Airborne emissions of mercury from municipal solid waste. I: new measurements from six operating landfills in Florida

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg(O)) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from approximately 1-10 ng m(-2) hr(-1) over aged landfill cover, from approximately 8-20 mg/hr from LFG flares (LFG included Hg(O) at microg/m3 concentrations), and from approximately 200-400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg(O), the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10-50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.     

Chromium occurrence in the environment and methods of its speciation

This article includes a survey of chromium (Cr) occurrence in different environmental compartments, its pathways in the environment and the cross-sectional presentation of Cr speciation methods against the background of Cr chemistry. The aim of the article is to demonstrate that knowledge of interconversion processes between different Cr forms is necessary to understand its behaviour and role in the environment, in addition to enabling reliable Cr speciation analysis to be performed. The current methods of Cr speciation are presented, characterized and their usefulness discussed. These must rely on superior separation and detection capabilities since Cr in environmental compartments is mostly at trace or ultra-trace level. The need for using unique techniques of sampling, storage, handling and separation for Cr speciation is documented.     

Sulfur processing in the marine atmospheric boundary layer: A review and critical assessment of modeling uncertainties

Sulfur is an extremely motile and vital element in the Earth's biogeochemical environment, one whose active redox chemistry maintains small reservoirs in the atmosphere and biosphere yet large fluxes through both. Essential for life, intimately linked to the climate state, and an important component of air quality, sulfur and its transport and processing in the atmosphere have been the subject of active research for several decades. This review article describes the current state of our understanding of the atmospheric sulfur cycle, focusing on the marine atmospheric boundary layer, with the aim of identifying the largest roots of uncertainty that most inhibit accurate simulation of sulfur cycling in the atmosphere. An overview of the emissions by phytoplankton and shipping, dispersion and entrainment in the marine boundary layer, and chemical processing by aerosols, clouds, and dry deposition is presented. Analysis of 20 contemporary modeling studies suggests that the greatest ambiguity in global sulfur cycling derives from (in descending order) wet deposition of aerosol sulfate, dry deposition of sulfur dioxide to the Earth's surface, and the heterogeneous oxidation of SO₂ in aerosols and clouds.     

Ocean to continent transfer of atmospheric Se as revealed by epiphytic lichens

There is still a long-term debate concerning the relative contributions of naturally emitted and anthropogenic Se at the regional and local scales. Here, Se and heavy metal concentrations are reported for epiphytic lichens collected in coastal and inland areas from the USA, Canada and France for assessing atmospheric Se source. Correlations found between Se and Cl in lichens confirmed the major marine biogenic source for atmospheric Se. Continental samples do not show systematic relationships between Se and other metal (Pb, Cu, In …) contents, even for lichens collected in the vicinity of smelters or close to urban areas. Our results suggest that, although anthropogenic Se may be present, the marine biogenic Se source is a major contributor to atmospheric Se for our sampling locations. The contribution of naturally emitted atmospheric Se may be significant in urban and industrial areas and should be taken into account for further studies.     

Airborne Emissions of Mercury from Municipal Solid Waste. I: New Measurements from Six Operating Landfills in Florida

Abstract

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg⁰) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from ～1–10 ng m^?2 hr^?1 over aged landfill cover, from ～8–20 mg/hr from LFG flares (LFG included Hg⁰ at μg/m³ concentrations), and from ～200–400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10–50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.     

Source apportionment and source/sink relationships of PAHs in the coastal atmosphere of Chicago and Lake Michigan

Multivariate statistical techniques were used to investigate source apportionment and source/sink relationships for polycyclic aromatic hydrocarbons (PAHs) in the urban and adjacent coastal atmosphere of Chicago/Lake Michigan in 1994–1995. The PAH signatures for the atmospheric particle phase, surface water particle phase and sediments indicate that atmospheric deposition is the major source of PAHs to the sediments and water column particulate phase of Lake Michigan. The PAH signature for the atmospheric gas phase and water dissolved phase indicate an intimate linkage between the lake and its overlying atmosphere. A modified factor analysis-multiple regression model was successfully applied to the source apportionment of atmospheric PAHs (gas+particle). Coal combustion accounted for 48±5% of the ΣPAH concentration in both the urban and adjacent coastal atmosphere, natural gas combustion accounted for 26±2%, coke ovens accounted for 14±3%, and vehicle emissions (gas+diesel) accounted for 9±4%. Each is an identified source category for the region. These results are consistent with the mix of fossil fuel combustion sources and ratios of indicator PAHs.     

