Concentrations of Volatile Methyl Siloxanes in New York City Reflect Emissions from Personal Care and Industrial Use.

Volatile methyl siloxanes (VMS) are a group of organosilicon compounds of interest because of their potential health effects, their ability to form secondary organic aerosols, and their use as tracer compounds. VMS are emitted in the gas-phase from using consumer and personal care products, including deodorants, lotions, and hair conditioners. Because of this emission route, airborne concentrations are expected to increase with population density, although there are few studies in large urban centers. Here, we report summertime concentrations and daily variations of VMS congeners measured in New York City. Median concentrations of the 6 studied congeners, D3 (20 ng m-3), D4 (57 ng m-3), D5 (230 ng m-3), D6 (11 ng m-3), L5 (2.5 ng m-3), and L7 (1.3 ng m-3) are among the highest reported outdoor concentrations in the literature to date. Average congener ratios of D5:D4 and D5:D6 were consistent with previously reported emissions ratios, suggesting that concentrations were dominated by local emissions. Measured concentrations agree with previously published results from a Community Multiscale Air Quality model and support commonly accepted emissions rates for D4, D5, and D6 of 32.8, 135, and 6.1 mg per capita per day. Concentrations of D4, D5, D6, L5, and L7 and total VMS were significantly lower during the day than during the night, consistent with daytime oxidation reactivity. Concentrations of D3 did not show the same diurnal trend but exhibited a strong directional dependence, suggesting that it may be emitted by industrial point sources in the area rather than personal care product use. Concentrations of all congeners had large temporal variations but showed relatively weak relationships with wind speed, temperature, and mixing height.

A Survey Study of Motivators for Pediatric Hospitalists to Work in the Community.

BACKGROUND AND OBJECTIVE: The loss of pediatric beds in the community has contributed to decreased access to pediatric inpatient and emergency services. Community pediatric hospitalist programs could reduce the overhead of inpatient care, promoting the financial feasibility of caring for hospitalized children closer to home. This study aims to determine which career motivators are the most important for pediatric hospitalists to begin working in, remain in, and leave the community setting. METHODS: A survey was sent to a convenience sample of 269 community hospitalists from 31 different sites. Sites were invited if the program director was known to the authors. Responses were evaluated and χ-square or Fisher's exact test were used to compare the differences. RESULTS: One hundred twenty six community pediatric hospitalists completed the survey (response rate 49.1%). The 3 most important motivators for pediatric hospitalists to begin working in the community were work-life integration (80%), geographic location (75%), and flexible hours (71%). Pediatric hospitalists who planned to leave the community setting were more likely to cite mentoring and teaching opportunities (76% vs 32%, P = .0002), opportunities for research and quality improvement (29% vs 10%, P = .021), and paid time for nonclinical interests (52% vs 26%, P = .02) as very important. CONCLUSIONS: This study demonstrates key motivators for pediatric hospitalists to work in the community and elucidates motivators for transitioning to larger pediatric centers. This knowledge may be used to guide community pediatric hospital medicine recruitment and program development that could lead to improved retention.

LOCALIZED MYOSITIS AND TRANSIENT ENCEPHALOPATHY AS PRESENTING SYMPTOMS IN MURINE TYPHUS.

Murine typhus in the pediatric population has increased substantially in recent years. The most common clinical presentation of murine typhus includes fever, rash, headaches and myalgias. Murine typhus presenting with predominant myositis and/or encephalopathy is rare. It is important to recognize unusual clinical manifestations of murine typhus in children for early diagnosis and treatment.

Polyurethane Foam Emission Samplers to Identify Sources of Airborne Polychlorinated Biphenyls from Glass-Block Windows and Other Room Surfaces in a Vermont School.

