Assessing the impact of weather events at mid-latitudes on the atmospheric transport of chemical pollutants using a 2-dimensional multimedia meteorological model

Gasic, B; MacLeod, M; Scheringer, M; Hungerbuhler, K
2010 | Atmos. Environ. | 44 (35) (4489-4496)

We investigate the long-range transport potential (LRTP) of five different classes of hypothetical chemical pollutants (volatile, multimedia, semivolatile, particle-associated and hydrophilic) during a low pressure weather event using a novel 2 (x- and z-axis)-Dimensional Multi-Media Meteorological Model (2D4M). The atmosphere (z-axis) is described by three atmospheric layers, where two layers constitute the boundary layer and the third layer the free troposphere. The 2D4M can describe distinct weather events on a regional scale and calculate the LRTP of chemicals as a function of time during these events. Four weather factors are used to model weather events and their influence on the atmospheric transport of chemicals: (1) temperature, (2) wind speed and mixing dynamics of the troposphere, (3) hydroxyl radical concentrations and (4) precipitation. We have modeled the impact of variability in each of these factors on LRTP of pollutants during a front event associated with a low pressure period that interrupts a dominant high pressure system. The physico-chemical properties of the pollutant determine which specific weather factors contribute most to variability in transport potential during the event. Volatile and multimedia chemicals are mainly affected by changing atmospheric mixing conditions, wind speeds and OH radical concentrations, while semivolatile substances are also affected by temperature. Low-vapor-pressure pollutants that are particle-associated, and water-soluble pollutants are most strongly affected by precipitation. Some chemical pollutants are efficiently transported from the boundary layer into the upper troposphere during the modeled low pressure event and are transported by much higher wind speeds than in the boundary layer. Our model experiments show that the transport potential of volatile, multimedia and semivolatile compounds is significantly increased during a front event as a result of efficient tropospheric mixing and fast wind speeds in the upper troposphere, whereas low-volatility and hydrophilic chemicals are largely scavenged from the atmosphere. In future LRTP assessment of chemical contaminants as required by the Stockholm Convention and the convention on long-range transboundary air pollution, it is therefore advised to prioritize volatile, multimedia and semivolatile chemicals that are identified in initial screening. (C) 2010 Elsevier Ltd. All rights reserved.

Quantifying Remoteness from Emission Sources of Persistent Organic Pollutants on a Global Scale

von Waldow, H.; MacLeod, M.; Scheringer, M.; Hungerbuhler, K.
2010 | Environ. Sci. Technol. | 44 (8) (2791-2796)

One of the four screening criteria that are assessed when a chemical substance is nominated for international regulation under the Stockholm Convention is potential for long-range transport. Measured levels of a chemical in locations distant from sources can be used as evidence of long-range environmental transport, but until now, there has been no quantitative measure of the distance of a location from likely source areas of chemicals. Here we use a global atmospheric transport model to calculate atmospheric concentrations for a set of volatile tracers that differ in their effective atmospheric residence time. We then derive an empirical relationship to express these concentrations as a function of the atmospheric residence time and a location-specific parameter, the remoteness index, RI. We present maps of RI for two generic emissions scenarios that represent areas for emissions of industrial and technical chemicals and pesticides, respectively. Our results can be used to better interpret spatial patterns of measured and modeled concentrations of chemicals in the global environment and to derive long-range transport potential metrics for specific substances. We thus provide, to our knowledge for the first time, a description of remoteness that is applicable to measurement sites of continental- and global-scale monitoring programmes. Our results can be used to plan future measurement campaigns and extend monitoring networks.

Diurnal Fluctuations in Polybrominated Diphenyl Ether Concentrations During and After a Severe Dust Storm Episode in Kuwait City, Kuwait

Gevao, B; Jaward, FM; MacLeod, M; Jones, KC
2010 | Environ. Sci. Technol. | 44 (21) (8114-8120)

Concentrations of polybrominated diphenyl ethers (PBDEs) were quantified in four-hour integrated air samples obtained serially over a five day period in May 2007 in Kuwait City during and after a severe dust storm. The Sigma PBDE concentrations ranged from 51 to 1307 pg m(-3) for the first two days of sampling and 20 to 148 pg m(-3) for the rest of the sampling period. The first two days of sampling occurred during a severe dust storm episode when the total suspended particulates (TSP) in air exceeded 1000 mu g/m(3) with concentrations peaking during the day and decreasing at night During this dust episode, the peak nighttime PBDE concentration was 30 times higher than the minimum daytime concentration. Although Sigma PBDE concentrations peaked at night during the first two sampling days, the fluctuations in the BDE 47:99 ratio tracked changes in ambient temperature remarkably well, following a clear diurnal pattern. The fraction of congeners in the gas phase varied inversely with solar flux and was lower on days with a high number of hours of sunshine, suggesting that photolytic degradation of gas-phase PBDEs was occurring.

