This document describes a method for analyzing ultratrace levels of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and furans (PBDDs/Fs), and polychlorinated dibenzo-p-dioxins and furans (PCDDs/Fs) from combustion flue gas samples. The method was optimized to address potential degradation issues for brominated compounds during extraction, cleanup, and analysis. Modifications included selecting solvents to minimize debromination, optimizing extraction time, adapting cleanup and fractionation steps, and replacing liquid chromatography with high-resolution gas chromatography to separate PBDFs from interfering PBDEs before mass spectrome
This document describes a new strategy for comprehensively analyzing polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) using gas chromatography coupled with mass spectrometry. The method allows for the purification and fractionation of the target compound groups in a simple multi-step automated clean-up. The compounds are then analyzed using a single benchtop mass spectrometer in four separate injections. Electron impact ionization followed by tandem mass spectrometry provides the required sensitivity for environmental levels while maintaining selectivity, accuracy, and repeatability.
DIOXIN AND POP-CONTAMINATED SITES • SERIES • RESEARCH ARTICLE.docxlynettearnold46882
DIOXIN AND POP-CONTAMINATED SITES • SERIES • RESEARCH ARTICLE
Exposure assessment at a PCDD/F contaminated site
in Sweden—field measurements of exposure media
and blood serum analysis
Annika Åberg & Mats Tysklind & Tohr Nilsson & Matthew MacLeod & Annika Hanberg &
Rolf Andersson & Sture Bergek & Richard Lindberg & Karin Wiberg
Received: 25 March 2009 /Accepted: 19 June 2009 /Published online: 30 July 2009
# Springer-Verlag 2009
Abstract
Background, aim, and scope The main pathway for human
exposure to the highly toxic polychlorinated-p-dioxins and
polychlorinated furans [polychlorinated dibenzo-p-dioxins
and dibenzofurans (PCDD/Fs)] is via dietary intake. Other
exposure pathways may, however, be important in close
proximity to point sources, such as wood preservation sites,
where PCDD/F contaminated chlorophenols (CP) were
previously used. In this study, a heavily PCDD/F contam-
inated CP saw mill site in Sweden was investigated. Human
exposure through a broad spectrum of exposure pathways was
assessed. Such studies are in demand since the question
whether contaminated sites represent a current or future risk
can only be answered by detailed site-specific risk assessments.
Materials and methods Sampling of exposure media (soil,
air, groundwater, raspberries, carrots, potatoes, grass, milk,
eggs, and chicken fodder) was made. Exposure media
concentrations and congener distribution patterns were used
to investigate the mobilization of PCDD/Fs from soil to the
environment and to calculate exposure levels for adults.
Blood serum levels from site-exposed and control individ-
uals were also analyzed.
Results Congener distribution patterns at the site were
generally dominated by a specific marker congener
(1234678-HpCDF), which is highly abundant in the
polluted soil. The dioxin toxic equivalents (TEQ) concen-
trations were notably elevated as compared to national
reference samples for most exposure media, and the marker
congener was a major contributor to increased TEQ levels.
There were also indications of soil-to-air volatilization of
tetra- and penta-CDD/Fs. People who participated in the
restoration of a contaminated building showed higher levels
of 1234678-HpCDF compared to controls, and calculated
exposure levels suggest that several site-specific exposure
routes may be of importance for the daily intake of PCDD/F.
Conclusions, recommendations, and perspectives Despite
low mobility of higher chlorinated PCDD/Fs, these con-
taminants were transferred from the polluted soil to the
surroundings and into human tissue. The extent of
increased exposure from contaminated sites depends on
the PCDD/F source strength of the soil, composition of the
pollution, human activities, and dietary patterns of the
residents. Impact from the contaminated soil on other
exposure media was seen also for areas with low to
Electronic supplementary material The online version of this article
(doi:10.1007/s11356-009-0223-4) contains supplementary material,
which i.
This document summarizes information about 2,3,7,8-tetrachlorodibenzo-para-dioxin (TCDD), 2,3,4,7,8-pentachlorodibenzofuran (PeCDF), and 3,3',4,4',5-pentachlorobiphenyl (PCB 126). It describes their identification, occurrence, use, human exposure including occupational exposure, and background levels found in tissues. TCDD is an unintended byproduct formed during production of chlorophenols and herbicides. PeCDF is emitted from combustion sources while PCBs were commercially produced but their manufacture stopped in 1977 due to environmental contamination. Human exposures can
Sipma, 2004, Effect Of Carbon Monoxide, Hydrogen And Sulfate On Thermophilic ...roelmeulepas
This document summarizes a study on the conversion of carbon monoxide (CO) by two anaerobic sludge samples at 55°C. The study aimed to elucidate the conversion routes and determine the effect of substrate (CO) concentration and the presence of hydrogen gas. Inhibition experiments showed CO conversion occurred via a hydrogenogenic population producing hydrogen and carbon dioxide, with the products then used by methanogens, acetogens, or sulfate reducers depending on sludge source and inhibitors. Both sludges could produce hydrogen from CO, indicating potential for biological hydrogen production from synthesis gas containing CO. The paper mill sludge was also capable of sulfate reduction using hydrogen produced from high CO concentrations, showing CO-rich synthesis gas can efficiently
Presentation at the ESPP workshop Pharmaceuticals in sewage biosolids, Malmo, 27-10-2016
European Sustainable Phosphorus Platform (ESPP)
www.phosphorusplatform.eu
Sustainable management of nutrients is crucial for agriculture, food, industry, water and the environment. ESPP brings together companies and stakeholders to address the Phosphorus Challenge and its opportunities for the circular economy.
Countries:
Austria AT
Belgium BE
Bulgaria BG
Cyprus CY
Czech Republic CZ
Germany DE
Denmark DK
Estonia EE
Spain ES
Finland FI
France FR
Greece EL
Hungary HU
Ireland IE
Italy IT
Lithuania LT
Luxembourg LU
Latvia LV
Malta MT
Netherlands NL
Poland PL
Portugal PT
Romania RO
Sweden SE
Slovenia SI
Slovakia SK
United Kingdom UK
Switzerland CH
Phosphorus:
Fosfor
Fosfor
Fòsfòr
Фосфор
Fosfor
Фосфор
Fosfor
Fosfor
Фосфор
Фосфор
Fosforas
Fosfors
Fuosfuors
Fosfor
Ffуsfforws
Fosfar
Fosfaras
Fosfaar
Fosforus
Φωσφορος
Ֆոսֆոր
Fosfor
Fosfor
Фосфор
Фосфор
ফসফরাস
فسفر
ફૉસ્ફરસનો
फास्फोरस
Fosfor
Fosfori
Foszfor
Фосфор
Фосфор
Паликандур
Fosfor
Fosfor
Фосфор
Фосфор
Фосфор
Фосфор
Fosfor
فوسفور
Fosfor
Fosforoa
ფოსფორი
[fūsfūr]
זרחן
Fosfru
Lìn
リン
인
ฟอสฟอรัส
Photpho
磷
Posporo
Fosfor
Pūtūtae-whetū
Fosforus
ഫോസ്ഫറസ്
பொஸ்பரசு
Fosofo
Fosforase
Posfori
Fósforo
Phusphuru
Fosforimi
Fosforo
Fosforon
Pesticium
DNAPL Remediation with ClO2_UV-published paperDarcy Bye
This study investigated the sorption of PAHs, PCBs, phenols, and BTEX hydrocarbons from groundwater onto a subsoil core sample. It also examined the destruction of these contaminants in ClO2/UV solution systems using methanol as the carrier solvent. Sorption experiments showed the contaminants formed S-type isotherms and could be modeled using the Freundlich equation. Off-site travel times for the contaminants in groundwater ranged from 145 to 80,817 years based on sorption. Treatment with ClO2/UV destroyed 76-98% of the contaminants and produced no dioxins or furans as byproducts, demonstrating this method's potential for remediating recal
This document describes a new strategy for comprehensively analyzing polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) using gas chromatography coupled with mass spectrometry. The method allows for the purification and fractionation of the target compound groups in a simple multi-step automated clean-up. The compounds are then analyzed using a single benchtop mass spectrometer in four separate injections. Electron impact ionization followed by tandem mass spectrometry provides the required sensitivity for environmental levels while maintaining selectivity, accuracy, and repeatability.
DIOXIN AND POP-CONTAMINATED SITES • SERIES • RESEARCH ARTICLE.docxlynettearnold46882
DIOXIN AND POP-CONTAMINATED SITES • SERIES • RESEARCH ARTICLE
Exposure assessment at a PCDD/F contaminated site
in Sweden—field measurements of exposure media
and blood serum analysis
Annika Åberg & Mats Tysklind & Tohr Nilsson & Matthew MacLeod & Annika Hanberg &
Rolf Andersson & Sture Bergek & Richard Lindberg & Karin Wiberg
Received: 25 March 2009 /Accepted: 19 June 2009 /Published online: 30 July 2009
# Springer-Verlag 2009
Abstract
Background, aim, and scope The main pathway for human
exposure to the highly toxic polychlorinated-p-dioxins and
polychlorinated furans [polychlorinated dibenzo-p-dioxins
and dibenzofurans (PCDD/Fs)] is via dietary intake. Other
exposure pathways may, however, be important in close
proximity to point sources, such as wood preservation sites,
where PCDD/F contaminated chlorophenols (CP) were
previously used. In this study, a heavily PCDD/F contam-
inated CP saw mill site in Sweden was investigated. Human
exposure through a broad spectrum of exposure pathways was
assessed. Such studies are in demand since the question
whether contaminated sites represent a current or future risk
can only be answered by detailed site-specific risk assessments.
Materials and methods Sampling of exposure media (soil,
air, groundwater, raspberries, carrots, potatoes, grass, milk,
eggs, and chicken fodder) was made. Exposure media
concentrations and congener distribution patterns were used
to investigate the mobilization of PCDD/Fs from soil to the
environment and to calculate exposure levels for adults.
Blood serum levels from site-exposed and control individ-
uals were also analyzed.
Results Congener distribution patterns at the site were
generally dominated by a specific marker congener
(1234678-HpCDF), which is highly abundant in the
polluted soil. The dioxin toxic equivalents (TEQ) concen-
trations were notably elevated as compared to national
reference samples for most exposure media, and the marker
congener was a major contributor to increased TEQ levels.
There were also indications of soil-to-air volatilization of
tetra- and penta-CDD/Fs. People who participated in the
restoration of a contaminated building showed higher levels
of 1234678-HpCDF compared to controls, and calculated
exposure levels suggest that several site-specific exposure
routes may be of importance for the daily intake of PCDD/F.
Conclusions, recommendations, and perspectives Despite
low mobility of higher chlorinated PCDD/Fs, these con-
taminants were transferred from the polluted soil to the
surroundings and into human tissue. The extent of
increased exposure from contaminated sites depends on
the PCDD/F source strength of the soil, composition of the
pollution, human activities, and dietary patterns of the
residents. Impact from the contaminated soil on other
exposure media was seen also for areas with low to
Electronic supplementary material The online version of this article
(doi:10.1007/s11356-009-0223-4) contains supplementary material,
which i.
This document summarizes information about 2,3,7,8-tetrachlorodibenzo-para-dioxin (TCDD), 2,3,4,7,8-pentachlorodibenzofuran (PeCDF), and 3,3',4,4',5-pentachlorobiphenyl (PCB 126). It describes their identification, occurrence, use, human exposure including occupational exposure, and background levels found in tissues. TCDD is an unintended byproduct formed during production of chlorophenols and herbicides. PeCDF is emitted from combustion sources while PCBs were commercially produced but their manufacture stopped in 1977 due to environmental contamination. Human exposures can
Sipma, 2004, Effect Of Carbon Monoxide, Hydrogen And Sulfate On Thermophilic ...roelmeulepas
This document summarizes a study on the conversion of carbon monoxide (CO) by two anaerobic sludge samples at 55°C. The study aimed to elucidate the conversion routes and determine the effect of substrate (CO) concentration and the presence of hydrogen gas. Inhibition experiments showed CO conversion occurred via a hydrogenogenic population producing hydrogen and carbon dioxide, with the products then used by methanogens, acetogens, or sulfate reducers depending on sludge source and inhibitors. Both sludges could produce hydrogen from CO, indicating potential for biological hydrogen production from synthesis gas containing CO. The paper mill sludge was also capable of sulfate reduction using hydrogen produced from high CO concentrations, showing CO-rich synthesis gas can efficiently
Presentation at the ESPP workshop Pharmaceuticals in sewage biosolids, Malmo, 27-10-2016
European Sustainable Phosphorus Platform (ESPP)
www.phosphorusplatform.eu
Sustainable management of nutrients is crucial for agriculture, food, industry, water and the environment. ESPP brings together companies and stakeholders to address the Phosphorus Challenge and its opportunities for the circular economy.
