Thermal treatment of municipal solid waste incineration fly ash: Impact of gas atmosphere on the volatility of major, minor, and trace elements.

Development of thermal processes for selective recovery of Zn and other valuable elements from municipal solid waste incineration (MSWI) fly ash requires comprehensive knowledge of the impact of gas atmosphere on the volatile behaviour of the element constituents of the ash at different reaction temperatures. This study assesses the partitioning of 18 elements (Al, As, Bi, C, Ca, Cd, Cl, Cu, K, Mg, Na, P, Pb, S, Sb, Sn, Ti, and Zn) between condensed and gaseous phases during thermal treatment of MSWI fly ash in both oxidising gas and reducing gas atmospheres, at different temperatures spanning the range 200-1050 °C. The operating atmosphere had major impacts on the partitioning of the following elements: As, Bi, C, Cd, Cu, Na, Pb, S, Sb, Sn, and Zn. The partitioning of these elements cannot be accurately predicted over the full range of investigated operating conditions with global thermodynamic equilibrium calculations alone, i.e. without also considering chemical kinetics and mass transfer. In oxidising conditions, the following elements were predominately retained in condensed phases, even at high temperatures: As, Bi, Sb, Sn, and Zn. All these elements, except As, were largely released to the gas phase (>70%) at high temperatures in reducing conditions. The impact of gas atmosphere on the volatility of Cd and Pb was greatest at low reaction temperatures (below ~750 °C). Results for volatile matrix elements, specifically C, Cl, K, Na, and S, are interpreted in terms of the mechanisms governing the release of these elements to the gas phase.

Air quality intervention during the Nanjing youth olympic games altered PM sources, chemical composition, and toxicological responses.

Ambient particulate matter (PM) is a leading global environmental health risk. Current air quality regulations are based on airborne mass concentration. However, PM from different sources have distinct chemical compositions and varied toxicity. Connections between emission control measures, air quality, PM composition, and toxicity remain insufficiently elucidated. The current study assessed the composition and toxicity of PM collected in Nanjing, China before, during, and after an air quality intervention for the 2014 Youth Olympic Games. A co-culture model that mimics the alveolar epithelium with the associated macrophages was created using A549 and THP-1 cells. These cells were exposed to size-segregated inhalable PM samples. The composition and toxicity of the PM samples were influenced by several factors including seasonal variation, emission sources, and the air quality intervention. For example, we observed a size-dependent shift in particle mass concentrations during the air quality intervention with an emphasized proportion of smaller particles (PM2.5) present in the air. The roles of industrial and fuel combustion and traffic emissions were magnified during the emission control period. Our analyses revealed that the PM samples demonstrated differential cytotoxic potencies at equal mass concentrations between sampling periods, locations, and time of day, influenced by variations in the predominant emission sources. Coal combustion and industrial emissions were the most important sources affecting the toxicological responses and displayed the least variation in emission contributions between the sampling periods. In conclusion, emission control mitigated cytotoxicity and oxidative stress for particles larger than 0.2 µm, but there was inadequate evidence to determine if it was the key factor reducing the harmful effects of PM0.2.

The effect of the shoeless course on particle concentrations and dust composition in schools.

Airborne particles may effect on indoor air quality in schools. One significant particle source is outdoor dust and soil transported indoors on people's shoes, which may be resuspended, and further inhaled by pupils and teachers. In many Finnish schools, shoes are taken off by coat racks near the classrooms (shoe schools). The new course of action is to take shoes off right when entering the building (sock schools). In this study, particle mass and number concentrations, together with chemical composition of the dust were investigated in sock and shoe schools. According to results, PM10 and PM15 concentrations in corridors were significantly higher in shoe schools compared to sock schools (p < 0.05). The shoeless course did not affect on the particle number concentrations, but the increases in the number concentrations originated from diners. The elemental concentrations (Li, Al, Si, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, Pb) in settled dust were also higher in shoe schools compared to sock schools, and the Zn concentrations differed significantly (p < 0.05). In conclusion, this study showed that by taking the shoes off when entering the school building you can enhance the indoor air quality by reducing the particle mass concentrations.

Volatilisation of major, minor, and trace elements during thermal processing of fly ashes from waste- and wood-fired power plants in oxidising and reducing gas atmospheres.

