IMPACT OF 2000-2050 CLIMATE CHANGE ON GLOBAL ATMOSPHERIC TRANSPORT AND DEPOSITION OF MERCURY

Since it is very toxic and accumulates in organisms, particularly in fish, mercury is a very important pollutant and one of the most studies. And this concern over the toxicity and human health risks of mercury has prompted efforts to regulate anthropogenic emissions. As mercury pollution problem is getting increasingly serious, we are curious about how serious this problem will be in the future. What is more, how the climate change in the future will affect the mercury concentration in the atmosphere. So we investigate the impact of climate change on mercury concentration in the atmosphere. We focus on the comparison between the mercury data for year 2000 and for year 2050. The GEOS-Chem model shows that the mercury concentrations for all tracers (1 to 3), elemental mercury (Hg(0)), divalent mercury (Hg(II)) and primary particulate mercury (Hg(P)) have differences between 2000 and 2050 in most regions over the world. From the model results, we can see the climate change from 2000 to 2050 would decrease Hg(0) surface concentration in most of the world. The driving factors of Hg(0) surface concentration changes are natural emissions(ocean and vegetation) and the transformation reactions between Hg(0) and Hg(II). The climate change from 2000 to 2050 would increase Hg(II) surface concentration in most of mid-latitude continental parts of the world while decreasing Hg(II) surface concentration in most of high-latitude part of the world. The driving factors of Hg(II) surface concentration changes is deposition amount change (majorly wet deposition) from 2000 to 2050 and the transformation reactions between Hg(0) and Hg(II). Climate change would increase Hg(P) concentration in most of mid-latitude area of the world and meanwhile decrease Hg(P) concentration in most of high-latitude regions of the world. For the Hg(P) concentration changes, the major driving factor is the deposition amount change (mainly wet deposition) from 2000 to 2050.

Polychlorinated Biphenyls in Glaciers. 2. Model Results of Deposition and Incorporation Processes

In previous work, Alpine glaciers have been identified as a secondary source of persistent organic pollutants (POPs). However, detailed understanding of the processes organic chemicals undergo in a glacial system was missing. Here, we present results from a chemical fate model describing deposition and incorporation of polychlorinated biphenyls (PCBs) into an Alpine glacier (Fiescherhorn, Switzerland) and an Arctic glacier (Lomonosovfonna, Norway). To understand PCB fate and dynamics, we investigate the interaction of deposition, sorption to ice and particles in the atmosphere and within the glacier, revolatilization, diffusion and degradation, and discuss the effects of these processes on the fate of individual PCB congeners. The model is able to reproduce measured absolute concentrations in the two glaciers for most PCB congeners. While the model generally predicts concentration profiles peaking in the 1970s, in the measurements, this behavior can only be seen for higher-chlorinated PCB congeners on Fiescherhorn glacier. We suspect seasonal melt processes are disturbing the concentration profiles of the lower-chlorinated PCB congeners. While a lower-chlorinated PCB congener is mainly deposited by dry deposition and almost completely revolatilized after deposition, a higher-chlorinated PCB congener is predominantly transferred to the glacier surface by wet deposition and then is incorporated into the glacier ice. The incorporated amounts of PCBs are higher on the Alpine glacier than on the Arctic glacier due to the higher precipitation rate and aerosol particle concentration on the former. Future studies should include the effects of seasonal melt processes, calculate the quantities of PCBs incorporated into the entire glacier surface, and estimate the quantity of chemicals released from glaciers to determine the importance of glaciers as a secondary source of organic chemicals to remote aquatic ecosystems.

