plays a relatively more important role than anthropogenic emissions in explaining the spring ozone differences between the two years. We additionally identified (1) reduced NO2 and HCHO concentrations as chemical reasons, and (2) lower temperature, higher humidity, increased wind speed, and a stronger Bermuda High as meteorological reasons for lower ozone levels in 2021 compared to 2017. The quantification of the different roles of meteorology and ozone precursor concentrations helps understand the cause and variation of ozone changes in San Antonio over recent years.

Marine Submicron Aerosols from the Gulf of Mexico: Polluted and Acidic with Rapid Production of Sulfate and Organosulfates.

We measured submicron aerosols (PM1) at a beachfront site in Texas in Spring 2021 to characterize the "background" aerosol chemical composition advecting into Texas and the factors controlling this composition. Observations show that marine "background" aerosols from the Gulf of Mexico were highly processed and acidic; sulfate was the most abundant component (on average 57% of total PM1 mass), followed by organic material (26%). These chemical characteristics are similar to those observed at other marine locations globally. However, Gulf "background" aerosols were much more polluted; the average non-refractory (NR-) PM1 mass concentration was 3-70 times higher than that observed in other clean marine atmospheres. Anthropogenic shipping emissions over the Gulf of Mexico explain 78.3% of the total measured "background" sulfate in the Gulf air. We frequently observed haze pollution in the air mass from the Gulf, with significantly elevated concentrations of sulfate, organosulfates, and secondary organic aerosol associated with sulfuric acid. Analysis suggests that aqueous oxidation of shipping emissions over the Gulf of Mexico by peroxides in the particles might potentially be an important pathway for the rapid production of acidic sulfate and organosulfates during the haze episodes under acidic conditions.

Traffic, transport, and vegetation drive VOC concentrations in a major urban area in Texas.

The population of Texas has increased rapidly in the past decade. The San Antonio Field Study (SAFS) was designed to investigate ozone (O3) production and precursors in this rapidly changing, sprawling metropolitan area. There are still many questions regarding the sources and chemistry of volatile organic compounds (VOCs) in urban areas like San Antonio which are affected by a complex mixture of industry, traffic, biogenic sources and transported pollutants. The goal of the SAFS campaign in May 2017 was to measure inorganic trace gases, VOCs, methane (CH4), and ethane (C2H6). The SAFS field design included two sites to better assess air quality across the metro area: an urban site (Traveler's World; TW) and a downwind/suburban site (University of Texas at San Antonio; UTSA). The results indicated that acetone (2.52 ± 1.17 and 2.39 ± 1.27 ppbv), acetaldehyde (1.45 ± 1.02 and 0.93 ± 0.45 ppbv) and isoprene (0.64 ± 0.49 and 1.21 ± 0.85 ppbv; TW and UTSA, respectively) were the VOCs with the highest concentrations. Additionally, positive matrix factorization showed three dominant factors of VOC emissions: biogenic, aged urban mixed source, and acetone. Methyl vinyl ketone and methacrolein (MVK + MACR) exhibited contributions from both secondary photooxidation of isoprene and direct emissions from traffic. The C2H6:CH4 demonstrated potential influence of oil and gas activities in San Antonio. Moreover, the high O3 days during the campaign were in the NOx-limited O3 formation regime and were preceded by evening peaks in select VOCs, NOx and CO. Overall, quantification of the concentration and trends of VOCs and trace gases in a major city in Texas offers vital information for general air quality management and supports strategies for reducing O3 pollution. The SAFS campaign VOC results will also add to the growing body of literature on urban sources and concentrations of VOCs in major urban areas.

Assessing the atmospheric fate of pesticides used to control mosquito populations in Houston, TX.

