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Background: Brominated flame retardants (BFRs) are widely utilized to mitigate the flammability of various materials. Previous studies have revealed the impact of BFRs exposure on hormonal disruption and bone metabolism which are closely related to periodontitis. However, it remains unknown the potential relationship between BFRs and periodontitis. This study aimed to explore the association between BFRs exposure and periodontitis in US adults. Methods: The data analyzed in this study were obtained from the National Health and Nutrition Examination Survey (NHANES) 2009–2014. Twelve serum BFRs were quantified using isotope dilution gas chromatography high-resolution mass spectrometry. Univariable and multivariable logistic regression was employed to evaluate the association between serum BFRs and periodontitis. Bayesian kernel machine regression (BKMR) analyses were utilized to assess the association between mixtures of BFRs and periodontitis. Results: A total of 3311 eligible participants were included. Serum BFRs (PBDE-47, PBDE-99, and PBDE-154) were significantly associated with periodontitis, and the odds ratios (ORs) and corresponding 95% confidence intervals(CIs) were 1.15(1.01,1.29), 1.10(1.01,1.20), and 1.12(1.01,1.25), respectively. Notably, these three BFRs were also significantly associated with the severity of periodontitis. Additionally, the BKMR model revealed a significant association between the mixture of all twelve BFRs and periodontitis. Conclusions: This preliminary study suggests a significant association between specific serum BFRs (PBDE-47, PBDE-99, and PBDE-154) and periodontitis and its severity. Further prospective and experimental studies are warranted to validate our findings. [ABSTRACT FROM AUTHOR]

There exists significant heterogeneity in the 'freshness' of consumer marine- and plant-derived omega-3 (Ω3) supplements. Fears of rancidity, or the oxidation of consumer Ω3 supplements, has been debated in the literature with several prior authors reporting contradictory findings. We report the peroxide value (PV), para-anisidine value (p-AV) and total oxidation values (TOTOX) associated with 72 consumer Ω3 supplements sold in the United States sampled from 2014–2020. The effect of flavoring on the oxidation of the supplements was examined in an adjusted fixed effects model controlling for type of delivery system (enteric, liquid, animal- and vegetable-derived gelatin softgel, spray), source (algae, calamari, fish, krill, mussels), and certifications assigned by third-party organizations (e.g. USP). Overall, our results revealed that 68% (23/34) of flavored and 13% (5/38) unflavored consumer Ω3 supplements exceeded the TOTOX upper limit set by the Global Organization for EPA and DHA (GOED) voluntary monograph standard of ≤ 26, with 65% (22/34) flavored supplements and 32% (12/38) unflavored supplements failing the PV upper limit of ≤ 5 and 62% (21/34) flavored supplements exceeding the p-AV upper limit of ≤ 20. To our knowledge, no prior authors have modeled the impact of flavoring on oxidative status in 72 marine- and plant-derived Ω3 products sold in the U.S. We present our findings in this context and discuss the clinical implications related to the consumption of oxidized consumer fish oils and their effects on human health. [ABSTRACT FROM AUTHOR]

The United States Agriculture Improvement Act passed in December of 2018 legalized the growing of Cannabis sativa containing not more than 0.3% total Delta-9 tetrahydrocannabinol (THC) in the country. While Cannabis sativa has been cultivated for hundreds of years, the illegal status of the plant in the United States, and elsewhere, has hindered the development of plant cultivars that meet this legal definition. To assess sampling strategies, and conformance to the THC limit, 14 cultivars of hemp were grown and tested by using gas chromatography with flame ionization detection for total delta-9 THC and total cannabidiol (CBD) during 2020, 2021 and 2022. Each year, samples of fresh plant material were collected from each cultivar weekly, beginning in mid-August and ending in late October, to examine the rate of increase in THC and CBD for different cultivars and select individual plants. The sampling demonstrated that both CBD and THC increase rapidly over a 1–2-week time frame with maximum concentrations (about 16% and 0.6%, respectively) around late September to early October. The testing of individual plants on the same day for select cultivars showed that while the ratio of CBD to THC remains constant (about 20:1 in compliant hemp) during the growing season, the individual plants are highly variable in concentration. Whereas previous studies have shown cultivar-dependent variability in THC production, this study demonstrated a novel plant-to-plant variability in the levels of THC within the same hemp cultivar. Understanding variability within and between hemp cultivars is useful to determine field sampling strategies and to assess the risk of crop embargoes to growers by compliance regulators. [ABSTRACT FROM AUTHOR]

Among the first 20 high-priority chemical substances selected by USEPA to undergo risk evaluation as part of the Toxic Substances Control Act, as amended by the Frank R. Lautenberg Chemical Safety for the 21st Century Act of 2016 is 1,3-butadiene (1,3-BD). Because much of the literature related to occupational exposure to 1,3-BD is associated with the use of the substance in synthetic rubber production and few data have been published for exposures to 1,3-BD manufacturing workers, existing industrial hygiene data collected at facilities where the substance is manufactured or processed as a reactant were compiled and analyzed. The dataset was comprised of personal air samples collected between 2010 and 2019 at facilities located throughout the United States and was compiled into a single database using a uniform data collection template. Data designated by the companies as full-shift were stratified by job group and one of three operational conditions of the workplace: routine, turnaround, and non-routine. Data designated by the companies as short-term and task-level were stratified by task description, sample duration, and operational condition. The final aggregated database contained a total of 5,676 full-shift personal samples. Mean concentrations of 1,3-BD for the job groups ranged from 0.012 ppm to 0.16 ppm. High-end estimates of 1,3-BD air concentrations for the job groups under routine operations ranged from 0.014 ppm to 0.23 ppm. The aggregated database also included 1,063 short-term and task-level personal samples. For short-term samples (< =15 min), mean concentrations ranged from 0.49 ppm to 3.9 ppm, with the highest concentrations observed for the cleaning and maintaining equipment tasks. For task samples with durations greater than 15 min, mean concentrations ranged from 0.49 to 3.6 ppm, with the highest concentrations observed for the unloading and loading task. In addition to the personal air sampling records, information on the use of PPE during various tasks was compiled and analyzed. This data set provides robust quantitative air concentration data and exposure control information for which occupational exposures to 1,3-BD in the Manufacturing and Processing as a Reactant condition of use can be assessed. [ABSTRACT FROM AUTHOR]

The article discusses the growing concerns on the potential adverse health effects of airborne exposure to microplastics (MP) and nanoplastics (NP). According to UniLaSalle Associate Professor Messika Revel, humans are eating, drinking, and breathing plastic particles. Also cited is how plastic polymers can exert biological effects through their physical presence.

Cheddar cheese is the most popular cheese in the United States, and the demand for specialty categories of cheese, such as smoked cheese, are rising. The objective of this study was to characterize the flavor differences among Cheddar cheeses smoked with hickory, cherry, or apple woods, and to identify important aroma-active compounds contributing to these differences. First, the aroma-active compound profiles of hickory, cherry, and apple wood smokes were analyzed by solid-phase microextraction (SPME) gas chromatography-olfactometry (GCO) and gas chromatography-mass spectrometry (GC-MS). Subsequently, commercial Cheddar cheeses smoked with hickory, cherry, or apple woods, as well as an unsmoked control, were evaluated by a trained sensory panel and by SPME GCO and GC-MS to identify aroma-active compounds. Selected compounds were quantified with external standard curves. Seventy-eight aroma-active compounds were identified in wood smokes. Compounds included phenolics, carbonyls, and furans. The trained panel identified distinct sensory attributes and intensities among the 3 cheeses exposed to different wood smokes (P < 0.05). Hickory smoked cheeses had the highest intensities of flavors associated with characteristic "smokiness" including smoke aroma, overall smoke flavor intensity, and meaty, smoky flavor. Cherry wood smoked cheeses were distinguished by the presence of a fruity flavor. Apple wood smoked cheeses were characterized by the presence of a waxy, green flavor. Ninety-nine aroma-active compounds were identified in smoked cheeses. Phenol, guaiacol, 4-methylguaiacol, and syringol were identified as the most important compounds contributing to characteristic "smokiness." Benzyl alcohol contributed to the fruity flavor in cherry wood smoked cheeses, and 2-methyl-2-butenal and 2-ethylfuran were responsible for the waxy, green flavor identified in apple wood smoked cheeses. These smoke flavor compounds, in addition to diacetyl and acetoin, were deemed important to the flavor of cheeses in this study. Results from this study identified volatile aroma-active compounds contributing to differences in sensory perception among Cheddar cheeses smoked with different wood sources. [ABSTRACT FROM AUTHOR]