Countries:
Austria AT
Belgium BE
Bulgaria BG
Cyprus CY
Czech Republic CZ
Germany DE
Denmark DK
Estonia EE
Spain ES
Finland FI
France FR
Greece EL
Hungary HU
Ireland IE
Italy IT
Lithuania LT
Luxembourg LU
Latvia LV
Malta MT
Netherlands NL
Poland PL
Portugal PT
Romania RO
Sweden SE
Slovenia SI
Slovakia SK
United Kingdom UK
Switzerland CH
Phosphorus:
Fosfor
Fosfor
Fòsfòr
Фосфор
Fosfor
Фосфор
Fosfor
Fosfor
Фосфор
Фосфор
Fosforas
Fosfors
Fuosfuors
Fosfor
Ffуsfforws
Fosfar
Fosfaras
Fosfaar
Fosforus
Φωσφορος
Ֆոսֆոր
Fosfor
Fosfor
Фосфор
Фосфор
ফসফরাস
فسفر
ફૉસ્ફરસનો
फास्फोरस
Fosfor
Fosfori
Foszfor
Фосфор
Фосфор
Паликандур
Fosfor
Fosfor
Фосфор
Фосфор
Фосфор
Фосфор
Fosfor
فوسفور
Fosfor
Fosforoa
ფოსფორი
[fūsfūr]
זרחן
Fosfru
Lìn
リン
인
ฟอสฟอรัส
Photpho
磷
Posporo
Fosfor
Pūtūtae-whetū
Fosforus
ഫോസ്ഫറസ്
பொஸ்பரசு
Fosofo
Fosforase
Posfori
Fósforo
Phusphuru
Fosforimi
Fosforo
Fosforon
Pesticium
DNAPL Remediation with ClO2_UV-published paperDarcy Bye
This study investigated the sorption of PAHs, PCBs, phenols, and BTEX hydrocarbons from groundwater onto a subsoil core sample. It also examined the destruction of these contaminants in ClO2/UV solution systems using methanol as the carrier solvent. Sorption experiments showed the contaminants formed S-type isotherms and could be modeled using the Freundlich equation. Off-site travel times for the contaminants in groundwater ranged from 145 to 80,817 years based on sorption. Treatment with ClO2/UV destroyed 76-98% of the contaminants and produced no dioxins or furans as byproducts, demonstrating this method's potential for remediating recal
This document summarizes formaldehyde levels found in tobacco smoke and their potential health effects:
1) Formaldehyde concentrations vary widely between studies but mainstream smoke contains 10-100 micrograms per cigarette on average. Sidestream smoke contains up to 48 parts per million.
2) Environmental tobacco smoke studies report substantially higher formaldehyde production rates than mainstream-sidestream studies, likely due to different measurement methods.
3) While tobacco smoke increases indoor formaldehyde levels under extreme conditions, it does not normally significantly increase vapor-phase levels in indoor environments. However, formaldehyde exposure from mainstream smoke may increase cancer risks for smokers.
Novel approach to synthesis of pentofurano nucleoside assisted natural phosph...Alexander Decker
This document describes a novel method for synthesizing various ribonucleosides using natural phosphate doped with CF3SO3H (NP/CF3SO3H) as a catalyst. Several ribonucleosides were prepared from 1-O-acetyl-2,3,5-tri-O-benzoyl-β-D-ribofuranoside and silylated nucleobases under mild conditions using NP/CF3SO3H. The reaction proceeded through an oxonium intermediate to provide the desired nucleosides in good yields ranging from 20-35%. The method was found to be regioselective, stereoselective, simple, efficient and environmentally friendly for synthesizing various D
EPA Report- Flame Retardant Alternatives for HexaBromoCyclodecane (HBCD)Dr Dev Kambhampati
This report identifies alternatives to hexabromocyclododecane (HBCD), which is used as a flame retardant in polystyrene building insulation. The report was developed by the EPA and stakeholders to identify viable flame retardant alternatives for HBCD in expanded and extruded polystyrene foam insulation. Three alternatives were identified: a butadiene styrene brominated copolymer, a tetrabromobisphenol A bis brominated ether derivative, and tetrabromobisphenol A bis(2,3-dibromopropyl) ether. Hazard profiles found the butadiene styrene copolymer likely poses lower human health risks but is very persistent in the
Toxic Equivalency Factors for Dioxin-Like PCBsv2zq
This document summarizes a consultation held by the WHO-ECEH and IPCS to derive toxic equivalency factors (TEFs) for dioxin-like polychlorinated biphenyls (PCBs). Researchers collected data on the relative toxicities of PCBs compared to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) from studies. At the consultation, they analyzed the data to define criteria for TEFs and derive TEFs for 13 PCBs. TEFs indicate the relative toxicity of PCBs compared to TCDD. The consultation recommended expanding the project to include more compounds and exploring separate TEFs for different applications like
This document describes a study that evaluated a hybrid membrane bioreactor process for removing hydrogen sulfide (H2S) from biogas. The process used a polydimethylsiloxane membrane to first absorb H2S from biogas into an alkaline liquid, followed by biological oxidation of H2S in the liquid. The effects of absorption liquid pH, biogas flowrate, and dissolved oxygen concentration on H2S removal efficiency and selectivity were investigated. The results showed that pH 7 performed better than pH 8.5, and H2S removal exceeded 97% at flowrates below 148 g H2S/m3d and dissolved oxygen below 1 mg/L. This novel hybrid process provides an effective and low-cost
COD reduction of aromatic polluted waste water by Advanced Oxidation Process ...Wade Bitaraf
In most petrochemical complexes and oil refineries the wastewater contains the aromatic compounds among which Benzene, Toluene, Ethyl Benzene and Xylene (BTEX) have harmful effects on environment and human health. The present work mainly deals with the UV-based advanced oxidation processes (AOPs), UV/H2O2 were tested in batch reactor systems to evaluate the removal efficiencies and optimal conditions for the photodegradation of BTEX in order to wastewater treatment. The efficiency of this method was analyzed by evaluating the Chemical Oxygen Demand (COD) as a pollution criterion through the COD reactor. The influence of the basic operational parameters such as initial concentration of H2O2, pH, Temperature, irradiation time and UV amount on the photo degradation of BTEX were also studied. The oxidation rate of BTEX and respectively the reduction rate of COD were low when the oxidation was carried out in the absence of H2O2 or UV light. The addition of proper amount of hydrogen peroxide improved the degradation, while the excess hydrogen peroxide could quench the formation of hydroxyl radicals (•OH). The optimal conditions of suspended slurry with 1.11(g/l) initial concentration of H2O2 and pH value of 3.1 were obtained under three UV lights illumination (6 W). Under the optimal conditions, COD reduction during the initial period of 180 min in UV/H2O2 systems reached about 90%.
A STUDY OF MOLYBDENUM CARBIDE CATALYST FOR FISCHER-TROPSCH SYNTHESIS-MEngSc P...Farhan Munir
This document is a thesis submitted by Farhan Munir for the degree of Master of Engineering Science in Process Engineering at the University of New South Wales in November 2001. The thesis studies molybdenum carbide catalyst for Fischer-Tropsch synthesis. It begins with acknowledgments and a table of contents. Chapter 1 provides an introduction on Fischer-Tropsch synthesis and motivation for studying Mo2C catalyst. Chapter 2 discusses Fischer-Tropsch synthesis background including reactions, thermodynamics, kinetics and mechanisms. Chapter 3 discusses Fischer-Tropsch catalysts including active metals, supports, and preparation methods. Chapter 4 focuses specifically on molybdenum carbide catalyst. The objectives, experimental details, results
Schiff Base Bridged Phenolic Diphenylamines for Highly Efficient and Superior...Ishfaq Ahmad
This document describes the design and synthesis of novel antioxidant additives called Schiff base bridged phenolic diphenylamines (SPDs) for lubricating oils. SPDs were designed to combine sterically hindered phenol and diphenylamine moieties into a single molecule using a Schiff base bridge. Two SPD compounds were synthesized and shown to have better thermal stability and antioxidant efficiency than commercial antioxidants. Formulations containing SPDs along with other additives also exhibited improved antioxidant performance at high temperatures, demonstrating their potential for use in the lubricant industry.
Innovative Phosphorous Removal and Recovery StrategiesWaterWeUpTo
This document compares advanced oxidation and traditional chemical treatment methods for removing phosphorus from water bodies. Specifically, it evaluates using UV/H2O2 treatment to oxidize dissolved organic phosphorus (DOP) into more readily removable orthophosphate (PO4). The research found that 50 mg/L H2O2 and 60 minutes of UV exposure was very effective (80-100%) at oxidizing DOP to PO4 in model waters. Varying water chemistry did not affect oxidation rates. Treatment combining 50 mg/L H2O2 and 12 minutes of UV was also effective at oxidizing DOP. UV/H2O2 treatment removed natural organic matter more preferentially than DOP.
Synthesis of novel and tunable Micro Mesoporous carbon nitrides for Ultra Hig...farnaztabarkhoon
Carbon nitride (CN) materials with intrinsic high nitrogen content are potential candidates for acidic gas
adsorption. However, these nanomaterials should be further treated to achieve tunable textural properties for
ultra-high gas adsorption. Herein, we synthesized dual-pore carbon nitride materials (DP-CN) with a series of
ethylenediamine to carbon tetrachloride ratios with different amounts of potassium hydroxide (KOH) as a
chemical activator using nanosilica (SiO2) as a hard template to tune the physicochemical properties of the
materials. The prepared DP-CN adsorbents had a large surface area (up to 2036.9 m2/g), great pore volume (up
to 1.15 cm3/g), and high nitrogen content (10.6 to 15.1 wt%). The best DP-CN displayed ultra-high CO2 and H2S
adsorption capacity at 1 bar (8.3 and 13.8 mmol/g, respectively), 10 bar (16.9 and 23.1 mmol/g, respectively),
and 30 bar (22.9 mmol/g for CO2) at 25 ◦C, which was significantly higher than those of other pure mesoporous
carbon nitrides (M-CN) and carbon-based adsorbents. Moreover, the best adsorbent exhibited good CO2/N2,
CO2/CH4, H2S/N2, and H2S/CH4 selectivity, suitable heat of adsorption, and excellent cyclic stability. According
to density functional theory calculations, H2S adsorbs more strongly than CO2 on carbon nitride surfaces, and the
adsorption energies of CO2 and H2S are related to charge-transfer values from the surface to the adsorbed species.
The results revealed that the exceptional textural properties and high nitrogen content of the materials could play
the main role in the superior adsorption of CO2 and H2S. This generation of CN materials is expected to be
practical for a various range of separation processes, catalysis, capacitors, and energy storage.
1,3-Dihydroxypropan-2-one (DHA) synthesis from Glycerol for pharmaceutical ap...Simone Ripandelli
- Glycerol is a low-cost starting material for the synthesis of dihydroxyacetone (DHA) due to the surplus production of glycerol from biodiesel fuel production.
- Pt-Bi bimetallic nanoparticles supported on carbon showed the highest selectivity (33%) for the aerobic oxidation of glycerol to DHA.
- Homogeneous palladium complexes were also investigated as catalysts for this reaction, achieving up to 99% selectivity for DHA. However, further optimization of reaction conditions was needed to improve DHA yield and reduce reaction time.
PRODUCTION, CHARACTERIZATION AND FUEL PROPERTIES OF ALTERNATIVE DIESEL FUEL F...Anand Mohan
1. The document describes the production and characterization of an alternative diesel fuel produced from the pyrolysis of plastic grocery bags. Plastic grocery bags made of high-density polyethylene were pyrolyzed in a batch reactor at 420-440°C to produce a plastic crude oil.
2. The plastic crude oil was distilled into fractions equivalent to gasoline and diesel fuels, which were then characterized through GC-MS, simulated distillation, SEC, NMR and FT-IR analysis. The analyses showed that the fractions consisted of mixtures of hydrocarbons similar to petroleum fuels.
3. Properties of the diesel fractions like cloud point, pour point and cetane number were comparable or better than conventional ultra-low sulfur diesel
This study investigated the impact of removing carbon dioxide (CO2) from the headspace of a continuous flow biohydrogen production system on hydrogen (H2) yield, microbial communities, and metabolic pathways. The system was operated with and without potassium hydroxide (KOH) in the reactor headspace to sequester CO2. Headspace CO2 sequestration increased the H2 yield by 22% and influenced the metabolic pathways. Analysis of microbial communities before and after CO2 sequestration revealed significant impacts on diversity and species distribution, rationalizing changes in metabolic pathways.
