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.     

The study of heptenophos and triazophos residues in vegetables treated with the organophosphorus insecticides Hostaquick and Hostathion

The residues of heptenophos and triazophos (active components of Hostaquick and Hostathion) were determined in several vegetable crops during the growing period. Heptenophos residues decreased below the limit of detection (0.001 mg/kg) in most of the crops one week after the treatment. However, the decline of triazophos in vegetables below the limit of detection (0.002 mg/kg) depended on the method of crop treatment.     

Imposex occurrence in marine whelks at a military facility in the high Arctic

Imposex was found in the Arctic whelk Buccinum finmarkianum at several marine stations off Thule Air Base, an US military facility in Northwest Greenland. This indicates a widespread contamination with the antifouling agents, tributyltin (TBT) or triphenyltin (TPhT) in the area, but such contamination was not supported by the organotin analyses in sediments, whelks and clams, which in general was below the analytical detection limit. Organotin concentrations above the detection limit were found only at one station close to a quay, where the highest frequency of imposex also occurred. This suggests that imposex in B. finmarkianum is a biomarker of TBT more sensitive than the detection limits, which the analytical chemistry could achieve in this study.     

Methyl tert-butyl ether (MTBE) in finished drinking water in Germany

In the present study 83 finished drinking water samples from 50 cities in Germany were analyzed for methyl tert-butyl ether (MTBE) content with a detection limit of 10 ng/L. The detection frequency was 46% and the concentrations ranged between 17 and 712 ng/L. Highest concentrations were found in the community water systems (CWSs) of Leuna and Spergau in Saxony-Anhalt. These CWSs are supplied with water possibly affected by MTBE contaminated groundwater. MTBE was detected at concentrations lower than 100 ng/L in drinking water supplied by CWSs using bank filtered water from Rhine and Main Rivers. The results from Leuna and Spergau show that large groundwater contaminations in the vicinity of CWSs pose the highest risk for MTBE contamination in drinking water. CWSs using bank filtered water from Rhine and Main Rivers are susceptible to low MTBE contaminations in finished drinking water. All measured MTBE concentrations were below proposed limit values for drinking water.     

Application of TLC for confirmation and screening of pesticide residues in fruits, vegetables, and cereal grains: Part 2. Repeatability and reproducibility of Rf and MDQ values

This paper illustrates the effect of major factors influencing the reproducibility of thin layer chromatography (TLC) separation and detection under largely differing environmental and laboratory conditions. The optimum conditions for reproducibility and detection sensitivity was obtained on 20 x 20 cm layer in the retention factor (Rf) range of 0.2-0.7 by applying the sample in spots of 3-4 mm diameter at 2 cm from the edge of the plate. The reproducibility rapidly decreased below Rf = 0.2. Above Rf = 0.2 the within-laboratory reproducibility of 219 pesticides obtained in ethyl acetate silica gel elution system by several laboratories was typically below 10%. The among-laboratories reproducibility of the average retention factors was generally below 12%. The minimum detectable quantities (MDQ) of 219 pesticide residues were determined with nine detection methods. The MDQ values largely varied depending on the mode of detection. Bioassay methods enabled the detection down to 0.1-10 ng, while 20-100 ng could be achieved with the chemical reagents. Higher MDQ values are also reported in order to assist the identification of compounds potentially present. The between-laboratories reproducibility of MDQ values was typically 1-5 MDQmin.     

Polybrominated diphenyl ethers and organochlorine pesticides in sewage sludge of wastewater treatment plants in China

The concentrations of chemicals in sewage sludge from wastewater treatment plants (WWTPs) may relate to their levels of use and environmental pollution in the region. In this work, sludge samples were collected from 31 WWTPs in 26 cities in China and analyzed for polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs). The concentrations of SigmaPBDE (sum of congeners 17, 28, 47, 66, 71, 85, 99, 100, 138, 153, 154, and 183) ranged from 6.2 to 57ng/g (dw). The concentration of decabromodiphenyl ether (BDE-209) ranged from below limit of detection (LOD) to 1109ng/g (dw) (with a median of 27ng/g (dw)), and averaged 55% (median 69%) of the total PBDEs. These levels are about 10-100 times lower than those found in Europe and North America. PBDE levels in sludge were not found to depend on the location and capacity of the WWTPs. Concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDTs) and its major degradation products, and hexachlorobenzene (HCB) ranged from below detection limit to 167ng/g (dw), 11 to 1065ng/g (dw), and 7.5 to 319ng/g (dw), respectively. The major DDT degradation products were p,p'-DDE and p,p'-DDD. The major hexachlorocyclohexane (HCH) isomer in sludge is beta-HCH, reflecting its higher affinity to solids and resistance to degradation than other isomers.     

