The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.     

Distribution and spatial trends of PAHs and PCBs in soils in the Seine River basin, France

Persistent organic pollutants (PAHs and PCBs) in soil samples from seven sites across the Seine basin were analysed. Samples were taken from industrialized, urban, suburban and remote sites. Results showed spatial differences, in terms of concentrations and congener profiles. PAH (Sigma14 PAHs) and PCB (Sigma 7 PCBs) concentrations ranged from 450 to 5650 microg kg(-1) and 0.09 to 150 microg kg(-1), respectively. A clear gradient from industrial to remote sites was highlighted, with a ratio of up to one order of magnitude for PAHs and two orders of magnitude for PCBs. Fluoranthene and pyrene were predominant, while the carcinogenic PAHs represented 15-46% of the total PAH content. Using hierarchical cluster analysis, soil samples profiles were compared and the influence of site location and potential sources were identified: automobile traffic, domestic heating, and industrial emissions were the prevalent PAHs sources in the Seine basin. PCB profiles suggested different transport patterns among congeners. For remote sites, the congener fingerprint showed a relatively higher proportion of the most volatile congeners, which were attributed to increased atmospheric residence times. Thus, PAH and PCB distributions in soils provided information on sources and evidence for short-range transport, and profiles of compounds reflected differences between regional and local emissions. This study demonstrates that soil sampling can be used to investigate spatial differences in atmospheric inputs of persistent organic pollutants based on differences in the mixtures of compounds, reflecting differences in regional and local atmospheric emissions.     

Global fate of POPs: current and future research directions

For legacy and emerging persistent organic pollutants (POPs), surprisingly little is still known in quantitative terms about their global sources and emissions. Atmospheric transport has been identified as the key global dispersal mechanism for most legacy POPs. In contrast, transport by ocean currents may prove to be the main transport route for many polar, emerging POPs. This is linked to the POPs' intrinsic physico-chemical properties, as exemplified by the different fate of hexachlorocyclohexanes in the Arctic. Similarly, our current understanding of POPs' global transport and fate remains sketchy. The importance of organic carbon and global temperature differences have been accepted as key drivers of POPs' global distribution. However, future research will need to understand the various biogeochemical and geophysical cycles under anthropogenic pressures to be able to understand and predict the global fate of POPs accurately.     

The emission inventory of PCDD/PCDF in Taiwan

Establishment of a country or region-based dioxin inventory was considered a crucial step toward elimination of worldwide dioxins/POPs contaminations, although no harmonized method for the preparation of an inventory is available at present. In this study, we used limited data and information to generate an inventory of dioxin emissions from some major sources in Taiwan. A total of 67.25 g I-TEQ of dioxins released annually was estimated. Unlike most of the industrialized countries, municipal waste incineration is not the highest contributor for dioxins released into the atmosphere. In contrast, secondary copper smelting accounts for more than 39% of the total dioxin emissions, and is higher than those from all waste incinerators combined (23.7%). Cement kilns and electric arc furnaces for steels also produced significant portion (both >10%) of dioxins into the environment, followed by secondary aluminum smelting (6.53%), industrial oil combustion (5.02%) and power plants fueled by coal (5.01%). Other known sources are either insignificant with respect to their dioxin emissions or not included in this inventory due to lack of information or uncertainty of the results. Data presented in this report provide a general picture of dioxin emissions in Taiwan, but were mostly based on less reliable or representative information, especially with respect to emission factors from different emission sources. It is necessary to establish background information relative to our own environment at present. Upon available, the inventory should be updated accordingly for proper environmental management on dioxins.     