During the summer months, urban areas are literal hot spots of mosquito-borne disease transmission and air pollution. Public health authorities release aerosolized pesticides directly into the atmosphere to help control adult mosquito populations and thereby reduce the threat of diseases, such as Zika Virus. The primary adulticides (i.e. pesticides used to control adult mosquito populations) in Houston, TX are permethrin and malathion. These adulticides are typically sprayed at night using ultra-low volume sprayers. Particulate matter (PM) samples including total suspended and fine PM (PM < 2.5 µm in aerodynamic diameter) were collected at four ground-based sites across Houston in 2013 and include daytime, nighttime, and 24 h samples. Malathion is initially sprayed as coarse aerosol (5-25 µm), but is measured in fine aerosol (<2.5 µm) and coarse aerosol in the urban atmosphere. Particle size is relevant both for deposition velocities and for human exposure. Atmospheric permethrin concentrations measured in nighttime samples peak at 60 ng m-3, while malathion nighttime concentrations peak near 40 ng m-3. Malaoxon, an oxidation product of malathion, was also frequently detected at concentrations >10 ng m-3, indicating significant nighttime oxidation. Based on the loss of malathion and the increase in malaoxon, the atmospheric half-life of malathion in Houston was estimated at <12 h, which was significantly shorter than previous half-life estimates (∼days). Importantly, malaoxon is estimated to be 22-33 times more toxic to humans than malathion. Both the aerosol size and the half-life are critical for mosquito control, human exposure, and risk assessment of these routine pesticides.

Apportioned primary and secondary organic aerosol during pollution events of DISCOVER-AQ Houston.

Understanding the drivers for high ozone (O3) and atmospheric particulate matter (PM) concentrations is a pressing issue in urban air quality, as this understanding informs decisions for control and mitigation of these key pollutants. The Houston, TX metropolitan area is an ideal location for studying the intersection between O3 and atmospheric secondary organic carbon (SOC) production due to the diversity of source types (urban, industrial, and biogenic) and the on- and off-shore cycling of air masses over Galveston Bay, TX. Detailed characterization of filter-based samples collected during Deriving Information on Surface Conditions from Column and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) Houston field experiment in September 2013 were used to investigate sources and composition of organic carbon (OC) and potential relationships between daily maximum 8 h average O3 and PM. The current study employed a novel combination of chemical mass balance modeling defining primary (i.e. POC) versus secondary (i.e. SOC) organic carbon and radiocarbon (14C) for apportionment of contemporary and fossil carbon. The apportioned sources include contemporary POC (biomass burning [BB], vegetative detritus), fossil POC (motor vehicle exhaust), biogenic SOC and fossil SOC. The filter-based results were then compared with real-time measurements by aerosol mass spectrometry. With these methods, a consistent urban background of contemporary carbon and motor vehicle exhaust was observed in the Houston metropolitan area. Real-time and filter-based characterization both showed that carbonaceous aerosols in Houston was highly impacted by SOC or oxidized OC, with much higher contributions from biogenic than fossil sources. However, fossil SOC concentration and fractional contribution had a stronger correlation with daily maximum 8 h average O3, peaking during high PM and O3 events. The results indicate that point source emissions processed by on- and off-shore wind cycles likely contribute to peak events for both PM and O3 in the greater Houston metropolitan area.

Evidence of multi-decadal behavior and ecosystem-level changes revealed by reconstructed lifetime stable isotope profiles of baleen whale earplugs.

Biological time series datasets provide an unparalleled opportunity to investigate regional and global changes in the marine environment. Baleen whales are long-lived sentinel species and an integral part of the marine ecosystem. Increasing anthropogenic terrestrial and marine activities alter ocean systems, and such alterations could change foraging and feeding behavior of baleen whales. In this study, we analyzed δ13C and δ15N of baleen whale earplugs from three different species (N = 6 earplugs, n = 337 laminae) to reconstruct the first continuous stable isotope profiles with a six-month resolution. Results of our study provide an unprecedented opportunity to assess behavioral as well as ecological changes. Abrupt shifts and temporal variability observed in δ13C and δ15N profiles could be indicative of behavior change such as shift in foraging location and/or trophic level in response to natural or anthropogenic disturbances. Additionally, five out of six individuals demonstrated long-term declining trends in δ13C profiles, which could suggest influence of emission of depleted 13CO2 from fossil fuel combustion referred to as the Suess effect. After adjusting the δ13C values of earplugs for the estimated Suess effect and re-evaluating δ13C profiles, significant decline in δ13C values as well as different rate of depletion suggest contribution of other sources that could impact δ13C values at the base of the food web.

