Numerous studies have established the influence of detrimental home conditions on child cognition and behavior; however, fewer have assessed these outcomes in the context of relatively "normal" range of home environmental conditions. Given the exquisite sensitivity to the environment of the neural substrates that undergird executive functioning (EF) and behavioral self-regulation in children, it is possible that a range of conditions within the home, even in the absence of maltreatment or economic deprivation, may impact these outcomes. The purpose of the present exploratory investigation was to further define the relationship between features of the home environment using the HOME inventory (a structured interview and observation of parent and child) and several dimensions of child EF and behavioral problems. In addition, this study sought to elucidate potentially differential associations between home and parent-reported neighborhood conditions-a hypothetically less direct influence on cognition in this age group-and level of child functioning. A battery of EF performance tasks and a widely-used checklist of behavioral problems were administered to 66 children, 8-11 years old from a lower middle income, working class sample. Results showed significant relationships between the home environment and several dimensions of EF and behavioral problems. In contrast, neighborhood conferred additional effects only on rule-breaking and aggression, not cognition, which is consistent with evidence that externalizing behavior in this age group becomes increasingly oriented toward outside influences. These findings warrant follow-up studies to establish causality. A broader program of research designed to delve further into the relationship between nuanced influences from the home and child cognition and behavior has implications for parenting strategies that foster healthy development. Neighborhood contexts should also be considered during early and mid-adolescent years based on existing studies and findings reported herein suggesting that this period of newfound autonomy and the heightened significance of peer relationships may influence externalizing behaviors, with implications for protective courses of action.
Population-based estimates of pesticide intake are needed to characterize exposure for particular demographic groups based on their dietary behaviors. Regression modeling performed on measurements of selected pesticides in composited duplicate diet samples allowed (1) estimation of pesticide intakes for a defined demographic community, and (2) comparison of dietary pesticide intakes between the composite and individual samples. Extant databases were useful for assigning individual samples to composites, but they could not provide the breadth of information needed to facilitate measurable levels in every composite. Composite sample measurements were found to be good predictors of pyrethroid pesticide levels in their individual sample constituents where sufficient measurements are available above the method detection limit. Statistical inference shows little evidence of differences between individual and composite measurements and suggests that regression modeling of food groups based on composite dietary samples may provide an effective tool for estimating dietary pesticide intake for a defined population.
The calculation of dietary intake of selected pesticides was accomplished using food samples collected from individual representatives of a defined demographic community using a community duplicate diet approach. A community of nine participants was identified in Apopka, FL from which intake assessments of organophosphate (OP) and pyrethroid pesticides were made. From these nine participants, sixty-seven individual samples were collected and subsequently analyzed by gas chromatography/mass spectrometry. Measured concentrations were used to estimate dietary intakes for individuals and for the community. Individual intakes of total OP and pyrethroid pesticides ranged from 6.7 to 996ng and 1.2 to 16,000ng, respectively. The community intake was 256ng for OPs and 3430ng for pyrethroid pesticides. The most commonly detected pesticide was permethrin, but the highest overall intake was of bifenthrin followed by esfenvalerate. These data indicate that the community in Apopka, FL, as represented by the nine individuals, was potentially exposed to both OP and pyrethroid pesticides at levels consistent with a dietary model and other field studies in which standard duplicate diet samples were collected. Higher levels of pyrethroid pesticides were measured than OPs, which is consistent with decreased usage of OPs. The diversity of pyrethroid pesticides detected in food samples was greater than expected. Continually changing pesticide usage patterns need to be considered when determining analytes of interest for large scale epidemiology studies. The Community Duplicate Diet Methodology is a tool for researchers to meet emerging exposure measurement needs that will lead to more accurate assessments of intake which may enhance decisions for chemical regulation. Successfully determining the intake of pesticides through the dietary route will allow for accurate assessments of pesticide exposures to a community of individuals, thereby significantly enhancing the research benefit realized from epidemiological exposure studies.
