Percentile estimation using variable censored data

Much progress has been made in recent years to address the estimation of summary statistics, using data that are subject to censoring of results that fall below the limit of detection (LOD) for the measuring instrument. Truncated data methods (e.g., Tobit regression) and multiple-imputation are two approaches for analyzing data results that are below the LOD. To apply these methods requires an assumption about the underlying distribution of the data. Because the log-normal distribution has been shown to fit many data sets obtained from environmental measurements, the common practice is to assume that measurements of environmental factors can be described by log-normal distributions. This article describes methods for obtaining estimates of percentiles and their associated confidence intervals when the results are log-normal and a fraction of the results are below the LOD. We present limited simulations to demonstrate the bias of the proposed estimates and the coverage probability of their associated confidence intervals. Estimation methods are used to generate summary statistics for 2,3,7,8-tetrachloro dibenzo-p-dioxin (2,3,7,8-TCDD) using data from a 2001 background exposure study in which PCDDs/PCDFs/cPCBs in human blood serum were measured in a Louisiana population. Because the congener measurements used in this study were subject to variable LODs, we also present simulation results to demonstrate the effect of variable LODs on the multiple-imputation process.     

Analysis of Toxic Air Contaminant Data Containing Concentrations Below the Limit of Detection

Air quality data often contain several observations reported only as below the analytical limit of detection (LOD), resulting in “censored” data sets. Such censored and/or truncated data sets tend to complicate statistical analysis. This paper discusses various procedures for estimating mean concentration and Its 95 percent confidence bounds from air contaminant data sets which contain values that are reported as below the LOD, A quantitative approach for assessing the uncertainty Inherent In the estimated mean concentration due to (a) presence of values below the LOD In the data set, and (b) natural variability of atmospheric concentration data, is described. The utility of this approach In the analysis and interpretation of ambient pollutant concentration data Is demonstrated for both hypothetical and observed singly-censored data sets, and for a multiply-censored, multi-pollutant observed concentration data set. The methodologies discussed here should be particularly useful In verifying compliance with environmental regulations, and In estimating the risks associated with long-term exposure of populations to toxic air contaminants and assessing the uncertainty associated with these estimates.     

Air sampling and analysis of volatile organic compounds with solid phase microextraction

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Comments on the NAS Report: Odors From Stationary and Mobile Sources

ABSTRACT

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Assigning concentration values for dioxin and furan congeners in human serum when measurements are below limits of detection: an observational approach

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in dietary sources for humans have been declining over the previous two decades. These declines have been accompanied by decreases in concentrations of these compounds in humans, as evidenced by measurements in blood and milk. Because of the decreasing concentrations of PCDD/PCDFs in the environment and in humans, measuring PCDD/PCDF congeners in humans has become increasingly difficult, despite advances in analytic methods. An observational approach was recently described to address the quandary of non-detectable results in determining toxic equivalents. This approach, called the congener ratio approach, is specifically for cases where concentrations of 2,3,7,8-TCDD (TCDD) are below the limit of detection (LOD), and where concentrations of 1,2,3,7,8-pentachlorodibenzo-p-dioxin (PeCDD) are equal to or above the LOD. Development of this approach relied on evaluating data on measured concentrations of TCDD and PeCDD in human serum from the general population. The congener ratio approach for TCDD and PeCDD was based on the concentration of TCDD being approximately 40% that of PeCDD in serum from the general population. Additional analyses presented here reveal that when concentrations of both congeners are above the LOD, the data appear to generally support the congener ratio approach for TCDD and PeCDD, with the caveat that gender may affect the ratio. However, the TCDD/PeCDD relation is less clear when TCDD is less than the LOD; in this situation, the relation overpredicts levels of TCDD approximately 80% of the time for the 2001-2002 NHANES database. Using the congener ratio approach for other PCDD/PCDF congeners requires assessing the correlation and the frequency of detection for both TCDD and PeCDD.     

