Reproducibility and imputation of air toxics data

Ambient air quality datasets include missing data, values below method detection limits and outliers, and the precision and accuracy of the measurements themselves are often unknown. At the same time, many analyses require continuous data sequences and assume that measurements are error-free. While a variety of data imputation and cleaning techniques are available, the evaluation of such techniques remains limited. This study evaluates the performance of these techniques for ambient air toxics measurements, a particularly challenging application, and includes the analysis of intra- and inter-laboratory precision. The analysis uses an unusually complete-dataset, consisting of daily measurements of over 70 species of carbonyls and volatile organic compounds (VOCs) collected over a one year period in Dearborn, Michigan, including 122 pairs of replicates. Analysis was restricted to compounds found above detection limits in > or =20% of the samples. Outliers were detected using the Gumbell extreme value distribution. Error models for inter- and intra-laboratory reproducibility were derived from replicate samples. Imputation variables were selected using a generalized additive model, and the performance of two techniques, multiple imputation and optimal linear estimation, was evaluated for three missingness patterns. Many species were rarely detected or had very poor reproducibility. Error models developed for seven carbonyls showed median intra- and inter-laboratory errors of 22% and 25%, respectively. Better reproducibility was seen for the 16 VOCs meeting detection and reproducibility criteria. Imputation performance depended on the compound and missingness pattern. Data missing at random could be adequately imputed, but imputations for row-wise deletions, the most common type of missingness pattern encountered, were not informative. The analysis shows that air toxics data require significant efforts to identify and mitigate errors, outliers and missing observations, and that these steps are essential and should be performed prior to using these data in receptor, exposure, health and other applications.     

Characteristics of steel slag under different cooling conditions

Four types of steel slags, a ladle slag, a BOF (basic oxygen furnace) slag and two different EAF (electric arc furnace) slags, were characterized and modified by semi-rapid cooling in crucibles and rapid cooling by water granulation. The aim of this work was to investigate the effect of different cooling conditions on the properties of glassy slags with respect to their leaching and volume stability. Optical microscopy, X-ray diffraction, scanning electron microscope and a standard test leaching (prEN 12457-2/3) have been used for the investigation. The results show that the disintegrated ladle slag was made volume stable by water granulation, which consisted of 98% glass. However EAF slag 1, EAF slag 2 and the BOF slag formed 17%, 1% and 1% glass, respectively. The leaching test showed that the glass-containing matrix did not prevent leaching of minor elements from the modified slags. The solubility of chromium, molybdenum and vanadium varied in the different modifications, probably due to their presence in different minerals and their different distributions.     

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.     

Constructed wetlands for environmental pollution control: a review of developments, research and practice in Ireland

For the purpose of synthesizing a compendium of efforts aimed at environmental pollution control through the use of constructed wetlands systems (CWs) in Ireland, a detailed review of CWs was undertaken. Emphasis was placed on the diverse range of development, practice and researches on CWs technology, placing them in the overall context of the need for low-cost and sustainable wastewater treatment systems. The potential use of CWs in protecting estuarine quality within the current legislative framework is considered, as well as the emerging concept of integrated constructed wetlands (ICWs). In addition, an assessment of the efficiency of CWs in operation in Ireland towards abating environmental pollution was done, and compared with CWs operating in other European countries. The need for sufficient and appropriate data to assist in further development of CWs and modelling studies, and instilling confidence in the public is also highlighted.     

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.     

Local PM10 and PM2.5 emission inventories from agricultural tillage and harvest in northeastern China

Mineral particles or particulate matters(PMs) emitted during agricultural activities are major recurring sources of atmospheric aerosol loading.However,precise PM inventory from agricultural tillage and harvest in agricultural regions is challenged by infrequent local emission factor(EF) measurements.To understand PM emissions from these practices in northeastern China,we measured EFs of PM_(10) and PM_(2.5) from three field operations(i.e.,tilling,planting and harvesting) in major crop production(i.e.,corn and soybean),using portable real-time PM analyzers and weather station data.County-level PM_(10) and PM_(2.5) emissions from agricultural tillage and harvest were estimated,based on local EFs,crop areas and crop calendars.The EFs averaged(107 ± 27),(17 ± 5) and 26 mg/m~2 for field tilling,planting and harvesting under relatively dry conditions(i.e.,soil moisture 15%),respectively.The EFs of PM from field tillage and planting operations were negatively affected by topsoil moisture.The magnitude of PM_(10) and PM_(2.5) emissions from these three activities were estimated to be 35.1 and 9.8 kilotons/yr in northeastern China,respectively,of which Heilongjiang Province accounted for approximately45%.Spatiotemporal distribution showed that most PM_(10) emission occurred in April,May and October and were concentrated in the central regions of the northeastern plain,which is dominated by dryland crops.Further work is needed to estimate the contribution of agricultural dust emissions to regional air quality in northeastern China.     

Identification of differentially expressed genes response to TCDD in rat brain after long-term low-dose exposure

Several cohort studies have reported that dioxin and dioxin-like polychlorinated biphenyls might impair the nervous system and lead to neurological or neurodegenerative diseases in the elder people, but there is limited research on the involved mechanism. By using microarray analysis, we figured out the differentially expressed genes between brain samples from SD rats after low-dose(0.1 μg/(kg?bw)) dioxin exposure for six months and controls. To investigate the function changes in the course of dioxin exposure, Gene Ontology(GO) annotation and Kyoto Encyclopedia of Genes and Genomes(KEGG) pathway analysis were performed on the differentially expressed genes. And the changes of several picked genes have been verified by real-time PCR. A total of 145 up-regulated and 64 down-regulated genes were identified. The metabolic processes, interleukin-1 secretion and production were significantly associated with the differentially expressed genes. And the genes regulated by dioxin also clustered to cholinergic synapse and long-term potentiation. Candidate biomarker genes such as egr1, gad2, gabrb3, abca1, ccr5 and pycard may be toxicological targets for dioxin. Furthermore, synaptic plasticity and neuro-immune system may be two principal affected areas by dioxin.     

Spatial distribution analysis on climatic variables in northeast China

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