Ammonia in the atmosphere: a review on emission sources, atmospheric chemistry and deposition on terrestrial bodies

Gaseous ammonia (NH₃) is the most abundant alkaline gas in the atmosphere. In addition, it is a major component of total reactive nitrogen. The largest source of NH₃ emissions is agriculture, including animal husbandry and NH₃-based fertilizer applications. Other sources of NH₃ include industrial processes, vehicular emissions and volatilization from soils and oceans. Recent studies have indicated that NH₃ emissions have been increasing over the last few decades on a global scale. This is a concern because NH₃ plays a significant role in the formation of atmospheric particulate matter, visibility degradation and atmospheric deposition of nitrogen to sensitive ecosystems. Thus, the increase in NH₃ emissions negatively influences environmental and public health as well as climate change. For these reasons, it is important to have a clear understanding of the sources, deposition and atmospheric behaviour of NH₃. Over the last two decades, a number of research papers have addressed pertinent issues related to NH₃ emissions into the atmosphere at global, regional and local scales. This review article integrates the knowledge available on atmospheric NH₃ from the literature in a systematic manner, describes the environmental implications of unabated NH₃ emissions and provides a scientific basis for developing effective control strategies for NH₃.     

Polynuclear aromatic hydrocarbons in the United Kingdom environment: a preliminary source inventory and budget

This paper presents the first attempt to quantify the production, cycling, storage and loss of PAHs in the UK environment. Over 53 000 tonnes of sigmaPAHs (sum of 12 individual compounds) are estimated to reside in the contemporary UK environment, with soil being the major repository. If soils at contaminated sites are included, this estimate increases dramatically. Emission of PAHs to the UK atmosphere from primary combustion sources are estimated to be greater than 1000 tonnes sigmaPAHs per annum, with over 95% coming from domestic coal combustion, unregulated fires and vehicle emissions. It is estimated that approximately 210 tonnes of sigmaPAH are delivered to terrestrial surfaces each year via atmospheric deposition. Therefore, inputs of PAHs to the UK atmosphere outweigh the outputs by a factor of over 4. This may be explained by enhanced particulate deposition near point sources, PAH degradation in the atmosphere and transport away from the UK with prevailing winds. Disposal of waste residues is estimated to contribute a further 1000 tonnes of sigmaPAH per year to the terrestrial environment. It is illustrated that the use of creosote has the potential to release considerable quantities of PAHs to the UK environment. Temporal trends in PAH cycling are then considered. There is good evidence to suggest that air concentrations and fluxes to the UK surface are now lower than at any time throughout this century. Nonetheless, the UK sigmaPAH burden is still increasing at the present time, principally through retention by soils. However, there are marked differences in the behaviour of individual compounds: there is evidence, for example, that phenanthrene concentrations in soils have declined since the 1960s, although soil concentrations of benzo[a]pyrene and other heavier PAHs have continued to increase through this century. Volatilisation of low molecular weight PAHs accumulated in soils over previous decades may be making an important contribution to the current atmospheric burden. The major uncertainties identified by data on this budget are: (1) the lack of PAH concentrations in some environmental matrices; (2) the possible importance of contaminated soils as a major repository and source of PAHs; (3) the lack of emission data (especially vapour phase releases) for some PAH sources; (4) the importance of biodegradation and volatilisation as loss mechanisms for low molecular weight PAHs in soils; and (5) the importance of creosote use in the PAH cycle.     