• Plasma fatty acid analysis is necessary for assessing omega-3 fatty acid levels. • Women had a more heart-healthy fatty acid profile than men. • Subjects ≥65 years old had higher omega-3 values than subjects <30 years old. • Subjects in southern and midwestern states had below median EPA levels. • EPA levels by state correlated inversely with reported heart disease mortality rates. Fatty acids (FA) play an important role in health and heart disease risk. We evaluated relationships of plasma FA levels, especially omega-3 FA, with sex, age, and reported heart disease mortality rates by state in a very large clinical population. Plasma FA were measured by gas chromatography/mass spectrometry after lipid extraction in 1,169,621 fasting United States subjects grouped according to sex (56.2% female), age (<30, 30-<45, 45-<55, 55-<65, ≥65 years; median age 58.2 years), and state of residence. Plasma FA index values (median±interquartile range), expressed as a percent of total plasma FA, in all subjects were: saturated (14:0+16:0+18:0) 31.4±1.5%; monounsaturated (16:1n7- cis +18:1n9- cis) 21.3±2.2%; trans (16:1n7- trans +18:1n9- trans) 0.45±0.08%; omega-6 (18:2n6- cis +20:3n6+20:4n6) 42.5±3.0%; and omega-3 (20:5n3+22:6n3) 2.57±0.81%. The median eicosapentaenoic acid (EPA, 20:5n3) concentration was 22.1±9.7 μg/mL. Females had significantly (P <0.0001) higher omega-3 FA indices (+6.82%) than males. Subjects ≥65 years of age had a higher omega-3 FA index (+29.68%) and higher EPA levels (+57.05%) than subjects <30 years of age (P <0.00001). EPA concentrations and omega-3 FA indices were below overall median levels in most southern and midwestern states. State-reported heart disease mortality rates were inversely correlated with EPA levels (r =-0.504) and omega-3 FA indices (r =-0.570), and positively correlated with saturated FA indices (r =0.450), all P <0.01. In our large population, females, subjects ≥65 years, and those living in northeastern and western states had higher omega-3 fatty acid levels and lower saturated fatty acid levels than other subjects. Such changes were associated with lower state-wide heart disease death rates. [ABSTRACT FROM AUTHOR]

On 27 June 2021, Harold Monroe McNair passed away peacefully in his home, surrounded by his family. Harold's career as a chromatographer spanned over 60 years, from his 1959 authoring of the first gas chromatography (GC) doctoral thesis in the United States on stationary phase chemistry to the first edition of his classic book, Basic Gas Chromatography, in 1964, to a 2019 journal article on the diet of post-weaning heifers (cows). McNair's remarkable career and writings spanned the entire breadth of chromatography and separation science. Using McNair's early writings and works as a guide, I explore three fundamental areas of understanding in GC, seeing ideas about problems that still challenge gas chromatographers today. With McNair, we explore stationary phase chemistry, computers in chromatography, and liquid chromatography (LC) compared to GC. [ABSTRACT FROM AUTHOR]

We present emission measurements of volatile organic compounds (VOCs) for western U.S. wildland fires made on the NSF/NCAR C‐130 research aircraft during the Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) field campaign in summer 2018. VOCs were measured with complementary instruments onboard the C‐130, including a proton‐transfer‐reaction time‐of‐flight mass spectrometer (PTR‐ToF‐MS) and two gas chromatography (GC)‐based methods. Agreement within combined instrument uncertainties (<60%) was observed for most co‐measured VOCs. GC‐based measurements speciated the isomeric contributions to selected PTR‐ToF‐MS ion masses and generally showed little fire‐to‐fire variation. We report emission ratios (ERs) and emission factors (EFs) for 161 VOCs measured in 31 near‐fire smoke plume transects of 24 specific individual fires sampled in the afternoon when burning conditions are typically most active. Modified combustion efficiency (MCE) ranged from 0.85 to 0.94. The measured campaign‐average total VOC EF was 26.1 ± 6.9 g kg−1, approximately 67% of which is accounted for by oxygenated VOCs. The 10 most abundantly emitted species contributed more than half of the total measured VOC mass. We found that MCE alone explained nearly 70% of the observed variance for total measured VOC emissions (r2 = 0.67) and >50% for 57 individual VOC EFs representing more than half the organic carbon mass. Finally, we found little fire‐to‐fire variability for the mass fraction contributions of individual species to the total measured VOC emissions, suggesting that a single speciation profile can describe VOC emissions for the wildfires in coniferous ecosystems sampled during WE‐CAN. Key Points: A total of 161 measured volatile organic compound emission factors is 26.1 ± 6.9 g kg−1, 67% of which is from oxygenated species76% of the total volatile organic compound emitted mass shows statistically significant dependence on modified combustion efficiencyMass fraction contributions of individual species to the total measured emissions have little variability in 24 western U.S. fires [ABSTRACT FROM AUTHOR]

Recently, N-nitrosamines have been unexpectedly found in generic sartan products. Herein, we developed a sensitive and stable GC-MS/MS method with multiple reactions monitoring mode for the simultaneous determination of four N-nitrosamines in sartan substances, namely, N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodibutylamine, and N-nitrosodiisopropylamine. The conditions of gas chromatography and mass spectrometry were optimized. The method was validated according to the International Council for Harmonization guidelines in terms of sensitivity, linearity, accuracy, precision, specificity, and stability. The limits of detection of N-nitrosamines in sartan substances ranged from 0.002 to 0.150 ppm, and the corresponding limits of quantification were in the range of 0.008-0.500 ppm, which met the sensitivity requirements for the limits set by the Food and Drug Administration of the United States. The internal standard curve of four N-nitrosamines showed good linearity of regression coefficients over 0.99. The recoveries of N-nitrosamines in selected sartan drugs ranged from 87.68 to 123.76%. The intraday and interday relative standard deviation values were less than 9.15%. Therefore, this proposed method exhibited good sensitivity and precision, high accuracy, and fast analysis speed, which provide a reliable method for quality control of N-nitrosamines in sartan products. [ABSTRACT FROM AUTHOR]

2,4‐dinitrophenol (2,4‐DNP) is a compound used in the early 1900s as a weight‐loss drug but later prohibited due to its severe adverse effects, including death. It has however been attracting interest, due to its weight‐loss properties, and appears to be re‐emerging in forensic casework. As 2,4‐DNP is available for use in industry and as a pesticide and easily accessible online, the dissemination of this drug can be fast. The compound exerts its effects through inhibition of ATP synthesis, and corresponding thermogenic energy loss which can be fatal. A method for qualitative and quantitative analysis of 2,4‐DNP in blood and urine specimens using GC‐MS with hydrogen as carrier gas is described. The method was validated and displayed acceptable performance parameters with linearity (R2 higher than 0.998), inter‐assay imprecision (lower than 10.6%), intra‐assay imprecision (lower than 10.7%), and extraction efficiency (92.1%). Stability of 2,4‐DNP in blood and urine was studied, and the drug was stable up to 30 days refrigeration or frozen. Six cases in United States suspected to be related to 2,4‐DNP were analyzed. Three cases were found to be positive for 2,4‐DNP. Concentrations of 2,4‐DNP were in the range of 61.6–220 mg/L in urine and <3–114 mg/L in blood. Based on our findings, we suggest that medical examiners and forensic toxicologists be aware of the reappearance of 2,4‐DNP, including this compound as a target in death investigations related to weight‐loss drugs. [ABSTRACT FROM AUTHOR]

This is the first report regarding the characterization of the new synthetic cannabinoid 4F‐MDMB‐BINACA. 4F‐MDMB‐BINACA was first analytically confirmed in seized drug material using gas chromatography–mass spectrometry (GC‐MS), liquid chromatography–quadrupole time‐of‐flight mass spectrometry (LC‐QTOF), and nuclear magnetic resonance (NMR) spectroscopy. Subsequent to this characterization, 4F‐MDMB‐BINACA was detected in biological specimens collected as part of forensically relevant casework, including medicolegal death investigations and drug impaired driving investigations, from a variety of regions in the United States. Further analysis of biological specimens resulted in the identification of the metabolites 4F‐MDMB‐BINACA 3,3‐dimethylbutanoic acid and 4‐OH‐MDMB‐BINACA. 4F‐MDMB‐BINACA is appearing with increasing frequency as a contributory factor in deaths, creating morbidity and mortality risks for drug users. Laboratories must be aware of its presence and impact, incorporating 4F‐MDMB‐BINACA into workflows for detection and confirmation. [ABSTRACT FROM AUTHOR]