We hypothesized that emissions of polychlorinated biphenyls (PCBs) from Aroclor mixtures present in building materials explain their concentrations in school air. Here, we report a study of airborne concentrations and gas-phase emissions in three elementary school rooms constructed in 1958. We collected airborne PCBs using polyurethane foam passive air samplers (PUF-PAS, n = 6) and PCB emissions from building materials using polyurethane foam passive emission samplers (PUF-PES, n = 17) placed over flat surfaces in school rooms, including vinyl tile floors, carpets, painted bricks, painted drywall, and glass-block windows. We analyzed all 209 congeners represented in 173 chromatographic separations and found that the congener distribution in PUF-PES strongly resembled the predicted diffusive release of gas-phase PCBs from a solid material containing Aroclor 1254. Concentrations of airborne total PCBs ranged from 38 to 180 ng m-3, a range confirmed by an independent laboratory in the same school. These levels exceed action levels for all aged children set by the State of Vermont and exceed guidance levels set by the U.S. EPA for children under age 3. Emissions of PCBs from the glass-block windows (30,000 ng m-2 d-1) greatly exceeded those of all other surfaces, which ranged from 35 to 2700 ng m-2 d-1. This study illustrates the benefit of the direct measurement of PCB emissions to identify the most important building remediation needed to reduce airborne PCB concentrations in schools.

Congener-Specific Emissions from Floors and Walls Characterize Indoor Airborne Polychlorinated Biphenyls.

To reconcile the federal regulation of material polychlorinated biphenyl (PCB) concentrations with recently implemented state regulations of airborne PCBs, there is a need to characterize the relationship between PCB emissions from surfaces and air concentrations. We hypothesized that the magnitude and congener distribution of emissions from floors and walls fully account for the airborne PCBs measured in rooms constructed during the height of PCB production and sales. We measured emissions of PCB congeners from various wall and floor materials using polyurethane foam passive emission samplers before and after hexane wiping. Our results revealed that PCB emissions from flooring adequately predicted the magnitude and congener distribution of PCBs observed in the room air. Emissions varied by material within a single building (5 × 103 ng m-2 day-1 from wood panel walls to 3 × 104 ng m-2 day-1 from vinyl tile) and within the same room. Yet congener distributions between material emission PCB profiles and room air PCB profiles were statistically similar. Hexane wiping significantly reduced PCB emissions (>60%), indicating the importance of surface films as an ongoing source of airborne PCBs. The magnitude and congener distribution of material bulk concentrations did not explain that of material emissions or air concentrations. Passive measurements of polychlorinated biphenyl emissions from floors in a university building predict the concentrations of PCBs in room air.

Impact of COVID-19 on the Sense of Job Security Among Community Pediatric Hospitalists.

OBJECTIVES: The coronavirus disease 2019 (COVID-19) pandemic offers a prime opportunity to examine the ability of community pediatric hospital medicine programs to respond to external stressors. This study aims to characterize the impact of the COVID-19 pandemic on compensation and furlough among community pediatric hospitalists, as well as self-reported sense of job security. METHODS: This study was part of a larger quantitative project investigating community pediatric hospitalists' career motivators. The survey was drafted through an iterative process by the authors. It was disseminated via e-mail to a convenience sample of community pediatric hospitalists obtained through direct contact with community pediatric hospital medicine programs. Data were collected on changes in compensation and furlough because of COVID-19, as well as worry about job security measured as self-reported worry about one's job being permanently terminated on a 5-point Likert scale. RESULTS: Data were collected from 31 hospitals across the United States with 126 completed surveys. Because of COVID-19, many community pediatric hospitalists experienced reduced base pay and benefits and a minority experienced furlough. Nearly two-thirds (64%) reported some worry about job security. Initial base pay reduction, working in suburban areas compared with rural areas, and affiliation with a university-based center or free-standing children's hospital were significantly associated with greater worry about job security. CONCLUSIONS: The initial response to the COVID-19 pandemic resulted in changes in compensation and furlough for some community pediatric hospitalists and many expressed concerns about job security. Future studies should identify protective factors for community pediatric hospitalists' job security.

Lab-scale biodegradation assay using passive samplers to determine microorganisms' ability to reduce polychlorinated biphenyl (PCB) volatilization from contaminated sediment.