Nitrogen-doped carbon materials have been one of the most remarkable families of materials with promising applications in many fields. In this study, a series of nitrogen-doped carbon nanotubes frameworks (NCNTFs) with distinguishable nitrogen content and graphitization degree have been successfully prepared through in situ transformation of ZIF-67 under N2/H2 atmosphere at different pyrolysis temperature. Compared with conventional nitrogen-doped carbon materials derived from metal-organic frameworks, the formation of intertwined carbon nanotubes harvests desirable mesoporous structure that is favorable for the mass transfer and diffusion of reaction substances. When they are applied for catalytic degradation of Bisphenol A (BPA) in the presence of peroxymonosulfate (PMS), NCNTFs-800 (pyrolyzed at 800 °C) promises higher BPA removal efficiency than its counterparts from other pyrolysis temperature, as well as porous carbon derived from ZIF-8. Radical-quenching tests and electron paramagnetic resonance measurements verify that non-radical process (1O2) dominates BPA degradation over NCNTFs-800, and some common radicals (such as OH, SO4− and O2−) only play auxiliary roles. It is believed that the good balance between surface graphitic nitrogen sites and graphitization degree is responsible for the enhanced catalytic performance, and facilitates electron transfer from BPA to PMS to induce the non-radical pathways. Besides, some potential influential factors, including catalyst/Oxone dosage and reaction temperature are investigated, and the effects of anions, humic acid, and actual wastewater on BPA degradation are also elucidated in detail. Finally, several intermediates are identified by GC–MS analysis and the possible degradation pathways are deduced tentatively.
An observational field study was conducted to assess the feasibility of a community duplicate diet collection method; a dietary monitoring tool that is population-based. The purpose was to establish an alternative procedure to duplicate diet sampling that would be more efficient for a large, defined population, e. g., in the National Children's Study (NCS). Questionnaire data and food samples were collected in a residence so as not to lose the important component of storage, preparation, and handling in a contaminated microenvironment. The participants included nine Hispanic women of child bearing age living in Apopka, FL, USA. Foods highly consumed by Hispanic women were identified based on national food frequency questionnaires and prioritized by permethrin residue concentrations as measured for the Pesticide Data Program. Participants filled out questionnaires to determine if highly consumed foods were commonly eaten by them and to assess the collection protocol for the food samples. Measureable levels of permethrin were found in 54% of the samples. Questionnaire responses indicated that the collection of the community duplicate diet was feasible for a defined population.
A total of 256 men were studied to evaluate whether serum concentrations of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) impacted semen quality or reproductive hormones. Blood and semen were collected and analyzed for perfluorochemicals and reproductive and thyroid hormones. Semen quality was assessed using standard clinical methods. Linear and logistic modeling was performed with semen profile measurements as outcomes and PFOS and PFOA in semen and plasma as explanatory variables. Adjusting for age, abstinence, and tobacco use, there was no indication that PFOA or PFOS was significantly associated with volume, sperm concentration, percent motility, swim-up motility and concentration, and directional motility (a function of motility and modal progression). Follicle-stimulating hormone was not associated with either PFOA or PFOS. Luteinizing hormone was positively correlated with plasma PFOA and PFOS, but not semen PFOS. Important methodological concerns included the lack of multiple hormonal measurements necessary to address circadian rhythms.
The physical and chemical environment influences children's exposures to pesticides in and around the home. Children's activities,. which increase their potential for exposure especially during eating, have been captured in the Children's Dietary Intake Model (CDIM). In addition to the chemical exposure associated with the food itself, this model incorporates excess dietary exposures due to handling of food during consumption. To stochastically evaluate CDIM, distributions of measured, and in some cases estimated, model factors were determined from measurements of permethrin, chlorpyrifos, and diazinon derived from assembled databases and laboratory experiments. Using the distributions of these factors, Monte Carlo simulations were performed to obtain distributions of total dietary intake of pesticides. To target the sources of pesticide contamination that were influencing total dietary intake, each factor was evaluated. We found pesticide surface concentration to be highly influential. By excluding surface concentration, we were also able to determine the influence of the other factors based on the F-statistic. Transfer efficiencies, followed by pesticide residue in consumed foods and amount of food consumed, were the next most influential factors within the model. With these distributions for model inputs, CDIM has the potential to more accurately predict total dietary intake of a contaminant by a child.
Henry's law constants (k(H)) were measured (at 30 degrees C) and modeled for a suite of fragrance and solvent compounds in aqueous solutions of three structurally diverse industrial surfactants: sodium dodecylbenzene sulfonate (NaDBS), tetradecylbenzyldimethyl ammonium chloride (TDBAC), and a linear alkyl ethoxylate, Neodol 1,9. k(H) values for limonene, beta-pinene, toluene, and trichloroethene were examined as a function of surfactant concentration. When compared to TCE and toluene, the fragrances limonene and P-pinene with their larger values of molecular polarizability (alpha(mol) = (17.94 +/- 0.5) angstrom(3) and (17.34 +/- 0.5) angstrom(3), respectively) and greater hydrophobic character exhibited greater affinity for micelles of the linear alkyl ethoxylate relative to those of NaDBS and TDBAC and greater selectivity overall in their interaction(s) with micelles of varying carbon content (C-n). Using a linear solvation energy relationship (LSER) of the form In k(H) = C + s pi(2)* + a Sigma alpha(2) + b Sigma beta(2) (pi(2)* = solute dipolarity/polarizability; Sigma alpha(2) = overall solute hydrogen-bond-donor acidity; Sigma beta(2) overall solute hydrogen-bond-acceptor basicity; C = a regression constant) as an additional correlation and characterization tool, we find the large negative coefficients on pi(2)*, Sigma alpha(2), and Sigma beta(2) consistent with the inverse correlation between In kH and the magnitude of solute-solvent interactions in the condensed phase; C decreases with increasing size of the micellar phase. The dominance of HBD and HBA interactions (Sigma alpha(2) and Sigma beta(2), respectively) in the LSER for the alkyl ethoxylate points to the role of the ethylene oxide outer portion of the Neodol 1,9 micelles along with the effect of intercalated water.