Measuring atmospheric composition change

Scientific findings from the last decades have clearly highlighted the need for a more comprehensive approach to atmospheric change processes. In fact, observation of atmospheric composition variables has been an important activity of atmospheric research that has developed instrumental tools (advanced analytical techniques) and platforms (instrumented passenger aircrafts, ground-based in situ and remote sensing stations, earth observation satellite instruments) providing essential information on the composition of the atmosphere. The variability of the atmospheric system and the extreme complexity of the atmospheric cycles for short-lived gaseous and aerosol species have led to the development of complex models to interpret observations, test our theoretical understanding of atmospheric chemistry and predict future atmospheric composition. The validation of numerical models requires accurate information concerning the variability of atmospheric composition for targeted species via comparison with observations and measurements.In this paper, we provide an overview of recent advances in instrumentation and methodologies for measuring atmospheric composition changes from space, aircraft and the surface as well as recent improvements in laboratory techniques that permitted scientific advance in the field of atmospheric chemistry. Emphasis is given to the most promising and innovative technologies that will become operational in the near future to improve knowledge of atmospheric composition. Our current observation capacity, however, is not satisfactory to understand and predict future atmospheric composition changes, in relation to predicted climate warming. Based on the limitation of the current European observing system, we address the major gaps in a second part of the paper to explain why further developments in current observation strategies are still needed to strengthen and optimise an observing system not only capable of responding to the requirements of atmospheric services but also to newly open scientific questions.     

Gaseous Sulfur Pollutants from Urban and Natural Sources

Major aspects of the circulation through the atmospheric environment of sulfur pollutants have been estimated, including source magnitudes, residual atmospheric concentrations, and scavenging processes. The compounds considered include SO₂ and H₂S, as well as sulfates. One-third of the sulfur reaching the atmosphere comes from pollutant sources, mainly as SO₂. Within the atmosphere there is a net transfer of sulfur from land to ocean areas. Pollutant sources annually amount to 73 × 10⁶ tons as sulfur while natural sources amount to 142 × 10⁶ tons, mainly as H₂S and sulfate sea spray. More than two thirds of the natural and pollutant sulfur emissions occur in the northern hemisphere. When only pollutant emissions are considered, 93 per cent occur in the northern hemisphere.     

Primary sources of selected POPs: regional and global scale emission inventories

During the last decade, a number of studies have been devoted to the sources and emissions of Persistent Organic Pollutants (POPs) at regional and global scales. While significant improvements in knowledge have been achieved for some pesticides, the quantitative understanding of the emission processes and emission patterns for "non-pesticide" POPs are still considered limited. The key issues remaining for the non-pesticide POPs are in part determined by their general source classification. For industrial chemicals, such as the polychlorinated biphenyls (PCBs), there is considerable uncertainty with respect to the relative importance of atmospheric emissions from various source categories. For PCBs, temperature is discussed as a potential key factor influencing atmospheric emission levels and patterns. When it comes to the unintentional by-products of combustion and industrial processes (PCDD/Fs), there is still a large uncertainty with respect to the relative contribution of emissions from unregulated sources such as backyard barrel burning that requires further consideration and characterisation. For hexachlorobenzene (HCB), the relative importance of primary and secondary atmospheric emissions in controlling current atmospheric concentrations remains one of the key uncertainties. While these and other issues may remain unresolved, knowledge concerning the emissions of POPs is a prerequisite for any attempt to understand and predict the distribution and fate of these chemicals on a regional and global scale as well as to efficiently minimise future environmental burdens.     

A congener-specific PCDD/F emissions inventory for the UK: do current estimates account for the measured atmospheric burden?