Mineral dust deposition in interglacial and glacial climate conditions: model results

The global aerosol/climate model ECHAM5-HAM is used in order to investigate the dust cycle for four interglacial and one glacial climate conditions. The 20-year time-slices are the pre-industrial control (CTRL), mid-Holocene (6000 years BP), last glacial inception (115000 years BP), Eemian (126000 years BP) and Last Glacial Maximum (LGM) (21000 years BP) time intervals. The study is focused on the Antarctic region. The model is able to reproduce the magnitude order of dust deposition globally for the pre-industial and LGM climates. Correlation coefficient of the natural logarithm of the observed and modeled values is 0.78 for the CTRL and 0.81 for the LGM. For the pre-industrial simulation the model overestimates observed values in Antarctica by a factor of about 2-3 due to overestimation of the Australian dust source and too high wet deposition in the Antarctica interior. In the LGM, the model underestimates dust deposition in eastern Antarctica by a factor of about 4-5 due to underestimation of the South American dust source. More records are needed to validate dust deposition for the past interglacial time-slices. The modeled results show that dust deposition in Antarctica in the past interglacial time-slices is higher than in the CTRL simulation. The largest increase of dust deposition in Antarctica is simulated for the LGM, showing about 10-fold increase compared to CTRL.

Relating vehicle generated pollutants to urban stormwater quality

Rapid urbanisation and resulting continuous increase in traffic has been recognised as key factors in the contribution of increased pollutant loads to urban stormwater and in turn to receiving waters. Urbanisation primarily increases anthropogenic activities and the percentage of impervious surfaces in urban areas. These processes are collectively responsible for urban stormwater pollution. In this regard, urban traffic and land use related activities have been recognised as the primary pollutant sources. This is primarily due to the generation of a range of key pollutants such as solids, heavy metals and PAHs. Appropriate treatment system design is the most viable approach to mitigate stormwater pollution. However, limited understanding of the pollutant process and transport pathways constrains effective treatment design. This highlights necessity for the detailed understanding of traffic and other land use related pollutants processes and pathways in relation to urban stormwater pollution. This study has created new knowledge in relation to pollutant processes and transport pathways encompassing atmospheric pollutants, atmospheric deposition and build-up on ground surfaces of traffic generated key pollutants. The research study was primarily based on in-depth experimental investigations. This thesis describes the extensive knowledge created relating to the processes of atmospheric pollutant build-up, atmospheric deposition and road surface build-up and establishing their relationships as a chain of processes. The analysis of atmospheric deposition revealed that both traffic and land use related sources contribute total suspended particulate matter (TSP) to the atmosphere. Traffic sources become dominant during weekdays whereas land use related sources become dominant during weekends due to the reduction in traffic sources. The analysis further concluded that atmospheric TSP, polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs) concentrations are highly influenced by total average daily heavy duty traffic, traffic congestion and the fraction of commercial and industrial land uses. A set of mathematical equation were developed to predict TSP, PAHs and HMs concentrations in the atmosphere based on the influential traffic and land use related parameters. Dry deposition samples were collected for different antecedent dry days and wet deposition samples were collected immediately after rainfall events. The dry deposition was found to increase with the antecedent dry days and consisted of relatively coarser particles (greater than 1.4 ìm) when compared to wet deposition. The wet deposition showed a strong affinity to rainfall depth, but was not related to the antecedent dry period. It was also found that smaller size particles (less than 1.4 ìm) travel much longer distances from the source and deposit mainly with the wet deposition. Pollutants in wet deposition are less sensitive to the source characteristics compared to dry deposition. Atmospheric deposition of HMs is not directly influenced by land use but rather by proximity to high emission sources such as highways. Therefore, it is important to consider atmospheric deposition as a key pollutant source to urban stormwater in the vicinity of these types of sources. Build-up was analysed for five different particle size fractions, namely, <1 ìm, 1-75 ìm, 75-150 ìm, 150-300 ìm and >300 ìm for solids, PAHs and HMs. The outcomes of the study indicated that PAHs and HMs in the <75 ìm size fraction are generated mainly by traffic related activities whereas the > 150 ìm size fraction is generated by both traffic and land use related sources. Atmospheric deposition is an important source for HMs build-up on roads, whereas the contribution of PAHs from atmospheric sources is limited. A comprehensive approach was developed to predict traffic and other land use related pollutants in urban stormwater based on traffic and other land use characteristics. This approach primarily included the development of a set of mathematical equations to predict traffic generated pollutants by linking traffic and land use characteristics to stormwater quality through mathematical modelling. The outcomes of this research will contribute to the design of appropriate treatment systems to safeguard urban receiving water quality for future traffic growth scenarios. The „real world. application of knowledge generated was demonstrated through mathematical modelling of solids in urban stormwater, accounting for the variability in traffic and land use characteristics.