Hormone comparison between right and left baleen whale earplugs.

Marine animals experience additional stressors as humans continue to industrialize the oceans and as the climate continues to rapidly change. To examine how the environment or humans impact animal stress, many researchers analyse hormones from biological matrices. Scientists have begun to examine hormones in continuously growing biological matrices, such as baleen whale earwax plugs, baleen and pinniped vibrissae. Few of these studies have determined if the hormones in these tissues across the body of the organism are interchangeable. Here, hormone values in the right and left earplugs from the same individual were compared for two reasons: (i) to determine whether right and left earplug hormone values can be used interchangeably and (ii) to assess methods of standardizing hormones in right and left earplugs to control for individuals' naturally varying hormone expressions. We analysed how absolute, baseline-corrected and Z-score normalized hormones performed in reaching these goals. Absolute hormones in the right and left earplugs displayed a positive relationship, while using Z-score normalization was necessary to standardize the variance in hormone expression. After Z-score normalization, it was possible to show that the 95% confidence intervals of the differences in corresponding lamina of the right and left earplugs include zero for both cortisol and progesterone. This indicates that the hormones in corresponding lamina of right and left earplugs are no different from zero. The results of this study reveal that both right and left earplugs from the same baleen whale can be used in hormone analyses after Z-score normalization. This study also shows the importance of Z-score normalization to interpretation of results and methodologies associated with analysing long-term trends using whale earplugs.

Eighty years of chemical exposure profiles of persistent organic pollutants reconstructed through baleen whale earplugs.

Despite decades of effort, significant knowledge gaps still exist regarding the global transport and distribution of persistent organic pollutants (POPs) in marine ecosystems, especially for periods prior to the 1970s. Furthermore, for long-lived marine mammals such as baleen whales, POPs impacts on early developmental (first years of life), as well as lifetime exposure profiles for periods of use and phase-out, are not well characterized. Recently, analytical techniques capable of reconstructing lifetime (i.e., birth to death; ~6 mos. resolution) chemical exposure profiles in baleen whale earplugs have been developed. Earplugs represent a unique opportunity to examine the spatiotemporal trends of POPs in the marine ecosystem. Baleen whale earplugs were collected from six whales (one blue whale (Balaenoptera musculus) and five fin whales (Balaenoptera physalus)), including four from archived collections and two from recent strandings. Lifespans for some of these individuals date back to the 1930s and provide insight into early periods of POP use. POP concentrations (reported in ng g-1 dry wt.) were determined in laminae (n = 35) and were combined with age estimates and calendar year to reconstruct lifetime POP exposure profiles and lifetime bioaccumulation rates. Dichlorodiphenyltrichloroethane (DDT) and polychlorinated biphenyls (PCBs) were found to be the most dominant POPs (spanning the past 80 y), were detected as early as the 1930s and were ubiquitous in the North Pacific and Atlantic Oceans. Lifetime bioaccumulation rates determined using baleen whale earplugs were 56 times higher in the North Pacific as compared to the North Atlantic. This suggest baleen whales from the North Pacific may be to be exposed to increased levels of POPs.

Baleen whale cortisol levels reveal a physiological response to 20th century whaling.

One of the most important challenges researchers and managers confront in conservation ecology is predicting a population's response to sub-lethal stressors. Such predictions have been particularly elusive when assessing responses of large marine mammals to past anthropogenic pressures. Recently developed techniques involving baleen whale earplugs combine age estimates with cortisol measurements to assess spatial and temporal stress/stressor relationships. Here we show a relationship between baseline-corrected cortisol levels and corresponding whaling counts of fin, humpback, and blue whales in the Northern Hemisphere spanning the 20th century. We also model the impact of alternative demographic and environmental factors and determine that increased anomalies of sea surface temperature over a 46-year mean (1970-2016) were positively associated with cortisol levels. While industrial whaling can deplete populations by direct harvest, our data underscore a widespread stress response in baleen whales that is peripheral to whaling activities or associated with other anthropogenic change.