Spatial charge separation on the (110)/(102) facets of cocatalyst-free ZnIn2S...Pawan Kumar
Photorefining of biomass and its derivatives to value-added chemicals is an alternative solution to address the global energy shortage and environmental issues. Herein, efficient and selective oxidation of 5-hydroxymethylfurfural (HMF, 91.1% conversion) to 2,5-diformylfuran (DFF, 99.4% selectivity) is demonstrated by visible light-driven photocatalysis over cocatalyst-free ZnIn2S4 nanosheets with crystal facet engineering. The spatial accumulation of photogenerated electrons and holes on the (110) and (102) crystal facets triggers a two-electron oxygen reduction reaction (2e-ORR) for H2O2 generation and HMF oxidation into DFF, respectively. The severe attenuation of photostability is caused by the irreversible photocorrosion of Zn–S with the formation of Zn–O chemical bonds by the formation of ˙OH from the in situ decomposition of H2O2. Spontaneous substitution of oxygen with sulfur has been proven to efficiently improve the photostability of ZnIn2S4. This present work provides insights into improving the durability of ZnIn2S4 and sheds new light on biomass valorization via photorefinery.
- The study examined carbon processing in peatland soils under anaerobic conditions by adding traditional and non-traditional methanogenic substrates.
- The additions had no significant effect on methane or carbon dioxide production in bog soil.
- Between 45-100% of the added carbon substrates could not be accounted for in measured carbon pools like methane, carbon dioxide, and glucose. Future isotopic data may provide insight into methanogenic pathways and the fate of missing carbon.
ACETYLATION OF BENZYLIC ALCOHOLS OVER BiFeO3 (BFO), Bi0.86Sm0.07Eu0.07FeO3 (B...EDITOR IJCRCPS
BiFeO3 (BFO), Bi0.86Sm0.07Eu0.07FeO3 (BSEFO), and Bi0.86Sm0.07Cd0.07FeO3 (BSCFO) nanopowders were prepared by the sol-gel
combustion method and the catalytic performances were evaluated in acetylation reaction of benzyl alcohol. The physical chemical
properties of catalysts were characterized by using XRD, FT-IR, scanning electron microscope (SEM), EDX and BET surface.
Efficient acetylation of benzyl alcohol was carried out over all the nano powders using acetyl chloride/ acetonitrile at room
temperature. Among the nanopowders, BSCFO showed the highest catalytic performance and the yield of benzyl acetate was 89,
45, and 69 percent over BSCFO, BFO, and BSEFO, respectively. Partial substitution of Sm-Eu and Sm-Cd in bismuth ferrite
improved the catalytic performance and increased the specific surface area of the catalysts. A direct relationship was resulted
between catalytic performance and surface of catalysts, where BSCFO with the highest surface area (111m2/g) exhibited the
superior catalytic performance. The quantitative yield for acetate product was also resulted for acetylation of p-methyl benzyl
alcohol, p-nitro benzyl alcohol and p-chloro benzyl alcohol on BSCFO. The catalysts showed good reusability in the process. The
study confirmed the catalysts could be promising catalyst for acetylation of alcohols.
Keywords: Europium, Samarium, Bismuth ferrites, nano perovskite, doping, Acetylation, benzylic alcohols.
This document provides an overview of week 1 topics on physical and thermal waste processing. It introduces the learning objectives, references, and various waste processing methods including physical, chemical, thermal, and biological. Specifically, it discusses size reduction, separation, compaction, and other physical processing techniques. It also explains thermal processing methods like combustion, pyrolysis, gasification and their chemical transformations. Proximate analysis, fusing point, ultimate analysis and energy content testing for thermal waste treatment are outlined.
This document provides a history of dioxins in the environment over the last 50 years. It discusses how dioxins originated as byproducts in industrial processes like herbicide and pesticide production. Major events discussed include chick edema disease in the 1950s traced to dioxin-contaminated chicken feed, the use of Agent Orange in Vietnam which introduced large amounts of dioxins, and two major dioxin contamination incidents in Missouri in the 1970s involving waste oil. The document examines the health impacts and cleanup efforts related to these events.
This document summarizes the results of an experimental campaign to measure emissions of dioxins, furans, and polycyclic aromatic hydrocarbons (PAHs) from a hospital and cemetery waste incinerator. Samples were taken from the afterburning chamber, after the heat exchanger, and at the stack. While pollutant concentrations decreased after the heat exchanger and flue gas treatment systems, emission limits for dioxins were not met at the stack. Emission factors for dioxins through air and solid residues were calculated. Tests with cemetery waste generally showed lower dioxin emission factors than tests with hospital waste. PAH emission factors were within typical ranges reported for other waste incinerators.
This method describes the determination of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans from municipal waste combustors. Samples are collected isokinetically from the gas stream using a glass fiber filter and packed adsorbent column. The compounds are extracted from the sample, separated by gas chromatography, and measured by high resolution mass spectrometry. The document provides details on the sampling apparatus and procedures, reagents, analytical equipment, and quality control checks.
This document summarizes formaldehyde levels found in tobacco smoke and their potential health effects:
1) Formaldehyde concentrations vary widely between studies but mainstream smoke contains 10-100 micrograms per cigarette on average. Sidestream smoke contains up to 48 parts per million.
2) Environmental tobacco smoke studies report substantially higher formaldehyde production rates than mainstream-sidestream studies, likely due to different measurement methods.
3) While tobacco smoke increases indoor formaldehyde levels under extreme conditions, it does not normally significantly increase vapor-phase levels in indoor environments. However, formaldehyde exposure from mainstream smoke may increase cancer risks for smokers.
Novel approach to synthesis of pentofurano nucleoside assisted natural phosph...Alexander Decker
This document describes a novel method for synthesizing various ribonucleosides using natural phosphate doped with CF3SO3H (NP/CF3SO3H) as a catalyst. Several ribonucleosides were prepared from 1-O-acetyl-2,3,5-tri-O-benzoyl-β-D-ribofuranoside and silylated nucleobases under mild conditions using NP/CF3SO3H. The reaction proceeded through an oxonium intermediate to provide the desired nucleosides in good yields ranging from 20-35%. The method was found to be regioselective, stereoselective, simple, efficient and environmentally friendly for synthesizing various D
EPA Report- Flame Retardant Alternatives for HexaBromoCyclodecane (HBCD)Dr Dev Kambhampati
This report identifies alternatives to hexabromocyclododecane (HBCD), which is used as a flame retardant in polystyrene building insulation. The report was developed by the EPA and stakeholders to identify viable flame retardant alternatives for HBCD in expanded and extruded polystyrene foam insulation. Three alternatives were identified: a butadiene styrene brominated copolymer, a tetrabromobisphenol A bis brominated ether derivative, and tetrabromobisphenol A bis(2,3-dibromopropyl) ether. Hazard profiles found the butadiene styrene copolymer likely poses lower human health risks but is very persistent in the
Toxic Equivalency Factors for Dioxin-Like PCBsv2zq
This document summarizes a consultation held by the WHO-ECEH and IPCS to derive toxic equivalency factors (TEFs) for dioxin-like polychlorinated biphenyls (PCBs). Researchers collected data on the relative toxicities of PCBs compared to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) from studies. At the consultation, they analyzed the data to define criteria for TEFs and derive TEFs for 13 PCBs. TEFs indicate the relative toxicity of PCBs compared to TCDD. The consultation recommended expanding the project to include more compounds and exploring separate TEFs for different applications like
This document describes a study that evaluated a hybrid membrane bioreactor process for removing hydrogen sulfide (H2S) from biogas. The process used a polydimethylsiloxane membrane to first absorb H2S from biogas into an alkaline liquid, followed by biological oxidation of H2S in the liquid. The effects of absorption liquid pH, biogas flowrate, and dissolved oxygen concentration on H2S removal efficiency and selectivity were investigated. The results showed that pH 7 performed better than pH 8.5, and H2S removal exceeded 97% at flowrates below 148 g H2S/m3d and dissolved oxygen below 1 mg/L. This novel hybrid process provides an effective and low-cost
COD reduction of aromatic polluted waste water by Advanced Oxidation Process ...Wade Bitaraf
In most petrochemical complexes and oil refineries the wastewater contains the aromatic compounds among which Benzene, Toluene, Ethyl Benzene and Xylene (BTEX) have harmful effects on environment and human health. The present work mainly deals with the UV-based advanced oxidation processes (AOPs), UV/H2O2 were tested in batch reactor systems to evaluate the removal efficiencies and optimal conditions for the photodegradation of BTEX in order to wastewater treatment. The efficiency of this method was analyzed by evaluating the Chemical Oxygen Demand (COD) as a pollution criterion through the COD reactor. The influence of the basic operational parameters such as initial concentration of H2O2, pH, Temperature, irradiation time and UV amount on the photo degradation of BTEX were also studied. The oxidation rate of BTEX and respectively the reduction rate of COD were low when the oxidation was carried out in the absence of H2O2 or UV light. The addition of proper amount of hydrogen peroxide improved the degradation, while the excess hydrogen peroxide could quench the formation of hydroxyl radicals (•OH). The optimal conditions of suspended slurry with 1.11(g/l) initial concentration of H2O2 and pH value of 3.1 were obtained under three UV lights illumination (6 W). Under the optimal conditions, COD reduction during the initial period of 180 min in UV/H2O2 systems reached about 90%.
A STUDY OF MOLYBDENUM CARBIDE CATALYST FOR FISCHER-TROPSCH SYNTHESIS-MEngSc P...Farhan Munir
This document is a thesis submitted by Farhan Munir for the degree of Master of Engineering Science in Process Engineering at the University of New South Wales in November 2001. The thesis studies molybdenum carbide catalyst for Fischer-Tropsch synthesis. It begins with acknowledgments and a table of contents. Chapter 1 provides an introduction on Fischer-Tropsch synthesis and motivation for studying Mo2C catalyst. Chapter 2 discusses Fischer-Tropsch synthesis background including reactions, thermodynamics, kinetics and mechanisms. Chapter 3 discusses Fischer-Tropsch catalysts including active metals, supports, and preparation methods. Chapter 4 focuses specifically on molybdenum carbide catalyst. The objectives, experimental details, results
Schiff Base Bridged Phenolic Diphenylamines for Highly Efficient and Superior...Ishfaq Ahmad
This document describes the design and synthesis of novel antioxidant additives called Schiff base bridged phenolic diphenylamines (SPDs) for lubricating oils. SPDs were designed to combine sterically hindered phenol and diphenylamine moieties into a single molecule using a Schiff base bridge. Two SPD compounds were synthesized and shown to have better thermal stability and antioxidant efficiency than commercial antioxidants. Formulations containing SPDs along with other additives also exhibited improved antioxidant performance at high temperatures, demonstrating their potential for use in the lubricant industry.
Innovative Phosphorous Removal and Recovery StrategiesWaterWeUpTo
This document compares advanced oxidation and traditional chemical treatment methods for removing phosphorus from water bodies. Specifically, it evaluates using UV/H2O2 treatment to oxidize dissolved organic phosphorus (DOP) into more readily removable orthophosphate (PO4). The research found that 50 mg/L H2O2 and 60 minutes of UV exposure was very effective (80-100%) at oxidizing DOP to PO4 in model waters. Varying water chemistry did not affect oxidation rates. Treatment combining 50 mg/L H2O2 and 12 minutes of UV was also effective at oxidizing DOP. UV/H2O2 treatment removed natural organic matter more preferentially than DOP.
Synthesis of novel and tunable Micro Mesoporous carbon nitrides for Ultra Hig...farnaztabarkhoon
Carbon nitride (CN) materials with intrinsic high nitrogen content are potential candidates for acidic gas
adsorption. However, these nanomaterials should be further treated to achieve tunable textural properties for
ultra-high gas adsorption. Herein, we synthesized dual-pore carbon nitride materials (DP-CN) with a series of
ethylenediamine to carbon tetrachloride ratios with different amounts of potassium hydroxide (KOH) as a
chemical activator using nanosilica (SiO2) as a hard template to tune the physicochemical properties of the
materials. The prepared DP-CN adsorbents had a large surface area (up to 2036.9 m2/g), great pore volume (up
to 1.15 cm3/g), and high nitrogen content (10.6 to 15.1 wt%). The best DP-CN displayed ultra-high CO2 and H2S
adsorption capacity at 1 bar (8.3 and 13.8 mmol/g, respectively), 10 bar (16.9 and 23.1 mmol/g, respectively),
and 30 bar (22.9 mmol/g for CO2) at 25 ◦C, which was significantly higher than those of other pure mesoporous
carbon nitrides (M-CN) and carbon-based adsorbents. Moreover, the best adsorbent exhibited good CO2/N2,
CO2/CH4, H2S/N2, and H2S/CH4 selectivity, suitable heat of adsorption, and excellent cyclic stability. According
to density functional theory calculations, H2S adsorbs more strongly than CO2 on carbon nitride surfaces, and the
adsorption energies of CO2 and H2S are related to charge-transfer values from the surface to the adsorbed species.
The results revealed that the exceptional textural properties and high nitrogen content of the materials could play
the main role in the superior adsorption of CO2 and H2S. This generation of CN materials is expected to be
practical for a various range of separation processes, catalysis, capacitors, and energy storage.
1,3-Dihydroxypropan-2-one (DHA) synthesis from Glycerol for pharmaceutical ap...Simone Ripandelli
- Glycerol is a low-cost starting material for the synthesis of dihydroxyacetone (DHA) due to the surplus production of glycerol from biodiesel fuel production.