Plant nutrients and major ions in the Little Sea, Studland, Dorset

This short paper records some measurements made on the Little Sea, a shallow, coastal, acidic lake on Studland Heath, Dorset. The lake, formed about 100 years ago by dunes cutting off a sea inlet, has not received any input of agricultural fertilizers or other waste products for at least the last 30 years. It is a Site of Special Scientific Interest (SSSI). Samples of surface water were taken from the northern and southern ends of the lake at 3-monthly intervals, from July 1995 to April 1996. The first samples in July 1995 were taken during a period of drought; rain, sometimes very heavy, came in late September. With the exception of silicate, potassium and phosphate, there were no large changes in plant nutrient concentrations during the year. The concentration of nitrate-nitrogen was very low (close to the limits of analytical detection), but total phosphorus at ca. 30 mu g per litre was similar to concentrations found in some of the Cumbrian eutrophic lakes. The large number of algal species at low cell/colony concentrations suggested that the lake is mesotrophic. Sodium, chloride and magnesium in the lake water were close to the same proportions as those found in sea water. Dry and wet deposition of sea-salts on the lake surface and its catchment area probably is the major source of sodium, magnesium and chloride ions in the lake, and also accounts for about half of the mean potassium and sulphate concentrations.

Iron organic speciation determination in rainwater using cathodic stripping voltammetry

A sensitive method using Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) has been developed to determine for the first time iron (Fe) organic speciation in rainwater over the typical natural range of pH. We have adapted techniques previously developed in other natural waters to rainwater samples, using the competing ligand 1-nitroso-2-naphthol (NN). The blank was equal to 0.17 ± 0.05 nM (n = 14) and the detection limit (DL) for labile Fe was 0.15 nM which is 10–70 times lower than that of previously published methods. The conditional stability constant for NN under rainwater conditions was calibrated over the pH range 5.52–6.20 through competition with ethylenediaminetetraacetic acid (EDTA). The calculated value of the logarithm of β′Fe3+3(NN)β′Fe3+(NN)3 increased linearly with increasing pH according to log β′Fe3+3(NN)=2.4±0.6×pH+11.9±3.5log β′Fe3+(NN)3=2.4±0.6×pH+11.9±3.5 (salinity = 2.9, T = 20 °C). The validation of the method was carried out using desferrioxamine mesylate B (DFOB) as a natural model ligand for Fe. Adequate detection windows were defined to detect this class of ligands in rainwater with 40 μM of NN from pH 5.52 to 6.20. The concentration of Fe-complexing natural ligands was determined for the first time in three unfiltered and one filtered rainwater samples. Organic Fe-complexing ligand concentrations varied from 104.2 ± 4.1 nM equivalent of Fe(III) to 336.2 ± 19.0 nM equivalent of Fe(III) and the logarithm of the conditional stability constants, with respect to Fe3+, varied from 21.1 ± 0.2 to 22.8 ± 0.3. This method will provide important data for improving our understanding of the role of wet deposition in the biogeochemical cycling of iron.

Seasonal ITCZ migration dynamically controls the location of the (sub)tropical Atlantic biogeochemical divide

Inorganic nitrogen depletion restricts productivity in much of the low-latitude oceans, generating a selective advantage for diazotrophic organisms capable of fixing atmospheric dinitrogen (N2). However, the abundance and activity of diazotrophs can in turn be controlled by the availability of other potentially limiting nutrients, including phosphorus (P) and iron (Fe). Here we present high-resolution data (∼0.3°) for dissolved iron, aluminum, and inorganic phosphorus that confirm the existence of a sharp north–south biogeochemical boundary in the surface nutrient concentrations of the (sub)tropical Atlantic Ocean. Combining satellite-based precipitation data with results from a previous study, we here demonstrate that wet deposition in the region of the intertropical convergence zone acts as the major dissolved iron source to surface waters. Moreover, corresponding observations of N2 fixation and the distribution of diazotrophic Trichodesmium spp. indicate that movement in the region of elevated dissolved iron as a result of the seasonal migration of the intertropical convergence zone drives a shift in the latitudinal distribution of diazotrophy and corresponding dissolved inorganic phosphorus depletion. These conclusions are consistent with the results of an idealized numerical model of the system. The boundary between the distinct biogeochemical systems of the (sub)tropical Atlantic thus appears to be defined by the diazotrophic response to spatial–temporal variability in external Fe inputs. Consequently, in addition to demonstrating a unique seasonal cycle forced by atmospheric nutrient inputs, we suggest that the underlying biogeochemical mechanisms would likely characterize the response of oligotrophic systems to altered environmental forcing over longer timescales.