Polychlorinated biphenyl (PCB) contamination in Galveston Bay, Texas: Comparing concentrations and profiles in sediments, passive samplers, and fish.

The industrialized portion of the Houston Ship Channel (HSC) is heavily contaminated with anthropogenic contaminants, most prominent of which are the polychlorinated biphenyls (PCBs). This contamination has driven adaptive evolution in a keystone species for Galveston Bay, the Gulf killifish (Fundulus grandis). We investigated the geographical extent of PCB impacts by sampling 12 sites, ranging from the heavily industrialized upper portion of the HSC to Galveston Island. At each site, PCB concentrations and profiles were determined in three environmental compartments: sediment, water (polyethylene passive samplers), and fish tissue (resident Gulf killifish). We observed a steep gradient of PCB contamination, ranging from 4.00 to 100,000 ng/g organic carbon in sediment, 290-110,000 ng/g lipid in fish, and 4.5-2300 ng/g polyethylene in passive samplers. The PCB congener profiles in Gulf killifish at the most heavily contaminated sites were shifted toward the higher chlorinated PCBs and were highly similar to the sediment contamination profiles. In addition, while magnitude of total PCB concentrations in sediment and total fish contamination levels were highly correlated between sites, the relative PCB congener profiles in fish and passive samplers were more alike. This strong correlation, along with a lack of dependency of biota-sediment accumulation factors with total contamination rates, confirm the likely non-migratory nature of Gulf killifish and suggest their contamination levels are a good site-specific indicator of contamination in the Galveston Bay area. The spatial gradient of PCB contamination in Galveston Bay was evident in all three matrices studied and was observed effectively using Gulf killifish contamination as an environmentally relevant bioindicator of localized contamination in this environment.

Persistent Organic Pollutant and Hormone Levels in Harbor Porpoise with B Cell Lymphoma.

B-cell lymphoma, a common morphologic variant of non-Hodgkin lymphoma, has been associated with persistent pollutants in humans, but this association is not well-characterized in top-level predators sharing marine resources with humans. We characterized and compared blubber contaminants and hormones of a pregnant harbor porpoise (Phocoena phocoena) with B-cell lymphoma, with those in two presumed healthy fishery by-caught porpoises with no lymphoma: a pregnant adult and female juvenile. Common historic use compounds, including polychlorinated biphenyls, polybrominated diphenyl ethers, and pesticides, were evaluated in blubber samples from three porpoises. In addition, blubber cortisol and progesterone levels (ng/g) were determined in all three animals. Total pollutant concentrations were highest in the juvenile porpoise, followed by the lymphoma porpoise and the nonlymphoma adult. Blubber cortisol concentrations were 191% greater in the pregnant with lymphoma porpoise compared with the pregnant no lymphoma porpoise, and 89% greater in the juvenile female compared with the pregnant no lymphoma porpoise. Although both adults were pregnant, progesterone levels were substantially greater (90%) in the healthy compared with the lymphoma adult. Health monitoring of top-level marine predators, such as porpoise, provides a sentinel measure of contaminants that serve as indicators of potential environmental exposure to humans.

Spatial and Temporal Distributions of Organophosphate Ester Concentrations from Atmospheric Particulate Matter Samples Collected across Houston, TX.

Atmospheric particulate matter (PM) samples were collected from four ground-based sites located in the Houston, TX (September 21-28, 2013) and were analyzed for 12 organophosphate esters (OPEs; current-use plasticizers and flame retardants). Samples analyzed included daytime, nighttime, and 24 h PM of <2.5 µm aerodynamic diameter (PM2.5) and total suspended particulate (TSP) samples. PM2.5 and TSP atmospheric ΣOPE concentrations varied over an order of magnitude and were statistically significantly different between urban and suburban and industrial sites. Additionally, significant temporal variability was also identified; for example, daytime atmospheric concentrations of 2-ethylhexyl diphenyl phosphate (EHDPP; 610 ± 220 pg m-3) measured in TSP samples were significantly higher than nighttime concentrations (280 ± 180 pg m-3; p = 0.03). Detailed discussions of the spatial and temporal distribution are given for Tris-(1-chloro-2-propyl) phosphate (TCiPP), EHDPP, tri-n-butyl phosphate (TnBP), and triphenyl phosphate (TPhP). Correlations to bulk measurements of carbonaceous PM including organic carbon, elemental carbon, and water-soluble organic carbon were used to understand potential sources and urban atmospheric transport. These results highlight the fundamental complexity associated with assessing OPE atmospheric concentrations across a large urban landscape and specific knowledge gaps at the intersection of consumer products and safety with environmental and human health.