Quantification of organotin compounds and determination of imposex in populations of dogwhelks (Nucella lapillus) from Norway

Unintentional effects of the antifouling agent tributyltin (TBT) have been discovered in marine gastropods as the induction of male sex characters in females, known as imposex. The occurrence of imposex in dogwhelks (Nucella lapillus) was investigated in 41 populations sampled in 1993-1995 along the Norwegian coast. A method for quantification of organotin species using gas chromatography and atomic emission detection (GC-AED) was developed. Some degree of imposex occurred in almost all populations of dogwhelks studied, except in four from Northern Norway. The concentration of organotin compounds in the gastropods from the unaffected populations was below the detection limit (7 ng Sn/g d.w.). The concentration of TBT in dogwhelks from affected populations was in the range 48-1096 ng Sn/g d.w. A positive relation between the concentration of TBT in dogwhelks and the degree of imposex was found.     

Analysis of volatile and semivolatile organic compounds in municipal wastewater using headspace solid-phase microextraction and gas chromatography.

The aim of this work was to develop a simple and fast analytical method for the determination of a wide range of organic compounds (volatile and semivolatile compounds) in municipal wastewater. The headspace-solid-phase microextraction (HS-SPME) and gas chromatography (with mass spectroscopy) was used for determination of the organic compounds. In this study, 39 organic compounds were determined, including 3 sulfur compounds, 28 substituted benzenes, and 8 substituted phenols. The extraction parameters, such as types of SPME fiber, extraction temperature, extraction time, desorption time, salt effect, and magnetic stirring, were investigated. The method had very good repeatability, because the relative standard deviations ranged from 0.5 to 12%. The detection limit of each compound was at or below the microgram-per-liter level. This method was applied for determination of the organic compounds in raw wastewater, primary effluent, secondary effluent, and chlorinated secondary effluent samples from the Chania Municipal Wastewater Treatment Plant (Crete, Greece).     

Conditional effect of governance quality on the finance-environment nexus in a multivariate EKC framework: evidence from the method of moments-quantile regression with fixed-effects models

This paper investigates the mitigating effect of governance quality on the finance-environment nexus in a multivariate EKC framework in 123 selected countries during the 1990–2017 period. We mainly employ the method of moments-quantile regression (MM-QR) with the fixed-effects model, among others. First, the MM-QR estimator reveals that financial development reduces environmental quality more significantly in countries with initially higher levels (the 75^th and 90^th quantiles) of CO₂ emissions than in other countries (the 25^th and 10^th quantiles). Second, the attenuating effect of governance quality on the finance-environment nexus is more remarkable in nations with low initial levels (the 25^th and 10^th quantiles) of CO₂ emissions. Third, we find that the marginal positive effect of financial development on CO₂ emissions is smaller under a good regulatory framework than under corruption control and the rule of law, especially in the top emitters (the 75^th and 90^th quantiles). Fourth, unlike oil, which has a considerable negative impact on the environmental quality of the major emitters, renewable energy usage reduces CO₂ emissions in countries in all quantiles, primarily in the lowest quantiles. Fifth, the findings also show that urbanization dramatically worsens environmental quality in all economies, particularly those in the lowest quantiles. Finally, we confirm that the EKC hypothesis holds in all countries across different quantiles. The study’s final section discusses policy implications for sustainable development in all countries.

     

Characterizing perfluorooctanoate in ambient air near the fence line of a manufacturing facility: comparing modeled and monitored values

In order to improve our understanding of the nature, measurement and prediction of salts of perfluorooctanoic acid (PFOA) in air, two studies were performed along the fence line of a fluoropolymer manufacturing facility. First, a six-event, 24-hr monitoring series was performed around the fence line using the OSHA versatile sampler (OVS) system. Perfluorooctanoate concentrations were determined as perfluorooctanoic acid (PFOA) via liquid chromatography and mass spectrometry. Those data indicated that the majority of the PFOA was present as a particulate. No vapor-phase PFOA was detected above a detection limit of approximately 0.07 microg/m3. A follow-up study using a high-volume cascade impactor verified the range of concentrations observed in the OVS data. Both studies aligned with the major transport direction and range of concentrations predicted by an air dispersion model, demonstrating that model predictions agreed with monitoring results. Results from both monitoring methods and predictions from air dispersion modeling showed the primary direction of transport for PFOA was in the prevailing wind direction. The PFOA concentration measured at the site fence over the 10-week sampling period ranged from 0.12 to 0.9 microg/m3. Modeled predictions for the same time period ranged from 0.12 to 3.84 microg/m3. Less than 6% of the particles were larger than 4 microm in size, while almost 60% of the particles were below 0.3 microm. These studies are believed to be the first published ambient air data for PFOA in the environment surrounding a manufacturing facility.     

