Apportionment of Ambient Primary and Secondary Pollutants during a 2001 Summer Study in Pittsburgh Using U.S. Environmental Protection Agency UNMIX

Abstract

Apportionment of primary and secondary pollutants during the summer 2001 Pittsburgh Air Quality Study (PAQS) is reported. Several sites were included in PAQS, with the main site (the supersite) adjacent to the Carnegie Mellon University campus in Schenley Park. One of the additional sampling sites was located at the National Energy Technology Laboratory, located ～18 km southeast of downtown Pittsburgh. Fine particulate matter (PM_2.5) mass, gas-phase volatile organic material (VOM), particulate semivolatile and nonvolatile organic material (NVOM), and ammonium sulfate were apportioned at the two sites into their primary and secondary contributions using the U.S. Environmental Protection Agency UNMIX 2.3 multivariate receptor modeling and analysis software. A portion of each of these species was identified as originating from gasoline and diesel primary mobile sources. Some of the organic material was formed from local secondary transformation processes, whereas the great majority of the secondary sulfate was associated with regional transformation contributions. The results indicated that the diurnal patterns of secondary gas-phase VOM and particulate semivolatile and NVOM were not correlated with secondary ammonium sulfate contributions but were associated with separate formation pathways. These findings are consistent with the bulk of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport and, thus, decoupled from local activity involving organic pollutants in the metropolitan area.     

Heavy metal bioaccumulation in selected medicinal plants collected from Khetri copper mines and comparison with those collected from fertile soil in Haridwar,India

Heavy metal distribution in medicinal plants is gaining importance not only as an alternative medicine, but also for possible concern due to effects of metal toxicity. The present study has been focused on emphasizing the heavy metal status and bioaccumulation factors of V, Mn, Fe, Co, Cu, Zn, Se (essential metals) and Cr, Ni, Cd, As and Pb (potentially toxic metals) in medicinal plants grown under two different environmental conditions e.g., near to Khetri copper mine and those in fertile soils of Haridwar, both in India, using Instrumental Neutron Activation Analysis (relative method) and Atomic Absorption Spectrometry. The copper levels in the medicinal plants from Khetri were found to be 3-4 folds higher (31.6–76.5 mg kg^?1) than those from Haridwar samples (7.40–15.3 mg kg^?1), which is correlated with very high copper levels (763 mg kg^?1) in Khetri soil. Among various heavy metals, Cr (2.60–5.92 mg kg^?1), Cd (1.47–2.97 mg kg^?1) and Pb (3.97–6.63 mg kg^?1) are also higher in concentration in the medicinal plants from Khetri. The essential metals like Mn (36.4–69.3 mg kg^?1), Fe (192–601 mg kg^?1), Zn (24.9–49.9 mg kg^?1) and Se (0.13–0.91 mg kg^?1) and potentially toxic metals like Ni (3.09–9.01 mg kg^?1) and As (0.41–2.09 mg kg^?1) did not show much variations in concentration in the medicinal plants from both Khetri and Haridwar. The medicinal plants from Khetri, e.g., Ocimum sanctum, Cassia fistula, Withania somnifera and Azadirachta Indica were found rich in Ca and Mg contents while Aloe barbadensis showed moderately high Ca and Mg. Higher levels of Ca-Mg were found to correlate with Zn (except Azadirachta Indica). The bioaccumulation factors (BAFS) of the heavy metals were estimated to understand the soil-to-plant transfer pattern of the heavy metals. Significantly lower BAF values of Cu and Cr were found in the medicinal plants from Khetri, indicating majority fraction of these metals are precipitated and were immobilized species unsuitable for plant uptake. Overall, Withania somnifera (Ashwagandha) showed very high metal bioaccumulation.     