Considerable effort has been expended in the UK and elsewhere to quantify and rank PCDD/F primary sources and emissions to the environment, principally the atmosphere, so that cost-effective source reduction measures can be taken. Here, we predict a congener-specific emissions inventory for primary and secondary nondioxin-regulated sources to the UK atmosphere, estimated to have ranged from 3 to 22 kg in 1996. The inventory profile is dominated by OCDD (approximately 30-40%), 1,2,3,4,6,7,8-HpCDD (approximately 15-19%) and 1,2,3,4,6,7,8-HpCDF (approximately 14-19%). Congeners 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD dominate the sigmaTEQ composition. Mass balance modelling suggests that the predicted congener pattern in UK air (based on the emission inventory) is similar to observed measurements, with absolute concentrations being estimated within a factor of 2 for most congeners. Calculations taking into account atmospheric weathering processes and long range (advective) transport suggest that PCDD/F sources to ambient air are primarily ongoing and that atmospheric mixing will mask individual emission source profiles/identities. This supports measured evidence for the consistency of PCDD/F air profiles observed around the UK throughout the year.     

Ubiquity of bisphenol A in the atmosphere

Bisphenol A (BPA) is a suspected endocrine disruptor in the environment. However, little is known about its distribution and transport in the atmosphere. Here, the concentrations of BPA in the atmospheric aerosols from urban, rural, marine, and the polar regions were measured using solvent extraction/derivatization and gas chromatography/mass spectrometry technique. The concentrations of BPA (1-17,400 pg m⁻³) ranged over 4 orders of magnitude in the world with a declining trend from the continent (except for the Antarctica) to remote sites. A positive correlation was found between BPA and 1,3,5-triphenylbenzene, a tracer for plastic burning, in urban regions, indicating that the open burning of plastics in domestic waste should be a significant emission source of atmospheric BPA. Our results suggest that the ubiquity of BPA in the atmosphere may raise a requirement for the evaluation of health effects of BPA in order to control its emission sources, for example, from plastic burning.     

Nitrogen isotopes: Tracers of origin and processes affecting PM10 in the atmosphere of Paris

Nitrogen in atmospheric particles in an urban environment is the result of complex primary and secondary processes, which renders identifying its origin somewhat complicated. Using the example of PM₁₀ in the atmosphere of Paris (France), it is shown that the use of stable nitrogen-isotope compositions (δ¹⁵N) alleviates this difficulty and provides clear information on the sources of primary and possibly of secondary nitrogen. Characterization of emissions of the different types of emitters in the city (road traffic, waste incinerators and heating sources) shows that these are clearly discriminated by specific isotope signatures. δ¹⁵N is particularly useful in showing that a substantial portion of the nitrogen is the result of secondary reactions, reactions that are different in summer and winter, as are the corresponding pollution sources. While it is unclear, among point sources, what the winter source of primary nitrogen is, road traffic appear to be the source of primary nitrogen in summer. Identification of the sources of the secondary nitrogen strongly depends on the nitrogen isotope fractionations (Δ¹⁵N) associated to atmospheric conversion of NO_x to nitrate, but hypothesises presented here hint at the possible corresponding pollution sources.     

Megacities and Large Urban Agglomerations in the Coastal Zone: Interactions Between Atmosphere, Land, and Marine Ecosystems

Megacities are not only important drivers for socio-economic development but also sources of environmental challenges. Many megacities and large urban agglomerations are located in the coastal zone where land, atmosphere, and ocean meet, posing multiple environmental challenges which we consider here. The atmospheric flow around megacities is complicated by urban heat island effects and topographic flows and sea breezes and influences air pollution and human health. The outflow of polluted air over the ocean perturbs biogeochemical processes. Contaminant inputs can damage downstream coastal zone ecosystem function and resources including fisheries, induce harmful algal blooms and feedback to the atmosphere via marine emissions. The scale of influence of megacities in the coastal zone is hundreds to thousands of kilometers in the atmosphere and tens to hundreds of kilometers in the ocean. We list research needs to further our understanding of coastal megacities with the ultimate aim to improve their environmental management.     