Statistical evaluation of an analytical IC method for the determination of trace level perchlorate

Trace level perchlorate analysis in water initiated a new development in the Ion Chromatography (IC) technology. Maintenance of a low detection limit may be highly affected by the operating conditions of the IC system. In this paper the homoscedasticity of the IC system within the calibration concentration range, the effect of the system drift on the calibration curve and the effect of the self regeneration suppressor (SRS) current on the detection limit were investigated. The experimental results were evaluated by statistical methods such as the Cochran test and the lack of fit test. The detection limits were obtained by two ways. One through method detection limit (MDL) and the other through detection limit from the calibration curve (DTC). The Cochran test results revealed the homoscedasticity of the IC system. The effect of system drift on the calibration curve was noticed by the lack of fit test. MDL yielded a lower but less reliable detection limit than DTC. An acceptable detection limit can be achieved under the lower SRS current (100 mA).     

Monitoring of ambient air PCDD/F levels in Portugal

As part of a monitoring program conducted by IDAD--Institute for Environment and Development and supported by regional municipal solid waste (MSW) management authorities, dioxin concentrations in ambient air were measured in three regions of Portugal: Porto, Lisbon and Madeira. These independent studies were performed with the intention of providing data as a basis for the evaluation of potential impacts of the operation of recently built MSW incinerators. Thus, 170 samples were collected in nine different sites from January 1999 till present. The measured levels revealed an extremely variable content of PCDDs/PCDFs depending both on the area and the season of the year. Samples taken in Porto and Lisbon reveal a similar homologue structure even if concentrations measured in the Porto region are significantly greater. Data from Madeira is characteristic of a remote site with some of the congeners concentrations below the detection limit.     

Evaluation of cetacean exposure to organotin compounds in Brazilian waters through hepatic total tin concentrations

In Brazil, there is no restriction to the use of organotins (OTs). Previous investigations have shown that hepatic ∑Sn in cetaceans is predominantly organic. Hepatic ∑Sn concentrations were determined by GFAAS in 67 cetaceans (13 species) that stranded on Rio de Janeiro (RJ) and Espirito Santo (ES) states. Concentrations (in ng/g wet wt.) of marine tucuxis (n = 20) from the highly contaminated Guanabara Bay (in RJ) varied from 1703 to 9638. Concentrations of three marine tucuxi foetuses and one newborn calf (all from Guanabara Bay) varied between 431 and 2107. Contrastingly, the maximum level among 19 oceanic dolphins was 346, and 15 out of these 19 specimens presented concentrations below detection limit. The levels of Sn in six marine tucuxis from a less contaminated area (ES) varied from below detection limit to 744. Comparing to the literature, coastal cetaceans from Brazil appear to be highly exposed to OTs.     

Detection limits can influence the interpretation of pesticide monitoring data in Canadian surface waters

Water quality monitoring programs rely on residue data that are frequently left censored, due to some observations occurring below the Method Detection Limit (MDL). Our objective was to determine the influence the MDL has on the interpretation of pesticide residues in surface waters. Water samples from tributaries in southern and central Ontario were collected by Environment Canada from 2003 to 2008 and were analyzed for 27 pesticides, with MDLs that averaged 7.02 ng⁻¹ L (range 0.39-25.1 ng⁻¹ L). We then simulated MDLs ranging from 25 to 1700 ng⁻¹ L, to determine the impact this would have on the reporting of pesticide concentrations and detections. The mean number of pesticides detected simultaneously declined with increasing, i.e. less sensitive MDLs, from 5.02 pesticides (native MDL) to 0.08 pesticides detected (MDL < 1700 ng⁻¹ L). We compared the proportion of sites where pesticides were detected in surface waters under five MDL scenarios for 13 selected pesticides. The proportions decreased sharply with increasing MDLs. We calculated detection probabilities in an effort to compensate for higher MDLs using maximum likelihood; while adjusting for detection probabilities generally improved estimates of the presence of pesticides, as the MDLs increased the ability to compensate for detection probabilities deteriorated and became unviable at high MDLs. Depending on the method of substitution for observations below MDL (replacement with ½ × or 0 × MDL), the mean and median pesticide residues became increasingly over- and underestimated, respectively, at higher MDLs. Although monitoring programs that are focused on exceedences of water quality guidelines may not require low MDLs, the achievable goals of monitoring programs oriented towards other ecological and toxicological objectives may be limited by higher MDLs.     

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.     

Fabricating data: how substituting values for nondetects can ruin results, and what can be done about it

The most commonly used method in environmental chemistry to deal with values below detection limits is to substitute a fraction of the detection limit for each nondetect. Two decades of research has shown that this fabrication of values produces poor estimates of statistics, and commonly obscures patterns and trends in the data. Papers using substitution may conclude that significant differences, correlations, and regression relationships do not exist, when in fact they do. The reverse may also be true. Fortunately, good alternative methods for dealing with nondetects already exist, and are summarized here with references to original sources. Substituting values for nondetects should be used rarely, and should generally be considered unacceptable in scientific research. There are better ways.     