Application of a permethrin immunosorbent assay method to residential soil and dust samples

A low-cost, high throughput bioanalytical screening method was developed for monitoring cis/trans-permethrin in dust and soil samples. The method consisted of a simple sample preparation procedure [sonication with dichloromethane followed by a solvent exchange into methanol:water (1:1)] with bioanalytical detection using a magnetic particle enzyme-linked immunosorbent assay (ELISA). Quantitative recoveries (83–126 %) of cis/trans-permethrin were obtained for spiked soil and dust samples. The percent difference of duplicate ELISA analyses was within ± 20 % for standards and ± 35 % for samples. Similar sample preparation procedures were used for the conventional gas chromatography/mass spectrometry (GC/MS) analysis except that additional cleanup steps were required. Recoveries of cis/trans-permethrin ranged from 81 to 108 % for spiked soil and dust samples by GC/MS. The ELISA-derived permethrin concentrations were highly correlated with the GC/MS-derived sum of cis/trans-permethrin concentrations with a correlation coefficient (r) of 0.986. The ELISA method provided a rapid qualitative screen for cis/trans-permethrin in soil and dust while providing a higher sample throughput with a lower cost as compared to the GC/MS method. The ELISA can be applied as a complementary, low-cost screening tool to prioritize and rank samples prior to instrumental analysis for exposure studies.     

Development of an analytical method for analysis of flubendiamide,des-iodo flubendiamide and study of their residue persistence in tomato and soil

Flubendiamide is a new insecticide that has been found to give excellent control of lepidopterous pests of tomato. This study has been undertaken to develop an improved method for analysis of flubendiamide and its metabolite des-iodo flubendiamide and determine residue retention in tomato and soil. The analytical method developed involved extraction of flubendiamide and its metabolite des-iodo flubendiamide with acetonitrile, liquid-liquid partitioning into hexane-ethyl acetate mixture (6:4, v v^?1) and cleanup with activated neutral alumina. Finally the residues were dissolved in gradient high pressure liquid chromatography (HPLC) grade acetonitrile for analysis by HPLC. The mobile phase, acetonitrile-water at 60:40 (v v^?1) proportion and the wavelength of 235 nm gave maximum peak resolution. Using the above method and HPLC parameters described, nearly 100 % recovery of both insecticides were obtained. There was no matrix interference and the limit of quantification (LOQ) of the method was 0.01 mg kg^?1. Initial residue deposits of flubendiamide on field-treated tomato from treatments @ 48 and 96 g active ingredient hectare^?1 were 0.83 and 1.68 mg kg^?1,respectively. The residues of flubendiamide dissipated at the half-life of 3.9 and 4.4 days from treatments @ 48 and 96 g a.i. ha^?1, respectively and persisted for 15 days from both the treatments. Des-iodo flubendiamide was not detected in tomato fruits at any time during the study period. Residues of flubendiamide and des-iodo flubendiamide in soil from treatment @ 48 and 96 g a.i. ha^?1 were below detectable level (BDL, < 0.01 mg kg^?1) after 20 days. Flubendiamide completely dissipated from tomato within 20 days when the 480 SC formulation was applied at doses recommended for protection against lepidopterous pests.     

Microwave enhanced advanced oxidation process for treating dairy manure at low pH

This study investigated the treatment of dairy manure using the microwave enhanced advanced oxidation process (MW-AOP) at pH 2. An experimental design was developed based on a statistical program using response surface methodology to explore the effects of temperature, hydrogen peroxide dosage and heating time on sugar production, nutrient release and solids destruction. Temperature, hydrogen peroxide dosage and acid concentration were key factors affecting reducing sugar production. The highest reducing sugar yield of 7.4% was obtained at 160°C, 0 mL, 15 min heating time, and no H₂O₂ addition. Temperature was a dominant factor for an increase of soluble chemical oxygen demand (SCOD) in the treated dairy manure. The important factors for volatile fatty acids (VFA) production were microwave temperature and hydrogen peroxide dosage. Temperature was the most important parameter, and heating time, to a lesser extent affecting orthophosphate release. Heating time, hydrogen peroxide dosage and temperature were significant factors for ammonia release. There was a maximum of 96% and 196% increase in orthophosphate and ammonia concentration, respectively at 160°C, 0.5 mL H₂O₂ and 15 min heating time. The MW-AOP is an effective method in dairy manure treatment for sugar production, nutrient solubilisation, and solids disintegration.     