Exposure assessment at a PCDD/F contaminated site in Sweden-field measurements of exposure media and blood serum analysis

Aberg, A.; Tysklind, M.; Nilsson, T.; MacLeod, M.; Hanberg, A.; Andersson, R.; Bergek, S.; Lindberg, R.; Wiberg, K.
2010 | Environ Sci Pollut Res Int | 17 (1) (26-39)

The main pathway for human exposure to the highly toxic polychlorinated-p-dioxins and polychlorinated furans [polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)] is via dietary intake. Other exposure pathways may, however, be important in close proximity to point sources, such as wood preservation sites, where PCDD/F contaminated chlorophenols (CP) were previously used. In this study, a heavily PCDD/F contaminated CP saw mill site in Sweden was investigated. Human exposure through a broad spectrum of exposure pathways was assessed. Such studies are in demand since the question whether contaminated sites represent a current or future risk can only be answered by detailed site-specific risk assessments. Sampling of exposure media (soil, air, groundwater, raspberries, carrots, potatoes, grass, milk, eggs, and chicken fodder) was made. Exposure media concentrations and congener distribution patterns were used to investigate the mobilization of PCDD/Fs from soil to the environment and to calculate exposure levels for adults. Blood serum levels from site-exposed and control individuals were also analyzed. Congener distribution patterns at the site were generally dominated by a specific marker congener (1234678-HpCDF), which is highly abundant in the polluted soil. The dioxin toxic equivalents (TEQ) concentrations were notably elevated as compared to national reference samples for most exposure media, and the marker congener was a major contributor to increased TEQ levels. There were also indications of soil-to-air volatilization of tetra- and penta-CDD/Fs. People who participated in the restoration of a contaminated building showed higher levels of 1234678-HpCDF compared to controls, and calculated exposure levels suggest that several site-specific exposure routes may be of importance for the daily intake of PCDD/F. Despite low mobility of higher chlorinated PCDD/Fs, these contaminants were transferred from the polluted soil to the surroundings and into human tissue. The extent of increased exposure from contaminated sites depends on the PCDD/F source strength of the soil, composition of the pollution, human activities, and dietary patterns of the residents. Impact from the contaminated soil on other exposure media was seen also for areas with low to moderate soil contamination. In the future, not only the levels of PCDD/F soil pollution but also the composition must be considered in risk assessments of contaminated sites.

Quantification of sources of PCBs to the atmosphere in urban areas: A comparison of cities in North America, Western Europe and former Yugoslavia

Gasic, B.; MacLeod, M.; Klanova, J.; Scheringer, M.; Ilic, P.; Lammel, G.; Pajovic, A.; Breivik, K.; Holoubek, I.; Hungerbuhler, K.
2010 | Environ. Pollut. | 158 (10) (3230-3235)

We present estimated emission source strengths of seven polychlorinated biphenyl (PCB) congeners for Banja Luka, a city that was affected by the civil war in Bosnia and Hercegovina (former Yugoslavia) in the 1990s. These emission estimates are compared to PCB emission rates estimated for the cities of Zurich, Switzerland, and Chicago, USA using an approach that combines multimedia mass balance modeling and measurement data. Our modeled per-capita emission estimates for Banja Luka are lower by a factor of ten than those for Zurich and Chicago, which are similar. This indicates that the sources of PCB emissions in Banja Luka are likely to be weaker than in the Western European and North American cities which show relatively high PCB emissions. Our emission rates from the three cities agree within a factor of ten with emission estimates from a global PCB emission inventory derived from production and usage estimates and emission factors. (C) 2010 Elsevier Ltd. All rights reserved.