Background: Previous studies on health effects of trans fatty acids (TFA) have focused mainly on cardiovascular health. Little is known about the association of TFA with brain or mental health. In this study, we examined the associations of objectively-measured plasma TFA concentrations with depression in a large population-based cross-sectional study among U.S. adults.Methods: We included 2136 non-pregnant participants aged 20 years or older from the National Health and Nutrition Examination Survey 2009-2010. Four major TFAs, including palmitelaidic acid (C16:1n-7t), elaidic acid (C18:1n-9t), vaccenic acid (C18:1n-7t), and linoelaidic acid (C18:2n-6t, 9t), were measured in fasting plasma using gas chromatography/mass spectrometry. Depressive symptoms were assessed using the validated Patient Health Questionnaire-9.Results: Participants with depressive symptoms had a higher plasma concentration of total TFA compared with those without depressive symptoms (6.6 vs 6.0 μmol/g lipids, P = 0.046). After adjustment for other major risk factors, the odds ratio (OR) of depressive symptoms comparing the highest with lowest tertile of TFAs was 1.44 (95% CI, 0.86-2.39) for total TFAs (P for trend 0.15). For each individual type of TFA, the corresponding OR was 1.78 (1.03-3.07) for elaidic acid (P for trend 0.049), 1.23 (0.76-2.00) for linoelaidic acid (P for trend 0.37), 1.19 (0.75-1.87) for palmitelaidic acid (P for trend 0.46), and 1.20 (0.75-1.94) for vaccenic acid (P for trend 0.43).Limitations: The cross-sectional study design limited causal inferences of the findings.Conclusions: In a nationally representative population, plasma elaidic acid, a major trans fatty acid, was positively associated with depressive symptoms in adults. A positive but non-significant association of depressive symptoms was observed for total TFAs, linolelaidic acid, palmitelaidic acid, and vaccenic acid. [ABSTRACT FROM AUTHOR]

Objectives Workers using flavoring formulations containing diacetyl and 2,3-pentanedione may be at risk of inhalational exposure, as these volatile hazardous chemicals are emitted from the bulk material, especially at elevated temperatures. However, flavoring formulations that contain diacetyl and 2,3-pentanedione might not list these ingredients because they are generally recognized as safe to ingest, may be part of a proprietary mixture deemed a trade secret, or may not be required to be listed if they are present at <1% composition. The objective of this study was to investigate whether potential inhalational hazards present in flavoring samples were reported as chemical ingredients on their corresponding safety data sheets (SDSs). Methods A convenience sample of 26 bulk liquid flavorings obtained from two coffee roasting and packaging facilities in the USA was analyzed for 20 volatile organic chemicals present in the headspaces of vials containing flavoring liquids using gas chromatography-mass spectrometry. Flavoring samples were included in the study if headspace analysis results and SDSs were available. Flavoring samples included hazelnut, French vanilla, amaretto, chocolate, and caramel as well as some flavoring mixtures containing added fruit flavors such as cherry and raspberry. The presence of a chemical in the flavoring formulation was then compared to the ingredient list on the SDSs. Results All the flavoring SDSs contained trade secret designations. None of the SDSs listed diacetyl or 2,3-pentanedione. Headspace analyte concentrations revealed that diacetyl was present in 21 of 26 samples (81%) with a maximum concentration of 5.84 × 104 µg m−3 in flavor 18 (caramel). 2,3-Pentanedione was present in 15 flavors (58%) with a maximum concentration of 3.79 × 105 µg m−3 in flavor 24 (oatmeal cookies). Conclusions A majority of the flavorings tested had diacetyl, 2,3-pentanedione, or both as volatile constituents in the headspace. These chemicals were not listed on the SDSs, but inclusion of diacetyl and 2,3-pentanedione on SDSs would serve to protect downstream users from unrecognized exposure and potential respiratory disease. The headspace technique presented here is a viable tool to rapidly screen for volatile hazardous chemicals that may be present in flavoring formulations. Facilities that use flavorings should be aware that constituents in flavorings may present a potential inhalational hazard even if not identified as such by the SDS. A precautionary approach is warranted when working with flavorings, including exposure monitoring and effective exposure control strategies such as containment and local exhaust ventilation. [ABSTRACT FROM AUTHOR]

Context: The essential omega-3 fatty acids (m-3 FAs) eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) exhibit vital biological roles and are critical for cardiovascular and neurologic health. Compared with the general population, football athletes may be at an increased risk of cardiovascular disease. Further, those same athletes are also exposed to repetitive head impacts, which may lead to long-term neurologic deficits. Both diets high in m-3 FAs and supplementation with m-3 FAs have been reported to reduce the risk of cardiovascular disease, and early evidence suggests a potential neuroprotective effect of supplementation. Objective: To determine the (1) erythrocyte content of DHA and EPA, as measured by the Omega-3 Index, expressed as a percentage of total fatty acids, in National Collegiate Athletic Association Division I football athletes and (2) distribution across the Omega-3 Index risk zones established for cardiovascular disease: high risk, <4%; intermediate risk, 4% to 8%; and low risk, >8%. Design: Cross-sectional descriptive study. Setting: Multicenter trial. Patients or Other Participants: Deidentified data including complete erythrocyte fatty acid profile from the 2017-2018 season, age at time of testing, height, weight, and ethnicity were collected from 404 athletes. Main Outcome Measure(s): Omega-3 Index. Results: About 34% of athletes (n = 138) had an Omega-3 Index considered high risk (<4%), and 66% (n = 266) had a risk considered intermediate (4%-8%). None had a low-risk Omega- 3 Index. Conclusions: The Omega-3 Index is a simple, minimally invasive test of m-3 FA status. Our data indicate that football athletes may be deficient in the m-3 FAs DHA and EPA. The fact that no athlete had an Omega-3 Index associated with low risk suggests football athletes may be at increased risk for cardiovascular disease in later life. [ABSTRACT FROM AUTHOR]

There is limited evidence on the association between plasma trans-fatty acids (TFAs) and cardiometabolic risk factors. Therefore, we examined the association between plasma TFA concentrations and glucose homeostasis and cardiovascular (CV) risk factors in adult Americans from the 1999 to 2000 National Health and Nutrition Examination Survey participants. Derivatized TFAs were separated by capillary gas chromatography. Of the 1678 participants, 46.5% were men. The mean age was 50.5 years overall, with no significant difference between men and women (P = .101). In age-, sex- and race-adjusted analyses, mean waist circumference, fat-free mass, fat mass, C-peptide, insulin, hemoglobin A1c (HbA1c), homeostatic model assessment of insulin resistance (HOMA-IR), serum triglycerides (TGs), and total cholesterol (TC) increased across increasing quarters of TFAs (for all P < .001), while mean serum high-density lipoprotein cholesterol decreased across increasing quarters of plasma TFAs (P < .001). In multivariable adjusted linear regressions, there remained significant positive associations between all plasma TFAs and body mass index, waist circumference, fat-free mass, fat mass, C-peptide, insulin, fasting blood glucose, HOMA-IR, HbA1c, TGs, low-density lipoprotein cholesterol, and TC (P < .001). In conclusion, our findings support a possible association between plasma TFAs concentrations and measures of glucose homeostasis and several CV risk factors. [ABSTRACT FROM AUTHOR]