This study assesses the volatility of 15 elements (As, Bi, C, Cd, Cl, Cu, K, Mn, Na, P, Pb, S, Sb, Sn, and Zn) during thermal processing of fly ashes obtained from four waste-to-energy plants and one wood-combustion plant. Differences in volatility in oxidising and reducing atmospheres (air and 10% H2/90% N2) were assessed at two temperatures, 700 and 1000 °C. P and Mn were predominately retained in all ashes regardless of the operating atmosphere and temperature. Other elements showed significant variation in volatility depending on the type of fly ash, atmosphere, and temperature. Heat-treatment of the wood-combustion fly ash in the air atmosphere resulted in low release of K, Na, and all investigated heavy metals and metalloids. Several valuable elements, including Zn, Sb, Sn, and Bi, were significantly more volatile in the reducing atmosphere than in the oxidising atmosphere, particularly at 1000 °C. Other elements were either less volatile, equally volatile, or only marginally more volatile when the ashes were heated at 1000 °C in the reducing atmosphere. These elements include C, Cl, Cu, and, in the case of fly ashes derived from municipal solid waste, Cd and Pb. A two-step process, in which municipal solid waste incineration fly ash is first heated in an oxidising atmosphere and then in a reducing atmosphere, is proposed for production of a chloride-free zinc concentrate. Evaluation of the two-step process at 880 °C shows good potential for selective volatilisation of Zn with other valuable elements, including Sn, Sb, and Bi.

PM2.5 concentration and composition in the urban air of Nanjing, China: Effects of emission control measures applied during the 2014 Youth Olympic Games.

Industrial processes, coal combustion, biomass burning (BB), and vehicular transport are important sources of atmospheric fine particles (PM2.5) and contribute to ambient air concentrations of health-hazardous species, such as heavy metals, polycyclic aromatic hydrocarbons (PAH), and oxygenated-PAHs (OPAH). In China, emission controls have been implemented to improve air quality during large events, like the Youth Olympic Games (YOG) in August 2014 in Nanjing. In this work, six measurement campaigns between January 2014 and August 2015 were undertaken in Nanjing to determine the effects of emission controls and meteorological factors on PM2.5 concentration and composition. PAHs, OPAHs, hopanes, n­alkanes, heavy metals, and several other inorganic elements were measured. PM2.5 and potassium concentrations were the highest in May-June 2014 indicating the prevalence of BB plumes in Nanjing. Emission controls substantially reduced concentrations of PM2.5 (31%), total PAHs (59%), OPAHs (37%), and most heavy metals (44-89%) during the YOG compared to August 2015. In addition, regional atmospheric transport and meteorological parameters partly explained the observed differences between the campaigns. The most abundant PAHs and OPAHs were benzo[b,k]fluoranthenes, fluoranthene, pyrene, chrysene, 1,8­naphthalic anhydride, and 9,10­anthracenedione in all campaigns. Carbon preference index and the contribution of wax n­alkanes indicated mainly biogenic sources of n­alkanes in May-June 2014 and anthropogenic sources in the other campaigns. Hopane indexes pointed to vehicular transport as the major source of hopanes, but contribution of coal combustion was detected in winter 2015. The results provide evidence to the local government of the impacts of the air protection regulations. However, differences between individual components were observed, e.g., concentrations of potentially more harmful OPAHs decreased less than concentrations of PAHs. The results suggest that the proportions of hazardous components in the PM2.5 may also change considerably due to emission control measures.

Emissions and atmospheric processes influence the chemical composition and toxicological properties of urban air particulate matter in Nanjing, China.

Ambient inhalable particulate matter (PM) is a serious health concern worldwide, but especially so in China where high PM concentrations affect huge populations. Atmospheric processes and emission sources cause spatial and temporal variations in PM concentration and chemical composition, but their influence on the toxicological characteristics of PM are still inadequately understood. In this study, we report an extensive chemical and toxicological characterization of size-segregated urban air inhalable PM collected in August and October 2013 from Nanjing, and assess the effects of atmospheric processes and likely emission sources. A549 human alveolar epithelial cells were exposed to day- and nighttime PM samples (25, 75, 150, 200, 300 µg/ml) followed by analyses of cytotoxicity, genotoxicity, cell cycle, and inflammatory response. PM10-2.5 and PM0.2 caused the greatest toxicological responses for different endpoints, illustrating that particles with differing size and chemical composition activate distinct toxicological pathways in A549 cells. PM10-2.5 displayed the greatest oxidative stress and genotoxic responses; both were higher for the August samples compared with October. In contrast, PM0.2 and PM2.5-1.0 samples displayed high cytotoxicity and substantially disrupted cell cycle; August samples were more cytotoxic whereas October samples displayed higher cell cycle disruption. Several components associated with combustion, traffic, and industrial emissions displayed strong correlations with these toxicological responses. The lower responses for PM1.0-0.2 compared to PM0.2 and PM2.5-1.0 indicate diminished toxicological effects likely due to aerosol aging and lower proportion of fresh emission particles rich in highly reactive chemical components in the PM1.0-0.2 fraction. Different emission sources and atmospheric processes caused variations in the chemical composition and toxicological responses between PM fractions, sampling campaigns, and day and night. The results indicate different toxicological pathways for coarse-mode particles compared to the smaller particle fractions with typically higher content of combustion-derived components. The variable responses inside PM fractions demonstrate that differences in chemical composition influence the induced toxicological responses.