On the use of manned hydrogen-gas ballooning in boundary layer studies

Measurements of nitrogen dioxide, ozone and, for the first time, on-line, nonmethane hydrocarbons with a quasicontinuous gaschromatographic/flame ionization technique were performed on a manned hydrogen-gas balloon platform. A cycle time of 10 min allowed the determination of nonmethane hydrocarbons in the carbon number range of C₄-C₁₀ with a detection limit of 10 pptv. In addition, meteorological parameters (atmospheric pressure, temperature, humidity) along with GPS-data (global positioning system) was accomplished during the balloon flights. Balloon measurements of trace compounds provide valuable information about photochemical processes in the boundary layer since gas ballooning offers the only technique that stays in the same air parcel along Langrangian trajectories. In addition, gas ballooning represents a unique tool to elucidate micrometeorological observations such as atmospheric stability oscillations and local wind fields.     

Development of monoclonal antibody-based immunoassays for the analysis of bisphenol A in canned vegetables

The aim of this work was the development of monoclonal antibodies (MAbs) and highly sensitive immunoassays (ELISAs) to bisphenol A (BPA), a well-known endocrine disruptor able to migrate from the internal coating of cans to food contained inside, particularly vegetables. To produce MAbs to BPA, four synthetic compounds were conjugated to proteins and used as immunizing haptens in mice. By applying hybridoma technology, several MAbs were produced and selected. These antibodies were characterized in the conjugate-coated and in the antibody-coated formats, using both homologous and heterologous conjugates. Three indirect ELISA based on the MAbs showing the highest affinity to BPA were selected. The limit of detection of the most sensitive ELISA was 0.22 nM (0.05 ng/mL), with an I?? value of around 1 nM (0.23 ng/mL). An homologous ELISA based on the MAb BPAB-11 was applied to the simple, direct determination of BPA in the liquid portion of canned artichoke, peas, and sweet corn. Only sample dilution in an appropriate saline buffer was required to minimize matrix effects and to enter the ELISA working range. Recovery and precision of the method were evaluated by spiking the liquid portion of these cans with BPA at 20, 50, and 100 ng/mL. Coefficients of variation were below 20% in most cases. With regard to recovery, the analytical data obtained were also acceptable. This immunoassay has therefore proved its potential as a new tool for the rapid, sensitive and accurate determination of BPA in canned food.     

Combination of photoacoustic detector with gas diffusion probes for the measurement of methane concentration gradients in submerged paddy soil

Dissolved methane was monitored by means of a diffusion probe in combination with a photoacoustic (PA) detector cell placed in the cavity of a liquid nitrogen-cooled CO laser. The detection limit of the photoacoustic detector was 1 ppbv methane (≈ 2 μM in aqueous solution), the time response was 60 s, the spatial resolution was 1.36 mm. These limits were determined by the acoustic noise and the configuration of the diffusion probe. The combination of PA detector with gas diffusion probes was found to be useful for monitoring gaseous compounds. However, the membrane material of the diffusion probe was critical. Silicone as membrane material was useful only for measurement of CH₄. Goretex as membrane material was applicable to measurement of dimethylsulfide (DMS), but did not give a stable signal for trimethylamine (TMA).

Vertical concentration profiles of CH₄ in anoxic paddy soil agreed well with earlier results obtained with a gas chromatograph as detector. Methane was produced in anoxic soil layers below 8–10 mm depth and diffused upwards to the surface through a layer of CH₄-consuming bacteria situated at about 2 mm depth. In the oxic upper 2 mm soil layer the concentration of CH₄ decreased below the detection limit of our system. Methane-containing gas bubbles that were embedded in the soil were detected by a steep increase of the CH₄ signal. The combination of PA detector and gas diffusion probe was found to be a useful tool to measure CH₄ gradients in submerged soil or sediment with high temporal and spatial resolution, thus allowing the localization and quantification of CH₄ production and CH₄ oxidation rates within the soil profile.     

Detection and occurrence of pentachlorophenol residues in chicken liver and fat

A method for the detection of pentachlorophenol (PCP) residues in chicken liver and fat is presented. A detection limit of 0.002 mg/kg was achieved. Recoveries from liver and fat were in the range 82-88% and 95-97%, respectively. Low level residues of PCP were found in all 1072 liver and 723 fat samples. These levels were less than 0.010 mg/kg in 92.7% of the fat and 75.6% of the livers. Only 0.75% of the liver samples had PCP levels greater than 0.1 mg/kg. None of the more toxic impurities of PCP were detected in the chicken tissues.