Behavior of benzene and 1,3-butadiene concentrations in the urban atmosphere of Tokyo,Japan

Benzene and 1,3-butadiene concentration profiles in the urban ambient air were generated to investigate their levels at two specified sampling locations, roadside and residential, in Tokyo, Japan. Air monitoring data for benzene and 1,3-butadiene were obtained from the Air Quality Monitoring Information of the Tokyo Metropolitan Government. Air samples were continuously obtained and analyzed every hour for volatile organic compounds (VOCs) using an automated GC–MS system. The diurnal variations in benzene and 1,3-butadiene concentrations showed bi-modal patterns, which were considered to be related to the increasing and decreasing trends of vehicle emissions and vertical mixing depths in a day. The frequencies of occurrence of various benzene and 1,3-butadiene concentrations were examined. The results of each concentration showed log-normal forms with almost straight lines. The frequency distributions of both pollutants were confirmed to have a log-normal, rather than a simple normal, form. The relationship between benzene and 1,3-butadiene concentrations at both the roadside and residential site were examined. Separate observations of day and night trends revealed that photochemical decomposition showed a greater influence on the data in the residential site than that in the roadside site. These results were considered as direct evidences of photochemical decomposition of 1,3-butadiene in the atmosphere.     

Membrane introduction/laser photoionization time-of-flight mass spectrometry

Two-photon resonance enhanced multiphoton ionization (REMPI) has been shown to be a unique ionization method for mass spectrometry, exhibiting both high sensitivity and chemical selectivity. Because REMPI is a gas-phase method, its applications have been limited either to direct analysis of vapor phase samples, or in conjunction with an initial laser desorption or other vaporization step. We describe here for the first time a combination of membrane introduction mass spectrometry (MIMS) and REMPI with time-of-flight mass spectrometry (TOF-MS), which allows for the direct analysis of trace amounts of organic compounds in water samples. The objective of our research was the detection of very low levels of aromatic contaminants, particularly benzene, toluene, and xylene (BTX), in aqueous solutions without interference due to the water. We have measured limits of detection (LOD) for selected aromatics in water below 1 part-per-trillion with an averaging time of less than 10 s using a continuous sample flow.     

Microwave/SPME method to quantify pesticide residues in tomato fruits

A new analytical method using focused microwave-assisted extraction (FMAE), coupled with solid phase micro-extraction (SPME), has been elaborated to determine 25 pesticides used in tomato cultivation. Microwave energy was used for a fast and controlled heating of solvent to selectively extract compounds. Calibration curves were plotted from blank tomato samples spiked at different concentrations with standards. A linear response was obtained between 10 and 1000 μ g/Kg for pyrethroids and between 0.1 and 5000 μ g/Kg for other compounds. For all studied substances, the resulting correlation coefficient (r²) was greater than 0.99. Limits of detection (LOD) and quantification (LOQ) were measured lower than 8 and 25 μ g/Kg, respectively. The relative standard deviation (RSD) was determined below 15% for all pesticides. Field incurred tomato samples were used to validate the new FMAE/SPME method. Observed analysis results by using this technique were in good agreement compared to those obtained by two accredited trading laboratories using traditional methods. Four tomato samples, bought in a local market, were also tested with the FMAE/SPME method.     

Extreme Values in TSP Distribution Functions

The highest values in annual TSP distributions fall below the best-fit, log-normal straight line more than one would expect from ordinary sampling statistics but not dramatically so. The lowest values in annual TSP distributions overwhelmingly fall below the best-fit, log-normal straight line. The most highly improbable high values above the best-fit line in such distributions are very questionable and probably do not represent true air quality values. The most improbable cases of highest values falling below the best-fit, log-normal line are the result of data artifacts at the opposite end of the data distribution. They do not represent low probabilities and probably do represent true air quality values. The most improbable low values are all of highly doubtful validity.     