- Pt-Bi bimetallic nanoparticles supported on carbon showed the highest selectivity (33%) for the aerobic oxidation of glycerol to DHA.
- Homogeneous palladium complexes were also investigated as catalysts for this reaction, achieving up to 99% selectivity for DHA. However, further optimization of reaction conditions was needed to improve DHA yield and reduce reaction time.
PRODUCTION, CHARACTERIZATION AND FUEL PROPERTIES OF ALTERNATIVE DIESEL FUEL F...Anand Mohan
1. The document describes the production and characterization of an alternative diesel fuel produced from the pyrolysis of plastic grocery bags. Plastic grocery bags made of high-density polyethylene were pyrolyzed in a batch reactor at 420-440°C to produce a plastic crude oil.
2. The plastic crude oil was distilled into fractions equivalent to gasoline and diesel fuels, which were then characterized through GC-MS, simulated distillation, SEC, NMR and FT-IR analysis. The analyses showed that the fractions consisted of mixtures of hydrocarbons similar to petroleum fuels.
3. Properties of the diesel fractions like cloud point, pour point and cetane number were comparable or better than conventional ultra-low sulfur diesel
This study investigated the impact of removing carbon dioxide (CO2) from the headspace of a continuous flow biohydrogen production system on hydrogen (H2) yield, microbial communities, and metabolic pathways. The system was operated with and without potassium hydroxide (KOH) in the reactor headspace to sequester CO2. Headspace CO2 sequestration increased the H2 yield by 22% and influenced the metabolic pathways. Analysis of microbial communities before and after CO2 sequestration revealed significant impacts on diversity and species distribution, rationalizing changes in metabolic pathways.
Spatial charge separation on the (110)/(102) facets of cocatalyst-free ZnIn2S...Pawan Kumar
Photorefining of biomass and its derivatives to value-added chemicals is an alternative solution to address the global energy shortage and environmental issues. Herein, efficient and selective oxidation of 5-hydroxymethylfurfural (HMF, 91.1% conversion) to 2,5-diformylfuran (DFF, 99.4% selectivity) is demonstrated by visible light-driven photocatalysis over cocatalyst-free ZnIn2S4 nanosheets with crystal facet engineering. The spatial accumulation of photogenerated electrons and holes on the (110) and (102) crystal facets triggers a two-electron oxygen reduction reaction (2e-ORR) for H2O2 generation and HMF oxidation into DFF, respectively. The severe attenuation of photostability is caused by the irreversible photocorrosion of Zn–S with the formation of Zn–O chemical bonds by the formation of ˙OH from the in situ decomposition of H2O2. Spontaneous substitution of oxygen with sulfur has been proven to efficiently improve the photostability of ZnIn2S4. This present work provides insights into improving the durability of ZnIn2S4 and sheds new light on biomass valorization via photorefinery.
- The study examined carbon processing in peatland soils under anaerobic conditions by adding traditional and non-traditional methanogenic substrates.
- The additions had no significant effect on methane or carbon dioxide production in bog soil.
- Between 45-100% of the added carbon substrates could not be accounted for in measured carbon pools like methane, carbon dioxide, and glucose. Future isotopic data may provide insight into methanogenic pathways and the fate of missing carbon.
ACETYLATION OF BENZYLIC ALCOHOLS OVER BiFeO3 (BFO), Bi0.86Sm0.07Eu0.07FeO3 (B...EDITOR IJCRCPS
BiFeO3 (BFO), Bi0.86Sm0.07Eu0.07FeO3 (BSEFO), and Bi0.86Sm0.07Cd0.07FeO3 (BSCFO) nanopowders were prepared by the sol-gel
combustion method and the catalytic performances were evaluated in acetylation reaction of benzyl alcohol. The physical chemical
properties of catalysts were characterized by using XRD, FT-IR, scanning electron microscope (SEM), EDX and BET surface.
Efficient acetylation of benzyl alcohol was carried out over all the nano powders using acetyl chloride/ acetonitrile at room
temperature. Among the nanopowders, BSCFO showed the highest catalytic performance and the yield of benzyl acetate was 89,
45, and 69 percent over BSCFO, BFO, and BSEFO, respectively. Partial substitution of Sm-Eu and Sm-Cd in bismuth ferrite
improved the catalytic performance and increased the specific surface area of the catalysts. A direct relationship was resulted
between catalytic performance and surface of catalysts, where BSCFO with the highest surface area (111m2/g) exhibited the
superior catalytic performance. The quantitative yield for acetate product was also resulted for acetylation of p-methyl benzyl
alcohol, p-nitro benzyl alcohol and p-chloro benzyl alcohol on BSCFO. The catalysts showed good reusability in the process. The
study confirmed the catalysts could be promising catalyst for acetylation of alcohols.
Keywords: Europium, Samarium, Bismuth ferrites, nano perovskite, doping, Acetylation, benzylic alcohols.
This document provides an overview of week 1 topics on physical and thermal waste processing. It introduces the learning objectives, references, and various waste processing methods including physical, chemical, thermal, and biological. Specifically, it discusses size reduction, separation, compaction, and other physical processing techniques. It also explains thermal processing methods like combustion, pyrolysis, gasification and their chemical transformations. Proximate analysis, fusing point, ultimate analysis and energy content testing for thermal waste treatment are outlined.
This document provides a history of dioxins in the environment over the last 50 years. It discusses how dioxins originated as byproducts in industrial processes like herbicide and pesticide production. Major events discussed include chick edema disease in the 1950s traced to dioxin-contaminated chicken feed, the use of Agent Orange in Vietnam which introduced large amounts of dioxins, and two major dioxin contamination incidents in Missouri in the 1970s involving waste oil. The document examines the health impacts and cleanup efforts related to these events.
This document summarizes the results of an experimental campaign to measure emissions of dioxins, furans, and polycyclic aromatic hydrocarbons (PAHs) from a hospital and cemetery waste incinerator. Samples were taken from the afterburning chamber, after the heat exchanger, and at the stack. While pollutant concentrations decreased after the heat exchanger and flue gas treatment systems, emission limits for dioxins were not met at the stack. Emission factors for dioxins through air and solid residues were calculated. Tests with cemetery waste generally showed lower dioxin emission factors than tests with hospital waste. PAH emission factors were within typical ranges reported for other waste incinerators.
This method describes the determination of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans from municipal waste combustors. Samples are collected isokinetically from the gas stream using a glass fiber filter and packed adsorbent column. The compounds are extracted from the sample, separated by gas chromatography, and measured by high resolution mass spectrometry. The document provides details on the sampling apparatus and procedures, reagents, analytical equipment, and quality control checks.
The document describes a modification of an analytical method to allow for the determination of ultratrace levels of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and furans (PBDDs/Fs), and polychlorinated dibenzo-p-dioxins and furans (PCDDs/Fs) from a single combustion flue gas sample. The modifications addressed issues related to photolytic and thermal debromination of brominated compounds. This included optimization of extraction time and solvents, cleanup and fractionation steps, and high-resolution gas chromatography separation. The optimized method enabled quantification of 56 PBDE congeners, 15 PBDD/F
El documento habla sobre chimeneas y ventiladores. Explica que las chimeneas de ladrillo, hormigón y acero están sujetas a formar grietas y fugas con el tiempo. También describe cómo funciona el tiro natural de una chimenea y los factores que afectan su valor. Finalmente, detalla los diferentes tipos de ventiladores y sus usos, así como leyes básicas relacionadas a cambios en la velocidad, densidad y tamaño de los ventiladores.
El documento describe las principales fuentes de emisiones de gases de efecto invernadero procedentes de la agricultura, incluyendo la ganadería, el cultivo de arroz bajo riego, la quema de sabanas y residuos agrícolas, y las emisiones de suelos agrícolas. También explica los procesos por los cuales se producen las emisiones de metano, óxido nitroso y otros gases como resultado de la fermentación entérica en el ganado, el manejo de estiércol y las quemas agrícolas.
This document provides guidelines for boiler installation, start-up, water treatment and lay-up. It discusses performing a boil out of new boilers using trisodium phosphate and caustic soda to clean internal surfaces. For steam systems, it recommends connecting the boiler to the header to purge piping of debris using steam before reconnecting the condensate system. Proper pretreatment of make-up water is essential before boiler start-up. Guidelines are provided for short and long term lay-up of boilers when taken offline.
Este documento presenta una guía metodológica para la formulación y diseño de sistemas de acueducto rurales en Colombia. Explica los estudios previos, parámetros de diseño y procedimientos requeridos para el diseño detallado de cada componente, incluyendo captaciones, conducciones, tanques, redes y tratamiento. Además, indica los trámites ante autoridades ambientales y presenta un ejemplo completo de aplicación de la metodología.
Presented by The Global Peatlands Assessment: Mapping, Policy, and Action at GLF Peatlands 2024 - The Global Peatlands Assessment: Mapping, Policy, and Action
Microbial characterisation and identification, and potability of River Kuywa ...Open Access Research Paper
Water contamination is one of the major causes of water borne diseases worldwide. In Kenya, approximately 43% of people lack access to potable water due to human contamination. River Kuywa water is currently experiencing contamination due to human activities. Its water is widely used for domestic, agricultural, industrial and recreational purposes. This study aimed at characterizing bacteria and fungi in river Kuywa water. Water samples were randomly collected from four sites of the river: site A (Matisi), site B (Ngwelo), site C (Nzoia water pump) and site D (Chalicha), during the dry season (January-March 2018) and wet season (April-July 2018) and were transported to Maseno University Microbiology and plant pathology laboratory for analysis. The characterization and identification of bacteria and fungi were carried out using standard microbiological techniques. Nine bacterial genera and three fungi were identified from Kuywa river water. Clostridium spp., Staphylococcus spp., Enterobacter spp., Streptococcus spp., E. coli, Klebsiella spp., Shigella spp., Proteus spp. and Salmonella spp. Fungi were Fusarium oxysporum, Aspergillus flavus complex and Penicillium species. Wet season recorded highest bacterial and fungal counts (6.61-7.66 and 3.83-6.75cfu/ml) respectively. The results indicated that the river Kuywa water is polluted and therefore unsafe for human consumption before treatment. It is therefore recommended that the communities to ensure that they boil water especially for drinking.
Optimizing Post Remediation Groundwater Performance with Enhanced Microbiolog...Joshua Orris
Results of geophysics and pneumatic injection pilot tests during 2003 – 2007 yielded significant positive results for injection delivery design and contaminant mass treatment, resulting in permanent shut-down of an existing groundwater Pump & Treat system.
Accessible source areas were subsequently removed (2011) by soil excavation and treated with the placement of Emulsified Vegetable Oil EVO and zero-valent iron ZVI to accelerate treatment of impacted groundwater in overburden and weathered fractured bedrock. Post pilot test and post remediation groundwater monitoring has included analyses of CVOCs, organic fatty acids, dissolved gases and QuantArray® -Chlor to quantify key microorganisms (e.g., Dehalococcoides, Dehalobacter, etc.) and functional genes (e.g., vinyl chloride reductase, methane monooxygenase, etc.) to assess potential for reductive dechlorination and aerobic cometabolism of CVOCs.
In 2022, the first commercial application of MetaArray™ was performed at the site. MetaArray™ utilizes statistical analysis, such as principal component analysis and multivariate analysis to provide evidence that reductive dechlorination is active or even that it is slowing. This creates actionable data allowing users to save money by making important site management decisions earlier.
The results of the MetaArray™ analysis’ support vector machine (SVM) identified groundwater monitoring wells with a 80% confidence that were characterized as either Limited for Reductive Decholorination or had a High Reductive Reduction Dechlorination potential. The results of MetaArray™ will be used to further optimize the site’s post remediation monitoring program for monitored natural attenuation.
RoHS stands for Restriction of Hazardous Substances, which is also known as t...vijaykumar292010
RoHS stands for Restriction of Hazardous Substances, which is also known as the Directive 2002/95/EC. It includes the restrictions for the use of certain hazardous substances in electrical and electronic equipment. RoHS is a WEEE (Waste of Electrical and Electronic Equipment).
Epcon is One of the World's leading Manufacturing Companies.EpconLP
Epcon is One of the World's leading Manufacturing Companies. With over 4000 installations worldwide, EPCON has been pioneering new techniques since 1977 that have become industry standards now. Founded in 1977, Epcon has grown from a one-man operation to a global leader in developing and manufacturing innovative air pollution control technology and industrial heating equipment.
