Determination of polybrominated diphenyl ethers and PBDD/Fs during the recycling of high impact polystyrene containing decabromodiphenyl ether and antimony oxide

A high impact polystyrene (HIPS) plastic, flame retarded with decabromodiphenyl ether (DecaBDE) and antimony trioxide (Sb2O3) has been repeatedly processed and the amount of debromination of the flame retardant and possible formation of PBDD/F was monitored. No indications of debromination were found. The reprocessed (recycled) plastic was found to comply with the German Chemicals Banning Ordinance. The concentrations of relevant PBDD/F congeners were at least one order of magnitude below the regulated limit values for PBDD/F (1 ppb for the sum of four congeners, 5 ppb for the sum of all eight regulated congeners).     

Vegetation fire emissions and their impact on air pollution and climate

Gaseous and particulate emissions from vegetation fires substantially modify the atmospheric chemical composition, degrade air quality and can alter weather and climate. The impact of vegetation fire emissions on air pollution and climate has been recognised in the late 1970s. The application of satellite data for fire-related studies in the beginning of the 21th century represented a major break through in our understanding of the global importance of fires. Today the location and extent of vegetation fires, burned area and emissions released from fires are determined from satellite products even though many uncertainties persist. Numerous dedicated experimental and modeling studies contributed to improve the current knowledge of the atmospheric impact of vegetation fires. The motivation of this paper is to give an overview of vegetation fire emissions, their environmental and climate impact, and what improvements can be expected in the near future.     

Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures

Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2′,4,4′-tetrabromo diphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 °C and 500 °C. The formed reaction products were analysed by high resolution gas chromatography–low resolution mass spectrometry (HRGC-LRMS). Among others brominated–chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated–chlorinated benzenes.     

A comparison of the properties of the major commercial PBDPO/PBDE product to those of major PBB and PCB products

Decabromodiphenyl oxide (DBDPO), a highly effective polybrominated diphenyl oxide (PBDPO) flame retardant (FR) used primarily in electrical and electronic equipment, is the second highest volume brominated flame retardant (BFR) and accounts for 82% of the PBDPO usage globally. The apparent similarities in chemical structure between the DBDPO, polychlorinated and polybrominated biphenyl (PCB, PBB) molecules have led to the presumption that these substances also share similar toxicological and environmental properties. However, DBDPO's physical/chemical properties, applications, environmental release, and toxicology differ substantially from the former PCB/PBB products. DBDPO is a heavier and larger molecule than components of the predominant PCB/PBB products used in the past, and the commercial DBDPO product has a lower water solubility and vapor pressure than the former PCB and PBB products. DBDPO's detection in the environment is generally in sediments near known point sources, and its primary use in thermoplastics limits its environmental release from end products. PBB environmental release has been primarily associated with one accident occurring in the US in 1973. The PCBs, used in applications with a high potential for environmental release, were detected in diverse locations around the world as early as in the 1970s. Current releases of PCB are considered related to an environmental cycling process of congeners previously released into the environment; however, DBDPO's physical/chemical properties do not indicate a similar potential. Extensive testing of the DBDPO commercial product has demonstrated that it is toxicologically and pharmacokinetically different from the predominant PCB and PBB products used in the past. Thus, although the chemical structures of DBDPO, PBB, and PCB appear similar, the properties of DBDPO are distinctly different.     

An overview of brominated flame retardants in the environment

The presence of brominated flame retardant (BFR) chemicals, and particularly polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD), has become of increasing concern to scientists over the past decade. Environmental studies conducted primarily in Europe, Japan and North America indicate that these chemicals are ubiquitous in sediment and biota. The levels of PBDEs seem to be increasing, and several trends, including in humans, indicate that this increase may be rapid. The occurrence of high concentrations of certain PBDE isomers may be sufficient to elicit adverse effects in some wildlife. There is also concern that levels could cause adverse effects in sensitive human populations such as young children, indigenous peoples, and fish consumers. However, our knowledge about these chemicals, their sources, environmental behavior, and toxicity is limited, making risk assessment difficult. In this paper, the current state of knowledge is reviewed and areas for further research recommended to improve future monitoring and risk assessment efforts.     

Emissions from an automobile fire

The emissions from automobile fires have been investigated. The main gas phase components were analysed in small-scale tests with representative material from an automobile. A more detailed investigation of full-scale simulated automobile fires was also conducted, including the characterisation of gas phase components, particulates and run-off water from extinguishing activities. Three separate full scale fire tests have been characterised: a fire ignited and developed in the engine compartment; a fire ignited inside the coupé, that was extinguished in the early stages; and a similar fire ignited inside the coupé that was allowed to spread until the entire vehicle was involved in the fire. The quantitative analysis of the smoke gases from the full-scale fires showed that emissions with a potentially negative impact on the environment, or chronic toxic effect on humans, were produced in significant quantities. These emissions included HCl, SO2, VOCs (e.g. benzene), PAHs, and PCDDs/PCDFs. Analysis of run-off water indicated that it was severely contaminated, containing elevated levels of both organic compounds and metals. Comparison with data from other vehicle fires found in the literature shows that contamination by lead, copper, zinc, and antimony appears to be significant in water run-off from these types of fires.     