Many PCB-degrading aerobes have been identified which may serve as bioaugmentation strains for aerobic, in situ bioremediation or in combination with dredging operations. The present work describes a lab-scale PCB biodegradation assay which can be used to screen potential bioaugmentation strains or consortia for their ability to decrease PCB mass flux from contaminated sediment to air through biodegradation of freely dissolved PCBs that have desorbed from sediment particles. The assay uses two types of passive samplers to simultaneously measure PCB mass that is freely dissolved in aqueous solution and PCB mass that has volatilized to the headspace of the bioreactor. Using this approach, relative comparisons of PCB mass accumulated in passive samplers between bioaugmented treatments and controls allow for practical assessment of a microbial strain's ability to reduce both freely dissolved and vapor phase PCB concentrations. The method is designed to be conducted using aliquots of homogenized, well-characterized, PCB-contaminated sediment gathered from a field site. This work details the experimental design methodology, required materials, bioreactor set-up, passive sampling, PCB-extraction, sample cleanup, and quantification protocols such that the biodegradation assay can be conducted or replicated. A step-by-step protocol is also included and annotated with photos, tips, and tricks from experienced analysts.•Relative comparisons of PCB mass accumulated in passive samplers between experimental treatments and controls allow for practical assessment of bioaugmentation strain's ability to reduce both freely dissolved and vapor phase PCB concentrations•Passive sampler preparation, deployment, PCB-extraction, cleanup procedures, and quantification are detailed step-by-step and annotated by experienced analysts.

Machine Learning-Assisted Identification and Quantification of Hydroxylated Metabolites of Polychlorinated Biphenyls in Animal Samples.

Laboratory studies of the disposition and toxicity of hydroxylated polychlorinated biphenyl (OH-PCB) metabolites are challenging because authentic analytical standards for most unknown OH-PCBs are not available. To assist with the characterization of these OH-PCBs (as methylated derivatives), we developed machine learning-based models with multiple linear regression (MLR) or random forest regression (RFR) to predict the relative retention times (RRT) and MS/MS responses of methoxylated (MeO-)PCBs on a gas chromatograph-tandem mass spectrometry system. The final MLR model estimated the retention times of MeO-PCBs with a mean absolute error of 0.55 min (n = 121). The similarity coefficients cos θ between the predicted (by RFR model) and experimental MS/MS data of MeO-PCBs were >0.95 for 92% of observations (n = 96). The levels of MeO-PCBs quantified with the predicted MS/MS response factors approximated the experimental values within a 2-fold difference for 85% of observations and 3-fold differences for all observations (n = 89). Subsequently, these model predictions were used to assist with the identification of OH-PCB 95 or OH-PCB 28 metabolites in mouse feces or liver by suggesting candidate ranking information for identifying the metabolite isomers. Thus, predicted retention and MS/MS response data can assist in identifying unknown OH-PCBs.

Assessment of Polychlorinated Biphenyls and Their Hydroxylated Metabolites in Postmortem Human Brain Samples: Age and Brain Region Differences.

Exposure to polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (OH-PCBs) has been implicated in neurodevelopmental disorders. However, the distribution of PCBs and OH-PCBs in the human brain has not been characterized. This study investigated the age-, sex-, and brain region-specific distribution of all 209 PCBs using gaschromatography-tandem mass spectrometry (GC-MS/MS) in neonatal (N = 7) and adult (N = 7) postmortem brain samples. OH-PCB analyses were performed by GC-MS/MS (as methylated derivatives) and, in a subset of samples, by nontarget liquid chromatography high-resolution mass spectrometry (Nt-LCMS). Fourteen higher chlorinated PCB congeners were observed with a detection frequency >50%. Six lower chlorinated PCBs were detected with a detection frequency >10%. Higher chlorinated PCBs were observed with higher levels in samples from adult versus younger donors. PCB congener profiles from adult donors showed more similarities across brain regions and donors than younger donors. We also assess the potential neurotoxicity of the PCB residues in the human brain with neurotoxic equivalency (NEQ) approaches. The median ΣNEQs, calculated for the PCB homologues, were 40-fold higher in older versus younger donors. Importantly, lower chlorinated PCBs made considerable contributions to the neurotoxic potential of PCB residues in some donors. OH-PCBs were identified for the first time in a small number of human brain samples by GC-MS/MS and Nt-LCMS analyses, and all contained four or fewer chlorine.