Mercury in European Blushers,Amanita rubescens,mushrooms and topsoils: Bioconcentration potential and intake assessment

Total mercury content has been determined in fruiting bodies of European Blushers and topsoils collected from 11 sites across Poland in 2006-2008. Mercury analysis was carried out using a validated analytical method and cold-vapour atomic absorption (CV-AAS). The European Blusher effectively accumulated mercury in fruiting bodies. The mean values of total mercury in caps of European Blushers from background (uncontaminated) areas were from 0.22 to 1.0 (0.067-3.2) and in stipes from 0.16 to 0.65 (0.071-2.7) μg/g dry weight. In topsoil beneath to fruiting bodies, the median Hg concentration at 10 sites in Northern Poland varied between 0.030 and 0.072 (0.0096–0.19) μg/g dw, and in one site in Southern Poland was 0.20 (0.079–0.34) μg/g dw. Data on Hg in European Blushers from different countries were reviewed. The mean concentrations of total Hg in caps of European Blushers from two “pristine” sites in northern part of Poland were ～1.0 μg/g dw. A meal made with 300–500 g of fresh caps of European Blushers collected at such sites (assuming 90% water content in caps) can result in Hg intake of 0.0003–0.0005 mg Hg/kg bm (assuming a 60 kg bm), which is a dose equipotent to a new provisional tolerable weekly intake (PTWI) value set for inorganic Hg.     

Production of the monoclonal antibody against tylosin for immunoassay of macrolide antibiotics in milk

The objective of the present study was to develop an immunoassay for multi-determination of the residues of four macrolide antibiotics in milk. Tylosin was derivatized with 6-aminohexanoic acid to synthesize a hapten that was used to produce the monoclonal antibody. The obtained monoclonal antibody simultaneously recognized tylosin, acetylisovaleryltylosin, tilmicosin and desmycosin with crossreactivities of 100%, 91%, 49% and 76%, respectively. Then an indirect competitive immunoassay was developed to determine the four analytes in milk simultaneously. The limits of detection for the four analytes were in the range of 5.5–11.7 ng/mL depending on the compound. The recoveries of the four analytes from fortified blank milk were in the range of 78%–96% with coefficients of variation lower than 11.4%. The developed immunoassay could be used as a practical tool for rapid screening the residues of the four anlytes in milk.     

A statistical model for predicting PM2.5 for the western United States

ABSTRACT

A new statistical model for predicting daily ground level fine scale particulate matter (PM_2.5) concentrations at monitoring sites in the western United States was developed and tested operationally during the 2016 and 2017 wildfire seasons. The model is site-specific, using a multiple linear regression schema that relies on the previous day’s PM_2.5 value, along with fire and smoke related variables from satellite observations. Fire variables include fire radiative power (FRP) and the National Fire Danger Rating System Energy Release Component index. Smoke variables, in addition to ground monitored PM_2.5, include aerosol optical depth (AOD) and smoke plume perimeters from the National Oceanic and Atmospheric Administration’s Hazard Mapping System. The overall statistical model was inspired by a similar system developed for British Columbia (BC) by the BC Center for Disease Control, but it has been heavily modified and adapted to work in the United States. On average, our statistical model was able to explain 78% of the variance in daily ground level PM_2.5. A novel method for implementation of this model as an operational forecast system was also developed and was tested and used during the 2016 and 2017 wildfire seasons. This method focused on producing a continuously-updating prediction that incorporated the latest information available throughout the day, including both updated remote sensing data and real-time PM_2.5 observations. The diurnal pattern of performance of this model shows that even a few hours of data early in the morning can substantially improve model performance.

Implications: Wildfire smoke events produce significant air quality impacts across the western United States each year impacting millions. We present and evaluate a statistical model for making updating predictions of fine particulate (PM_2.5) levels during smoke events. These predictions run hourly and are being used by smoke incident specialists assigned to wildfire operations, and may be of interest to public health officials, air quality regulators, and the public. Predictions based on this model will be available on the web for the 2019 western U.S. wildfire season this summer.     