The National Human Exposure Assessment Survey (NHEXAS) field study in EPA Region V (one of three NHEXAS field studies) provides extensive exposure data on a representative sample of 249 residents of the Great Lakes states. Concentration data were obtained for both metals and volatile organic compounds (VOCs) from multiple environmental media and from human biomarkers. A variance model for the logarithms of concentration measurements is used to define intraclass correlations between observations within primary sampling units (PSUs) (nominally counties) and within secondary sampling units (SSUs) (nominally Census blocks). A model for the total cost of the study is developed in terms of fixed costs and variable costs per PSU, SSU, and participant. Intraclass correlations are estimated for media and analytes with sufficient sample sizes. We demonstrate how the intraclass correlations and variable cost components can be used to determine the sample allocation that minimizes cost while achieving pre-specified precision constraints for future studies that monitor environmental concentrations and human exposures for metals and VOCs.
Multimedia data from two probability-based exposure studies were investigated in terms of how missing data and measurement-error imprecision affected estimation of population parameters and associations. Missing data resulted mainly from individuals'refusing to participate in certain measurement activities, rather than from field or laboratory problems; it suggests that future studies should focus on methods for maximizing participation rates. Measurement error variances computed from duplicate-sample data were small relative to the inherent variation in the populations; consequently, adjustments in nonparametric percentile estimates to account for measurement imprecision were small. Methods of adjustment based on lognormality assumptions, however, appeared to perform poorly.
A National Human Exposure Assessment Survey (NHEXAS) was performed in U.S. Environmental Protection Agency (U.S. EPA) Region V, providing population-based exposure distribution data for metals and volatile organic chemicals (VOCs) in personal, indoor, and outdoor air, drinking water, beverages, food, dust, soil, blood, and urine. One of the principal objectives of NHEXAS was the testing of protocols for acquiring multimedia exposure measurements and developing databases for use in exposure models and assessments. Analysis of the data quality is one element in assessing the performance of the collection and analysis protocols used in NHEXAS. In addition, investigators must have data quality information available to guide their analyses of the study data. At the beginning of the program quality assurance (QA) goals were established for precision, accuracy, and method quantification limits. The assessment of data quality was complicated. First, quality control (QC) data were not available for all analytes and media sampled, because some of the QC data, e.g., precision of duplicate sample analysis, could be derived only if the analyte was present in the media sampled in at least four pairs of sample duplicates. Furthermore, several laboratories were responsible for the analysis of the collected samples. Each laboratory provided QC data according to their protocols and standard operating procedures (SOPs). Detection limits were established for each analyte in each sample type. The calculation of the method detection limits (MDLs) was different for each analytical method. The analytical methods for metals had adequate sensitivity for arsenic, lead, and cadmium in most media but not for chromium. The QA goals for arsenic and lead were met for all media except arsenic in dust and lead in air. The analytical methods for VOCs in air, water, and blood were sufficiently sensitive and met the QA goals, with very few exceptions. Accuracy was assessed as recovery from field controls. The results were excellent (≥98%) for metals in drinking water and acceptable (≥75%) for all VOCs except o -xylene in air. The recovery of VOCs from drinking water was lower, with all analytes except toluene (98%) in the 60–85% recovery range. The recovery of VOCs from drinking water also decreased when comparing holding times of <8 and >8 days. Assessment of the precision of sample collection and analysis was based on the percent relative standard deviation (% RSD) between the results for duplicate samples. In general, the number of duplicate samples (i.e., sample pairs) with measurable data were too few to assess the precision for cadmium and chromium in the various media. For arsenic and lead, the precision was excellent for indoor, and outdoor air (<10% RSD) and, although not meeting QA goals, it was acceptable for arsenic in urine and lead in blood, but showed much higher variability in dust. There were no data available for metals in water and food to assess the precision of collection and analysis.