Epidemiology and variability in management of acute mastoiditis in children.

BACKGROUND: To evaluate the epidemiology, management and outcome of acute mastoiditis (AM) in children and to improve strategies for antimicrobial stewardship. METHODS: We conducted a retrospective observational study of children aged >6 months to ≤18 years of age admitted to a tertiary care hospital with AM over an 8-year period (2011-2019). Electronic medical records were reviewed to collect data. RESULTS: A total of 129 patients met inclusion criteria for AM during this time period. Eighty-one (63 %) were males with 110 (81 %) White and 67 (52 %) non-Hispanic. The median age at presentation was 6.4 years (3-10.1 years). Ear protrusion was associated with reduced odds of having AM with intracranial extension (ICE) (OR 0.307, 95 % CI = 0.107-0.883) whereas presence of headaches and/or neck pain increased the odds of having AM with ICE (OR = 3.96, 95%CI 1.29-12.1). The most common etiologies were Streptococcus pyogenes (n = 23, 19.2 %), Pseudomonas aeruginosa (n = 20, 17 %), and Streptococcus pneumoniae (n = 15, 12.5 %). Empiric antibiotic selection and duration of therapy was highly variable. The most common empiric antibiotic used was intravenous vancomycin with a third generation cephalosporin (n = 45, 34.8 %). Majority completed course (n = 92; 73 %) with an oral antibiotic. Shorter (≤10 and ≤14 days) versus longer courses (>10 and >14 days) did not affect readmission rates for AM without ICE. CONCLUSION: There is high variability of treatment of AM in children. Broad spectrum antibiotics, especially vancomycin were used most frequently despite low rates of Methicillin Resistant Staphylococcus aureus. The use of antibiotic stewardship is essential for judicious antibiotic use.

PCB Sulfates in Serum from Mothers and Children in Urban and Rural U.S. Communities.

Serum samples from 24 subjects (6 mother-daughter and 6 mother-son dyads) in a rural community (Columbus Junction, Iowa) and 24 subjects (6 mother-daughter and 6 mother-son dyads) in an urban community (East Chicago, Indiana) were analyzed for 74 sulfated metabolites of polychlorinated biphenyls (PCBs). We detected significantly higher mean concentrations of total assessed PCB sulfates in the urban group (110-8900 ng/g fresh weight of serum, mean = 3400 ng/g, standard error = 300) than in the rural cohort (530-6700 ng/g fresh weight of serum, mean = 1800 ng/g, standard error = 500). Eight PCB sulfate congeners (4-PCB 2 sulfate, 4'-PCB 2 sulfate, 2'-PCB 3 sulfate, 4'-PCB 3 sulfate, 4-PCB 11 sulfate, 4'-PCB 18 sulfate, 4'-PCB 25 sulfate, and 4-PCB 52 sulfate) contributed over 90% of the total assessed PCB sulfates in most individuals. The serum samples were enriched in PCB sulfates with fewer than 5 chlorine atoms, and this congener distribution differed from those of PCBs and hydroxylated PCBs in previous studies in the same communities. Regression analysis indicated several significant congener-specific correlations in mother-child dyads, and these relationships differed by location and by mother-daughter or mother-son dyads. This is the first study reporting a broad range of PCB sulfates in populations from urban and rural areas.

Room-to-Room Variability of Airborne Polychlorinated Biphenyls in Schools and the Application of Air Sampling for Targeted Source Evaluation.