Spatial and Temporal Distribution of Current-Use Pesticides in Atmospheric Particulate Matter in Houston, Texas.

The atmospheric concentrations of seven current-use pesticides in particulate matter were determined at four locations throughout the Houston metropolitan area in TSP and PM2.5 samples from September 2013. Atmospheric concentrations in both TSP and PM2.5 ranged from below method detection limits (MDLs) to nearly 1100 pg m-3. The three compounds most frequently detected above MDLs were chlorothalonil, bifenthrin, and λ-cyhalothrin. Atmospheric chlorothalonil concentrations were above 800 pg m-3 in several TSP samples, but

Temporal variation in groundwater quality in the Permian Basin of Texas, a region of increasing unconventional oil and gas development.

The recent expansion of natural gas and oil extraction using unconventional oil and gas development (UD) practices such as horizontal drilling and hydraulic fracturing has raised questions about the potential for environmental impacts. Prior research has focused on evaluations of air and water quality in particular regions without explicitly considering temporal variation; thus, little is known about the potential effects of UD activity on the environment over longer periods of time. Here, we present an assessment of private well water quality in an area of increasing UD activity over a period of 13months. We analyzed samples from 42 private water wells located in three contiguous counties on the Eastern Shelf of the Permian Basin in Texas. This area has experienced a rise in UD activity in the last few years, and we analyzed samples in four separate time points to assess variation in groundwater quality over time as UD activities increased. We monitored general water quality parameters as well as several compounds used in UD activities. We found that some constituents remained stable over time, but others experienced significant variation over the period of study. Notable findings include significant changes in total organic carbon and pH along with ephemeral detections of ethanol, bromide, and dichloromethane after the initial sampling phase. These data provide insight into the potentially transient nature of compounds associated with groundwater contamination in areas experiencing UD activity.

Pressurized liquid extraction technique for the analysis of pesticides, PCBs, PBDEs, OPEs, PAHs, alkanes, hopanes, and steranes in atmospheric particulate matter.

An analytical method has been developed for the pressurized liquid extraction (PLE) of a wide range of semi-volatile organic compounds (SVOCs) from atmospheric particulate matter. Approximately 130 SVOCs from eight compound classes were selected as molecular markers of (1) agricultural activity (30 current and historic-use pesticides), (2) industrial activity (18 PCBs), (3) consumer products and building materials (16 PBDEs, 11 OPEs), and (4) motor vehicle exhaust (22 PAHs, 16 alkanes, 9 hopanes, 8 steranes). Currently, there is no analytical method validated for the extraction of all eight compound classes in a single automated technique. The extraction efficiencies of varying solvents and solvent combinations at high temperatures and pressures were examined. Extracts were concentrated and analyzed by gas chromatography coupled with mass spectrometry. The optimized PLE method utilized methylene chloride:acetone (2:1 v/v) at 100 °C with three (5 min) static cycles, flush volume of 80%, and a 100 s N2 purge. Spike and recovery experiments (n=7) provided average percent recoveries for pesticides, PCBs, PBDEs, OPEs, PAHs, alkanes, hopanes, and steranes of 88.8±4.0%, 86.9±2.6%, 83.8±2.9%, 101±6%, 90.3±6.1%, 74.4±8.8%, 104±8%, and 86.5±8.6%, respectively. The developed method was applied to atmospheric particulate matter samples collected in the greater Houston, TX metropolitan area. Ambient concentrations of eight classes of compounds (92 SVOCs) were reported in pg m(-3).