Air-sea exchange of methanol and acetone during HiWinGS: Estimation of air phase, water phase gas transfer velocities

The air-sea fluxes of methanol and acetone were measured concurrently using a proton-transfer-reaction mass spectrometer (PTR-MS) with the eddy covariance (EC) technique during the High Wind Gas Exchange Study (HiWinGS) in 2013. The seawater concentrations of these compounds were also measured twice daily with the same PTR-MS coupled to a membrane inlet. Dissolved concentrations near the surface ranged from 7 to 28 nM for methanol and from 3 to 9 nM for acetone. Both gases were consistently transported from the atmosphere to the ocean as a result of their low sea surface saturations. The largest influxes were observed in regions of high atmospheric concentrations and strong winds (up to 25 m s(-1)). Comparison of the total air-sea transfer velocity of these two gases (K-a), along with the in situ sensible heat transfer rate, allows us to constrain the individual gas transfer velocity in the air phase (k(a)) and water phase (k(w)). Among existing parameterizations, the scaling of k(a) from the COARE model is the most consistent with our observations. The k(w) we estimated is comparable to the tangential (shear driven) transfer velocity previously determined from measurements of dimethyl sulfide. Lastly, we estimate the wet deposition of methanol and acetone in our study region and evaluate the lifetimes of these compounds in the surface ocean and lower atmosphere with respect to total (dry plus wet) atmospheric deposition.

Air-Sea Exchange of Legacy POPs in the North Sea Based on Results of Fate and Transport, and Shelf-Sea Hydrodynamic Ocean Models

The air-sea exchange of two legacy persistent organic pollutants (POPs), γ-HCH and PCB 153, in the North Sea, is presented and discussed using results of regional fate and transport and shelf-sea hydrodynamic ocean models for the period 1996–2005. Air-sea exchange occurs through gas exchange (deposition and volatilization), wet deposition and dry deposition. Atmospheric concentrations are interpolated into the model domain from results of the EMEP MSC-East multi-compartmental model (Gusev et al, 2009). The North Sea is net depositional for γ-HCH, and is dominated by gas deposition with notable seasonal variability and a downward trend over the 10 year period. Volatilization rates of γ-HCH are generally a factor of 2–3 less than gas deposition in winter, spring and summer but greater in autumn when the North Sea is net volatilizational. A downward trend in fugacity ratios is found, since gas deposition is decreasing faster than volatilization. The North Sea is net volatilizational for PCB 153, with highest rates of volatilization to deposition found in the areas surrounding polluted British and continental river sources. Large quantities of PCB 153 entering through rivers lead to very high local rates of volatilization.

Lagrangian analysis of low level anthropogenic plume processing across the North Atlantic

The photochemical evolution of an anthropogenic plume from the New-York/Boston region during its transport at low altitudes over the North Atlantic to the European west coast has been studied using a Lagrangian framework. This plume, originally strongly polluted, was sampled by research aircraft just off the North American east coast on 3 successive days, and 3 days downwind off the west coast of Ireland where another aircraft re-sampled a weakly polluted plume. Changes in trace gas concentrations during transport were reproduced using a photochemical trajectory model including deposition and mixing effects. Chemical and wet deposition processing dominated the evolution of all pollutants in the plume. The mean net O3 production was evaluated to be -5 ppbv/day leading to low values of O3 by the time the plume reached Europe. Wet deposition of nitric acid was responsible for an 80% reduction in this O3 production. If the plume had not encountered precipitation, it would have reached the Europe with O3 levels up to 80-90 ppbv, and CO levels between 120 and 140 ppbv. Photochemical destruction also played a more important role than mixing in the evolution of plume CO due to high levels of both O3 and water vapour showing that CO cannot always be used as a tracer for polluted air masses, especially for plumes transported at low altitudes. The results also show that, in this case, an important increase in the O3/CO slope can be attributed to chemical destruction of CO and not to photochemical O3 production as is often assumed.