Improving the viability of probiotics by encapsulation methods for developmen...Open Access Research Paper
The popularity of functional foods among scientists and common people has been increasing day by day. Awareness and modernization make the consumer think better regarding food and nutrition. Now a day’s individual knows very well about the relation between food consumption and disease prevalence. Humans have a diversity of microbes in the gut that together form the gut microflora. Probiotics are the health-promoting live microbial cells improve host health through gut and brain connection and fighting against harmful bacteria. Bifidobacterium and Lactobacillus are the two bacterial genera which are considered to be probiotic. These good bacteria are facing challenges of viability. There are so many factors such as sensitivity to heat, pH, acidity, osmotic effect, mechanical shear, chemical components, freezing and storage time as well which affects the viability of probiotics in the dairy food matrix as well as in the gut. Multiple efforts have been done in the past and ongoing in present for these beneficial microbial population stability until their destination in the gut. One of a useful technique known as microencapsulation makes the probiotic effective in the diversified conditions and maintain these microbe’s community to the optimum level for achieving targeted benefits. Dairy products are found to be an ideal vehicle for probiotic incorporation. It has been seen that the encapsulated microbial cells show higher viability than the free cells in different processing and storage conditions as well as against bile salts in the gut. They make the food functional when incorporated, without affecting the product sensory characteristics.
Kinetic studies on malachite green dye adsorption from aqueous solutions by A...Open Access Research Paper
Water polluted by dyestuffs compounds is a global threat to health and the environment; accordingly, we prepared a green novel sorbent chemical and Physical system from an algae, chitosan and chitosan nanoparticle and impregnated with algae with chitosan nanocomposite for the sorption of Malachite green dye from water. The algae with chitosan nanocomposite by a simple method and used as a recyclable and effective adsorbent for the removal of malachite green dye from aqueous solutions. Algae, chitosan, chitosan nanoparticle and algae with chitosan nanocomposite were characterized using different physicochemical methods. The functional groups and chemical compounds found in algae, chitosan, chitosan algae, chitosan nanoparticle, and chitosan nanoparticle with algae were identified using FTIR, SEM, and TGADTA/DTG techniques. The optimal adsorption conditions, different dosages, pH and Temperature the amount of algae with chitosan nanocomposite were determined. At optimized conditions and the batch equilibrium studies more than 99% of the dye was removed. The adsorption process data matched well kinetics showed that the reaction order for dye varied with pseudo-first order and pseudo-second order. Furthermore, the maximum adsorption capacity of the algae with chitosan nanocomposite toward malachite green dye reached as high as 15.5mg/g, respectively. Finally, multiple times reusing of algae with chitosan nanocomposite and removing dye from a real wastewater has made it a promising and attractive option for further practical applications.
Evolving Lifecycles with High Resolution Site Characterization (HRSC) and 3-D...Joshua Orris
The incorporation of a 3DCSM and completion of HRSC provided a tool for enhanced, data-driven, decisions to support a change in remediation closure strategies. Currently, an approved pilot study has been obtained to shut-down the remediation systems (ISCO, P&T) and conduct a hydraulic study under non-pumping conditions. A separate micro-biological bench scale treatability study was competed that yielded positive results for an emerging innovative technology. As a result, a field pilot study has commenced with results expected in nine-twelve months. With the results of the hydraulic study, field pilot studies and an updated risk assessment leading site monitoring optimization cost lifecycle savings upwards of $15MM towards an alternatively evolved best available technology remediation closure strategy.
Evolving Lifecycles with High Resolution Site Characterization (HRSC) and 3-D...
Determination of ultralevels.pdf
1. Same-Sample Determination of Ultratrace Levels
of Polybromodiphenylethers,
Polybromodibenzo-p-dioxins/Furans, and
Polychlorodibenzo-p-dioxins/Furans from
Combustion Flue Gas
Barbara Wyrzykowska,†,‡
Dennis Tabor,†
and Brian K. Gullett*,†
National Risk Management Research Laboratory, Office of Research and Development, United States Environmental
Protection Agency, E305-01, Research Triangle Park, North Carolina 27711, and Oak Ridge Institute for Science and
Education Research Postdoctoral Program, P.O. Box 117, Oak Ridge, Tennessee 37831-0117
The analytical method used for determination of polychlo-
rinated dibenzo-p-dioxins and -furans (PCDDs/Fs) emis-
sions from municipal waste combustors (MWCs) and
other stationary sources was modified and validated to
additionally allow for analysis of ultratrace levels of
polybrominated diphenyl ethers (PBDEs) and polybro-
minated dibenzo-p-dioxins and -furans (PBDDs/Fs) from
a common flue gas sample. Potential methodological
problems related to physicochemical properties of bro-
minated compounds, including UV- and temperature-
induced debromination and degradation, were addressed.
The selection of solvents, optimization of extraction time,
and adaptation of the cleanup and fractionation steps
increased mean recoveries of 13
C12-labeled PBDE and
PBDD/F isotope dilution surrogates about 18% and
25%, respectively. The customary liquid chromatog-
raphy isolation of PBDEs and PBDDs/Fs was replaced
by optimization of high-resolution gas chromatography
to separate target PBDFs (2,3,7,8-Br-substituted) from
potentially interfering PBDEs before mass spectro-
scopic identification. The optimized method allowed
quantitative determination of 56 mono- through deca-
bromodiphenylether congeners, 15 congeners of 2,3,7-
and 2,3,7,8-Br-substituted tri- to octabromodibenzo-
p-dioxins and -furans, and all 210 polychlorinated
dibenzo-p-dioxins and -furans present in the flue gas
at levels of picogram to microgram per normalized
cubic meter.
Polybrominated diphenyl ether (PBDE) is a common flame
retardant that has been found in environmental matrixes world-
wide.1
The environmental levels of brominated diphenyl ether are
of concern for the United States, where human breast milk and
blood levels of PBDEs are among the highest in the world.2,3
Interestingly, a new U.S. market basket survey measuring values
of PBDEs in foods suggested that, contrary to polychlorinated
dibenzodioxins/furans (PCDDs/Fs), food is not the major pathway
of human exposure to PBDEs.4
Even though there has been
significant research on brominated flame retardants, relatively little
is known about their possible thermal breakdown products,
polybrominated dibenzo-p-dioxins and -furans (PBDDs/Fs), which
reportedly can exhibit toxicity and persistence similar to PCDDs/
Fs and recently have been found in several environmental
matrixes, including humans.5-9
Combustion-related processes, including municipal solid waste
incineration, are known to be a major source of atmospheric
pollution with PCDD/F.10
The regulations concerning thresholds
of PCDD/F emissions from stationary sources have triggered
demand for development of analytical methods suitable for
determination of trace levels of PCDD/F in flue gases and resulted
in numerous standard methods worldwide (e.g., U.S. EPA Method
23 and European Standard EN 1948-1-3:2006).11-14
Widespread
monitoring programs and effective implementation of environ-
* To whom correspondence should be addressed.
†
United States Environmental Protection Agency.
‡
Oak Ridge Institute for Science and Education Research Postdoctoral
Program.
(1) de Wit, C. A. Chemosphere 2002, 46, 583–624.
(2) Schecter, A.; Johnson-Welch, S.; Kuang, C.; Harris, T. R.; Päpke, O.; Rosen,
R. J. Toxicol. Environ. Health, Part A 2007, 70, 1–6.
(3) Mazdai, A.; Dodder, N. G.; Abernathy, M. P.; Hites, R. A.; Bigsby, R. M.
Environ. Health Perspect. 2003, 111, 1249–1252.
(4) Schecter, A.; Päpke, O.; Harris, T. R.; Tung, K. C.; Musumba, A.; Olson, J.;
Birnbaum, L. Environ. Health Perspect. 2006, 114, 1515–1520.
(5) Birnbaum, L. S.; Staskal, D. F.; Diliberto, J. J. Environ. Int. 2003, 29, 855–
860.
(6) Watanabe, I.; Sakai, S. Environ. Int. 2003, 29, 665–682.
(7) Sakai, S.; Watanabe, J.; Honda, Y.; Takatsuki, H.; Aoki, I.; Futamatsu, M.;
Shiozaki, K. Chemosphere 2001, 42, 519–531.
(8) WHO/ICPS. Environmental Health Criteria 162: Brominated Diphenyl
Ethers; Geneva, Switzerland, 1994.
(9) WHO/ICPS. Environmental Health Criteria 205: Polybrominated Dibenzo-
p-dioxins and Dibenzofurans; Geneva, Switzerland, 1998.
(10) UNEP. Dioxin and Furan Inventories. National and Regional Emissions of
PCDD/PCDF, UNEP Chemicals; Geneva, Switzerland, 1999.
(11) U.S. EPA Test Method 23, 1996. Sampling Method for Polychlorinated
Dibenzo-p-dioxins and Polychlorinated Dibenzofuran Emissions from
Stationary Sources; Office of Solid Waste and Emergency Response,
Environmental Protection Agency: Washington, DC, 1996.
(12) European Standard EN 1948-1:2006. Stationary source emissions. Deter-
mination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs.
Part 1: Sampling of PCDDs/PCDFs; European Committee for Standariza-
tion, CEN: Brussels, Belgium, 2006.
Anal. Chem. 2009, 81, 4334–4342
10.1021/ac900105a Not subject to U.S. Copyright. Publ. 2009 Am. Chem. Soc.
4334 Analytical Chemistry, Vol. 81, No. 11, June 1, 2009
Published on Web 05/07/2009
2. mental laws caused decreases in PCDD/F emissions from point
sources in the industrialized nations over past 2 decades.10,15
For
instance, the U.S. atmospheric emissions of PCDDs/Fs from
municipal waste combustion have been reduced by approximately
99% between 1987 and 2000 (from 8905 g TEQ/year to 83.8 g
TEQ/year, respectively).15
Therefore, extending analytical meth-
ods initially developed for PCDD/F determination to halogenated
organics of growing environmental concern, e.g., bromodioxins/
furans and their abundant precursorssPBDEs, is essential.
Highly sensitive, selective, and specific analytical methods are
required for analysis of PBDD/Fs and PBDEs. It is because of
the large number of congeners (209 and 210 possible PBDE and
PBDD/F congeners, respectively), their low concentrations (PB-
DDs/Fs levels in the flue gases are usually very low, sometimes
less than 0.1% of the level reported for PCDDs/Fs), and meth-
odological problems related to thermal and photolytic degrada-
tion.16-25
Brominated compounds are in general more readily
dehalogenated than chlorinated species, because of the smaller
bond energy of C-Br (276 kJ/mol) than that of C-Cl (328 kJ/
mol).22
Many experiments have shown reductive debromination
to be a major photochemical decomposition pathway of bromi-
nated compounds, with the reaction rate depending on the
bromine substitution pattern (higher brominated congeners and
thosewithlateralbromineshavereportedlyshorterUVhalf-lives).23,24
Studies on decabromodiphenylether (DcBDE-209) degradation
kinetics under natural sunlight resulted in estimation of half-lives
as approximately 75 min (when DcBDE-209 was sorbed on
kaolinite).25
The half-lives of bromodioxins on soot or dust under
direct sunlight exposure might be as low as several hours.9
Photodegradation of PBDEs and PBDDs/Fs have been also often
demonstrated in various organic solutions.9,23-25
For instance,
sunlight-induced half-lives for bromodioxins in organic solutions
are reportedly as low as minutes (e.g., 0.8 min for 2,3,7,8-
tetrabromodibenzo-p-dioxin (2,3,7,8-TeBDD).9
The efficiency of
UV-related debromination of bromodiphenylether in organic
solvents reportedly depends on the number of bromine atoms,
polarity of the solvent, and the presence of various surfaces (e.g.,
silica, gel, sand) in the solution.23,24
Photodegradation rates tend
to be higher for highly brominated compounds in less polar
solvents and in the presence of a surface.23,24
DcBDE-209 is
particularly sensitive to ultraviolet exposure in organic solvents;
the UV degradation half-life of DcBDE-209 in a methanol/water
solution was 30 min compared to 12 days for 2,2′,4,4′-tetrabro-
modiphenylether (TeBDE-47).24
The exposure of BDE organic
solutions to UV light might not only cause debromination but also
formation of PBDF.9,23
In experiments with UV and sunlight
exposure of DecaBDE commercial formulation in hexane, a
complex mixture of tri- to octabromodiphenylether (Tri- to Oc-
BDE) congeners was detected as well as a large number of mono-
to hexabrominated dibenzofuran (Mo- to Hx-BDF) congeners.