Impacts of prescribed fires and benefits from their reduction for air quality,health, and visibility in the Pacific Northwest of the United States

Using a WRF-SMOKE-CMAQ modeling framework, we investigate the impacts of smoke from prescribed fires on model performance, regional and loc al air quality, health impacts, and visibility in protected natural environments using three different prescribed fire emission scenarios: 100% fire, no fire, and 30% fire. The 30% fire case reflects a 70% reduction in fire activities due to harvesting of logging residues for use as a feedstock for a potential aviation biofuel supply chain. Overall model performance improves for several performance metrics when fire emissions are included, especially for organic carbon, irrespective of the model goals and criteria used. This effect on model performance is more pronounced for the rural and remote IMPROVE sites for organic carbon and total PM_2.5. A reduction in prescribed fire emissions (30% fire case) results in significant improvement in air quality in areas in western Oregon, northern Idaho, and western Montana, where most prescribed fires occur. Prescribed burning contributes to visibility impairment, and a relatively large portion of protected class I areas will benefit from a reduced emission scenario. For the haziest 20% days, prescribed burning is an important source of visibility impairment, and approximately 50% of IMPROVE sites in the model domain show a significant improvement in visibility for the reduced fire case. Using BenMAP, a health impact assessment tool, we show that several hundred additional deaths, several thousand upper and lower respiratory symptom cases, several hundred bronchitis cases, and more than 35,000 workday losses can be attributed to prescribed fires, and these health impacts decrease by 25–30% when a 30% fire emission scenario is considered.

Implications: This study assesses the potential regional and local air quality, public health, and visibility impacts from prescribed burning activities, as well as benefits that can be achieved by a potential reduction in emissions for a scenario where biomass is harvested for conversion to biofuel. As prescribed burning activities become more frequent, they can be more detrimental for air quality and health. Forest residue-based biofuel industry can be source of cleaner fuel with co-benefits of improved air quality, reduction in health impacts, and improved visibility.     

Combustion of brominated flame retardants and behavior of its byproducts

The substance flow rate of PBDDs/DFs into flue gas and incineration residues from incineration of three types of waste samples containing brominated flame retardants were examined. The samples used consisted of PBDEs (a typical retardant), used TV casing materials (actual waste materials), and waste printed circuit boards. PBDDs/DFs concentrations in the experimental samples of PBDEs/PE, waste TV casing materials and printed circuit boards ranged between 3000 and 130,000 ng/g. These values are very high when compared to other investigations. The increase of chlorine concentration in input sample reduced the ratio of PBDDs/DFs in flue gas and raised the ratio of PCDDs/DFs. With adequate combustion control and flue gas treatment, the amount of PBDDs/DFs released from the incineration of resin containing brominated flame retardants was lower than the input amount. The presence of PBDDs/DFs in incineration residues dominated the total amount of dioxins released. When PBDDs/DFs, PCDDs/DFs and PXDDs/DFs were considered as a total, the total amount released was lower than the total amount input.     

How changing fire management policies affect fire seasonality and livelihoods

There is a long history of fire management in African savannas, but knowledge of historical and current use of fire is scarce in savanna-woodland biomes. This study explores past and present fire management practices and perceptions of the Khwe (former hunter-gatherers) and Mbukushu (agropastoralists) communities as well as government and non-government stakeholders in Bwabwata National Park in north-east Namibia. Semi-structured interviews and focus groups were used in combination with satellite data (from 2000 to 2015), to investigate historical and current fire management dynamics. Results show that political dynamics in the region disrupted traditional fire practices, specifically a policy of fire suppression was initiated by colonial governments in 1888 and maintained during independence until 2005. Both the Khwe and Mbukushu communities use early season (i.e. between April and July) fires for diverse interrelated historical and current livelihood activities, and park management for managing late season fires. The Mbukushu community also use late season burns to prepare land for crops. In this study, we use a pyrogeographic framework to understand the human dimension of fires. This study reveals how today’s fire management practices and policies, specifically the resurgence of early season burning are entrenched in the past. Understanding and acknowledging the social and cultural dynamics of fire, alongside participatory stakeholder engagement is critical for managing fires in the future.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01351-7) contains supplementary material, which is available to authorized users.     

The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer

Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.     