Airborne polychlorinated biphenyl (PCB) concentrations are higher indoors than outdoors due to their historical use in building materials and their presence in modern paints and surface treatments. For some populations, including school children, PCB levels indoors result in inhalation exposures that may be greater than or equivalent to exposure through diet. In a school, PCB exposure may come from multiple sources. We hypothesized that there are both Aroclor and non-Aroclor sources within a single school and that PCB concentration and congener profiles differ among rooms within a single building. To evaluate this hypothesis and to identify potential localized sources, we measured airborne PCBs in nine rooms in a school. We found that schoolroom concentrations exceed outdoor air concentrations. Schoolroom concentrations and congener profiles also varied from one room to another. The concentrations were highest in the math room (35.75 ng m-3 ± 8.08) and lowest in the practice gym (1.54 ng m-3 ± 0.35). Rooms in the oldest wing of the building, originally constructed between 1920 and 1970, had the highest concentrations. The congener distribution patterns indicate historic use of Aroclor 1254 as well as modern sources of non-Aroclor congeners associated with paint pigments and surface coatings. Our findings suggest this noninvasive source identification method presents an opportunity for targeted source testing for more cost-effective prioritization of materials remediation in schools.

Dataset describing biodegradation of individual polychlorinated biphenyl congeners (PCBs) by Paraburkholderia xenovorans LB400 in presence and absence of sediment slurry.

This dataset describes the biodegradation of polychlorinated biphenyl (PCB) congeners by Paraburkholderia xenovorans LB400 in absence and presence of PCB-contaminated sediment slurry, over time [1]. In absence of sediment, PCBs were extracted from aqueous bioreactors by liquid-liquid extraction (LLE) with hexane. In presence of sediment, the extraction method used was a modification of U.S. EPA Method 3545 [3]. Sediment slurry samples were extracted from bioreactors using pressurized fluid extraction (Accelerated Solvent Extractor; Dionex ASE-200) with equal parts acetone and hexane. GC-MS/MS triple quadrapole technology in multiple reaction monitoring mode (MRM) was used for identification and quantification of 209 PCBs as 174 chromatographic peaks. Samples were processed in batches of five along with one method blank per batch. All materials used in sample extraction had either been triple rinsed with solvent (methanol, acetone, and hexane) or combusted overnight at 450 °C to prevent background PCB contamination. Results from the method blanks were used to determine the limit of quantification (LOQ) as the upper limit of the 95% confidence interval (average mass plus two times the standard deviation). PCB congener masses were corrected for surrogate recoveries less than 100%. The PCB concentration dataset was dichotomized at the threshold of the congener specific LOQ. Concentrations of congeners below the LOQ were treated as zero. During analysis, PCB concentration data was filtered to include only congeners belonging to the commercial PCB mixture, Aroclor 1248. LOQ corrected data can inform future experimental design and be reused by other researchers for further analysis and / or interpretive insights.

Detection and Quantification of Polychlorinated Biphenyl Sulfates in Human Serum.

Polychlorinated biphenyls (PCBs) are persistent toxic chemicals with both legacy sources (e.g., Aroclors) and new sources (e.g., unintentional contaminants in some pigments and varnishes). PCB sulfates are derived from further metabolism of hydroxylated PCBs (OH-PCBs), which are oxidative metabolites of PCBs. While OH-PCBs and PCB sulfates are implicated in multiple toxicological effects, studies of PCB sulfates in human serum have been limited by available analytical procedures. We have now developed a method for extraction of PCB sulfates from serum followed by differential analysis with, and without, sulfatase-catalyzed hydrolysis to OH-PCBs. A sulfatase from Helix pomatia was purified by affinity chromatography, and it displayed broad specificity for PCB sulfates without contaminant glucuronidase activity. Following sulfatase-catalyzed hydrolysis of the PCB sulfates extracted from serum, the corresponding OH-PCBs were derivatized to methoxy-PCBs and quantitated by GC-MS/MS. In a pooled sample of human serum, we identified 10 PCB sulfates, with three PCB sulfate congeners exhibiting the highest concentrations from 1200 to 3970 pg/g of serum. In conclusion, we have developed a sensitive and specific method for the determination of PCB sulfates in human serum.

Biodegradation of PCB congeners by Paraburkholderia xenovorans LB400 in presence and absence of sediment during lab bioreactor experiments.