After 16 h of the sunlight exposure the yield of the Mo- to Hx-
BDFs formed was 10% of the total DecaBDE technical product.)9
After 16 h UV exposure of toluene solution of DecaBDE technical
product, yields of the 27 Mo- to Hx-BDFs formed were up to 1.2%
of the initial amount of technical DecaBDE.23
Thermodegradation
issues are often associated with the residence time of highly
brominated compounds’ in the gas chromatographic (GC) sys-
tems, often with connection to injection port temperature.17,20,21
Possible photodegradation and thermodegradation of PBDEs
and PBDDs/Fs need to be taken into account while developing
integrated analytical methods; however, overall extraction, cleanup,
and fractionation methods for PBDDs/Fs and PBDEs analysis do
not appear to be fundamentally different for those routinely used
for PCDDs/Fs. The solvents recommended for removal of PBDEs
and PBDD/Fs from environmental matrixes are usually toluene
and methylene chloride, less often hexane and hexane/acetone
mixtures.17,22,26
Nonpolar organic solvents (e.g., hexane) have
high solubility for most bromoorganics but are not sufficient for
extraction of matrixes rich in organic matter (containing many
polar groups of amines, phenols, and carboxylic acids).17
The
extraction methods (Soxhlet extraction, accelerated solvent ex-
traction, pressurized liquid extraction, supercritical fluid extraction,
microwave-assisted extraction) and times vary significantly among
studies, i.e., from 6 to 24 h, depending on extraction procedure
and sample volume.17,25,27
Conventional cleanup and fractionation
techniques used for PCDDs/Fs (multilayer silica gel-, alumina-,
activated carbon-column chromatography, Florisil cleanup, and
gel permeation chromatography) reportedly work also for PBDEs
and PBDDs/Fs.17
The main differences between procedures used
for PBDEs and PBDDs/Fs versus those routinely employed for
PCDDs/Fs are usually changes in composition/concentration of
eluting organic solvents and modifications of the fractionation step
(usually performed by means of liquid chromatography).17,27-33
For instrumental analysis of PBDEs and PBDD/Fs, both gas
chromatography/mass spectrometry (GC/MS) and gas chroma-
tography with electron capture detector (GC-ECD) are commonly
(13) European Standard EN 1948-2:2006. Stationary source emissions. Deter-
mination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs.
Part 2: Extraction and clean-up of PCDDs/PCDFs; European Committee
for Standarization, CEN: Brussels, Belgium, 2006.
(14) European Standard EN 1948-3:2006. Stationary source emissions. Deter-
mination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs.
Part 3: Identification and quantification of PCDDs/PCDFs; European
Committee for Standarization, CEN: Brussels, Belgium, 2006.
(15) An Inventory of Sources and Environmental Releases of Dioxin-Like
Compounds in the United States for the Years 1987, 1995, and 2000; EPA/
600/P-03/002F; National Center for Environmental Assessment, U.S. EPA:
Washington, DC, 2006.
(16) Wang, L.-C.; Chang-Chien, G.-P. Environ. Sci. Technol. 2007, 41, 1159–
1165.
(17) Covaci, A.; Voorspoel, S.; de Boer, J. Environ. Int. 2003, 29, 735–756.
(18) Eljarrat, E.; de la Cal, A.; Barceló, D. J. Chromatogr., A 2003, 1008, 181–
192.
(19) Stapleton, H. M. Anal. Bioanal. Chem. 2006, 386, 807–817.
(20) de Boer, J.; Wells, D. Organohalogen Compd. 2004, 66, 510–518.
(21) de Boer, J.; Cofino, W. P. Chemosphere 2002, 46, 625–633.
(22) Takahashi, S.; Sakai, S.; Watanabe, I. Chemosphere 2006, 64, 234–244.
(23) Hagberg, J.; Olsman, H.; van Bavel, B.; Engwall, M.; Lindström, G. Environ.
Int. 2006, 32, 851–857.
(24) Eriksson, J.; Green, N.; Marsh, G.; Bergman, A. Environ. Sci. Technol.
2004, 38, 3119–3125.
(25) Gerecke, A. C. Organohalogen Compd. 2006, 68, 1979–1982.
(26) van Bavel, B.; Andersson, P.; Takeda, N.; Rappe, C. Chemosphere 1998,
31, 2077–2089.
(27) Björklund, E.; Sporring, S.; Wiberg, K.; Haglund, P.; von Holst, C. Trends
Anal. Chem. 2006, 25, 318–325.
(28) Focant, J.-F.; Pirard, C.; De Pauw, E. Talanta 2004, 63, 1101–1113.
(29) Ebert, J.; Lorenz, W.; Bahadir, M. Chemosphere 1999, 39, 977–986.
(30) van Bavel, B.; Ericsson, I.; Björnfoth, H.; Hagberg, J.; Lindström, G.
Organohalogen Compd. 2004, 66, 107–111.
(31) Hanari, N.; Kannan, K.; Miyake, Y.; Okazawa, T.; Kodavanti, P.; Aldous,
K.; Yamashita, N. Environ. Sci. Technol. 2006, 40, 4400–4405.
(32) Okazawa, T.; Hanari, N.; Guruge, K.; Wyrzykowska, B.; Orlikowska, A.;
Yamashita, N.; Falandysz, J. Organohalogen Compd. 2004, 66, 2222–2228.
(33) Söderström, G.; Marklund, S. Organohalogen Compd. 2000, 47, 225–228.
4335
Analytical Chemistry, Vol. 81, No. 11, June 1, 2009
3. used techniques (similar to PCDDs/Fs, high-resolution mass
spectrometry, HRMS, is needed for analysis of PBDDs/Fs). Only
recently have other techniques (gas chromatography two-
dimensional mass spectrometry GC/MS/MS, gas chromatography
time-of-flight mass spectrometry GC/TOFMS, two-dimensional
gas chromatography time-of-flight mass spectrometry GC/GC/
TOFMS, proton nuclear magnetic resonance 1
H NMR) been
successfully applied to analysis of PBDEs in environmental
matrixes and in technical bromodiphenylether mixtures.17,19,34,35
The amount of published work on various analytical techniques
for PBDE and PBDD/F analyses in environmental samples could
suggest that methodology is well-established. However, the results
of international calibration studies on brominated flame retardants
(BFRs) and PBDDs/Fs confirmed that determination of certain
bromoorganics is still an analytical challenge.20-22
Despite con-
siderable improvement in performance of the analytical laborato-
ries over the past few years, further development of extraction
and cleanup procedures, and validation of instrumental methods
analysis, are still needed.20-22
The goal of this research was to validate an analytical method
for analysis of trace levels of PCCDs/Fs and 2,3,7,8-substituted
PBDDs/Fs, as well as PBDEs (including several “dioxin-like”
congeners substituted in non-, mono-, and diortho positions), in
combustion samples. Bromoorganics analysis required (1) com-
prehensive presampling, pre-extraction, and recovery spikes for
the isotope dilution method, with internal standards covering the
full degree of bromination of target PBDEs and PBDDs/Fs, (2)
prevention of photo- and thermoinduced debromination by mini-
mizing UV exposure, (3) selection of extraction solvents and
optimization of sequential extraction time, (4) modification of
elution solutions and steps for liquid chromatography-based
cleanup, and (5) optimization of gas chromatographic system
parameters (column length, temperature of injection port) for high-
resolution gas chromatography/high-resolution mass spectrom-
etry (HRGC/HRMS) analysis.
EXPERIMENTAL SECTION
Target Matrix and Sampling. Flue gas samples were col-
lected in December 2006 from a U.S. municipal waste combustor
(MWC). Sampling at postboiler (prior to the air pollution control
system) and stack locations were performed. The flue gases were
taken isokinetically using a modified version of U.S. EPA Method
23 (M-23) routinely used for sampling of PCDD/F from MWCs
and other stationary sources.11,36
In this study, the M-23 sampling
protocol was adapted for simultaneous sampling of PBDEs and
PBDDs/Fs by addition of 13
C12-labeled PBDE and PBDD/F
presampling spikes and restrictive measures to avoid direct
sunlight exposure (covering the sampling trains with aluminum
foil during both sampling and transportation/handling). The
field blanks processed for sampling consisted of a sample
cartridge containing XAD and filter that was spiked with the
presampling spike solution, shipped to the field, installed on
the sampler, and passively exposed at the sampling area (the
sampler is not operated). Field blanks were sealed and returned
to the laboratory for extraction, cleanup, and HRGC/HRMS
analysis and were treated in exactly the same manner as a test
sample.
Chemicals. The internal standard mixtures were prepared in-
house from individual 13
C12-labeled PBDEs and PBDDs/Fs
solutions and commercially available custom-made 13
C12-labeled
PCDDs/Fs mixes. The composition of 13
C12-labeled PBDEs and
PBDDs/Fs spikes is given in the Supporting Information,
Tables S-1 and S-2. The standard used for PBDEs identification
and quantification was a mixture of brominated flame retardants
(BFR-PAR; Wellington Laboratories, Canada), which consisted of
mono- to decabrominated diphenyl ether congeners. The PBDD/F
standard contained tetra- through octabromodioxins and/or furans
congeners (EDF-5059, CIL Cambridge Isotope Laboratories Inc.,
U.S.A.). The standard used for chlorinated dioxin/furan identifica-
tion and quantification was a mixture of standards containing
mono- to octa-PCDD/F native and 13
C12-labeled congeners
designed for modified U.S. EPA Methods 0023a/8290 (ED-
2521, EDF-4137A, EDF-4136A, EF-4134, ED-4135, CIL Cam-
bridge Isotope Laboratories Inc., U.S.A.).22
All solvents were
HPLC/GC/spectrophotometry grade ACS/HPLC certified (Bur-
dick and Jackson, Honeywell, U.S.A.). Multilayer silica, carbon,
and alumina columns were prepacked, disposable cartridges
available from FMS Fluid Management Systems, Inc., U.S.A.
The glass microfiber high-purity thimbles and filters were
purchased from Whatman, U.S.A., and the XAD-2 resin was
from Supelco, U.S.A.
Extraction. Extractions were initially performed according to
procedures for PCDD/F removal from M-23 train samples by means
of overnight Soxhlet extraction with toluene.11
Toluene extraction
has proven to be efficient for chlorodioxins analysis in similar
matrixes, including the samples collected during a preceding
sampling campaign at the same MWC. 11,17,26,37
Nevertheless, we
believe that toluene, because of its high boiling point, should
not be used for extraction of potentially thermally labile
brominated analytes, especially DcBDE-209. In addition pos-
sible photodegradation of PBDEs in toluene solutions or
formation of PBDFs during overnight Soxhlet extractions was
of concern, as long duration Soxhlet extractions at high
temperature (∼110 °C, for 16 h) may promote copper-catalyzed
dehalogenation and cyclization of PBDEs.22
Although copper
was not added to the extract in the present study, the presence
of copper or other transition metal catalysts in our study
samples cannot be excluded. PBDE debromination/degradation
and possible conversion of bromodiphenylethers to PBDFs in
toluene could be sources of artifacts in this study. Therefore,
the effect of adding a “soft” step, a short time extraction with
a low boiling point solvent, was tested. Methylene chloride was
selected as a solvent for the first step of the sequential
procedure (similar to toluene, methylene chloride is a medium
polar solvent, widely used for PBDDs/Fs and PBDEs extrac-
(34) Cochran, J.; Dorman, F.; Reiner, E.; Kolic, T.; MacPherson; K. GC-TOFMS
and GCxGC-TOFMS of Brominated Flame Retardants. Presented at BFR
2006sThe Eighth Annual Workshop on Brominated Flame Retardants in
the Environment, Toronto, Ontario, Canada, 2006.
(35) Konstantinov, A.; Arsenault, G.; Chittim, B.; McAlees, A.; McCrindle, R.;
Potter, D.; Tashiro, C.; Yeo, B. Identification of the Minor Components of
DE-79TM Technical Mix by Means of 1H NMR and GC-MS. Presented
at BFR 2006sThe Eighth Annual Workshop on Brominated Flame
Retardants in the Environment, Toronto, Ontario, Canada, 2006.
(36) Gullett, B. K.; Ryan, J. V.; Tabor, D. Organohalogen Compd. 1999, 40, 121–
124.
(37) Gullett, B.; Touati, A.; Oudejans, L.; Ryan, S.; Tabor, D. Organohalogen
Compd. 2006, 68, 143–146.
4336 Analytical Chemistry, Vol. 81, No. 11, June 1, 2009
4. tion; however, it has significantly lower boiling point than
toluene: 39.5 °C vs 110.6 °C, respectively).17,19
Toluene re-
mained the preferred solvent for the second step, as it is
required for extraction of PCDDs/Fs from carbonaceous
matrixes that contain soot particles.11
The final method
consisted of 3.5 h of methylene chloride extraction, followed
by 16 h of extraction with toluene. The methylene chloride
extract contained most of the brominated targets; for PBDEs,
depending on the degree of bromination, the methylene
chloride extracted an average of 99.7% of the total PBDEs,
whereas the toluene extract contained 0.3% on average (1.64%
maximum). Amounts of 94.1% and 8.9% of the total PBDDs/Fs
extracted were found in the methylene chloride and toluene
fractions, respectively. Fluorescent lights in the laboratory were
shielded with ultraviolet-absorbing filters, and incandescent
lighting was used. The extraction process itself was performed
in complete darkness, where the sash of the fume hood was
covered with aluminum foil. All raw extracts were concentrated
using three-ball Snyder columns, filtered, and concentrated
further in nitrogen to 1 mL using the automated evaporation
TurboVap workstation.