Background: The consumption of trans fatty acids (TFAs) is associated with an increased risk of cardiovascular disease, and reducing their consumption is a major public health objective. Food intake studies have provided estimates for TFA concentrations in the US population; however, there is a need for data on TFA blood concentrations in the population. Objective: The objective of this study was to determine plasma TFA concentrations in a nationally representative group of fasted adults in the US population in NHANES samples from 1999-2000 and 2009-2010. Design: Four major TFAs [palmitelaidic acid (C16:1n-7t), trans vaccenic acid (C18:1n-7t), elaidic acid (C18:1n-9t), and linoelaidic acid (C18:2n-6t,9t)] were measured in plasma in 1613 subjects from NHANES 1999-2000 and 2462 subjects from NHANES 2009-2010 by gas chromatography-mass spectrometry. Geometric means and distribution percentiles were calculated for each TFA and their sum by age, sex, and race/ethnicity (non-Hispanic white, non-Hispanic black, Mexican American), and covariate-adjusted geometric means were computed by using a model that included these demographic and other dietary factors, as well as survey year and any significant interaction terms. Results: These nationally representative data for the adult US population show that TFA concentrations were 54% lower in NHANES 2009-2010 than in NHANES 1999-2000. Covariate-adjusted geometric means for the sum of the 4 TFAs were 81.4 μmol/L (95% CI: 77.3, 85.6 μmol/L) and 37.8 μmol/L (95% CI: 36.4, 39.4 μmol/L) in NHANES 1999-2000 and 2009-2010, respectively. Even with the large decline in TFA concentrations, differences between demographic subgroups were comparable in the 2 surveys. Conclusion: The results indicate an overall reduction in TFA concentrations in the US population and provide a valuable baseline to evaluate the impact of the recent regulation categorizing TFAs as food additives. [ABSTRACT FROM AUTHOR]

Background: Docosahexaenoic acid (DHA), an omega-3 fatty acid found in breast milk, has many health benefits for both mother and baby. A 2007 meta-analysis found U.S. women had breast milk DHA levels (0.20% of total fatty acids) below the worldwide mean (0.32%). In 2008, international dietary recommendations were made for pregnant and lactating women to consume 200 mg of DHA per day. This community-based study aimed to define current milk DHA levels from upper Midwest USA lactating mothers and to determine if providing information about their own level along with dietary recommendations would incite changes to increase breast milk DHA content. Methods: New mothers attending lactation classes or using hospital pumping rooms in Sioux Falls, South Dakota, USA participated by providing one drop of breast milk on a card for fatty acid analysis at baseline and 1 month after initial reporting. DHA levels were analyzed by gas chromatography. Mothers received a report of their own breast milk level along with dietary recommendations on DHA intake for lactating women. Median baseline and follow-up DHA levels were determined and differences were compared by Wilcoxon signed-rank test. Results: At baseline, breast milk DHA content (n = 84) was highly variable (range 0.05 to 0.73%) with a median of 0.18% (IQR, 0.13, 0.28; mean ± SD, 0.22 ± 0.13%), well below the worldwide average (0.32%). Women who reported taking DHA supplements (n = 43) had higher levels than those who did not (0.23% vs. 0.15%, P < 0.0001). In a subset of 60 mothers who submitted a second sample, median breast milk DHA content increased from 0.19 to 0.22% (P < 0.01). Conclusions: Findings suggest that providing nursing mothers with their breast milk DHA level and education about DHA intake while breastfeeding motivates change to increase DHA levels. [ABSTRACT FROM AUTHOR]

Introduction: A significant portion of the increased risk of cancer and respiratory disease from exposure to cigarette smoke is attributed to volatile organic compounds (VOCs). In this study, 21 VOCs were quantified in mainstream cigarette smoke from 50U.S. domestic brand varieties that included high market share brands and 2 Kentucky research cigarettes (3R4F and 1R5F).Methods: Mainstream smoke was generated under ISO 3308 and Canadian Intense (CI) smoking protocols with linear smoking machines with a gas sampling bag collection followed by solid phase microextraction/gas chromatography/mass spectrometry (SPME/GC/MS) analysis.Results: For both protocols, mainstream smoke VOC amounts among the different brand varieties were strongly correlated between the majority of the analytes. Overall, Pearson correlation (r) ranged from 0.68 to 0.99 for ISO and 0.36 to 0.95 for CI. However, monoaromatic compounds were found to increase disproportionately compared to unsaturated, nitro, and carbonyl compounds under the CI smoking protocol where filter ventilation is blocked.Conclusions: Overall, machine generated "vapor phase" amounts (µg/cigarette) are primarily attributed to smoking protocol (e.g., blocking of vent holes, puff volume, and puff duration) and filter ventilation. A possible cause for the disproportionate increase in monoaromatic compounds could be increased pyrolysis under low oxygen conditions associated with the CI protocol.Implications: This is the most comprehensive assessment of volatile organic compounds (VOCs) in cigarette smoke to date, encompassing 21 toxic VOCs, 50 different cigarette brand varieties, and 2 different machine smoking protocols (ISO and CI). For most analytes relative proportions remain consistent among U.S. cigarette brand varieties regardless of smoking protocol, however the CI smoking protocol did cause up to a factor of 6 increase in the proportion of monoaromatic compounds. This study serves as a basis to assess VOC exposure as cigarette smoke is a principle source of overall population-level VOC exposure in the United States. [ABSTRACT FROM AUTHOR]

Objective: Most epidemiologic studies of circulating phospholipid fatty acids (PLFAs) and disease risk have used the relative concentration (percentage of total) of each fatty acid as the measure of exposure. Using relative concentrations, the total of all fatty acids is summed to 100% and thus the values of individual fatty acid are not independent. This has led to debate, along with the suggestion to use absolute concentrations of fatty acids. We aimed to examine the relationship between relative (weight percentage) and absolute (mg/L) concentrations of individual circulating PLFAs.Methods: Relative and absolute concentrations of 41 circulating PLFAs were measured by gas chromatography in samples from 3 diverse populations. Correlations between the relative and absolute concentrations for each fatty acid were used to measure agreement. Unadjusted correlations and correlations adjusting absolute PLFA concentrations for total cholesterol were calculated.Results: Unadjusted correlations between relative and absolute concentrations, as well as correlations adjusting absolute PLFA concentrations for total cholesterol, were high for most PLFAs in all 3 studies. Across the 3 studies, 28 of the 41 analyzed PLFAs had unadjusted correlations > 0.6 and 39 had adjusted correlations > 0.6.Conclusions: Choice of relative vs absolute concentration may not affect interpretation of results for most circulating PLFAs in studies of association between individual PLFAs and disease outcomes, especially if a covariate reflecting total lipids, such as total circulating cholesterol, is included in the model. However, for fatty acids, such as 16:0 (palmitic acid), with low correlation between the 2 metrics, using relative vs absolute concentration may lead to different inferences regarding their association with the outcome. Because both concentrations could be obtained simultaneously from the same laboratory assay, use of both metrics is warranted to better understand PLFA-disease relationships. [ABSTRACT FROM AUTHOR]

Objective: The objectives were: 1) measure polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in 100µL of human serum and 2) assess PAH and PCDD/PCDF as markers of burn pit exposures during military deployments. Methods: PAHs and PCDDs/PCDFs were analyzed in 100µL serum samples collected pre-and post-deployment from 200 persons deployed to Iraq or Afghanistan (CASE); 200 persons not deployed (CONTROL) with gas chromatography/ mass spectrometry. Results: Naphthalene was found in ~83% of the samples and was statistically different between post-deployment CASE personnel and pre-deployment. 1,2,3,4,6,7,8-Heptachlorodibenzo-p-dioxin, Octachlorodi-benzo-p-dioxin, 1,2,3,7,8,9-Hexachlorodibenzofuran, and 1.2,3.4,6,7.8-Hep-tachlorodibenzofuran were found in ~38% of samples. Concentrations were significantly different between CASE and CONTROL and between pre- and post-deployment samples. Conclusions: PAH and PCDD/PCDF in serum can serve as exposure markers and measurements in small volumes is feasible for quantifying exposure to burn pits. [ABSTRACT FROM AUTHOR]

Objective: The aim of this study was to maximize detection of serum metabolites with high-resolution metabolomics (HRM). Methods: Department of Defense Serum Repository (DoDSR) samples were analyzed using ultrahigh resolution mass spectrometry with three complementary chromatographic phases and four ionization modes. Chemical coverage was evaluated by number of ions detected and accurate mass matches to a human metabolomics database. Results: Individual HRM platforms provided accurate mass matches for up to 58% of the KEGG metabolite database. Combining two analytical methods increased matches to 72% and included metabolites in most major human metabolic pathways and chemical classes. Detection and feature quality varied by analytical configuration. Conclusions: Dual chromatography HRM with positive and negative electrospray ionization provides an effective generalized method for metabolic assessment of military personnel. [ABSTRACT FROM AUTHOR]