Peak exposures to main components of ash and gaseous diesel exhausts in closed and open ash loading stations at biomass-fuelled power plants.

Fly and bottom ashes are collected at power plants to reduce the environmental effects of energy production. However, handling the ashes causes health problems for operators, maintenance workers and truck drivers at the power plants. Hence, we evaluated ash loaders' peak inhalation exposures to the chemical components of ash and diesel exhausts in open and closed ash loading stations at biomass-fuelled combined heat and power plants. We also carried out chemical and morphological analyses of the ashes to evaluate their health hazard potential in order to find practical technical measures to reduce workers' exposure. On the basis of X-ray diffraction analyses, the main respirable crystalline ash compounds were SiO2, CaSO4, CaO, Ca2Al2SiO7, NaCl and Ca3Al2O6 in the fly ashes and SiO2, KAlSi3O8, NaAlSi3O8 and Ca2Al2SiO7 in the bottom ashes. The short-term exposure levels of respirable crystalline silica, inhalable inorganic dust, Cr, Mn, Ni and nitric oxide exceeded their Finnish eight hours occupational exposure limit values in the closed ash loading station. According to our observations, more attention should be paid to the ash-moistening process, the use of tank trucks instead of open cassette flatbed trucks, and the sealing of the loading line from the silo to the truck which would prevent spreading the ash into the air. The idling time of diesel trucks should also be limited, and ash loading stations should be equipped with exhaust gas ventilators. If working conditions make it impossible to keep to the OEL values, workers must use respirators and protect their eyes and skin.

In vitro toxicological effects of zinc containing nanoparticles with different physico-chemical properties.

Nanomaterials (NM) exhibit novel physicochemical properties that determine their interaction with biological substrates and processes. Recent nano-technological advances are leading to wide usage of metallic nanoparticles (NPs) in various fields. However, the increasing use of NPs has led to their release into environment and the toxicity of NPs on human health has become a concern. Moreover, there are inadvertently generated metallic NPs which are formed during various human activities (e.g. metal processing and energy production). Unfortunately, there are still widespread controversies and ambiguities with respect to the toxic effects and mechanisms of metallic NPs, e.g. metal oxides including ZnO. In this study, we generated zinc containing NMs, and studied them in vitro. Different nano-sized particles containing Zn were compared in in vitro study to elucidate the physicochemical characteristics (e.g. chemical composition, solubility, shape and size of the particles) that determine cellular toxicity. Zn induced toxicity in macrophage cell line (RAW 264.7) was detected, leading to the cell cycle disruption, cell death and excitation of release of inflammatory mediators. The solubility and the size of Zn compounds had a major role in the induced toxic responses. The soluble particles reduced the cell viability, whereas the less soluble NPs significantly increased inflammation. Moreover, uptake of large ZnO NPs inside the cells was likely to play a key role in the detected cell cycle arrest.

Particulate emissions from the combustion of birch, beech, and spruce logs cause different cytotoxic responses in A549 cells.

According to the World Health Organization particulate emissions from the combustion of solid fuels caused more than 110,000 premature deaths worldwide in 2010. Log wood combustion is the most prevalent form of residential biomass heating in developed countries, but it is unknown how the type of wood logs used in furnaces influences the chemical composition of the particulate emissions and their toxicological potential. We burned logs of birch, beech and spruce, which are used commonly as firewood in Central and Northern Europe in a modern masonry heater, and compared them to the particulate emissions from an automated pellet boiler fired with softwood pellets. We determined the chemical composition (elements, ions, and carbonaceous compounds) of the particulate emissions with a diameter of less than 1 µm and tested their cytotoxicity, genotoxicity, inflammatory potential, and ability to induce oxidative stress in a human lung epithelial cell line. The chemical composition of the samples differed significantly, especially with regard to the carbonaceous and metal contents. Also the toxic effects in our tested endpoints varied considerably between each of the three log wood combustion samples, as well as between the log wood combustion samples and the pellet combustion sample. The difference in the toxicological potential of the samples in the various endpoints indicates the involvement of different pathways of toxicity depending on the chemical composition. All three emission samples from the log wood combustions were considerably more toxic in all endpoints than the emissions from the pellet combustion. © 2016 Wiley Periodicals, Inc. Environ Toxicol 32: 1487-1499, 2017.