Coordination through databases can improve prescribed burning as a conservation tool to promote forest biodiversity

Prescribed fires are a common nature conservation practice. They are executed by several parties with limited coordination among them, and little consideration for wildfire occurrences and habitat requirements of fire-dependent species. Here, we gathered data on prescribed fires and wildfires in Sweden during 2011–2015 to (i) evaluate the importance and spatial extent of prescribed fires compared to wildfires and (ii) illustrate how a database can be used as a management tool for prescribed fires. We found that on average only 0.006% (prescribed 65%, wildfires 35%) of the Swedish forest burns per year, with 58% of the prescribed fires occurring on clearcuts. Also, both wildfires and prescribed fires seem to be important for the survival of fire-dependent species. A national fire database would simplify coordination and make planning and evaluation of prescribed fires more efficient. We propose an adaptive management strategy to improve the outcome of prescribed fires.     

Accuracy Assessment of EPA Protocol Gases Purchased In 1991

ABSTRACT

Fixed-roof tanks are used extensively at manufacturing, waste management, and other facilities to store or process liquids containing volatile organic compounds. Federal and state air standards require the control of organic air emissions from many of these tanks. A common practice used for some fixed-roof tanks that are required to use controls is to vent the tank through an activated carbon canister. When organic vapors are adsorbed on activated carbon, heat is released. Under certain conditions, the temperature of the carbon bed can increase to a level at which the carbon or organic vapors spontaneously ignite, starting a fire in the carbon bed. Bed fires in carbon canisters are not uncommon and can present a significant safety hazard at facilities if proper safety measures are not implemented. This article discusses how carbon adsorber bed fires occur and presents general guidance on safety measures for carbon canisters installed on fixed-roof tanks to reduce the likelihood of a carbon bed fire and to minimize the impact in the event of a fire.     

A review on the mechanism,risk evaluation,and prevention of coal spontaneous combustion in China

In recent years, the ecology, security, and sustainable development of modern mines have become the theme of coal mine development worldwide. However, spontaneous combustion of coal under conditions of oxygen supply and automatic exothermic heating during coal mining lead to coalfield fires. Coal spontaneous combustion (CSC) causes huge economic losses and casualties, with the toxic and harmful gases produced during coal combustion not only polluting the working environment, but also causing great damage to the ecological environment. China is the world’s largest coal producer and consumer; however, coal production in Chinese mines is seriously threatened by the CSC risk. Because deep underground mining methods are commonly adopted in Chinese coal mines, coupling disasters are frequent in these mines with the coalfield fires becoming increasingly serious. Therefore, in this study, we analyzed the development mechanism of CSC. The CSC risk assessment was performed from the aspects of prediction, detection, and determination of the “dangerous area” in a coal mine (i.e., the area most susceptible to fire hazards). A new geophysical method for CSC determination is proposed and analyzed. Furthermore, the main methods for CSC fire prevention and control and their advantages and disadvantages are analyzed. To eventually construct CSC prevention and control integration system, future developmental direction of CSC was given from five aspects. Our results can present a reference for the development of CSC fire prevention and control technology and promote the protection of ecological environment in China.     

Carbon bed fires and the use of carbon canisters for air emissions control on fixed-roof tanks

Fixed-roof tanks are used extensively at manufacturing, waste management, and other facilities to store or process liquids containing volatile organic compounds. Federal and state air standards require the control of organic air emissions from many of these tanks. A common practice used for some fixed-roof tanks that are required to use controls is to vent the tank through an activated carbon canister. When organic vapors are adsorbed on activated carbon, heat is released. Under certain conditions, the temperature of the carbon bed can increase to a level at which the carbon or organic vapors spontaneously ignite, starting a fire in the carbon bed. Bed fires in carbon canisters are not uncommon and can present a significant safety hazard at facilities if proper safety measures are not implemented. This article discusses how carbon adsorber bed fires occur and presents general guidance on safety measures for carbon canisters installed on fixed-roof tanks to reduce the likelihood of a carbon bed fire and to minimize the impact in the event of a fire.     

Analysis of the impact of the forest fires in August 2007 on air quality of Athens using multi-sensor aerosol remote sensing data,meteorology and surface observations

Data from multiple satellite remote sensors are integrated with ground measurements and meteorological data to study the impact of Greek forest fires in August 2007 on the air quality in Athens. Two pollution episodes were identified by ground PM₁₀ measurements between August 23 and September 4. In the first episode, Evia and Peloponnese fires contributed substantially to the air pollution levels in Athens. In the second episode, transport of industrial pollution from Italy and Western Europe as well as forest fires in Albania contributed substantially to the air pollution levels in Athens. Local air pollution sources also contributed to the observed particle levels during these episodes. Satellite data provide valuable insights into the spatial distribution of particle concentrations, thus they can be used identify pollution sources. In spite of a few weaknesses in current satellite data products identified in this analysis, combining satellite aerosol remote sensing data with trajectory models and ground measurements is a powerful tool to study intensive particle pollution events such as forest fires.     