Characterization and classification of complex PAH samples using GC-qMS and GC-TOFMS

The aim of this study was to compare the polycyclic aromatic hydrocarbon (PAH) contents in a number of complex samples, including soil samples from industrial sites, anti-skid sand, urban dust and ash samples from municipal solid waste incinerators. The samples were characterized by routine analysis of PAHs (gas chromatography–quadrupole mass spectrometry) and gas chromatography–time of flight mass spectrometry (GC–TOFMS). Classification of the samples by principal component analysis (PCA) according to their composition of PAHs revealed that samples associated with traffic and the municipal incinerator formed homogeneous clusters, while the PAH-contaminated soils clustered in separate groups. Using spectral data to resolve co-eluting chromatographic peaks, 962 peaks could be identified in the GC–TOFMS analysis of a pooled sample and 123–527 peaks in the individual samples. Many of the studied extracts included a unique set of chemicals, indicating that they had a much more diverse contamination profile than their PAH contents suggested. Compared to routine analysis, GC–TOFMS provided more detailed information about each sample and in this study a large number of alkylated PAHs were found to be associated with the corresponding unsubstituted PAHs. The possibility to filter peaks according to different criteria (e.g. to include only peaks that were detected in the analysis of another sample) was explored and used to identify unique as well as common compounds within samples. This procedure could prove to be valuable for obtaining relevant chemical data for use in conjunction with results from various biological test systems.     

The Precision Associated with the Sampling Frequency of Log-Normally Distributed Air Pollutant Measurements

The frequency of air monitoring necessary to characterize an air pollutant for a given time period and area is an important problem. This paper deals with the precision of measuring an air pollutant concentration. Past research has shown that the distribution of many air pollutants can be described as log-normal. Using this result equations have been developed that predict the precision of the sample mean of the air pollutant as a function of: the frequency of sampling, the standard deviation of the logarithms of the air pollution measurements, and the level of confidence. An illustration is given to demonstrate their use. The equations are used to compare sampling plans. Tables are presented showing the precision associated with five sampling plans, for three geometric standard deviations, for three levels of confidence, and five periods of time over which the sampling plan is employed.

In an Appendix a mathematical development is presented showing the theoretical derivation of the equations. With these equations the precision of a sampling plan can be determined for any level of confidence or period of time. All that is needed is an estimate of the geometric standard deviation for the air pollution measurements.

Finally, the theoretical model is applied to air monitoring data that were collected at Roselawn School in Cincinnati, Ohio, between January 3, 1968, and April 1, 1968. The 90-day period was divided into three 30-day periods. All possible samples of size three were taken from each of the 30-day periods and their means and confidence intervals were calculated. The number of times the confidence intervals contained the true means was determined. The actual number of samples accepted as having contained the true mean, for the 80, 90, 95, and 9 9% level of confidence compared favorably with the theoretical. It is concluded that the model adequately described the behavior of air pollutants.     

Fourth WHO-coordinated survey of human milk for persistent organic pollutants (POPs): Belgian results

Persistent organic pollutants (POPs) are chemicals that accumulate in the food chain and are toxic to humans and wildlife. The fourth World Health Organization (WHO) survey on POP levels in human milk (2006-2009) aims to provide baseline and trend information on human exposure to POPs. So far Belgium participated in all three previous rounds (1988, 1992, 2001). Whereas the first three rounds focused on determination of dioxins and PCBs in pooled (mixed) samples, the fourth survey comprised the analyses of individual milk samples for nine "basic POPs" (chlorinated pesticides and indicator PCBs) and of pooled milk samples for "basic POPs", "advanced POPs" (dioxins and dioxin-like PCBs) and "optional POPs" (polybrominated diphenylethers [PBDEs], polybrominated dioxins and dibenzofurans [PBrDD/F], mixed halogenated dioxins and dibenzofurans [PXDD/F] and hexabromocyclododecane [HBCD]). For the Belgian participation human milk samples were collected during the summer of 2006 from 197 women between 18 and 30 years old distributed over all Belgian provinces. The individual samples were analyzed in a Belgian Laboratory for "basic" POPs. A pooled sample was made from 178 individual samples and analyzed by the WHO Reference Laboratory for the "basic, advanced and optional" POPs. The results indicate that most organochlorinated pesticides banned 25-30 years ago were below or around detection limits in Belgian human milk samples although DDE was still found at low levels in all samples. Over the last five years the levels of marker PCBs and PCDD/Fs in Belgian human milk decreased, respectively, by 58% and 39%. For some of the other emerging or older compounds recent international data are needed to allow comparison. This shows the importance of international studies as run by WHO.     