Cleanup and Fractionation. For determination of PCDDs/
PCDFs and PBDDs/PBDFs/PBDEs, one-half and one-quarter
of the extract was cleaned and fractionated using an automated
liquid chromatography multicolumn Power Prep/Dioxin System
(FMS Fluid Management Systems, Inc., U.S.A.). The remaining
one-quarter of the extract was archived. Prior to the automated
cleanup process, extracts were concentrated and diluted in
n-hexane, then loaded and pumped sequentially through
individual sets of FMS proprietary columns: multilayer silica
(4 g acid, 2 g base, and 1.5 g neutral), followed by a basic
alumina (11 g) column and, in the case of PCDDs/Fs, also a
carbon column (0.34 g). The cleanup of PBDDs/Fs and PBDEs
required use of 100 mL of 100% methylene chloride to elute
those compounds from the alumina column, instead of 120 mL
of 50% methylene chloride in hexane used for elution of
PCDDs/Fs. The carbon column was problematic for the
cleanup of highly brominated PBDEs and PBDD/Fs, notably
affecting their recoveries (probably resulting from the steric
hindrance effect, which theoretically should increase in the
order F < Cl < Br < I and depends on the bulk of the substituent
halogens); hence, the use of the carbon column for the
bromoorganics was suspended. Recoveries for cleanup of
mixture of PBDEs/PBDDs/PBDFs standards employing a
carbon column are given in Figure S-2 of the Supporting
Information. Even though the matrix effect was not tested in
those experiments, recoveries obtained are in the range of
0.30-53.1% for PBDEs and 10.4-35.4% for PBDDs/Fs, there-
fore much lower than that obtained for cleanup with the
suspended carbon column step used for samples of flue gas
analyzed in this study, depending on bromination degree:
10.1-87.9% for PBDEs and 53.9-108.9% for PBDDs/Fs, re-
spectively. The details on PCDDs/Fs and PBDDs/PBDFs/
PBDEs cleanup and fractionation method are given in the
Supporting Information, Figure S-1. The aliquots of the PCDDs/
Fs and PBDDs/PBDFs/PBDEs fractions were concentrated to
a final volume of 100 µL using the automated TurboVap
concentration workstation (Caliper Life Sciences, Inc., U.S.A.)
and N-Evap nitrogen blow-down evaporator (Organomation
Associates, Inc., U.S.A.). Final extracts were transferred to
amber glass vials and refrigerated until analysis.
HRGC/HRMS Analysis. Concentrations of all target analytes
were determined by means of HRGC/HRMS using a Hewlett-
Packard gas chromatograph 6890 series equipped with a CTC
ANALYTICS Combi PAL autosampler (CTC Analytics, Switzerland
purchased from LEAP Technologies, U.S.A..) coupled to an
Autospec Micromass Premier (Waters Inc., U.K.) double-focusing
high-resolution mass spectrometer.
HRGC System. For analysis of mono- through octa-BDEs
and tri- through hexa-BDD/Fs, the GC was equipped with long
(60 m) capillary columns: HP-5 (SGE Analytical Science Pty.
Ltd., Australia) or DB-5 (J&W Scientific, U.S.A.). For nona-
through deca-BDEs and hepta- through octa-BDD/Fs analysis
a short (15 m) HP-5 column was used. Both short and long
columns were of 0.25 µm film thickness × 0.25 mm i.d. For
analysis of mono- through octa-CDDs/Fs, a 60 m DB-Dioxin
(J&W Scientific, U.S.A.) column was used (0.15 µm film
thickness × 0.25 mm i.d).
The GC oven temperature for PBDE and PBDD/F analysis
was programmed from 130 to 230 °C at 15 °C min-1
(5 min hold),
then to 280 °C at 10 °C min-1
(60 min hold), and then to 320
at 15 °C min-1
with a final hold time of 35 min on the 60 m
column and from 130 to 320 °C at 10 °C min-1
(15 min hold)
for the 15 m column. The temperature program for PCDD/F
was from an initial temperature of 130 to 260 °C at 6 °C min-1
with a final hold time of 50 min. The carrier gas (helium) flow
rate was 1 and 1.5 mL min-1
for brominated compounds
analysis (short and long column, respectively) and 0.9 mL min-1
for chlorinated compounds. Two microliters (2 µL) of the
extract was injected under splitless mode (injection port
temperature set as 270 and 300 °C for chlorinated and
brominated target analysis, respectively).
HRMS System. The HRMS was operated in an electron
impact (35 eV and 650 µA current) selective ion recording (SIR)
mode at resolution R > 10 000 (5% valley). The temperature of
the ion source was 280 °C for the PBDE and PBDD/F analyses,
whereas for PCDD/F, the ion source was kept at 250 °C. The
two strongest ions in the molecular cluster were monitored in
every retention time window for each native and labeled PBDD/
F, PCDD/F, and PBDE based on mass spectroscopy libraries and
literature data, unless interferences were present. In the case of
the nona- and decabrominated diphenyl ether congeners, the BDE
- 2Br fragment ion was monitored (ions selected for HRMS SIR
of PBDEs and PBDDs/Fs are given in the Supporting Information,
Table S-2). For the PBDFs fragment ion, -COBr was used to
confirm the assignment of several bromodibenzofuran congeners
which were not present in the calibration standards. For the data
collection, Mass Lynx software version 4.1 was used (including
Target Lynx 4.1. for processing and quantitation).
Quality Control/Quality Assurance. Sorbent (XAD-2) car-
tridges were prespiked with a mixture containing 13
C12-labeled
analogues of selected chlorinated and brominated target
compounds before sampling. All samples, including blanks,
were spiked with internal standards before extraction and again
before analysis (isotope dilution). Laboratory method blanks
representing the background contributions from glassware,
4337
Analytical Chemistry, Vol. 81, No. 11, June 1, 2009
5. extraction, and cleanup were analyzed by HRGC/HRMS in
exactly the same manner as the test samples.
The HRMS was tuned daily or prior to each sample acquisition.
Static resolving power checks were performed daily with a
perfluorokerosene (PFK) calibration standard to achieve required
resolution of 10 000 (5% valley). Peak responses for each of the
two selected molecular cluster ions were at least 3 times the noise
level (S/N > 3), and the bromine/chlorine isotope ratio for the
two molecular cluster ions was within ±20% of the correct iso-
tope ratio; otherwise they were considered below the limit of
detection. To produce the calibration curves sets, five calibration
solutions were prepared for PCDD/Fs, PBDDs/Fs, and PBDEs
(CS-1 to CS-5). The medium concentration (CS-3) standard was
used for calibration verification according to requirements of EPA
Method 8290 and EPA Method 1614.38,39
The PBDE calibration
standard contained 41 mono- through deca-BDE native congeners,
as well as all congeners present in 13
C12-labeled solutionssthe
surrogate standard, cleanup standard, and injection internal
standard. The calibration solution of PBDD/F contained 11
native 2,3,7,8-substituted analogues of polybrominated dibenzo-
p-dioxin and dibenzofuran and appropriate 13
C12-labeled com-
pounds. The calibration solution of PCDD/F contained native
mono- through octachlorinated 2,3,7,8-Cl-substituted dibenzo-
p-dioxin and furan and suitable 13
C12-labeled analogues, accord-
ing to modified U.S. EPA Methods 0023A/8290.11,36,38
The list
of all native PBDE and PBDD/F analytes is given in Tables S-3
and S-4 of the Supporting Information. The quality assurance/
quality control (QA/QC) measures in sampling, analysis, and
evaluation of data incorporate system and laboratory performance
requirements of the U.S. EPA Method 1614 for PBDEs and the
U.S. EPA Method 23 and 8290 for PCDDs/Fs and PBDDs/Fs.11,38,39
RESULTS AND DISCUSSION
Simultaneous Sampling of Bromoorganics and Chloroor-
ganics. All the requirements of the M-23 protocol are assumed
to be critical for collection of representative gas samples for
bromoorganics in this study. In addition, measures to avoid direct/
indirect sunlight exposure of the sample (not required for PCDDs/
Fs sampling) are considered to be critical for obtaining satisfactory
recoveries of the brominated analytes in this study. A good
indication of sampling efficiency is surrogate recovery, measured
relative to the internal standards. The presampling surrogates
recoveries in this study, 102% (±6.6% SD) for PCDDs/Fs, 105.4%
(±10.8% SD) for PBDDs/Fs, and 94.9% (±9.4% SD) for PBDEs,
respectively, are well within the range of 70-130% recommended
by U.S. EPA Method 23 for chlorinated dioxins.11
Optimization of Extraction. The sequential Soxhlet method
used in this study with methylene chloride (3.5 h) and toluene
(16 h; “overnight”) enabled effective removal of trace amounts of
chlorinated and brominated targets from the carbonaceous matrix
core of sampled material. However, filters in this study had
relatively light carbon loads compared to samples previously
collected from this MWC source. Therefore, applicability of our
method to carbon-rich matrixes from other combustion sources
should be tested. Because M-23 requires toluene use for PCDD/F
removal,11
methylene chloride and toluene extracts were com-
bined before further steps of PCDD/F analysis.
Selection of both the extraction medium (solvent) and time of
extraction had a significant impact on the recoveries of brominated
target compounds. As demonstrated in Figure 1, introduction of
the short (“soft”) methylene chloride step to the Soxhlet extraction
enhanced the recoveries of brominated analytes by approximately
20% (25% on average for PBDEs and 18% for PBDDs/Fs,
respectively) when compared to extraction with toluene only (both
extractions were performed with restricted exposure to UV light).
Obviously, these methodological adaptations of extraction aided
avoiding thermo- and photodegradation-related losses of bromi-
nated analytes in the present study.
The effect of the extraction solvent on recoveries of PCDDs/
Fs was certainly less prominent than in the case of brominated
analytes. The recoveries of PCDD/F 13
C12-labeled internal
standards were similar for samples extracted with methylene
chloride and toluene, compared to those treated with toluene
only. Interestingly, higher chlorinated congeners exhibited
better average recoveries in samples extracted by sequential
procedure (Figure 1b). This may be due to the slower photolytic
degradation rate of lower chlorinated dioxins and furans which
tend to be more stable in organic solvents than their brominated
analogues; the photolytic reaction of 1,2,3,4-TeBDD in 2,2,4-
trimethylpentane (iso-octane) is very rapid, with a half-life of 3
min, compared to 380 min for 1,2,3,4-TeCDD.9
Optimization of Cleanup and Fractionation. The multistep
cleanup and fractionation of the FMS Power-Prep system has been
extensively used for PCDD/F purification from numerous envi-
ronmental matrixes. However, the applications of Power-Prep for
purification of brominated compounds are relatively less studied.40
In this study, the method used for chlorinated dioxins/furans was
not only modified with regard to solvent concentration and
volumes but also modified by eliminating the last fractionation
step (carbon column) for bromoorganics (Figure S-1 of the
Supporting Information illustrates differences of the cleanup and
fractionation scheme used for chlorinated and brominated ana-
logues in this study). Importantly, the use of prepacked columns
minimizes the contact of the column bed with laboratory air
particles, which might contain flame retardants in high concentra-
tions (BDE-47, -99, -209 in indoor household dust were reported
at average concentrations of 51, 79, 470 ng g-1
, respectively).41
Both the minimized exposure of the sample to dust and the
use of relatively small volumes of solvents in the automated
fractionation process should be considered as particularly
valuable in the decabromodiphenyl analysis context where,
reportedly, high procedural blanks are often a problem.20,21
Only seven PBDE congeners were detected in some of the
procedural and field blanks in this study (TeBDE-47, PeBDE-99,
PeBDE-100, NoBDE-206, NoBDE-207, NoBDE-208, and DcBDE-
209); however, their concentration never exceeded their concen-
(38) U.S. EPA Test Method 8290, 1994. Polychlorinated Dibenzo-p-Dioxins
(PCDDs) and Polychlorinated Dibenzofurans (PCDFs) by High-Resolution
Gas Chromatography/High Resolution Mass Spectrometry (HRGC/
HRMS); Office of Solid Waste and Emergency Response, Environmental
Protection Agency: Washington, DC, 1994.
(39) U.S. EPA. Method 1614, 2007. Brominated Diphenyl Ethers in Water, Soil,
Sediment and Tissue by HRGC/HRMS; Office of Science and Technology,
Environmental Protection Agency: Washington, DC, 2007.
(40) Pirard, C.; De Pauw, E.; Focant, J.-F. J. Chromatogr., A 2003, 998, 169–
181.
(41) Karlsson, M.; Julander, A.; van Bavel, B.; Hardell, L. Environ. Int. 2007,
33, 62–69.
4338 Analytical Chemistry, Vol. 81, No. 11, June 1, 2009
6. trations in the flue gas (total concentration of PBDEs detected in
blanks was on average 2.8% of average total PBDEs detected).
PBDDs/Fs were not detected (<LOD) in the procedural and field
blanks in this study.
