Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have been globally detected in impacted natural waters. The detection of trace quantities of EDCs and PPCPs in the environment is of great concern since some of these compounds have known physiological responses at low concentrations. EDCs can have a wide range of polarities, acidic and basic moieties, and exist in trace quantities, which often requires numerous complex extractions, large sample collection volumes, and multiple instrumental analyses. A comprehensive method has been developed allowing for the analysis of 58 potential EDCs in various water matrices using a single solid-phase extraction (SPE) of a 1 L sample with subsequent analyses using both gas chromatography and liquid chromatography, each coupled with tandem mass spectrometry (GC–MS/MS and LC–MS/MS). Instrument detection limits ranged between 0.12–7.5 pg with corresponding method reporting limits of 1–10 ng l⁻¹ in water. Recoveries for most compounds were between 50% and 112% with good reproducibility (RSD 6–22%).     

Toxicity and repellency of hot pepper extracts to spider mite, Tetranychus urticae Koch

Increasing concern about persistence and environmental impact of synthetic pesticide residues require development of biodegradable and environmentally safe alternatives. The potential of using fruit extracts of hot pepper as alternatives to synthetic acaricides for controlling the two-spotted spider mite, Tetranychus urticae Koch, is explored in this study. Twenty-four Capsicum accessions (Solanaceae) were screened for their toxicity and repellency to the spider mites. Crude extracts from fruits of C. chinense, C. frutescens, C. baccatum, C. annuum, and C. pubescens were prepared in methanol and tested for their acaricidal properties. Spider mite mortality was greatest (45%) when fruit extract of accession Grif-9169 (C. annuum) was used. Results from diving board bioassays indicated that mites avoided filter paper strips treated with hot pepper extracts from accessions PI-596057 (C. baccatum), PI-195299 (C. annuum), and Grif- 9270 (C. annuum). This investigation suggests that methanolic extracts of these three accessions may have a great potential for repelling spider mites and should be field-tested on a large-scale to assess their value in managing populations of spider mites, which could reduce reliance on synthetic acaricides. An attempt was made to correlate repellency with chemical constituents of fruit extracts of the most repellent accessions to identify chemical sources of repellency. Capsaicin and dihydrocapsaicin, the pungent components of pepper fruit, were not correlated with toxicity or repellency, indicating that these are not likely related to the toxicity or repellency of the pepper fruit extracts. Other, unidentified chemicals are likely responsible for toxicity and repellency to the two-spotted spider mite.     

Antioxidants in hot pepper: variation among accessions

The U.S. Department of Agriculture (USDA) pepper (Capsicum spp.) germplasm collection contains several thousand members or accessions. Many of these species and cultivars have not been analyzed for their concentrations of ascorbic acid, capsaicin, and total phenolic compounds, which are important antioxidants having a number of benefits for human health. The objective of this investigation was to select candidate accessions of hot pepper having high concentrations of ascorbic acid, capsaicin, free sugars, and total phenols for use as parents in breeding for these compounds. Seventeen accessions of pepper from the core Capsicum germplasm collection (four accessions of Capsicum chinense; five accessions of C. baccatum; six accessions of C. annuum; and two of C. frutescens) were field grown and their mature fruits were analyzed for their antioxidant composition. Concentrations of these compounds tended to be higher in C. chinense and C. baccatum, than in C. annuum and C. frutescens. Across all accessions the concentration of total phenols was correlated with ascorbic acid (r = 0.97) and free sugars (r = 0.80). Concentrations of total phenols (1.4, 1.3, and 1.3 mg g-1 fruit) and ascorbic acid (1.6, 1.2, and 1.3 mg g-1 fruit) were significantly greater in PI-633757, PI-387833, and PI-633754, respectively, compared to other accessions analyzed. Total capsaicinoids concentrations were greatest (1.3 mg g-1 fruit) in PI-438622 and lowest (0.002 mg g-1 fruit) in Grif-9320. The great variability within and among Capsicum species for these phytochemicals suggests that these selected accessions may be useful as parents in hybridization programs to produce fruits with value-added traits.     

