Lisa Lundin

Emissions of PBDD/Fs, PCDD/Fs and PBDEs from flame-retarded high-impact polystyrene under thermal stress

The emissions of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and their chlorinated analogues (PCDD/Fs) during the thermal treatment of a high impact polystyrene (HIPS) TV casing were investigated. The halogenated compounds were analyzed in the original material and in the gases emitted during its treatment at temperatures between 50 °C and 250 °C. DecaBDE was the primary PBDE in the TV casing, which also contained high levels of PBDFs (ppm range). At the lower treatment temperatures, non-modified PBDEs evaporated from the samples. Conversely, at 200 °C or above, debromination reactions led to the formation of additional tri- through nonaBDE. The formation of new PBDD/Fs was also detected in the gas phase when the plastic was heated to 200 °C or 250 °C, with higher yields of furans than dioxins. This appreciably increased the toxic equivalent (TEQ) levels of the gas phase relative to those seen in the untreated sample. In all cases, the levels and TEQ contributions from PCDD/Fs were negligible compared to those for brominated analogues.

The behavior of PCDD and PCDF during thermal treatment of waste incineration ash

The polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) content of three fly ash samples with different elemental compositions from different municipal waste incinerators were analyzed before and after thermal treatment at 300 °C or 500 °C. Gas phase emissions during the treatments were also collected and analyzed. Substantial reductions in the total PCCD/F content of the ashes were observed after treatment at 500 °C, seemingly due to degradation rather than dechlorination. Treatment at 300 °C resulted in an increase in the PCDD/F content of the three ashes. Initial concentration of PCDD/F in the untreated ashes did not reflect the outcome of the treatment at the different temperatures. In addition, the composition of the ash was found to influence the rate of decomposition and formation of PCDD and PCDF during thermal treatment; the results showed that Cu, Fe, Ca and S play important roles in these processes.

Reduction of PCDD, PCDF and PCB during co-combustion of biomass with waste products from pulp and paper industry.

The use of waste wood as an energy carrier has increased during the last decade. However, elevated levels of alkali metals and chlorine in waste wood compared to virgin biomass can cause increased deposit formation and higher concentrations of organic pollutants. In this study, we investigated the effect of the ChlorOut technique on concentrations of organic pollutants. Ammonium sulfate was injected into the combustion system to inhibit formation of KCl (which causes deposits) and persistent organic pollutants, namely polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs). The results showed that concentrations of the toxic congeners of PCDD, PCDF and PCB decreased in the presence of ammonium sulfate.

The effects of fuel composition and ammonium sulfate addition on PCDD, PCDF, PCN and PCB concentrations during the combustion of biomass and paper production residuals

The use of waste wood as an energy carrier has increased during the last decade. However, the higher levels of alkali metals and chlorine in waste wood compared to virgin biomass can promote the formation of deposits and organic pollutants. Here, the effect of fuel composition and the inhibitory effects of ammonium sulfate, (NH4)2SO4, on the concentrations of persistent organic pollutants (POPs) in the flue gas of a lab-scale combustor was investigated. Ammonium sulfate is often used as a corrosion-preventing additive and may also inhibit formation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). In addition to PCDDs and PCDFs, polychlorinated naphthalenes (PCN) and biphenyls (PCB) were also analyzed. It was found that the flue gas composition changed dramatically when (NH4)2SO4 was added: CO, SO2, and NH3 levels increased, while those of HCl decreased to almost zero. However, the additives effects on POP formation were less pronounced. When (NH4)2SO4 was added to give an S:Cl ratio of 3, only the PCDF concentration was reduced, indicating that this ratio was not sufficient to achieve a general reduction in POP emissions. Conversely, at an S:Cl ratio of 6, significant reductions in the WHO-TEQ value and the PCDD and PCDF contents of the flue gas were observed. The effect on the PCDF concentration was especially pronounced. PCN formation seemed to be promoted by the elevated CO concentrations caused by adding (NH4)2SO4.