Selected organochlorine pesticide and polychlorinated biphenyl residues in house dust in Singapore

Although the use of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) has been prohibited in Singapore since 1980, OCPs and PCBs still can be detected in the environment and represent a potential threat to public health. In this study, OCPs and PCBs were measured in house dust samples collected from 31 homes across the island-state of Singapore. Organochlorine pesticides, such as hexachlorocyclohexanes (HCHs), chlordanes and dichlorodiphenyltrichloroethanes (DDTs) were tested, with a range of 相似文献   

Headspace solid phase microextraction method for determination of triazine and organophosphorus pesticides in soil

A headspace solid phase microextraction method (HS-SPME) for simultaneous determination of five pesticides belonging to triazine and organophosphorus pesticide groups in soil samples was developed. Microextraction conditions, such as temperature, extraction time and sodium chloride (NaCl) content were investigated and optimized using 100 μ m polydimethyl-siloxane (PDMS) fiber. Detection and quantification were done by gas chromatography-mass spectrometry (GC-MS). Relative standard deviation (RSD) and recovery values for multiple analysis of soil samples fortified at 30 μ g kg^{? 1} of each pesticide were below 13 % and higher than 70 %, respectively. Limits of detection (LOD) for all the compounds studied were less than 3.2 μ g kg^{? 1}. The proposed method was applied in the analysis of some agricultural soil samples.     

Ambient Air Analyses Using Nonspecific Flame lonization and Electron Capture Detection Compared to Specific Detection by Mass Spectroscopy

Ambient air samples from various studies were analyzed for a specific set of trace-level volatile organic compounds by using a gas chromatograph (GC) equipped with a flame ionization detector (FID) in parallel with an electron capture detector (ECD). The samples were then reanalyzed on a second GC system equipped with a mass selective detector (MSD). GC-FID/ECD data were compared to the nominally correct GC-MSD data to determine the accuracy of the nonspecific detectors, which often do not differentiate the targeted compound from Interfering compounds. Qualitative accuracy (capability for correctly identifying compounds on the basis of retention time only) and quantitative accuracy (capability for correctly measuring the concentration of an identified compound on the basis of peak area) were evaluated. Data are presented on a per-compound basis to provide the combined typical results from air samples collected in three geographic regions: Kanawha Valley, WV; Los Angeles, CA, area; and Houston, TX.     

Evolution of stratospheric aerosols in the post-Pinatubo period measured by solar occultation

This paper presents particle size distributions of stratospheric aerosols derived from solar occultation data measured by the instrument ORA (an acronym for Occultation RAdiometer) during the period August 1992–May 1993. Starting from the UV-visible wavelength dependence of extinction coefficient profiles, an algorithm is developed that allows to retrieve the three parameters of an equivalent log-normal distribution and that makes use of vertical regularization. Comparison of retrieved mode radius and particle number density with existing data is found to be satisfactory. The evolution of the stratospheric aerosols is clearly influenced by sedimentation and coagulation as expected but also by vertical circulation. In a simple 1-D model, we derive the vertical wind profile and we interpret the temporal evolution of the particle mode radius.     

Detection Limits for Hazardous and Radioactive Elements in Airborne Aerosols Using Inductively Coupled Air Plasma – Atomic Emission Spectrometry

Abstract

This research presents investigations into the use of inductively coupled air plasma – atomic emission spectrometry (air-plasma ICPAES) to determine the presence of inorganic contaminants in airborne aerosols. Limits of detection (LOD) in the ppm to ppb range for 19 hazardous metals and radionuclides were determined for aerosols of solutions nebulized into the air plasma. For many elements, the determined LOD surpass the threshold limit values established by the American Conference of Governmental Industrial Hygienists by one to three orders of magnitude. The potential of air-plasma ICPAES for continuous on-line monitoring of airborne contaminants is discussed.     