Figure 1. Comparison of the extraction solvent effect on recoveries of (a) bromodiphenylethers, extracted overnight in toluene only (TOL/ON)
vs extracted in methylene chloride only for 3.5 h (MeCl2/3.5 h), and (b) brominated dioxins/furans, extracted with toluene overnight only (TOL/
ON) vs extracted with methylene chloride only for 3.5 h (MeCl2/3.5 h), compared to recoveries of chlorinated dioxins/furans extracted with
toluene only (TOL/ON) vs methylene chloride followed by toluene overnight (MeCl2/3.5 h*), respectively. Given recoveries are calculated for the
complete analytical procedure, i.e., after cleanup and fractionation; IS ) internal standard; PBDE no. n ) PBDE IUPAC number. *: PBDD/F )
3.5 h methylene chloride vs toluene only, PCDD/F ) 3.5 h methylene chloride + toluene overnight vs toluene only.
4339
Analytical Chemistry, Vol. 81, No. 11, June 1, 2009
7. Optimization of the HRGC/HRMS System. The selection
of a capillary column for a chromatographic separation of PBDEs
and PBDDs/Fs was aided by several published retention time
(RT) databases and the recent intercalibration studies results.22,42-44
The narrow (0.25 mm) and very long (60 m) 5% phenyl-dimethyl
polysiloxane type columns (DB-5, HP-5) used in present study
served extremely well for separation of mono- through decabro-
minated diphenyl ethers (Figure S-3 of the Supporting Informa-
tion). The use of a 60 m column allowed separation of PBDE
congeners that coelute on shorter columns (e.g., normally co-
eluting HxBDE-156 and -169 were separated on the 60 m DB-5,
as demonstrated on Figure S-3b of the Supporting Information).
More importantly, the use of a 60 m column enabled HRGC
separation of all 2,3,7,8-substituted target PBDFs from their
potentially interfering PBDEs (PBnDFs and PBn+2DE after loss
of 2Br). HRGC separation of target native 2,3,7,8-PBDFs, as
well as 13
C12-labeled 2,3,7,8-PBDFs, from their potentially
interfering PBDE congeners on the 60 m DB-5 capillary column
is shown in Figure 2 (optimum settings for correct retention time
windows were verified experimentally by analyzing window-
defining mixture of mono- through deca-BDE parallel to PBDD/F
standards; chromatograms are available in the Supporting Infor-
mation, Figure S-4).
Because we experienced sensitivity problems in the determi-
nation of DcBDE-209 and octabromodibenzo-p-dioxin/furan (OcB-
DD/F) on the 60 m 5% phenyl/95% dimethyl polysiloxane type
(both HP-5 and DB-5) columns, we decided to use a multicolumn
technique, with a second, shorter, 15 m capillary column. The
use of a shorter column, to reduce PBDEs and PBDDs/Fs
residence time in the GC system, likely minimized thermal
degradation of the highly brominated targets and, together with
optimization of the injection port temperature, has improved
sensitivity for problematic compounds. Retention time windows
of nona- to deca-BDEs against hepta- and octa-BDD/F are available
in the Supporting Information, Figure S-5. Numerous injection
techniques (on-column, PTV, splitless) were successfully used for
bromoorganics analysis.17,19,22
However, due to widespread ac-
cessibility in analytical laboratories, splitless injections with an
autosampler are most often used for analysis of PBDEs and
PBDDs/Fs.17,19,22
The temperature of the injector for splitless
injections is normally between 250 and 300 °C.17,19,22
In this study,
(42) Korytár, P.; Covaci, A.; de Boer, J.; Gelbin, A.; Brinkman, U. J. Chromatogr.,
A 2005, 1065, 239–249.
(43) Wang, Y.; Li, A.; Liu, H.; Zhang, Q.; Ma, W.; Song, W.; Jiang, G.
J. Chromatogr., A 2006, 1103, 314–328.
(44) Liang, X.; Wang, W.; Wu, W.; Schramm, K.-W.; Henkelmann, B.; Oxynos,
K.; Kettrup, A. Chemosphere 2000, 41, 917–921.
Figure 2. HRGC separation of target native PBnDF/13
C12-labeled PBnDF congeners and potentially interfering PBn+2DE - 2Br congeners on
the 60 m DB-5 capillary column; relative retention times (RRTs) are calculated for the first eluting PBDE congener in the group as assigned
based on the PBDE window mix solution (BDE-WD; Wellington Laboratories, Canada) compared to the retention times of all target PBDFs
quantified. *: not present in the calibration standard; assignment based on isotope theoretical ratios and retention times of OBDD.
4340 Analytical Chemistry, Vol. 81, No. 11, June 1, 2009
8. optimal sensitivity for lower and higher brominated compounds
was achieved when the temperature of the injection port was set
at 300 °C for 2 µL splitless injection. Higher (320 °C) and lower
(270 °C) injection port temperatures tested in this study resulted
in poorer sensitivity. The high temperature (>320 °C) is often
reported to promote degradation of highly brominated com-
pounds, especially DcBDE, whereas lower temperature of the
injection port might have had a negative effect on volatilization
efficiency of compounds with high molecular mass.19,21,22,25
The
temperature of the ion source has not been optimized in our study;
it has been set at 280 °C based on literature data.17
After the
adaptation of the HRGC system, the electron impact (EI)-HRMS
detection method used in this project has resulted both in good
sensitivity (femto- to picogram per microliter instrumental detec-
tion limits) and selectivity (Supporting Information, Figures S-6-S-
8).
Validation of the Method. The optimized method allowed
quantitative determination of 56 mono- through decabromodiphe-
nylether congeners, 17 congeners of tri- to octabromodibenzo-p-
dioxin and furan (13 congeners substituted in 2,3,7,8-positions),
and all 210 polychlorinated dibenzo-p-dioxins and furans at levels
of picogram to microgram per normalized cubic meter of flue gas
(average total concentrations of all target compounds in the flue
gas are given at Figure S-9 of the Supporting Information;
concentrations of analytes in the flue gas varied significantly
during steady state and transients operating condition of the MWC
boiler tested).45,46
The recovery rates were 77.7% (±11.7% SD) for
di- through deca-13
C12-labeled BDEs internal standards (the
mean recovery of mono-13
C12-labeled BDE internal standard
were below 10%), 79% (±17.1% SD) for tetra- through octa-13
C12-
labeled PCDDs/Fs, and 85.8% (±14% SD) for tetra- through
octa-13
C12-labeled PBDDs/Fs, respectively (the mean recovery
of tri-13
C12-labeled BDF internal standard was below 60%).
The linear dynamic range, repeatability, and reproducibility
of the final instrumental method was tested with satisfactory
results. Five-point calibration curve concentrations, correlation
coefficients, relative response factors (RRFi’s), and repeatability
in relative standard deviations for brominated compounds analyzed
by isotope dilution compounds are given in Table 1. Results for
the complete set of analytes are given in Tables S-3 and S-4 of
the Supporting Information.
Conclusions. The analytical method developed enables sam-
pling and determination of the broad spectrum of brominated and
chlorinated dioxins, as well as bromodiphenylethers, including
the rarely analyzed coplanar PBDEs, in flue gases from MWCs
and other combustion/thermal sources. After employment of
additional standards and availability of PBDD/F window-defining
solutions, our method should be easily extended to analysis of
remaining 2,3,7,8-PBDDs/Fs that have not been reported in the
present study, as well as PBDDs/Fs congeners with different
substitution patterns. Upon future more wide availability of
PBCDDs/Fs standards, the method should be suitable for analysis
of mixed bromochlorodibenzo-p-dioxins and furans by isotope
dilution and HRGC/HRMS, as this rarely investigated class of
compounds has physicochemical properties similar to both
PCDDs/Fs and PBDDs/Fs. There are very few standard method
guidelines for acceptable recoveries of PBDEs and PBDDs/Fs in
environmental matrixes; the results of this study are well within
the range of recoveries suggested for 13
C12-labeled PBDE internal
standards in the U.S. EPA Method 1614 (25-200%).39
Our
results are also not only in the range reported in recent
intercalibration studies (40-120%) but also within the values
as acceptable thresholds, i.e., between 70% and 120%.17,22
The
integrated analytical protocol allows isolation of the different
groups of analytes from the same sample, their relatively rapid
(45) Wyrzykowska, B.; Gullett, B. K.; Tabor, D.; Touati, A. Organohalogen Compd.
2008, 70, 62–65.
(46) Gullett, B. K.; Touati, A.; Oudejans, L.; Tabor, D. Organohalogen Compd.
2008, 70, 481–484.
Table 1. Summary of the PBDE and PBDD/F Isotope Dilution Analysis, Concentration Range Where Linearity Was
Tested (Five-Point Calibration Curve, CS-1-CS-5), R2
(Correlation Coefficient), RRFi, (Relative Response Factor of
Analyte i), and Repeatability (Short-Term Relative Standard Deviation Estimated Based on 10-Times Analysis of
Middle Concentration [CS-3] PBDE and PBDD/F Calibration Standard)a
congener IUPAC no. CS-1-CS-5 dynamic range (ng·mL-1
) R2
RRFi (mean) repeatability (RSD %)
4-MoBDE 3 10-100 0.998 0.865 1.6
4,4′-DiBDE 15 10-100 0.998 0.603 0.91
2,4,4′-TriBDE 28 10-100 0.998 0.931 0.80
2,2′,4,4′-TeBDE 47 20-200 0.998 0.891 1.0
2,2′,4,4′,5-PeBDE 99 20-200 0.998 0.919 0.83
2,2′,3,4,4′,5′-HxBDE 138 20-200 0.997 0.974 4.3
2,2′,4,4′,5,5′-HxBDE 153 20-200 0.997 0.811 2.1
2,2′,3,4,4′,5′,6-HpBDE 183 40-400 0.998 0.857 2.4
2,2′,3,3′,4,4′,6,6′-OcBDE 197 40-400 0.999 0.827 2.8
2,2′,3,3′,4,4′,5,6,6′-NoBDE 207 100-1000 0.998 0.902 2.3
DcBDEb
209 100-1000 0.983 0.282 5.5
2,3,7,8-TeBDD 50-500 0.998 0.808 3.1
2,3,7,8-TeBDF 50-500 0.993 1.012 3.2
1,2,3,7,8,9-HxBDDc
50-500 0.994 1.599 6.0
OcBDD 50-500 0.976 0.864 9.2
a
Relative response factor (RRFi) of the native PCDDs/Fs, PBDDs/Fs, and PBDEs (As) in the calibration standard was relative to its labeled
internal standard (Ais) and was determined using the area responses of both the primary and secondary exact m/z’s of compound specified in
Supporting Information Table S-2 for each calibration standard, as follows: RRFi ) (A1s + A2s)Cis/(A1is + A2is)Cs, where A1s and A2s ) the
measured areas at the primary and secondary m/z for the target, A1is and A2is ) the measured areas at the primary and secondary m/z for the
internal standard, Cis ) the concentration of the internal standard, and Cs ) the concentration of the compound in the calibration standard. b
RRF
against 13
C12-labeled NoBDE which was used for quantification of DcBDE (due to observed variability between different lots of 13
C12-labeled DecaBDE
standard). c
RRF against 13
C12-labeled 1,2,3,7,8,9-HxBDD from 13
C12-labeled 1,2,3,6,7,8/1,2,3,7,8,9-HxBDD solution.
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Analytical Chemistry, Vol. 81, No. 11, June 1, 2009
9. automated fractionation, and improvement in the overall cost- and
time-effectiveness, without jeopardizing accuracy and robustness.
Our comprehensive congener-specific analysis tool will enable
a better understanding of “end-of-life products of brominated flame
retardants” in a waste stream and will provide much needed
information on levels, fate, and behavior of bromoorganics during
incineration of waste containing PBDEs to allow a more compre-
hensive picture about routes of human exposure to brominated
dioxins and brominated dioxin-like compounds.
ACKNOWLEDGMENT
This research was supported in part by the appointment of
the Postdoctoral Research Program at the National Risk Manage-
ment Research Laboratory, administered by the Oak Ridge
Institute for Science and Education through an Interagency
Agreement between the U.S. Department of Energy and the U.S.
Environmental Protection Agency. The authors thank Dr. Abder-
rahmane Touati (ARCADIS Inc., U.S.A.) for his technical help and
Dr. Heather Stapleton (Duke University) for providing standards
of selected hepta- and octa-BDEs. We want to express special
acknowledgments to all the staff at the MWC sampling site.
SUPPORTING INFORMATION AVAILABLE
Detailed conditions of cleanup and fractionation of target
halogenorganics, SIR chromatograms of all analyzed PBDEs,
HRGC separation tests between PBnDF and PBn+2DE - 2Br
congeners on 15 and 60 m DB5 columns, compositions of
PBDE/PBDD/PBDF presampling, preinjection, and pre-extrac-
tion spikes, detailed information on m/z selected for SIR
monitoring of PBDE and PBDD/F analytes, compound-specific
calibration data of all analyzed bromoorganics, instrumental
detection and quantification limits (LOD and LOQ), and
average total concentrations of all targets in the combustion
flue gas analyzed. This material is available free of charge via
the Internet at http://pubs.acs.org.
Received for review January 15, 2009. Accepted April 17,
2009.
AC900105A
4342 Analytical Chemistry, Vol. 81, No. 11, June 1, 2009