Evolved resistance to PCB- and PAH-induced cardiac teratogenesis, and reduced CYP1A activity in Gulf killifish (Fundulus grandis) populations from the Houston Ship Channel, Texas.

The Houston Ship Channel (HSC), connecting Houston, Texas to Galveston Bay and ultimately the Gulf of Mexico, is heavily industrialized and includes several areas that have historically been identified as containing significant levels of mercury, dioxins, furans, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). Gulf killifish, Fundulus grandis, inhabit this entire estuarine system, including the most contaminated areas. F. grandis is the sister species of the well-established estuarine model organism Fundulus heteroclitus, for which heritable resistance to both PCB and PAH toxicity has been documented in several populations. F. grandis collected from two Superfund sites on the HSC and from a reference population were used to establish breeding colonies. F1 embryos from HSC populations were approximately 1000-fold more resistant to PCB126- and 2-5-fold more resistant to coal tar-induced cardiovascular teratogenesis, relative to embryos from the reference population. Reciprocal crosses between reference and contaminated populations exhibit an intermediate level of resistance, confirming that observed protection is genetic and biparentally inherited. Ethoxyresorufin-O-deethylase (EROD) data confirm a reduction in basal and induced cytochrome P4501A (CYP1A) activity in resistant populations of F. grandis. This result is consistent with responses previously described for resistant populations of F. heteroclitus, specifically a recalcitrant aryl hydrocarbon receptor (AHR) pathway. The decreased levels of cardiovascular teratogenesis, and decrease in CYP1A inducibility in response to PCB126 and a PAH mixture, suggest that HSC F. grandis populations have adapted to chronic contaminants exposures via a mechanism similar to that previously described for F. heteroclitus. To the best of our knowledge, this is the first documentation of evolved pollution resistance in F. grandis. Additionally, the mechanistic similarities between the population adaptation observed in this study and previous work in F. heteroclitus suggest that genetic variation predating the evolutionary divergence of these two species may best explain the apparent rapid parallel evolution of pollution resistance in genetically and geographically distinct species and populations.

Development and application of a novel method for high-throughput determination of PCDD/Fs and PCBs in sediments.

A selective pressurized liquid extraction technique was developed for the simultaneous extraction of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) from contaminated sediments. The final method incorporated cleanup adsorbents (Florisil, alumina, and silica) into the extraction cell in a 1:1 ratio of matrix to individual adsorbent (w/w). Sulfur, a common interference found in sediments, was successfully removed by placing activated copper in the extraction bottle prior to extraction. No additional postextraction cleanup was required, and sample throughput was reduced to 2.5 h per sample. Target analytes were quantified using high-resolution gas chromatography/electron-capture negative ionization mass spectrometry and verified by high-resolution gas chromatography/high-resolution mass spectrometry. Though mean analyte recoveries (n = 3) of PCDD/Fs and dl-PCBs were 84 ± 5.8% and 70 ± 8.4%, respectively, mean surrogate recoveries for all PCDD/Fs using this novel method were greatly improved compared with US Environmental Protection Agency (USEPA) method 1613 (∼25-155%) and USEPA method 8290a (40-135%). After development, the method was used to examine surficial sediment samples from the San Jacinto River waste pits, a Superfund site in Houston, Texas, USA. In all samples, PCDD/Fs and dl-PCBs were detected, and the contaminant concentrations ranged over 5 orders of magnitude.

Selective pressurized liquid extraction technique capable of analyzing dioxins, furans, and PCBs in clams and crab tissue.