A synthesis of progress and uncertainties in attributing the sources of mercury in deposition

A panel of international experts was convened in Madison, Wisconsin, in 2005, as part of the 8th International Conference on Mercury as a Global Pollutant. Our charge was to address the state of science pertinent to source attribution, specifically our key question was: "For a given location, can we ascertain with confidence the relative contributions of local, regional, and global sources, and of natural versus anthropogenic emissions to mercury deposition?" The panel synthesized new research pertinent to this question published over the past decade, with emphasis on four major research topics: long-term anthropogenic change, current emission and deposition trends, chemical transformations and cycling, and modeling and uncertainty. Within each topic, the panel drew a series of conclusions, which are presented in this paper. These conclusions led us to concur that the answer to our question is a "qualified yes," with the qualification being dependent upon the level of uncertainty one is willing to accept. We agreed that the uncertainty is strongly dependent upon scale and that our question as stated is answerable with greater confidence both very near and very far from major point sources, assuming that the "global pool" is a recognizable "source." Many regions of interest from an ecosystem-exposure standpoint lie in between, where source attribution carries the greatest degree of uncertainty.     

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.     

Atmospheric emission of polychlorinated biphenyls from multiple industrial thermal processes

In this study, field measurements were conducted to estimate and characterize the atmospheric emission levels and profiles of polychlorinated biphenyls (PCBs) from multiple industrial thermal processes. The emission levels and profiles of PCBs from five types of thermal processes at twenty-three plants were studied and compared with eight processes reported in our previous studies. Correlation analysis was preformed to identify a marker congener for emission of ΣPCB. A significant correlation was observed between congener CB-118 and ΣPCB (R² = 0.65 and p < 0.01), which suggests that CB-118 is a good marker congener for emission of ΣPCB. The profiles of PCBs emitted from the thirteen thermal processes were compared, and this information could be used for studying source–receptor relationships and identifying the specific sources of PCBs. To prioritize the sources for control, the concentrations of PCBs from thirteen industrial thermal sources were compared. The PCB concentrations from secondary zinc smelting and thermal wire reclamation were about one to three order magnitude higher than those of other sources, which suggests that these two sources be given priority in PCB source control. Finally, the atmospheric emission factors of PCBs from the thirteen industrial sources were summarized, and these data will be useful for developing an integrated emission inventory of PCBs.     

The evolution of mass balance models of persistent organic pollutant fate in the environment

Current approaches to modelling the fate of persistent organic pollutants (POPs) in the environment have evolved in response to four dominant characteristics of these substances; namely: (1) the presence of POPs in virtually all environmental phases and the ease with which they move from one to the other requires multi-compartmental modelling. Describing transport across phase boundaries becomes as, or even more, important as quantifying transport within the phases; (2) POPs may persist in the environment for many decades. For chemicals that 'have time', concepts such as equilibrium partitioning and steady-state become more important than for short-lived substances whose fate is more controlled by the rates of transformation; (3) measuring POPs is difficult and expensive and observed concentrations of POPs are not available in high spatial or temporal resolution. Consequently, high resolution tends not to be a high priority in POP models; and (4) detrimental effects of POPs often manifest themselves in top predators, which has led to a focus on modelling biotic uptake and transfer within food chains. The task of building a POPs model is viewed as combining the four 'building blocks' of partitioning, transport, transformation and source data with the help of the law of the conservation of mass. Process models, evaluative models, models of real local, regional and global fate, as well as biological uptake models are presented and references to numerous examples are provided. An attempt is made to forecast future directions in the field of POPs modelling. It is expected that modelling techniques that do not rely on quantitative emission estimates as well as approaches that take into account spatial, temporal and climatic variability as well as parameter uncertainty will increase in importance. Finally, the relationship between modelling POPs and models of other pollutant issues is addressed, as are potential interactions between POPs and pollutant issues such as eutrophication, acidification and global climate change.     