Objective: A pilot study was conducted to test the feasibility of using Department of Defense Serum Repository (DoDSR) samples to study health and exposure-related effects. Methods: Thirty unidentified human serum samples were obtained from the DoDSR and analyzed for normal serum metabolites with high-resolution mass spectrometry and serum levels of free benzo(a)pyrene (BaP) by gas chromatography-mass spectrometry. Metabolic associations with BaP were determined using a metabolome-wide association study (MWAS) and metabolic pathway enrichment. Results: The serum analysis detected normal ranges of glucose, selected amino acids, fatty acids, and creatinine. Free BaP was detected in a broad concentration range. MWAS of BaP showed associations with lipids, fatty acids, and sulfur amino acid metabolic pathways. Conclusion: The results show that the DoDSR samples are of sufficient quality for chemical profiling of DoD personnel. [ABSTRACT FROM AUTHOR]

Introduction: In 2011 menthol cigarettes accounted for 32 percent of the market in the United States, but there are few literature reports that provide measured menthol data for commercial cigarettes. To assess current menthol application levels in the US cigarette market, menthol levels in cigarettes labeled or not labeled to contain menthol was determined for a variety of contemporary domestic cigarette products.Method: We measured the menthol content of 45 whole cigarettes using a validated gas chromatography/mass spectrometry method.Results: In 23 cigarette brands labeled as menthol products, the menthol levels of the whole cigarette ranged from 2.9 to 19.6mg/cigarette, with three products having higher levels of menthol relative to the other menthol products. The menthol levels for 22 cigarette products not labeled to contain menthol ranged from 0.002 to 0.07mg/cigarette. The type of packaging (soft vs. hard pack) for a given cigarette product does not appear to affect menthol levels based on the current limited data.Conclusions: Menthol levels in cigarette products labeled as containing menthol are approximately 50- to 5000-fold higher than those in cigarette products not labeled as containing menthol. In general, menthol content appears to occur within discrete ranges for both mentholated and nonmentholated cigarettes.Implications: This study shows that menthol may be present in non-mentholated cigarettes and adds to the understanding of how menthol may be used in cigarette products. It is the first systematic study from the same laboratory which will readily enable comparison among menthol and non-menthol cigarettes. [ABSTRACT FROM AUTHOR]

Introduction: Electronic cigarettes (E-Cigs) are popular alternatives to conventional tobacco cigarettes. Disposable E-Cigs are single-use devices that emit aerosols from a nicotine-containing solution (e-liquid) by activating a heating coil during puffing. However, due to lack of regulations and standards, it is unclear how product claims are aligning with actual content and performance. Some analytical methods for characterizing E-Cigs are still in an exploratory phase.Methods: Five products of disposable E-Cigs (purchased March-April, 2014 from a local smoke shop and an on-line US distributor) were studied for nicotine content, number of puffs obtained before depletion, portion of nicotine delivered via aerosolization, and e-liquid pH. Protocols were developed to consistently extract e-liquid from puffed and unpuffed E-Cigs. An in-house mechanical puffing machine was used to consistently puff E-Cig aerosols onto filter pads. A gas chromatography-mass spectrometry method was developed that produced sensitive and repeatable nicotine determinations.Results: Under our experimental parameters, results showed a disparity between nicotine content and number of puffs achieved relative to what was claimed on product packaging. The portion of nicotine delivered to filter pads was often less than half that which was available, indicating much of the nicotine may be left in the E-Cig upon depletion.Conclusions: Analyses of unpuffed E-Cigs by gas chromatography-mass spectrometry indicate the nicotine content of these products can be considerably different from manufacture's labeling. Furthermore, a large portion of the nicotine in E-Cigs may not be transferred to the user, and that which is transferred, may often be in the less bioavailable form. [ABSTRACT FROM AUTHOR]

Background and Objectives. Pain symptoms are common among Iraq/Afghanistan-era veterans, many of whom continue to experience persistent pain symptoms despite multiple pharmacological interventions. Preclinical data suggest that neurosteroids such as allopregnanolone demonstrate pronounced analgesic properties, and thus represent logical biomarker candidates and therapeutic targets for pain. Allopregnanolone is also a positive GABAA receptor modulator with anxiolytic, anticonvulsant, and neuroprotective actions in rodent models. We previously reported inverse associations between serum allopregnanolone levels and self-reported pain symptom severity in a pilot study of 82 male veterans. Methods. The current study investigates allopregnanolone levels in a larger cohort of 485 male Iraq/ Afghanistan-era veterans to attempt to replicate these initial findings. Pain symptoms were assessed by items from the Symptom Checklist-90-R (SCL-90-R) querying headache, chest pain, muscle soreness, and low back pain over the past 7 days. Allopregnanolone levels were quantified by gas chromatography/mass spectrometry. Results. Associations between pain ratings and allopregnanolone levels were examined with Poisson regression analyses, controlling for age and smoking. Bivariate nonparametric Mann- Whitney analyses examining allopregnanolone levels across high and low levels of pain were also conducted. Allopregnanolone levels were inversely associated with muscle soreness [P=0.0028], chest pain [P=0.032], and aggregate total pain (sum of all four pain items) [P=0.0001]. In the bivariate analyses, allopregnanolone levels were lower in the group reporting high levels of muscle soreness [P=0.001]. Conclusions. These findings are generally consistent with our prior pilot study and suggest that allopregnanolone may function as an endogenous analgesic. Thus, exogenous supplementation with allopregnanolone could have therapeutic potential. The characterization of neurosteroid profiles may also have biomarker utility. [ABSTRACT FROM AUTHOR]

Polybrominated diphenyl ethers (PBDEs) alter thyroid hormone homeostasis, but their relationship with thyroid cancer is unknown. To investigate whether serum concentrations of PBDE were associated with thyroid cancer, we conducted a nested, case-control study in the Prostate, Lung, Colorectal, and Ovarian Cancer Screening Trial, a large multicenter clinical trial in the United States. Cases with thyroid cancer (n = 104) were recruited from 1992 to 2001 and diagnosed through 2009, and controls (n = 208) were individually matched (2:1) to cases by race, sex, birth date (within 1 year), center, and blood collection date (within 15 days). We used gas chromatography isotope dilution high-resolution mass spectrometry to measure 10 tri- to heptabrominated diphenyl eithers in serum samples. Odds ratios and 95% confidence intervals were calculated using conditional logistic regression for lipidadjusted PBDE levels detected in more than 50% of controls and for the sum of these BDEs (∑PBDEs). We observed no significant differences between cases and controls in lipid-adjusted concentrations of ∑PBDEs (for cases, median = 12.8 ng/g lipid (interquartile range, 6.2-42.1); for controls, median = 19.4 ng/g lipid (interquartile range, 7.6-50.2)) or for individual congeners. Increasing quartiles of ∑PBDEs and 4 BDE congeners were not associated with risk of thyroid cancer (for the fourth vs. first quartile of ∑PBDEs, adjusted odd ratio = 0.62, 95% confidence interval: 0.29, 1.30; P for trend = 0.56). Our study does not support an association between exposure to PBDEs and thyroid cancer. [ABSTRACT FROM AUTHOR]

Objective Type 1 diabetes ( T1D) results from the inflammatory destruction of pancreatic β-cells. In this study, we investigated the effect of docosahexaenoic acid ( DHA) supplementation on stimulated inflammatory cytokine production in white blood cells ( WBC) from infants with a high genetic risk for T1D. Research design and methods This was a multicenter, two-arm, randomized, double-blind pilot trial of DHA supplementation, beginning either in the last trimester of pregnancy (41 infants) or in the first 5 months after birth (57 infants). Levels of DHA in infant and maternal red blood cell ( RBC) membranes and in breast milk were analyzed by gas chromatography/mass spectrometry. Inflammatory cytokines were assayed from whole blood culture supernatants using the Luminex multiplex assay after stimulation with high dose lipopolysaccharide ( LPS), 1 µg/ mL. Results The levels of RBC DHA were increased by 61-100% in treated compared to control infants at ages 6-36 months. There were no statistically significant reductions in production of the inflammatory cytokines, IL-1β, TNFα, or IL-12p40 at any of the six timepoints measured. The inflammatory marker, high-sensitivity C-reactive protein ( hsCRP), was significantly lower in breast-fed DHA-treated infants compared to all formula-fed infants at the age of 12 months. Three infants (two received DHA) were removed from the study as a result of developing ≥two persistently positive biochemical islet autoantibodies. Conclusions This pilot trial showed that supplementation of infant diets with DHA is safe and fulfilled the pre-study goal of increasing infant RBC DHA levels by at least 20%. Inflammatory cytokine production was not consistently reduced. [ABSTRACT FROM AUTHOR]