Changes in the global sulfate burden due to perturbations in global CO2 concentrations

A large ensemble of general circulation model (GCM) integrations coupled to a fully interactive sulfur cycle scheme were run on the climateprediction.net platform to investigate the uncertainty in the climate response to sulfate aerosol and carbon dioxide (CO2) forcing. The sulfate burden within the model (and the atmosphere) depends on the balance between formation processes and deposition (wet and dry). The wet removal processes for sulfate aerosol are much faster than dry removal and so any changes in atmospheric circulation, cloud cover, and precipitation will feed back on the sulfate burden. When CO2 is doubled in the Hadley Centre Slab Ocean Model (HadSM3), global mean precipitation increased by 5%; however, the global mean sulfate burden increased by 10%. Despite the global mean increase in precipitation, there were large areas of the model showing decreases in precipitation (and cloud cover) in the Northern Hemisphere during June–August, which reduced wet deposition and allowed the sulfate burden to increase. Further experiments were also undertaken with and without doubling CO2 while including a future anthropogenic sulfur emissions scenario. Doubling CO2 further enhanced the increases in sulfate burden associated with increased anthropogenic sulfur emissions as observed in the doubled CO2-only experiment. The implications are that the climate response to doubling CO2 can influence the amount of sulfate within the atmosphere and, despite increases in global mean precipitation, may act to increase it.

A Lagrangian model of air-mass photochemistry and mixing using a trajectory ensemble: the Cambridge Tropospheric Trajectory model of Chemistry And Transport (CiTTyCAT) version 4.2

A Lagrangian model of photochemistry and mixing is described (CiTTyCAT, stemming from the Cambridge Tropospheric Trajectory model of Chemistry And Transport), which is suitable for transport and chemistry studies throughout the troposphere. Over the last five years, the model has been developed in parallel at several different institutions and here those developments have been incorporated into one "community" model and documented for the first time. The key photochemical developments include a new scheme for biogenic volatile organic compounds and updated emissions schemes. The key physical development is to evolve composition following an ensemble of trajectories within neighbouring air-masses, including a simple scheme for mixing between them via an evolving "background profile", both within the boundary layer and free troposphere. The model runs along trajectories pre-calculated using winds and temperature from meteorological analyses. In addition, boundary layer height and precipitation rates, output from the analysis model, are interpolated to trajectory points and used as inputs to the mixing and wet deposition schemes. The model is most suitable in regimes when the effects of small-scale turbulent mixing are slow relative to advection by the resolved winds so that coherent air-masses form with distinct composition and strong gradients between them. Such air-masses can persist for many days while stretching, folding and thinning. Lagrangian models offer a useful framework for picking apart the processes of air-mass evolution over inter-continental distances, without being hindered by the numerical diffusion inherent to global Eulerian models. The model, including different box and trajectory modes, is described and some output for each of the modes is presented for evaluation. The model is available for download from a Subversion-controlled repository by contacting the corresponding authors.

Impact of the modal aerosol scheme GLOMAP-mode on aerosol forcing in the Hadley Centre Global Environmental Model