Measurement and modeling of urban atmospheric PCB concentrations on a small (8 km) spatial scale

Atmospheric transport and deposition of polychlorinated biphenyls (PCBs) is an important problem for ecosystems around the world. Data from several monitoring networks demonstrate that atmospheric PCB concentrations are dramatically elevated in urban areas compared to rural or background regions, such that these urban emissions of PCBs support the regional and global transport and deposition of PCBs to more remote areas. Identifying and controlling the sources of urban atmospheric PCBs is thus essential in minimizing the regional and global transport and deposition of these compounds. From December 1999 to November 2000, gas-phase PCB concentrations were measured at two monitoring locations, 8 km apart, within the New York City metropolitan area, at Jersey City and Bayonne, NJ. Concentrations, congener patterns, and temporal patterns of PCBs differ dramatically at the two sites, suggesting that a significant source of atmospheric PCBs exists within 8 km of the Bayonne site, resulting in spikes in gas-phase PCB concentration at Bayonne that are not observed at Jersey City. The Regional Atmospheric Model System (RAMS) coupled with the Hybrid Particle and Concentration Transport model (HYPACT) was used to estimate that the PCB source near Bayonne emits a flux of ΣPCBs on the order of 100 g d⁻¹. Extrapolation of this source magnitude to the area of New York City suggests that this urban area emits at least 300 kg yr⁻¹ ΣPCBs to the regional atmosphere, similar in magnitude to the flow of ΣPCB out of the Upper Hudson River into the New York/New Jersey Harbor.     

Quantifying the global fractionation of polychlorinated biphenyls

Due to the wide range of their physical-chemical properties, polychlorinated biphenyls (PCBs) have played an important role in the derivation of the global fractionation hypothesis, which predicts changes in the composition of persistent organic pollutant mixtures with latitude. Recent historical emission estimates, the derivation of an internally consistent property data set, in combination with a zonally averaged global fate and transport model, allow a quantitative investigation of the compositional shifts PCBs experience as a function of environmental compartment, latitude and time. Model simulations reproduce the higher relative abundance of lighter PCB congeners with increasing latitude, observed in air and soil, and quantify the relative importance of partitioning, persistence and emissions in establishing PCB patterns. Compositional variations consistent with global fractionation, as well as inverted concentration profiles with higher levels in the Arctic than at lower latitudes, are consistent with only minor fractions of the global PCB inventory being transferred northward.     

Transport impacts on atmosphere and climate: Metrics

The transport sector emits a wide variety of gases and aerosols, with distinctly different characteristics which influence climate directly and indirectly via chemical and physical processes. Tools that allow these emissions to be placed on some kind of common scale in terms of their impact on climate have a number of possible uses such as: in agreements and emission trading schemes; when considering potential trade-offs between changes in emissions resulting from technological or operational developments; and/or for comparing the impact of different environmental impacts of transport activities.Many of the non-CO₂ emissions from the transport sector are short-lived substances, not currently covered by the Kyoto Protocol. There are formidable difficulties in developing metrics and these are particularly acute for such short-lived species. One difficulty concerns the choice of an appropriate structure for the metric (which may depend on, for example, the design of any climate policy it is intended to serve) and the associated value judgements on the appropriate time periods to consider; these choices affect the perception of the relative importance of short- and long-lived species. A second difficulty is the quantification of input parameters (due to underlying uncertainty in atmospheric processes). In addition, for some transport-related emissions, the values of metrics (unlike the gases included in the Kyoto Protocol) depend on where and when the emissions are introduced into the atmosphere – both the regional distribution and, for aircraft, the distribution as a function of altitude, are important.In this assessment of such metrics, we present Global Warming Potentials (GWPs) as these have traditionally been used in the implementation of climate policy. We also present Global Temperature Change Potentials (GTPs) as an alternative metric, as this, or a similar metric may be more appropriate for use in some circumstances. We use radiative forcings and lifetimes from the literature to derive GWPs and GTPs for the main transport-related emissions, and discuss the uncertainties in these estimates. We find large variations in metric (GWP and GTP) values for NO_x, mainly due to the dependence on location of emissions but also because of inter-model differences and differences in experimental design. For aerosols we give only global-mean values due to an inconsistent picture amongst available studies regarding regional dependence. The uncertainty in the presented metric values reflects the current state of understanding; the ranking of the various components with respect to our confidence in the given metric values is also given. While the focus is mostly on metrics for comparing the climate impact of emissions, many of the issues are equally relevant for stratospheric ozone depletion metrics, which are also discussed.     