Persistent Organic Pollutants in Streamwater: Influence of Hydrological Conditions and Landscape Type

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and hexachlorobenzene (HCB) in streamwater were measured in a remote catchment in northern Sweden and downstream to the Baltic Sea. Sampling took place at seven sites during two years and under different hydrological conditions: during the snow-free, snow-covered, and spring-flood seasons. Concentrations varied substantially between seasons and were up to 20 times higher during the spring flood compared to the preceding snow-covered period. The increase in concentrations with runoff was due to higher levels of particle-associated contaminants, while the dissolved concentrations remained stable. Particulate-contaminant concentrations were positively correlated primarily to suspended particulate matter (SPM) at sites in areas with a high land-cover fraction of sorted sediment. When upstream sampling locations were compared, a mire-dominated stream had higher concentrations and a lower retention of atmospherically deposited contaminants than a forest stream of the same catchment size. Contaminant concentrations (normalized to volume) did not increase consistently downstream despite the presence of several point sources. However, when normalized to the amount of SPM, concentrations were on average >20 times higher at the outlet in the Baltic Sea compared to the outlet from the remote catchment without point sources.

Low temperature thermal degradation of PCDD/Fs in soil using nanosized particles of zerovalent iron and CaO.

This study investigated the degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in contaminated soil using low temperature treatment (200-280°C) both alone and in combination with nanosized zerovalent iron (nZVI) particles or CaO. Control soil samples and soil fortified with nZVI particles or CaO were treated at 200 and 250°C in sealed glass ampoules. Treatment of the ampouled samples at 250°C was more effective than treatment at 200°C and the reduction in PCDD/F concentration was greatest when soil was treated at 250°C with nZVI addition (indeed, treatment at 200°C in the absence of nZVI resulted in increases in total PCDD and PCDD/F concentrations). In larger-scale experiments based on the obtained results, using a rotary furnace, the greatest reduction in total PCDD/F concentration was achieved by treating soil at 280°C, and adding nZVI to the soil resulted in almost no detectable PCDD/F in the gas phase.

In-filter PCDF and PCDD formation at low temperature during MSWI combustion

This case study investigated PCDF and PCDD emissions from a 65 MW waste-to-energy plant to identify why an air pollution control system remodeling to accommodate increased production resulted in increased TEQ concentrations. Pre- and post-filter gases were collected simultaneously in four sample sets with varying filter temperatures and with/without activated carbon injection. Samples were analyzed to determine total PCDF and PCDD concentrations, as well as homologue profiles, and concentrations of individual congeners (some remained co-eluted). The total post filter PCDD concentrations where found to increase while the concentrations of PCDF and 2,3,7,8-substituted congeners declined. An investigation of the individual congener concentrations revealed that the increase of PCDD concentrations were due to a few congeners, suggesting a single formation route. The study also concludes that vital information about the formation could be obtained by not restricting the analysis to just the 2,3,7,8-substituted congeners.

14th congress of combustion by-products and their health effects—origin, fate, and health effects of combustion-related air pollutants in the coming era of bio-based energy sources

The 14th International Congress on Combustion By-Products and Their Health Effects was held in Umeå, Sweden from June 14th to 17th, 2015. The Congress, mainly sponsored by the National Institute of Environmental Health Sciences Superfund Research Program and the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning, focused on the “Origin, fate and health effects of combustion-related air pollutants in the coming era of bio-based energy sources”. The international delegates included academic and government researchers, engineers, scientists, policymakers and representatives of industrial partners. The Congress provided a unique forum for the discussion of scientific advances in this research area since it addressed in combination the health-related issues and the environmental implications of combustion by-products. The scientific outcomes of the Congress included the consensus opinions that: (a) there is a correlation between human exposure to particulate matter and increased cardiac and respiratory morbidity and mortality; (b) because currently available data does not support the assessment of differences in health outcomes between biomass smoke and other particulates in outdoor air, the potential human health and environmental impacts of emerging air-pollution sources must be addressed. Assessment will require the development of new approaches to characterize combustion emissions through advanced sampling and analytical methods. The Congress also concluded the need for better and more sustainable e-waste management and improved policies, usage and disposal methods for materials containing flame retardants.

Accurate sampling of PCDD/F in high temperature flue-gas using cooled sampling probes

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700°C and 400°C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700°C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400°C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700°C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe. Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.