Leaching,mobility and persistence of tebufenozide in columns packed with forest litter and soil

Abstract

Leaching, downward mobility and persistence of tebufenozide was investigated under laboratory conditions in columns packed with forest litter and soil, after fortification with the analytical grade material (purity > 99.6%) and with two commercial formulations, RH‐5992 2F (aqueous flowable) and RH‐5992 ES (emulsion suspension). Two types of litter and soil were used: one type with relatively high amounts of sand and the other with high amounts of clay.

The concentrations eluted in the leachates were lower when the analytical material (dissolved in acetone) was used for fortification, than when the two formulations (diluted with water) were used. The amount leached was higher for RH‐5992 2F than for RH‐5992 ES. The type of substrate, i.e., sandy or clay type, had only marginal influence on the amounts eluted in the leachates. Downward movement of tebufenozide from the top 2‐cm layer to the untreated middle and bottom layers (3‐cm segments) was consistently lower when the analytical material was used for fortification, than when the two formulations were used. Downward movement was higher for RH‐5992 2F than for RH‐5992 ES. Persistence of tebufenozide in substrates, maintained under submerged conditions for 70 days after leaching, indicated an initial 2‐week lag period prior to the onset of degradation. Formulation‐related differences were observed in the half‐life (DT₅₀) values. When the analytical material was used for fortification, the DT₅₀ ranged from ca 54 to 59 d. However, when the formulations were used for fortification, the DT₅₀ showed a higher range, i.e., from ca 62 to 67 d for RH‐5992 2F and ca 70 to 80 d for RH‐5992 ES. Formulation ingredients appear to have caused enhanced adsorption of tebufenozide onto the substrates, thus delaying degradation.     

Effect of tracer dyes on initial deposits and persistence of bacillus thuringiensis subsp. kurstaki toxin after application of two commercial formulations onto spruce trees

Abstract

The effect of two tracer dyes [Erio Acid Red (EAR) and Acid Black 48 (AB‐48)] on initial deposits and persistence of Bacillus thuringiensis subsp. kurstaki (Btk) toxin (delta‐endotoxin) was studied after spraying two commercial formulations, Foray® 48B and Foray® 76B, over potted white spruce [Picea glauca (Moench) Voss] seedlings, at a dosage rate of 30 billion international units (BIU) per ha. Spray was applied using a spinning disc atomizer calibrated to deliver droplet sizes similar to those utilized in ultra‐low‐volume (ULV) treatments in operational insect control programs. The sprayed seedlings were left outdoors at the Sault Ste. Marie laboratory for 18 days under natural conditions of sunlight, wind and rainfall. Initial deposits and persistence of delta‐endotoxin protein in spruce foliage were determined by immunoassay [enzyme linked immunosorbent assay (ELISA)] quantification of the delta‐endotoxin. The total protein (inactive plus active) and delta‐endotoxin (active protein) concentrations in the two formulations were determined by a gravimetric procedure and by ELISA respectively.

The initial deposit levels of the toxin on foliage were not markedly affected by the addition of either of the two tracer dyes, and showed only a narrow range of 1521 to 1625 ng/g foliage (fresh weight) for Foray 48B, and 1789 to 2056 ng/g for Foray 76B. However, the persistence of the toxin was significantly influenced by the presence of the dyes. The toxin persisted in foliage only for 7 d post‐spray When the EAR dye was added to Foray 48B, compared to 10 d when no dye was added. The average half‐life (DT₅₀) of disappearance was 17.4 h for Foray 48B with EAR, and 20.9 h when no dye was present. In contrast, the situation was reversed in Foray 76B, since the duration of persistence was 10 d when EAR was added to Foray 76B, compared to 7 d when no dye was added. The average DT₅₀ was 27.9 h for Foray 76B with EAR, and 22.2 h without the dye. Persistence was the longest (14 d) when the AB‐48 dye was added to Foray 76B, and the DT₅₀ was 44.9 h.