The Hadley Centre Global Environmental Model (HadGEM) includes two aerosol schemes: the Coupled Large-scale Aerosol Simulator for Studies in Climate (CLASSIC), and the new Global Model of Aerosol Processes (GLOMAP-mode). GLOMAP-mode is a modal aerosol microphysics scheme that simulates not only aerosol mass but also aerosol number, represents internally-mixed particles, and includes aerosol microphysical processes such as nucleation. In this study, both schemes provide hindcast simulations of natural and anthropogenic aerosol species for the period 2000–2006. HadGEM simulations of the aerosol optical depth using GLOMAP-mode compare better than CLASSIC against a data-assimilated aerosol re-analysis and aerosol ground-based observations. Because of differences in wet deposition rates, GLOMAP-mode sulphate aerosol residence time is two days longer than CLASSIC sulphate aerosols, whereas black carbon residence time is much shorter. As a result, CLASSIC underestimates aerosol optical depths in continental regions of the Northern Hemisphere and likely overestimates absorption in remote regions. Aerosol direct and first indirect radiative forcings are computed from simulations of aerosols with emissions for the year 1850 and 2000. In 1850, GLOMAP-mode predicts lower aerosol optical depths and higher cloud droplet number concentrations than CLASSIC. Consequently, simulated clouds are much less susceptible to natural and anthropogenic aerosol changes when the microphysical scheme is used. In particular, the response of cloud condensation nuclei to an increase in dimethyl sulphide emissions becomes a factor of four smaller. The combined effect of different 1850 baselines, residence times, and abilities to affect cloud droplet number, leads to substantial differences in the aerosol forcings simulated by the two schemes. GLOMAP-mode finds a presentday direct aerosol forcing of −0.49Wm−2 on a global average, 72% stronger than the corresponding forcing from CLASSIC. This difference is compensated by changes in first indirect aerosol forcing: the forcing of −1.17Wm−2 obtained with GLOMAP-mode is 20% weaker than with CLASSIC. Results suggest that mass-based schemes such as CLASSIC lack the necessary sophistication to provide realistic input to aerosol-cloud interaction schemes. Furthermore, the importance of the 1850 baseline highlights how model skill in predicting present-day aerosol does not guarantee reliable forcing estimates. Those findings suggest that the more complex representation of aerosol processes in microphysical schemes improves the fidelity of simulated aerosol forcings.

Impact of vegetation and preferential source areas on global dust aerosol: results from a model study

[1] We present a model of the dust cycle that successfully predicts dust emissions as determined by land surface properties, monthly vegetation and snow cover, and 6-hourly surface wind speeds for the years 1982–1993. The model takes account of the role of dry lake beds as preferential source areas for dust emission. The occurrence of these preferential sources is determined by a water routing and storage model. The dust source scheme also explicitly takes into account the role of vegetation type as well as monthly vegetation cover. Dust transport is computed using assimilated winds for the years 1987–1990. Deposition of dust occurs through dry and wet deposition, where subcloud scavenging is calculated using assimilated precipitation fields. Comparison of simulated patterns of atmospheric dust loading with the Total Ozone Mapping Spectrometer satellite absorbing aerosol index shows that the model produces realistic results from daily to interannual timescales. The magnitude of dust deposition agrees well with sediment flux data from marine sites. Emission of submicron dust from preferential source areas are required for the computation of a realistic dust optical thickness. Sensitivity studies show that Asian dust source strengths are particularly sensitive to the seasonality of vegetation cover.

Global and diffuse solar irradiances in urban and rural areas in southeast Brazil

The seasonal evolution of daily and hourly values of global and diffuse solar radiation at the surface are compared for the cities of Sao Paulo and Botucatu, both located in Southeast Brazil and representative of urban and rural areas, respectively. The comparisons are based on measurements of global and diffuse solar irradiance carried out at the surface during a six year simultaneous period in these two cities. Despite the similar latitude and altitude, the seasonal evolution of daily values indicate that Sao Paulo receives, during clear sky days, 7.8% less global irradiance in August and 5.1% less in June than Botucatu. On the other hand, Sao Paulo receives, during clear sky days, 3.6% more diffuse irradiance in August and 15.6% more in June than Botucatu. The seasonal variation of the diurnal cycle confirms these differences and indicates that they are more pronounced during the afternoon. The regional differences are related to the distance from the Atlantic Ocean, systematic penetration of the sea breeze and daytime evolution of the particulate matter in Sao Paulo. An important mechanism controlling the spatial distribution of solar radiation, on a regional scale, is the sea breeze penetration in Sao Paulo, bringing moisture and maritime aerosol that in turn further increases the solar radiation scattering due to pollution and further reduces the intensity of the direct component of solar radiation at the surface. Surprisingly, under clear sky conditions the atmospheric attenuation of solar radiation in Botucatu during winter - the biomass burning period due to the sugar cane harvest - is equivalent to that at Sao Paulo City, indicating that the contamination during sugar cane harvest in Southeast Brazil has a large impact in the solar radiation field at the surface.