Short-chain oxygenated VOCs: Emission and uptake by plants and atmospheric sources,sinks, and concentrations

Emissions of volatile organic compounds (VOCs) have multiple atmospheric implications and play many roles in plant physiology and ecology. Among these VOCs, growing interest is being devoted to a group of short-chain oxygenated VOCs (oxVOCs). Technology improvements such as proton transfer reaction-mass spectrometry are facilitating the study of these hydrocarbons and new data regarding these compounds is continuously appearing. Here we review current knowledge of the emissions of these oxVOCs by plants and the factors that control them, and also provide an overview of sources, sinks, and concentrations found in the atmosphere.The oxVOCs reviewed here are formic and acetic acids, acetone, formaldehyde, acetaldehyde, methanol, and ethanol. In general, because of their water solubility (low gas–liquid partitioning coefficient), the plant-atmosphere exchange is stomatal-dependent, although it can also take place via the cuticle. This exchange is also determined by atmospheric mixing ratios. These compounds have relatively long atmospheric half-lives and reach considerable concentrations in the atmosphere in the range of ppbv. Likewise, under non-stressed conditions plants can emit all of these oxVOCs together at fluxes ranging from 0.2 up to 4.8 μg(C)g⁻¹(leaf dry weight)h⁻¹ and at rates that increase several-fold when under stress.Gaps in our knowledge regarding the processes involved in the synthesis, emission, uptake, and atmospheric reactivity of oxVOCs precludes the clarification of exactly what is conditioning plant-atmosphere exchange—and also when, how, and why this occurs—and these lacunae therefore warrant further research in this field.     

The chemistry of atmospheric mercury: a review

The atmosphere is an important transient reservoir of mercury. In addition to its great capacity, the chemical processes transforming mercury between the elemental and divalent states strongly influence the transport characteristics and deposition rate of this toxic metal back to the ground. Modeling efforts to assess global cycling of mercury require an in-depth knowledge of atmospheric mercury chemistry. This review article provides selected physical and chemical properties of atmospheric mercury, and discusses the identified mercury transformation pathways mediated by ozone, S(IV), hydroperoxyl radical, hydroxyl radical, chlorine, nitrate radical and photolysis of Hg(II) complexes. Special attention is paid to the kinetics and mechanisms of the reactions interconverting mercury between elemental and divalent states. The significance and implications of each transformation pathway under atmospheric conditions are addressed. Future research areas that must be pursued to better understand the fate and transformation of mercury in the atmosphere are also projected.     

Oxygenated polycyclic aromatic hydrocarbons in atmospheric particulate matter: Molecular characterization and occurrence

Particulate matter (PM) has become a major research issue receiving increasing attention because of its significant negative impact on human health. There are main indicators that next to the morphological characteristics of the particle, also the chemical composition plays an important role in the adverse health effects of PM. In this context, the rather polar organic fraction of PM is expected to play a major role, and advanced analytical techniques are developed to improve the knowledge on the molecular composition of this fraction. One component class that deserves major attention consists of the oxygenated polycyclic aromatic hydrocarbons (PAHs). Those compounds are considered to be among the key compounds in PM toxicity. This paper presents a comprehensive review focusing on the analysis, fate and behavior of oxygenated PAHs in the atmosphere. The first part of the paper briefly introduces (i) the main sources and atmospheric pathways of oxygenated PAHs, (ii) available physical–chemical properties and (iii) their health effects. The second and main part of this paper gives a thorough discussion on the entire analytical sequence necessary to identify and quantify oxygenated PAHs on atmospheric PM. Special attention is given to critical parameters and innovations related to (i) sampling, (ii) sample preparation including both extraction and clean-up, and (iii) separation and detection. Third, the state-of-the-art knowledge about the atmospheric occurrence of oxygenated PAHs is discussed, including an extended overview of reported concentrations presented as a function of sampling season and geographical location. A clear seasonal effect is observed with the median of the oxygenated PAHs concentrations during winter being a factor of 3–4 higher than during summer. However, the oxygenated PAH/parent PAH ratio is about 20 times higher during summer, indicating the importance of photochemical activity in the atmosphere.