A selective pressurized liquid extraction technique (SPLE) was developed for the analysis of polychlorodibenzo-p-dioxins, polychlorodibenzofurans (PCDD/Fs) and dioxin-like polychlorobiphenyls (dl-PCBs) in clam and crab tissue. The SPLE incorporated multiple cleanup adsorbents (alumina, florisil, silica gel, celite, and carbopack) within the extraction cell. Tissue extracts were analyzed by high resolution gas chromatography coupled with electron capture negative ionization mass spectrometry. Mean recovery (n = 3) and percent relative standard deviation for PCDD/Fs and dl-PCBs in clam and crabs was 89 ± 2.3 and 85 ± 4.0, respectively. The SPLE method was applied to clams and crabs collected from the San Jacinto River Waste Pits, a Superfund site in Houston, TX. The dl-PCBs concentrations in clams and crabs ranged from 50 to 2,450 and 5 to 800 ng/g ww, respectively. Sample preparation time and solvents were reduced by 92 % and 65 %, respectively, as compared to USEPA method 1613.

Selective pressurized liquid extraction of pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in a whale earplug (earwax): a novel method for analyzing organic contaminants in lipid-rich matrices.

Lipid-rich matrices are often sinks for lipophilic contaminants, such as pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Typically methods for contaminant extraction and cleanup for lipid-rich matrices require multiple cleanup steps; however, a selective pressurized liquid extraction (SPLE) technique requiring no additional cleanup has been developed for the simultaneous extraction and cleanup of whale earwax (cerumen; a lipid-rich matrix). Whale earwax accumulates in select whale species over their lifetime to form wax earplugs. Typically used as an aging technique in cetaceans, layers or laminae that comprise the earplug are thought to be associated with annual or semiannual migration and feeding patterns. Whale earplugs (earwax) represent a unique matrix capable of recording and archiving whales' lifetime contaminant profiles. This study reports the first analytical method developed for identifying and quantifying lipophilic persistent organic pollutants (POPs) in a whale earplug including organochlorine pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). The analytical method was developed using SPLE to extract contaminants from ∼0.25 to 0.5g aliquots of each lamina of sectioned earplug. The SPLE was optimized for cleanup adsorbents (basic alumina, silica gel, and Florisil(®)), adsorbent to sample ratio, and adsorbent order. In the optimized SPLE method, the earwax homogenate was placed within the extraction cell on top of basic alumina (5g), silica gel (15g), and Florisil(®) (10g) and the target analytes were extracted from the homogenate using 1:1 (v/v) dichloromethane:hexane. POPs were analyzed using gas chromatography-mass spectrometry with electron capture negative ionization and electron impact ionization. The average percent recoveries for the POPs were 91% (±6% relative standard deviation), while limits of detection and quantification ranged from 0.00057 to 0.96ngg(-1) and 0.0017 to 2.9ngg(-1), respectively. Pesticides, PCBs, and PBDEs, were measured in a single blue whale (Balaenoptera musculus) cerumen lamina at concentrations ranging from 0.11 to 150ng g(-1).

Blue whale earplug reveals lifetime contaminant exposure and hormone profiles.

Lifetime contaminant and hormonal profiles have been reconstructed for an individual male blue whale (Balaenoptera musculus, Linnaeus 1758) using the earplug as a natural aging matrix that is also capable of archiving and preserving lipophilic compounds. These unprecedented lifetime profiles (i.e., birth to death) were reconstructed with a 6-mo resolution for a wide range of analytes including cortisol (stress hormone), testosterone (developmental hormone), organic contaminants (e.g., pesticides and flame retardants), and mercury. Cortisol lifetime profiles revealed a doubling of cortisol levels over baseline. Testosterone profiles suggest this male blue whale reached sexual maturity at approximately 10 y of age, which corresponds well with and improves on previous estimates. Early periods of the reconstructed contaminant profiles for pesticides (such as dichlorodiphenyltrichloroethanes and chlordanes), polychlorinated biphenyls, and polybrominated diphenyl ethers demonstrate significant maternal transfer occurred at 0-12 mo. The total lifetime organic contaminant burden measured between the earplug (sum of contaminants in laminae layers) and blubber samples from the same organism were similar. Total mercury profiles revealed reduced maternal transfer and two distinct pulse events compared with organic contaminants. The use of a whale earplug to reconstruct lifetime chemical profiles will allow for a more comprehensive examination of stress, development, and contaminant exposure, as well as improve the assessment of contaminant use/emission, environmental noise, ship traffic, and climate change on these important marine sentinels.