Environmental risks associated with nanoparticulate silver used as biocide, Household and Personal Care Today

Scheringer, M.; MacLeod, M.; Behra, R.; Sigg, L.; Hungerbuhler, K.
2010 | SU | 1 (28-31)

Nanosilver is increasingly used as a biocide in
many applications such as textile fibres, food containers,
medical devices and coatings of daily-use items. At the
same time, there are applications of biocidal silver that
have been in use for many years, including silver
formulations that contain nanoscale silver particles that are
used for water disinfection. In this situation, the question
needs to be clarified whether nanosilver applications lead
to human and environmental exposure and, subsequently,
toxic effects that are different from those caused by silver
emissions from other sources. We review recent information
about nanosilver uses and emissions to the aquatic
environment and about the environmental fate and toxicity
of nanosilver. On this basis, we discuss perspectives for an
environmental risk assessment of nanosilver and identify key
questions to be addressed in such an assessment. Our
conclusion is that currently environmental risks caused by
nanosilver applications are probably low, but that the rapid
growth of the use of silver as a biocide necessitates more
study of sources, fate and transport, and toxicity of
environmentally relevant forms of silver.

Photoreactions of Mercury in Surface Ocean Water: Gross Reaction Kinetics and Possible Pathways

Qureshi, A.; O'Driscoll, N.J.; MacLeod, M.; Neuhold, Y.M.; Hungerbuhler, K.
2010 | Environ. Sci. Technol. | 44 (2) (644-649)

We present pseudofirst order rate constants for gross photoreduction and gross photooxidation of mercury in surface water from the open Atlantic Ocean, determined under controlled laboratory conditions. Experiments using both unfiltered and filtered ocean water were carried out to characterize the importance of microbes and colloids on reaction kinetics. Results indicate that reduction and oxidation of mercury in ocean water does not follow a simple two-species reversible reaction pathway. We suggest two possible redox pathways that reproduce the pattern of dissolved gaseous mercury (DGM) concentrations observed in our laboratory experiments, and evaluate them using a controlled outdoor experiment. In both proposed pathways Hg(0), the major constituent of DGM, is converted to an unidentified exidized species that is different from the reducible form present initially. This reaction step plays a major role in the net formation of DGM in our experiments. Our results represent new quantitative information about the gross reaction kinetics for both reduction and oxidation of mercury in open ocean surface water. Pseudofirst order rate constants for reduction reactions that form DGM were determined to be in the range of 0.15-0.93 h(-1) and pseudofirst order rate constants for oxidation of Hg(0) to be in the range of 0.4-1.9 h(-1). Microbes and colloids did not appreciably influence the reduction and oxidation kinetics.

Past, Present, and Future Controls on Levels of Persistent Organic Pollutants in the Global Environment

Nizzetto, L.; MacLeod, M.; Borga, K.; Cabrerizo, A.; Dachs, J.; Di Guardo, A.; Ghirardello, D.; Hansen, K.M.; Jarvis, A.; Lindroth, A.; Ludwig, B.; Monteith, D.; Perlinger, J.A.; Scheringer, M.; Schwendenmann, L.; Semple, K.T.; Wick, L.Y.; Zhang, G.; Jones, K.C.
2010 | Environ. Sci. Technol. | 44 (17) (6526-6531)

Modeling the Global Fate and Transport of Perfluorooctane Sulfonate (PFOS) and Precursor Compounds in Relation to Temporal Trends in Wildlife Exposure

Armitage, J.M.; Schenker, U.; Scheringer, M.; Martin, J.W.; MacLeod, M.; Cousins, I.T.
2009 | Environ. Sci. Technol. | 43 (24) (9274-9280)

A global-scale fate and transport model was applied to investigate the historic and future trends in ambient concentrations of perfluorooctane sulfonate (PFOS) and volatile perfluorooctane sulfonyl fluoride (POSF)-based precursor compounds in the environment. First, a global emission inventory for PFOS and its precursor compounds was estimated for the period 1957-2010. We used this inventory as input to a global-scale contaminant fate model and compared modeled concentrations with field data. The main focus of the simulations was to examine how modeled concentrations of PFOS and volatile precursor compounds respond to the major production phase-out that occurred in 2000-2002. Modeled concentrations of PFOS in surface ocean waters are generally within a factor of 5 of field data and are dominated by direct emissions of this substance. In contrast, modeled concentrations of the precursor compounds considered in this study are lower than measured concentrations both before and after the production phase-out. Modeled surface ocean water concentrations of PFOS in source regions decline slowly in response to the production phase-out while concentrations in remote regions continue to increase until 2030. In contrast, modeled concentrations of precursor compounds in both the atmosphere and surface ocean water compartment in all regions respond rapidly to the production phase-out (i.e., decline quickly to much lower levels). With respect to wildlife biomonitoring data, since precursor compounds are bioavailable and degrade to PFOS in vivo, it is at least plausible that declining trends in PFOS body burdens observed in some marine organisms are attributable to this exposure pathway. The continued increases in PFOS body burdens observed in marine organisms inhabiting other regions may reflect exposure primarily to PFOS itself, present in the environment due to production and use of this compound as well as degradation of precursor compounds.