Prescribed burns and wildfires in Colorado: impacts of mitigation measures on indoor air particulate matter

Wildfires and prescribed burns are receiving increasing attention as sources of fine particulate matter (PM2.5). The goal of this research project was to understand the impact of mitigation strategies for residences impacted by scheduled prescribed burns and wildfires. Pairs of residences were solicited to have PM2.5 concentrations monitored inside and outside of their houses during four fires. The effect of using air cleaners on indoor PM2.5 was investigated, as well as the effect of keeping windows closed. Appropriately sized air cleaners were provided to one of each pair of residences; occupants of all of the residences were asked to keep windows shut and minimize opening of exterior doors. Additionally, residents were asked to record all of the activities that may be a source of particulate matter, such as cooking and cleaning. Measurements were made during one prescribed burn and three wildfires during the 2002 fire season. Outdoor 24-hr average PM2.5 concentrations ranging from 6 to 38 microg/m3 were measured during the fires, compared with levels of 2-5 microg/m3 during background measurements when no fires were burning. During the fires, PM2.5 was < 3 microg/m3 inside all of the houses with air cleaners installed. This corresponds with a decrease of 63-88% in homes with the air cleaners operating when compared with homes without air cleaners. In the homes without the air cleaners, measured indoor concentrations were 58-100% of the concentrations measured outdoors.     

The environmental occurrence of hexabromocyclododecane in Sweden

The brominated flame retardant hexabromocyclododecane (HBCD) is extensively used in Europe, but data on the environmental concentrations of this chemical are scarce. A first screening has been performed concerning the environmental occurrence of HBCD in Sweden, a country where the chemical is not produced and the current industrial use is very limited. Possible emission sources were identified through a systematic analysis of the use in a life cycle perspective. In addition to a few point sources, diffuse emissions from polymeric products are possible. Measurements have been performed close to certain possible point sources, in the urban environment and in remote regions, and included air, deposition, water, soil, sediments, sludge, biota and foodstuffs. HBCD was detected in all media analysed and in all environments. The relatively high concentrations detected in herring and foodstuffs provide evidence for bioaccumulation of HBCD. The presence of HBCD in remote background air implies that HBCD has potential for long-range atmospheric transport. There are also some indications that diffuse emissions of HBCD occur in the urban environment.     

Modelling plume rise and dispersion from pool fires

This paper describes an investigation into the behaviour of smoke plumes from pool fires, and the subsequent generation of empirical models to predict plume rise and dispersion from such a combustion source. Synchronous video records of plumes were taken from a series of small-scale (0.06–0.25m²) outdoor methanol/toluene pool fire experiments, and used to produce sets of images from which plume dimensions could be derived. Three models were used as a basis for the multiple regression analysis of the data set, in order to produce new equations for improved prediction. Actual plume observations from a large (20.7 m×14.2 m) aviation fuel pool fire were also used to test the predictions. The two theoretically based models were found to give a better representation of plume rise and dispersion than the empirical model based on measurements of small-scale fires. It is concluded that theoretical models tested on small-scale fires (heat output ≈70 kW) can be used to predict plume behaviour from much larger combustion sources (heat output ≈70 MW) under near neutral atmospheric conditions.     

Refining fire emissions for air quality modeling with remotely sensed fire counts: A wildfire case study

This paper examines the use of Moderate Resolution Imaging Spectroradiometer (MODIS) observed active fire data (pixel counts) to refine the National Emissions Inventory (NEI) fire emission estimates for major wildfire events. This study was motivated by the extremely limited information available for many years of the United States Environmental Protection Agency (US EPA) NEI about the specific location and timing of major fire events. The MODIS fire data provide twice-daily snapshots of the locations and breadth of fires, which can be helpful for identifying major wildfires that typically persist for a minimum of several days. A major wildfire in Mallory Swamp, FL, is used here as a case study to test a reallocation approach for temporally and spatially distributing the state-level fire emissions based on the MODIS fire data. Community Multiscale Air Quality (CMAQ) model simulations using these reallocated emissions are then compared with another simulation based on the original NEI fire emissions. We compare total carbon (TC) predictions from these CMAQ simulations against observations from the Inter-agency Monitoring of Protected Visual Environments (IMPROVE) surface network. Comparisons at three IMPROVE sites demonstrate substantial improvements in the temporal variability and overall correlation for TC predictions when the MODIS fire data is used to refine the fire emission estimates. These results suggest that if limited information is available about the spatial and temporal extent of a major wildfire fire, remotely sensed fire data can be a useful surrogate for developing the fire emissions estimates for air quality modeling purposes.