Background: Previous observational studies of self-reported dairy product consumption and stroke risk have reported mixed findings. Few studies have used circulating biomarkers that provide objective measures of dairy fat intake. Objectives: We tested the hypothesis that the circulating biomarkers of dairy fat, pentadecanoic acid (15:0), heptadecanoic acid (17:0), and trans palmitoleate (trans 16:1n-7), were associated with lower incidence of stroke, especially ischemic stroke. Secondarily, we evaluated 14:0, which is obtained from dairy products and beef, and also endogenously synthesized. Design: In participants from 2 large US cohorts (the Health Professionals Follow-Up Study: 51,529 men; the Nurses' Health Study: 121,700 women) with stored blood samples in 1993-1994 (n = 18,225) and 1989-1990 (n = 32,826), respectively, we prospectively identified 594 incident stroke cases (median follow-up: 8.3 y) and matched them 1:1 to risk-set-sampled control subjects by age, sex, race, and smoking. Total plasma and red blood cell (RBC) fatty acids were measured by using gas-liquid chromatography. Covariates were assessed by using validated questionnaires. Stroke events and subtypes were adjudicated by using medical records or other supporting documentation. We used conditional logistic regression to estimate associations of fatty acids with incident stroke, and cohort-specific findings were combined by inverse-variance weights. Results: After adjustment for demographic characteristics, lifestyle, cardiovascular disease risk factors, diet, and other circulating fatty acids, no significant associations with total stroke were seen for plasma 15:0 (pooled HR for highest compared with lowest quartiles: 0.85; 95% CI: 0.54, 1.33), 17:0 (0.99; 0.67, 1.49), trans 16:1 n-7 (0.89; 0.55, 1.45), or 14:0 (1.05; 0.62, 1.78). Results were similar for ischemic and hemorrhagic stroke subtypes, for RBC fatty acids, and in several different sensitivity analyses. Conclusion: In 2 large prospective cohorts, circulating biomarkers of dairy fat were not significantly associated with stroke. [ABSTRACT FROM AUTHOR]

There are over 450 000 sites contaminated by chemicals in the US. This large number of contaminated sites and the speed of subsurface migration of chemicals pose considerable risk to nearby residences and commercial buildings. The high costs for monitoring around these sites stem from the labor involved in placing and replacing the passive sorbent vapor samplers and the resultant laboratory analysis. This monitoring produces sparse data sets that do not track temporal changes well. To substantially reduce costs and better track exposures, less costly, unattended systems for monitoring soil gases and vapor intrusion into homes and businesses are desirable to aid in the remediation of contaminated sites. This paper describes progress toward the development of an inexpensive system specifically for monitoring vapor intrusion; the system can operate repeatedly without user intervention with low detection limits (1 × 10−9, or 1 part-per-billion). Targeted analytes include chlorinated hydrocarbons (dichloroethylene, trichloroethane, trichloroethylene, and perchloroethylene) and benzene. The system consists of a trap-and-purge preconcentrator for vapor collection in conjunction with a compact gas chromatography instrument to separate individual compounds. Chemical detection is accomplished with an array of chemicapacitors and a metal-oxide semiconductor combustibles sensor. Both the preconcentrator and the chromatography column are resistively heated. All components are compatible with ambient air, which serves as the carrier gas for the gas chromatography and detectors. [ABSTRACT FROM AUTHOR]

Largely missing from the debate surrounding the use of pottery among arctic and sub- arctic hunter-gatherers are site-based biomolecular studies of vessel contents. This study used lipid- residue analysis to elucidate vessel function at Nunalleq (GDN-248), a late Thule- period coastal village site in the Yup'ik area of Western Alaska. In total, 31 pottery sherds and five soil samples were analyzed using gas chromatography and/or gas chromatography--mass spectrometry. The ubiquitous presence of aquatic biomarkers in all the pottery sherds suggests that pottery function at the site was directly linked to the use of aquatic resources. This indication of relatively specialized use of pottery at Nunalleq is particularly interesting when considered within the context of the site's broader subsistence strategies, which included use of both aquatic and terrestrial resources. These findings appear to support a more general association between higher-latitude pottery traditions and the use of aquatic resources, though this topic requires further research. [ABSTRACT FROM AUTHOR]

De novo lipogenesis has been implicated in prostate carcinogenesis, and blood levels of specific saturated fatty acids (SFAs) and monounsaturated fatty acids (MUFAs) could reflect activity of this pathway. We used gas chromatography to measure blood SFA and MUFA levels in prediagnostic samples from 476 incident prostate cancer cases (1982–1995) in the Physicians' Health Study and an equal number of controls matched on age and smoking status. Five tagging polymorphisms in the fatty acid synthase (FASN) gene (rs1127678, rs6502051, rs4246444, rs12949488, and rs8066956) were related to blood SFA and MUFA levels. Conditional logistic regression was used to estimate the rate ratios, with 95% confidence intervals, of prostate cancer across quintiles of blood fatty acid levels. The polymorphisms rs6502051 and rs4246444 were associated with lower levels of 14:1n-5, 16:1n-7, and 18:1n-9. Blood levels of 16:1n-7 were associated with higher prostate cancer incidence, with rate ratios for men in increasing quintiles of 1.00, 1.40, 1.35, 1.44, and 1.97 (95% confidence interval: 1.27–3.06; Ptrend = 0.003). Furthermore, 16:1n-7 levels were positively related to incidence of high-grade (Gleason score ≥7) tumors (rate ratioQ5–Q1 = 3.92; 95% confidence interval: 1.72–8.94) but not low-grade tumors (rate ratioQ5–Q1 = 1.51; 95% confidence interval: 0.87–2.62) (Pheterogeneity = 0.02). Higher activity of enzymes involved in de novo lipogenesis, as reflected in blood levels of 16:1n-7, could be involved in the development of high-grade prostate cancer. [ABSTRACT FROM PUBLISHER]

The presence of phthalate esters (PAEs) in the environment is not desirable and therefore, needs to be monitored. This study reports the first data on the concentration levels of PAEs in water and sediments of the Jukskei River catchment area, South Africa. The study was conducted during the summer and winter seasons of 2005. Liquid-liquid extraction (LLE) and Soxhlet extraction (SE) methods were optimized, evaluated and used to determine PAEs of interest in water (unfiltered and filtered) and sediments samples, respectively. Mean percentage recoveries in spiked doubly distilled water ranged from 100 ± 5.32 dimethyl phthalate (DMP) – 122 ± 0.46 di-2-ethylhexyl phthalate (DEHP) and 91.6 ± 1.93 diethyl phthalate (DEP) – 117 ± 4.80 dibutyl phthalate (DBP) in sediments. The concentration levels of PAEs studied in unfiltered environmental water samples were in the range of 0.04(± 0.00) (DMP) − 9.76(± 00.1) ng mL−1(DEHP) for PAEs and from 0.09 (± 0.01) (DMP) – 4.38 (± 0.06) ng mL−1(DEHP) for filtered environmental water samples. Concentration levels obtained in sediments were from 0.05 (0.00) (DMP) – 4910 (0.36) ng/gdw (DEHP). PAEs adsorbed on the sample bottle gave concentration levels of up to 0.10 (± 0.03) ng mL−1for some samples and no analyte was detected (ND) in some cases Generally, concentrations obtained were below the water quality guideline values of United States Environmental Protection Agency (USEPA). [ABSTRACT FROM AUTHOR]