Modeling aerosol suspension from soils and oceans as sources of micropollutants to air

Qureshi, A.; MacLeod, M.; Hungerbuhler, K.
2009 | Chemosphere | 77 (4) (495-500)

Soil and marine aerosol suspension are two physical mass transfer processes that are not usually included in models describing fate and transport of environmental pollutants. Here, we review the literature on soil and marine aerosol suspension and estimate aerosol suspension mass transfer velocities for inclusion in multimedia models, as a global average and on a 1 x 1 scale. The yearly, global average mass transfer velocity for soil aerosol suspension is estimated to be 6 x 10(-10) m h(-1), approximately an order of magnitude smaller than marine aerosol suspension, which is estimated to be 8 x 10(-9) m h(-1). Monthly averages of these velocities can be as high as 10(-7) m h(-1) and 10(-5) m h(-1) for soil and marine aerosol suspension, respectively, depending on location. We use a unit-world multimedia model to analyze the relevance of these two suspension processes as a mechanism that enhances long-range atmospheric transport of pollutants. This is done by monitoring a metric of long-range transport potential, phi-one thousand (phi(1000)), that denotes the fraction of modeled emissions to air, water or soil in a source region that reaches a distance of 1000 km in air. We find that when the yearly, globally averaged mass transfer velocity is used, marine aerosol suspension increases phi(1000) only fractionally for both emissions to air and water. However, enrichment of substances in marine aerosols, or speciation between ionic and neutral forms in ocean water may increase the influence of this surface-to-air transfer process. Soil aerosol suspension can be the dominant process for soil-to-air transfer in an emission-to-soil scenario for certain substances that have a high affinity to soil. When a suspension mass transfer velocity near the maximum limit is used, soil suspension remains important if the emissions are made to soil, and marine aerosol suspension becomes important regardless of if emissions are made to air or water compartments, We recommend that multimedia models designed to assess the environmental fate and long-range transport behavior of substances with a range of chemical properties include both aerosol suspension processes, using the mass transfer velocities estimated here. (C) 2009 Elsevier Ltd. All rights reserved.

Modeling the Global Levels and Distribution of Polychlorinated Biphenyls in Air under a Climate Change Scenario

Lamon, L.; von Waldow, H.; MacLeod, M.; Scheringer, M.; Marcomini, A.; Hungerbuhler, K.
2009 | Environ. Sci. Technol. | 43 (15) (5818-5824)

We used the multimedia chemical fate model BETR Global to evaluate changes in the global distribution of two polychlorinated biphenyls, PCB 28 and PCB 153, under the influence of climate change. This was achieved by defining two climate scenarios based on results from a general circulation model, one scenario representing the last twenty years of the 20th century (20CE scenario) and another representing the global climate under the assumption of strong future greenhouse gas emissions (A2 scenario), The two climate scenarios are defined by four groups of environmental parameters: (1) temperature in the planetary boundary layer and the free atmosphere, (2) wind speeds and directions in the atmosphere, (3) current velocities and directions in the surface mixed layer of the oceans, and (4) rate and geographical pattern of precipitation. As a fifth parameter in our scenarios, we consider the effect of temperature on primary volatilization emissions of PCBs. Comparison of dynamic model results using environmental parameters from the 20CE scenario against historical long-term monitoring data of concentrations of PCB 28 and PCB 153 in air from 16 different sites shows satisfactory agreement between modeled and measured PCBs concentrations. The 20CE scenario and A2 scenario were compared using steady-state calculations and assuming the same source characteristics of PCBs. Temperature differences between the two scenarios is the dominant factor that determines the difference in PCB concentrations in air. The higher temperatures in the A2 scenario drive increased primary and secondary volatilization emissions of PCBs, and enhance transport from temperate regions to the Arctic. The largest relative increase in concentrations of both PCB congeners in air under the A2 scenario occurs in the high Arctic and the remote Pacific Ocean. Generally, higher wind speeds under the A2 scenario result in more efficient intercontinental transport of PCB 28 and PCB 153 compared to the 20CE scenario. Our modeling indicates that in a future impacted by climate change,we can expect increased volatilization emissions and increased mobility of persistent organic pollutants with properties similar to those of PCBs.

Modeling the global fate and transport of perfluorooctanoic acid (PFOA) and perfluorooctanoate (PFO) emitted from direct sources using a multispecies mass balance model

2009 | Environ. Sci. Technol. | 43 (1134-1140)

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