Experiments were conducted to measure biodegradation of polychlorinated biphenyl (PCB) congeners contained in mixture Aroclor 1248 and congeners present in wastewater lagoon sediment contaminated decades earlier at Altavista, Virginia. A well-characterized strain of aerobic PCB-degrading bacteria, Paraburkholderia xenovorans LB400 was incubated in laboratory bioreactors with PCB-contaminated sediment collected at the site. The experiments evaluated strain LB400's ability to degrade PCBs in absence of sediment and in PCB-contaminated sediment slurry. In absence of sediment, LB400 transformed 76% of Aroclor 1248 within seven days, spanning all homolog groups present in the mixture. In sediment slurry, only mono- and di-chlorinated PCB congeners were transformed. These results show that LB400 is capable of rapidly biodegrading most PCB congeners when they are freely dissolved in liquid but cannot degrade PCB congeners having three or more chlorine substituents in sediment slurry. Finally, using GC/MS-MS triple quadrupole spectrometry, this work distinguishes between physical (sorption to cells) and biological removal mechanisms, illuminates the process by which microorganisms with LB400-type congener specificity can selectively transform lower-chlorinated congeners over time, and makes direct comparisons to other studies where individual congener data is reported.

Signal Processing Methods to Interpret Polychlorinated Biphenyls in Airborne Samples.

The main contribution of this interdisciplinary work is a robust computational framework to autonomously discover and quantify previously unknown associations between well-known (target) and potentially unknown (non-target) toxic industrial air pollutants. In this work, the variability of polychlorinated biphenyl (PCB) data is evaluated using a combination of statistical, signal processing, and graph-based informatics techniques to interpret the raw instrument signal from gas chromatography-mass spectrometry (GC/MS/MS) data sets. Specifically, minimum mean-squared techniques from the adaptive signal processing literature are extended to detect and separate coeluted (overlapped) peaks in the raw instrument signal. A graph-based visualization is provided which bridges two complementary approaches to quantitative pollution studies: (i) peak-cognizant target analysis (limits data analysis to few well-known compounds) and (ii) chemometric analysis (statistical large-scale data analysis) that is agnostic of specific compounds. Further, peak fitting techniques based on L2 error minimization are employed to autonomously calculate the amount of each PCB present with a normalized mean square error of -18.4851 dB. Graph-based visualization of associations between known and unknown compounds are developed through principal component analysis and both fuzzy c-means (FCM) and k-means clustering techniques are implemented and compared. The efficiency of these methods are compared using 150 air samples analyzed for individual PCBs with GC/MS/MS against traditional target-only techniques that perform analysis across only the known (target) PCBs. Parameter optimization techniques are employed to evaluate the relative contribution of PCB signals against ten potential source signals representing legacy signatures from historical manufacture of Aroclors and modern sources of PCBs produced as by products of pigment and polymer manufacturing. Aroclors 1232, 1254, 1016, and 1221 as well as non-Aroclor 3, 3', dichlorobiphenyl (PCB 11) were found in many of the samples as unique source signals that describe PCB mixtures in air samples collected from Chicago, IL.

Polychlorinated Biphenyls in Food.

We measured the concentrations of 205 polychlorinated biphenyl (PCB) congeners in 26 food items: beef steak, butter, canned tuna, catfish, cheese, eggs, french fries, fried chicken, ground beef, ground pork, hamburger, hot dog, ice cream, liver, luncheon meat, margarine, meat-free dinner, milk, pizza, poultry, salmon, sausage, shrimp, sliced ham, tilapia, and vegetable oil. Using Diet History Questionnaire II, we calculated the PCB dietary exposure in mothers and children participating in the AESOP Study in East Chicago, Indiana, and Columbus Junction, Iowa. Salmon had the highest concentration followed by canned tuna, but fish is a minor contributor to exposure. Other animal proteins are more important sources of PCB dietary exposure in this study population. Despite the inclusion of few congeners and food types in previous studies, we found evidence of a decline in PCB concentrations over the last 20 years. We also found strong associations of PCB congener distributions with Aroclors in most foods and found manufacturing byproduct PCBs, including PCB11, in tilapia and catfish. The reduction in PCB levels in food indicates that dietary exposure is comparable to PCB inhalation exposures reported for the same study population.