Reconciling models and measurements to assess trends in atmospheric mercury deposition

Changes in atmospheric mercury deposition are used to evaluate the effectiveness of regulations controlling emissions. This analysis can be complicated by seemingly incongruent data from different model runs, model types, and field measurements. Here we present a case study example that describes how to identify trends in regional scale mercury deposition using best-available information from multiple data sources. To do this, we use data from three atmospheric chemistry models (CMAQ, GEOS-Chem, HYSPLIT) and multiple sediment archives (ombrotrophic bog, headwater lake, coastal salt marsh) from the Bay of Fundy region in Canada. Combined sediment and modeling data indicate that deposition attributable to US and Canadian emissions has declined in recent years, thereby increasing the relative significance of global sources. We estimate that anthropogenic emissions in the US and Canada account for 28-33% of contemporary atmospheric deposition in this region, with the rest from natural (14-32%) and global sources (41-53%).     

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m⁻³ (ND ∼ 617) and 1 fg WHO-TEQ m⁻³ (ND ∼ 0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p = 0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.     

Comparison of emissions estimates derived from atmospheric measurements with national estimates of HFCs,PFCs and SF6

This paper assesses the feasibility of using atmospheric measurement of fluorinated greenhouse gases (HFCs, PFCs and SF6) for the review and verification of greenhouse gas inventories provided by national governments. For this purpose, available data were compiled. It was found that atmospheric measurements of these gases are available and provide an indication of global annual emissions with sufficient certainty to reach the following conclusions: Within the uncertainty of the method, it was found that emissions of HFC-23, a by-product of HCFC-22 production, as obtained from atmospheric measurements did not decrease as fast, as the countries have reported. In contrast, SF6 concentrations in the atmosphere suggest higher emissions than reported by countries. Regional emission estimates from atmospheric measurements are still in a more pioneering state and cannot be compared to national estimates. Intensified efforts to measure HFCs, PFCs and SF6 in the atmosphere are recommended.     

A highly resolved temporal and spatial air pollutant emission inventory for the Pearl River Delta region, China and its uncertainty assessment

A highly resolved temporal and spatial Pearl River Delta (PRD) regional emission inventory for the year 2006 was developed with the use of best available domestic emission factors and activity data. The inventory covers major emission sources in the region and a bottom–up approach was adopted to compile the inventory for those sources where possible. The results show that the estimates for SO₂, NO_x, CO, PM₁₀, PM_2.5 and VOC emissions in the PRD region for the year 2006 are 711.4 kt, 891.9 kt, 3840.6 kt, 418.4 kt, 204.6 kt, and 1180.1 kt, respectively. About 91.4% of SO₂ emissions were from power plant and industrial sources, and 87.2% of NO_x emissions were from power plant and mobile sources. The industrial, mobile and power plant sources are major contributors to PM₁₀ and PM_2.5 emissions, accounting for 97.7% of the total PM₁₀ and 97.2% of PM_2.5 emissions, respectively. Mobile, biogenic and VOC product-related sources are responsible for 90.5% of the total VOC emissions. The emissions are spatially allocated onto grid cells with a resolution of 3 km × 3 km, showing that anthropogenic air pollutant emissions are mainly distributed over PRD central-southern city cluster areas. The preliminary temporal profiles were established for the power plant, industrial and on-road mobile sources. There is relatively low uncertainty in SO₂ emission estimates with a range of −16% to +21% from power plant sources, medium to high uncertainty for the NO_x emissions, and high uncertainties in the VOC, PM_2.5, PM₁₀ and CO emissions.     