Introduction: N′-nitrosonornicotine (NNN), an esophageal and oral carcinogen present in tobacco products, has a chiral center in its structure. Of its two enantiomers, (S)-NNN exhibits higher tumorigenic potency than (R)-NNN. There is no information available on the levels of (S)-NNN in various tobacco products currently marketed in the United States. Methods: We used chiral gas chromatography analysis to determine (S)-NNN levels in a convenience sample of 37 tobacco products currently marketed in the United States: conventional smokeless tobacco, novel smokeless tobacco products, and cigarette tobacco filler. Results: Among all products analyzed here, (S)-NNN averaged 62.9±6.3% (SD) of NNN. The absolute amount of (S)-NNN in conventional moist snuff averaged 1.26±0.5 µg/g tobacco; in novel smokeless products 0.70±0.2 µg/g tobacco; and in cigarette filler 1.36±0.6 µg/g tobacco (all values are per wet weight). For each cigarette brand, the enantiomeric composition of NNN in cigarette smoke was similar to that of the corresponding tobacco filler. Conclusions: Our results demonstrate that (S)-NNN is the predominant NNN enantiomer in moist snuff, novel smokeless tobacco products, and cigarettes currently marketed in the United States. Efforts toward the reduction of NNN in U.S. tobacco products should take into account its enantiomeric composition, with particular focus on (S)-NNN as a causative agent for esophageal and oral cancers associated with tobacco use. [ABSTRACT FROM AUTHOR]

JWH-018 (1-pentyl-3-(1-naphthoyl)indole) is one of numerous potential aminoalkylindoles contained in products marketed as 'K2' or 'Spice'. Investigation of the urinary metabolites from consumption of these compounds is important because they are banned in the United States and many European countries. An efficient extraction procedure and gas chromatography-mass spectrometry (GC-MS) method were developed for detection of 'K2' metabolites in urine from individuals suspected of using these products. Analytical standards were used to elucidate the structure-specific mass spectral fragmentations and retention properties to confirm proposed identifications and support quantitative studies. A procedure for the synthesis of one of these metabolites (5-hydroxypentyl JWH-018) was also developed. Results are comparable to existing LC-MS/MS methods, with the same primary metabolites detected. The specific metabolite hydrolysis products include 4-hydroxpentyl, 5-hydroxypentyl, and Npentanoic acid derivatives. [ABSTRACT FROM AUTHOR]

Abstract: Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from 3H/3He and SF6 data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800pgkg−1), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The 3H/3He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7a in periods of more average precipitation (2008–2009). The SF6 and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities. [Copyright &y& Elsevier]

The article discusses as study to evaluate whether exposure to short-term jet propulsion fuel 8 (JP-8) is associated with balance problems among U.S. Air Force (USAF) personnel. The study found that the balance control among USAF personnel decreased as the task became more challenging, and workday exposure to JP-8 was not related to postural sway. The factors actually responsible for postural sway include demographic variables like younger age, being a smoker, and higher body mass index (BMI).

The article describes outreach activities for rural high school students in the U.S. to help raise awareness about air pollution. Small groups tour, lectures about atmospheric sciences and chemical demonstrations to keep the interest of students about air pollution are the workshop's components. Topics discussed include energy and pollution control, air quality model, and airborne atmospheric research. The direct assessment of student learning about the topic is also provided.

Background: Although trans fatty acids (TFAs) may increase the risk of dyslipidemia and coronary artery disease (CAD), limited data are available on their association with heart failure (HF). Objective: Our goal was to assess associations of plasma and dietary TFAs with HF and CAD. Design: We used a prospective, nested case-control design to select 788 incident HF cases and 788 matched controls from the Physicians' Health Study for biomarker analyses and a prospective cohort for the dietary analyses. Plasma fatty acids were assessed by using gas chromatography, and dietary intake was estimated by using a food-frequency questionnaire. Self-reported HF was ascertained by using annual follow-up questionnaires with validation in a subsample. We used conditional logistic (or Cox) regression to estimate multivariable-adjusted ORs (or HRs) for HF and CAD. Results: Multivariable-adjusted ORs (95% CIs) for HF across consecutive quintiles of plasma trans 18:2 (linoleic acid) fatty acids were 1.0 (reference), 1.10 (0.79, 1.54), 0.88 (0.62, 1.25), 0.71 (0.49, 1.02), and 0.67 (0.45, 0.98) (P-trend = 0.01). Each SD of plasma trans 18:2 was associated with a 22% lower risk of HF (95% CI: 6%, 36%). Plasma trans 16:1 and 18:1 were not associated with risk of HF (P > 0.05). Dietary trans fats were not associated with incident HF or CAD. Conclusions: Our data are consistent with a lower risk of HF with higher concentrations of plasma trans 18:2 but not with trans 16:1 or trans 18:1 fatty acids in male physicians. Dietary TFAs were not related to incident HF or CAD. [ABSTRACT FROM AUTHOR]

Aims To investigate the relationships between tobacco dependence, biomarkers of nicotine and carcinogen exposure and biomarkers of nicotine and carcinogen exposure per cigarette in back and white smokers. Design, setting and participants A total of 204 healthy black ( n = 69) and white ( n = 135) smokers were enrolled into two clinical studies. Measurement Nicotine equivalents (nicotine and its metabolites), 4-(methylnitrosamino)-1-(3)pyridyl-1-butanol ( NNAL) and polycyclic aromatic hydrocarbon ( PAH) metabolites were measured in urine. The Fagerström Test for Nicotine Dependence ( FTND) and time to first cigarette ( TFC) measured tobacco dependence. Findings Average TFC and FTND for blacks and whites were not significantly different. Urine NNAL and nicotine equivalents increased with increasing FTND in whites but did not increase in blacks (race × FTND interaction, both P < 0.031). The interaction term was not significant for PAHs. An inverse relationship was seen between FTND and nicotine equivalents, NNAL and PAH metabolites per cigarette in blacks but remained flat in whites (race × FTND interaction, all P ≤ 0.039). Regardless of dependence (low dependence, TFC >15 minutes; high dependence, TFC ≤15 minutes), FTND and TFC were not correlated significantly with urine nicotine equivalents and carcinogen exposure in blacks. We found moderate correlations between FTND and TFC and nicotine equivalents and carcinogen exposure among whites of low dependence and non-significant correlations among whites of high dependence. Conclusion In the United States, tobacco dependence measures were related linearly to nicotine intake and carcinogen exposure in white but not in black smokers. The relationship between dependence measures and tobacco biomarkers in black smokers regardless of level of dependence resembled highly dependent white smokers. [ABSTRACT FROM AUTHOR]

Abstract: Nationwide sampling in the U.S. of whole large eggs, to update values in the United States Department of Agriculture (USDA) National Nutrient Database for Standard Reference (SR) (http://www.ars.usda.gov/nutrientdata), was conducted in 2000–2001 and in 2010. Retail cartons of large eggs were obtained from 12 supermarket locations using statistical sampling plans based on market share and census data. Cholesterol was analyzed at three laboratories using standard methods involving gas chromatography of the saponified total lipid extract. Vitamin D3 and 25-OH-vitamin D3 (2010 samples only) were analyzed by HPLC and UHPLC–MS/MS. Quality control materials were included to validate the accuracy and precision of measurements. The mean cholesterol content decreased 51mg/100g (12%; p <0.0001), from 423mg/100g in 2000–2001 to 372 (range 344–405) in 2010. Over the same period, average vitamin D3 increased by 60%, to 2.05μg [80IU]/100g (range 0.97–12.1). Samples from 2010 contained 0.65μg 25-OH-D3/100g (range 0.43–1.32). The disparate vitamin D (and cholesterol) content of eggs sampled from different locations may reflect industry efforts to modify poultry feed or supplements to affect the nutrient profile of eggs. Cholesterol and vitamin D3 data from this work were included in SR release 23, and support food consumption surveys, food and nutrition policy, and consumer education. [Copyright &y& Elsevier]

Abstract: Agriculture faces unique challenges as increasing world population places unprecedented demands on food, feed, and energy resources. In an effort to become more efficient and sustainable, marginal land, including regulatory brownfields prohibited for food consumption purposes could be utilized for bioenergy crop production. In 2006–2008, we evaluated soybean (Glycine Max (L.) Merr.), canola (Brassica napus L. var. napus), sunflower (Helianthus annuus L.), and switchgrass (Panicum virgatum L.) to determine crop suitability for bioenergy production on a regulatory brownfield site. Sites selected for the study included a remediated brownfield site in Rose Township, Oakland County, and a historically cropped agricultural site at East Lansing, Ingham County, serving as the control. Comparisons of biofuel quality components were conducted. The total oil yield of oilseed crops was not significantly different (p < 0.05) between locations. Concentrations of palmitic (C16:0), stearic (C18:0), oleic (C18:1), linoleic (C18:2), and linolenic (C18:3) fatty acids differed by location, yet oleic acid concentrations, optimal for quality biodiesel production, were not significantly different across all oilseed crops. Total crystalline cellulose levels from switchgrass were higher at the agricultural land site compared to the brownfield site in 2007 yielding 16% more crystalline cellulose; but there were no differences between locations in 2008. Detectable levels of PCB''s were found in soils at the brownfield site; however, transfer to grain or biomass was not detected. Results suggest that brownfield sites have the potential to produce feedstock of suitable quality for conversion to liquid transportation fuels. [Copyright &y& Elsevier]