Associations between driving under the influence or riding with an impaired driver and future substance use among adolescents

Objective: Risky driving behaviors among adolescents, such as riding with a drinking or impaired driver (RWID) or driving while under the influence (DUI) of alcohol or drugs, are significant public health concerns. Few studies have examined associations of RWID and DUI with future substance use and problems after controlling for baseline substance use. Given that the DUI/RWDD event may be a teachable moment to prevent future consequences (e.g., when injured or arrested), it is important to understand how this risk behavior relates to subsequent use and problems. This study therefore examined characteristics of adolescents who reported DUI and RWID and assessed their risk of future alcohol and marijuana use and consequences 6 months later.

Methods: Participants were 668 adolescents aged 12 to 18 (inclusive) recruited at 1 of 4 primary care clinics in Pittsburgh and Los Angeles as part of a larger randomized controlled trial. They completed surveys about their health behaviors at baseline and 6 months after baseline. We examined baseline characteristics of adolescents who reported DUI and RWID and then assessed whether past-year DUI and RWID at baseline were associated with alcohol and marijuana use and consequences 6 months after baseline.

Results: Fifty-eight percent of participants were female, 56% were Hispanic, 23% were Black, 14% were White, 7% were multiethnic or other, and the average age was 16 years (SD?=?1.9). At baseline, participants who reported RWID or DUI were more likely to be older, report past-year use of alcohol and marijuana, and more likely to have an alcohol use disorder or cannabis use disorder versus those who did not report RWID or DUI, respectively. At 6-month follow-up and after controlling for baseline demographics and baseline alcohol use, RWID was associated with more frequent drinking episodes in the past 3 months and greater number of drinks in the past month when they drank heavily. DUI at baseline was associated with more frequent heavy drinking episodes and alcohol and marijuana consequences 6 months later.

Conclusions: RWID and DUI are significantly associated with greater alcohol and marijuana use over time. This study highlights that teens may be at higher risk for problem substance use in the future even if they ride with someone who is impaired. Prevention and intervention efforts for adolescents need to address both driving under the influence and riding with an impaired driver to prevent downstream consequences.     

Effect of surfactants on Fenton's reagent-mediated degradation of Kraft black liquor

One of the limitations of the biodegradation of hydrophobic chemical compounds, like lignins, is their low solubility in the aqueous solution where this process takes place. To resolve this problem, surfactants have been used to improve the solubility of these hydrophobic compounds. In this investigation, we studied the effect of surfactants (anionic, cationic, and non-ionic) on the treatment of Kraft black liquor with Fenton's reagent. In the Fenton reaction, H2O2 (two different concentrations, 10 mM and 20 mM), FeCl2 (1 mM) and surfactant solution (10%) were used. Black liquor degradation was determined by UV/Visible spectrophotometry and by measuring phenolic groups. In the presence of Fenton's reagent, the optimum conditions for the oxidative degradation of black liquor were 10 mM H2O2, 1 microL of 10% solution of anionic surfactant (SDS). The importance of the use of surfactants for preparing black liquor for subsequent Fenton's reagent-mediated degradation was discussed.     

Effects of waterborne exposure to 4-nonylphenol on plasma sex steroid and vitellogenin concentrations in sexually mature male carp (Cyprinus carpio)