The revised EMEP/EEA Guidebook compared to the country specific inventory system in the Netherlands

Parties to the LRTAP convention have agreed to annually report atmospheric emissions and are required to set up an emission inventory. As a minimum, parties shall use the latest version of the EMEP/EEA Air Pollutant Inventory Guidebook, but most countries – including the Netherlands – have set up their own inventory, which uses country specific information to supplement the information from the Guidebook. In this study, emissions estimated within the Dutch Emission Inventory are compared to emissions estimated using Guidebook emission factors and Dutch statistics for the year 2005. The objective is to explore the quality of both methods and to find major differences and similarities. The comparison shows that for most sources, emission estimates are within uncertainty ranges for both methodologies, especially for sources where a higher Tier (more detailed) methodology is used to estimate the emissions. This is in line with the Guidelines which indicate that for key categories a more detailed methodology should be used. The comparison also shows some surprising differences, such as large differences in emission factors (especially Tier 1) and missing sources (fireworks and abrasion of railway overhead wires, causing 16% of total copper emissions in the Netherlands) which have not been included in the Guidebook. This comparison is shown to be a useful tool to identify areas where improvements and further research are necessary.     

On-road traffic emissions in a megacity

A new annual bottom–up emission inventory of criteria pollutants and greenhouse gases from on-road mobile sources was developed for 2006 for the metropolitan area of Buenos Aires, Argentina, within a four-year regional project aimed at providing tools for chemical weather forecast in South America. Under the scarcity of local emission factors, we collected data from measuring campaigns performed in Argentina, Brazil, Chile and Colombia and compiled a data set of regional emission factors representative of Latin American fleets and driving conditions. The estimated emissions were validated with respect to downscaled national estimates and the EDGAR global emission database. Our results highlight the role of older technologies accounting in average for almost 80% of the emissions of all species. The area exhibits higher specific emissions than developed countries, with figures two times higher for criteria pollutants. We analyzed the effect on emissions of replacing gasoline by compressed natural gas, occurring in Argentina since 1995. We identified (i) a relationship between number of vehicles and a compound socioeconomic indicator, and (ii) time-lags in vehicle technologies between developed and developing countries, which can be respectively applied for spatial disaggregation and the development of projections for other Latin American cities. The results may also be employed to complement global emission inventories and by local policy makers as an environmental management tool.     

Emissions of persistent organic pollutants and eight candidate POPs from UNECE–Europe in 2000, 2010 and 2020 and the emission reduction resulting from the implementation of the UNECE POP protocol

An emission inventory for persistent organic pollutants (POP) is made for the year 2000 based on submissions of emission data from the Parties to the Convention on LRTAP. The inventory covers the UNECE territory except Canada and the United States. For the countries, sources or compounds lacking in official submissions, default emission estimates have been prepared and applied to complete the inventory. An indicative comparison of the year 2000 emissions with the 1990 emission levels from a previous study is presented as well as emission projections for 2010, 2015, 2020 based on activity scenarios developed in the framework of the EU CAFE programme. The key source analysis of the projected emissions assuming full implementation of the UNECE protocols allows identification of remaining source strengths which subsequently are briefly discussed in terms of their potential for (further) reduction. A number of chemicals are currently being investigated for inclusion on the UN/ECE POPs protocol list of priority compounds but for these substances emission estimation methodologies are scarce or non-existent. For eight of these substances (dicofol, edosulfan, hexachlorobutadiene (HBU), pentabromodiphenyl ether (PBDE), pentachlorobenzene (PCBe), pentachlorophenol (PCP), polychloronated naftalenes (PCN) and short chained chlorinated paraffins (SCCPs)) an emission estimation methodology is proposed and a preliminary emission inventory for the year 2000 is presented.     

Estimating receptor sensitivity to spatial proximity of emissions sources

Spatial proximity of emissions sources to receptors may affect sensitivity to potential adverse human health effects. This research investigates whether receptor sensitivity to the location of emission sources can be utilized efficiently to minimize health risk in selecting sites for industrial enterprises, thermal electric stations, etc. A sensitivity function that is independent of the location of pre-existing emission sources is derived and applied to Minsk, Belarus. The function estimates exposures based on weather and climatic conditions as well as the distribution of population density at a given locality. Arraying prospective sites based on their sensitivity function magnitude provides a technique for minimizing health risk based on receptor sensitivity to the spatial proximity of atmospheric emissions sources.