Introduction: The electronic cigarette (EC) is a plastic device that imitates conventional cigarettes and was developed to deliver nicotine in a toxin-free vapor. Nicotine in a solution is heated and vaporized when a person puffs through the device and is inhaled as a vapor into the mouth. The EC is a new product on the market and little is known about its safety and nicotine delivery efficacy. The aim of the study was to analyze nicotine levels in vapor generated from various EC brands and models. The study was designed to assess efficacy and consistency of various ECs in converting nicotine to vapor and to analyze dynamics of nicotine vaporization. Methods: Sixteen ECs were selected based on their popularity in the Polish, U.K. and U.S. markets. Vapors were generated using an automatic smoking machine modified to simulate puffing conditions of real EC users. Nicotine was absorbed in a set of washing bottles with methanol and analyzed with gas chromatography. Results: The total level of nicotine in vapor generated by 20 series of 15 puffs varied from 0.5 to 15.4 mg. Most of the analyzed ECs effectively delivered nicotine during the first 150–180 puffs. On an average, 50%–60% of nicotine from a cartridge was vaporized. Conclusions: ECs generate vapor that contains nicotine, but EC brands and models differ in their efficacy and consistency of nicotine vaporization. In ECs, which vaporize nicotine effectively, the amount inhaled from 15 puffs is lower compared with smoking a conventional cigarette. [ABSTRACT FROM AUTHOR]

Bisphenol A (BPA) is identified as the suspected endocrine disrupter (ED) and is on the NORMAN list of emerging substances and is also on the list of substances for further investigation reported by the US EPA and European Union. Although BPA arouses a considerable public health concern, there is a general lack of the information on the levels of EDs in the countries of the Western Balkan region. A gas chromatographic-mass spectrometric method was used for the quantification of BPA in the Danube surface water samples. A solid-phase extraction procedure with two types of cartridges (C18 and Bond Elut Plexa) was used for preconcentration and removal of interferences. Characteristic chromatogram was obtained in SIM mode (retention time 15.054 min). BPA was detected in water samples collected in November 2012 on eight different locations of the Danube in the vicinity of Novi Sad, Serbia. BPA ranged from < 6 ng/L to 221.6 ng/L. Future investigations should be focused on seasonal variations of the BPA concentrations and the higher number of collected samples and more sampling sites of the Danube water. [ABSTRACT FROM AUTHOR]

Background: Although 1 in 5 adults will develop heart failure (HF) in their lifetime, data on the effect of plasma omega-6 (n-3) PUFAs on risk of HF are currently sparse. Objectives: We investigated whether plasma phospholipid omega-6 concentrations are associated with risk of HF in US male physicians. In a secondary analysis, we evaluated whether such an association differs between HF with and without previous myocardial infarction (MI). Design: With the use of a nested case-control design, this ancillary study comprised 788 cases and 788 matched controls from the Physicians' Health Study. Plasma omega-6 PUFAs were measured by using gas chromatography. Results: The mean age of subjects was 58.7 y with a mean follow-up time of 17.1 y. We did not show any evidence of a statistically significant relation between total omega-6 PUFAs and HF [OR (95% CI): 1.00; 0.85 (0.63, 1.14); 0.84 (0.63, 1.13); and 0.87 (0.63, 1.20) across consecutive quartiles of omega-6 PUFAs; P-linear trend = 0.39]. Results were similar for HF with and without previous MI. Conclusion: Our data showed no significant association between total plasma omega-6 PUFAs and risk of developing HF. [ABSTRACT FROM AUTHOR]

Background: Data on the relation of plasma and dietary omega-3 (n-3) fatty acids (FAs) with heart failure (HF) risk have been inconsistent. . Objective: We evaluated the relation of n-3 FAs with HF in US male physicians. Design: We used nested case-control (n = 1572) and prospective cohort study designs (n = 19,097). Plasma phospholipid n-3 FAs were measured by using gas chromatography, and food-frequency questionnaires were used to assess dietary n-3 FAs and fish intake. Incident HF was ascertained via annual follow-up questionnaires and validated in a subsample. Results: The mean age was 58.7 y at blood collection. In a multi- variable model, plasma a-linolenic acid (ALA) was associated with a lower risk of HF in a nonlinear fashion (P-quadratic trend = 0.02), and the lowest OR was observed in quintile 4 (0.66; 95% CI: 0.47, 0.94). Plasma EPA and DHA were not associated with HF, whereas plasma docosapentaenoic acid (DPA) showed a nonlinear inverse relation with HF for quintile 2 (OR: 0.55; 95% CI: 0.39, 0.79). Dietary marine n-3 FAs showed a trend toward a lower risk of HF in quintile 4 (HR: 0.81; 95% CI: 0.64, 1.02) and a nonlinear pattern across quintiles. Fish intake was associated with a lower risk of HF, with RRs of ~0.70 for all categories of fish consumption greater than one serving per month. Conclusions: Our data are consistent with an inverse and nonlinear relation of plasma phospholipid ALA and DPA, but not EPA or DHA, with HF risk. Fish consumption greater than once per month was associated with a lower HF risk. [ABSTRACT FROM AUTHOR]

Objective:To determine fatty acid levels in the US donor milk supply.Study Design:Donor human milk samples from Iowa (n=62), Texas (n=5), North Carolina (n=5) and California (n=5) were analyzed by gas chromatography. Levels in the Iowa donor milk were compared before and after pasteurization using Student's t-test. Docosahexaenoic acid (DHA) and arachidonic acid (ARA) levels were compared among all milk banks using analysis of variance.Result:ARA (0.4 pre, 0.4 post, P=0.18) and DHA (0.073 pre, 0.073 post, P=0.84) were not affected by pasteurization. DHA varied between banks (P<0.0001), whereas ARA did not (P=0.3). DHA levels from all banks were lower than published values for maternal milk and infant formula (P<0.0001).Conclusion:Pasteurization of breastmilk does not affect DHA or ARA levels. However, DHA content in US donor milk varies with bank location and may not meet the recommended provision for preterm infants. [ABSTRACT FROM AUTHOR]

Background: Few studies have evaluated the association between the n-3 fatty acid a-linolenic acid (ALA) and the incidence of congestive heart failure (CHF). Objective: We investigated whether plasma phospholipid concentrations and estimated dietary consumption of ALA are associated with incident CHF. Design: We used data from the Cardiovascular Health Study, a prospective cohort study of cardiovascular diseases among adults aged s65 y, from 4 US communities. A total of 2957 participants free of prevalent heart disease and with available fatty acid measurements were included in biomarker analyses (30,722 person-years and 686 incident CHF events). A total of 4432 participants free of prevalent heart disease were included in dietary analyses (52,609 person-years and 1072 events). We investigated the association of ALA with incident CHF by using Cox regression. Results: After adjustment for age, sex, race, education, smoking status, BMI, waist circumference, and alcohol consumption, plasma phospholipid ALA was not associated with incident CHF (HR for the highest compared with the lowest quartile: 0.97; 95% CI: 0.79, 1.21; P-trend = 0.85). Likewise, dietary ALA was not associated with incident CHF (adjusted HR for the highest compared with the lowest quartile: 0.96; 95% CI: 0.82, 1.20; PHrend = 0.97). We observed no association of biomarker or dietary ALA with nonvalvular CHF subtype. We also found little evidence of an association between ALA and CHF in subgroups based on age, sex, diabetes, fish consumption, BMI, or FADS2 genotype (rsl535). Conclusion: ALA intake is not associated with incident CHF in older adults. This trial was registered at clinicaltrials.gov as NCT00005133. [ABSTRACT FROM AUTHOR]