4-Nonylphenol (NP) has been shown to elicit estrogenic responses both in vivo and in vitro. The mechanism by which NP exerts estrogenic and other endocrine-modulating effects in vivo remains unclear, however. The goal of this study was to evaluate the ability of NP to elicit estrogenic responses through indirect mechanisms of action involving the modulation of endogenous steroid hormone concentrations. Sexually mature male common carp (Cyprinus carpio) were exposed to aqueous NP concentrations ranging from <0.05 to 5.4 microg NP/l for 28-31 d. Approximately 0.5-3.5 ppm of NP was detected in pooled plasma samples or tissue samples from the carp studied. NP exposure did not significantly increase plasma concentrations of 17beta-estradiol (E2), testosterone (T) or vitellogenin (VTG). Excluding outliers, plasma E2 concentrations ranged from <175 to 700 pg E2/ml. T concentrations ranged from 940 to 24,700 pg T/ml plasma. The greatest VTG concentration detected was 52 microg/ml. One-third of the plasma samples tested contained <1 microg VTG/ml. Overall, the results of this study did not support the hypothesis that exposure to waterborne NP can modulate concentrations of steroid hormones in the plasma of sexually mature male carp. The results did, however, raise a number of questions regarding the utility of estradiol equivalent (EEQ) estimates as a means of predicting in vivo effects of estrogenic substances. Furthermore, they provide information regarding the concentrations and variability of E2, T, and VTG in the plasma of sexually mature male carp, which may aid in design and interpretation of future studies.     

Regression comparisons of Tetrahymena pyriformis and Poecilia reticulata toxicity

The toxicity data of chemicals common to both the Poecilia reticulata mortality assay and the Tetrahymena pyriformis growth impairment assay were evaluated. Two chemicals were not toxic at saturation in the T. pyriformis assay. In addition, due to abiotic transformation, a third chemical was removed from further consideration. Each chemical was a priori assigned a mode of toxic action: neutral non-covalent, polar non-covalent, or electrophilic covalent toxicity. To further investigate comparisons between endpoints, polar and electrophilic chemicals were separated into class-based groups. The polar non-covalent chemicals were separated into phenols and anilines, while the electrophilic chemicals were separated into those reacting via Schiff-base formation (i.e., aldehydes) and those reacting via bimolecular substitution to a nucleophile (i.e., selected nitroaromatics). A comparison of toxic potency as a collective set was statistically described by the relationship; log(LC50(-1)) = 1.05(log(IGC50(-1))) + 0.56, n = 124; r2 = 0.85; s = 0.42; F = 682; Pr > F = 0.0001. The relationship between endpoints was inversely proportional to reactivity associated with the mode of action. While the comparative toxicity for neutral narcotics exhibited an excellent fit (r2 = 0.94), the fits for polar narcotics and electrophiles were poorer, r2 = 0.69 and 0.62, respectively. Investigations into class-based groupings indicated fit of toxic potency data for aldehydes (r2 = 0.85) and phenols (r2 = 0.81) were quite good. However, fits for anilines (r2 = 0.43) and nitroaromatics (r2 = 0.68) revealed that toxicity was not as well related between endpoints for these chemicals.     

Utilization of selected area electron diffraction patterns for characterization of air submicron particulate matter collected by a thermophoretic precipitator

A thermophoretic precipitator (TP) that uses a novelty of direct sampling of ambient air particulate matter (PM) onto transmission electron microscopy (TEM) grids was designed and utilized to determine its potential applicability for the collection and consequent qualitative analyses of representative PM in the air, especially those with aerodynamic diameter less than 1 microm (PM1.0). After a calibration process, preliminary field tests were performed under different weather conditions, locations, and time frames. TEM, selected area electron diffraction (SAED), and electron energy-dispersive X-ray spectrometry (EDS) analyses were performed on individual samples, and chemical species were analyzed. During this investigation, individual air PM with different sizes ranging from 10 microm to 10 nm for TEM analysis was collected. Two observations were made: (1) a large fraction of collected particulates were aggregates of very small particles of both organic and inorganic origin, and (2) a large fraction of the collected particulates were crystalline or polycrystalline. This study has demonstrated, by utilization of SAED patterns from TEM on air particles collected by a TP, the potential to analyze and identify individual air PM in a nanometer regime qualitatively by combining SAED and EDS data.