Evidence for the presence of a widespread PCDD source in coastal sediments and soils from Queensland, Australia

Recent studies have demonstrated the occurrence of elevated levels of higher chlorinated PCDDs in the coastal environment of Queensland, Australia. This study presents new data for OCDD contamination and full PCDD/F profile analysis in the environment of Queensland. Marine sediments, irrigation drain sediments and topsoil were collected from sites that were expected to be influenced by specific land-use types. High OCDD concentrations were associated mainly with sediments collected near the mouth of rivers which drain into large catchments in the tropical and subtropical regions. Further, analysis of sediments from irrigation drains could be clearly differentiated on the basis of OCDD contamination, with high concentrations in samples from sugarcane drains collected from coastal regions, and low concentrations in drain sediments from drier inland cotton growing areas. PCDD/F congener-specific analysis demonstrated almost identical congener profiles in all samples collected along the coastline. This indicates the source to be widespread. Profiles were dominated by higher chlorinated PCDDs, in particular OCDD whereas 2,3,7,8-substituted PCDFs were below the limit of quantification in the majority of samples. The full PCDD/F profile analysis of samples strongly resemble those reported for lake sediments from Mississippi and kaolinite samples from Germany. Strong similarities to these samples with respect to congener profiles and isomer patterns may indicate the presence of a similar source and/or formation process that is yet unidentified.     

Using a physiologically based pharmacokinetic model to link urinary biomarker concentrations to dietary exposure of perchlorate

Exposure to perchlorate is widespread in the United States and many studies have attempted to character the perchlorate exposure by estimating the average daily intakes of perchlorate. These approaches provided population-based estimates, but did not provide individual-level exposure estimates. Until recently, exposure activity database such as CSFII, TDS and NHANES become available and provide opportunities to evaluate the individual-level exposure to chemical using exposure surveillance dataset. In this study, we use perchlorate as an example to investigate the usefulness of urinary biomarker data for predicting exposures at the individual level. Specifically, two analyses were conducted: (1) using data from a controlled human study to examine the ability of a physiologically based pharmacokinetic (PBPK) model to predict perchlorate concentrations in single-spot and cumulative urine samples; and (2) using biomarker data from a population-based study and a PBPK model to demonstrate the challenges in linking urinary biomarker concentrations to intake doses for individuals. Results showed that the modeling approach was able to characterize the distribution of biomarker concentrations at the population level, but predicting the exposure-biomarker relationship for individuals was much more difficult. The type of information needed to reduce the uncertainty in estimating intake doses, for individuals, based on biomarker measurements is discussed.     

Per- and polyfluorinated compounds in house dust and indoor air from northern Norway - a pilot study

Polyfluorinated compounds (PFCs) are an extremely versatile class of compounds and are used in a variety of consumer applications and products. Recent studies have suggested that PFCs in indoor air and dust could act as sources of human exposure and outdoor air contamination. This study presents method development and analysis of a wide range of PFCs in dust and air using active sampling techniques with commercially available sampling equipment (forensic nozzles with filter housings for dust collection and polyurethane foam (PUF)-XAD₂-PUF sandwich-tubes for air sampling) using both liquid and gas chromatography mass spectrometry. The developed method was validated and tested for applicability to analyze dust and air samples at both low and high concentrations (0.5 ng and 25 ng per analyte per air sample, respectively). Samples from private households and an office building were analyzed to explore differences in distribution patterns and concentrations. Perfluorooctane sulfonate, perfluorodecane sulfonate, perfluoroheptanoate, perfluorooctanoate and perfluorononanoate were observed in all samples of dust from private households, in the range from 1 to 80.1 ng g⁻¹. Fluorotelomer alcohols (FTOHs) were the predominant PFCs in indoor air samples with ∑FTOHs ranging between 4.7 and 17.9 ng m⁻³. The concentrations found in the present study are generally lower than those previously reported. This variation may be due to differences associated with geographical locations and lifestyles. However, use of different sampling techniques and strategies among studies can introduce large variations in PFC concentration found, making direct comparisons challenging.