Parameterization of wet deposition of sulfate by precipitation rate

A method for the estimation of wet deposition of sulfate is developed using routinely available meteorological data and the observed airborne sulfate concentration. This approach takes into account different mechanisms of precipitation formation that determine sulfate concentration in precipitation water. Four different precipitating cloud types, including cold cloud, warm cloud, stratified layered cloud and convective cloud, according to their precipitation formations are incorporated differently to estimate sulfate concentration in precipitation water. This method is implemented to estimate wet deposition of sulfate in Seoul for the days when the airborne sulfate concentration is available. The estimated wet deposition of sulfate shows that the model slightly overestimates the wet deposition of sulfate especially for the warm cloud case while it does underestimate sulfate deposition for the Bergeron process in developing precipitation particularly when the input airborne sulfate concentration is small. The precipitation amount weighted mean wet deposition of sulfate obtained from the model, overestimates that observed by a factor of 1.6 for this case study. This discrepancy might be associated with non-steady revolutional features of precipitating clouds and the resolvable scaling difference between the model and observation.     

Estimates of regional contributions to wet acid deposition in western Massachusetts during the summer of 1984

The General Motors mobile Atmospheric Research Laboratory was situated in rural western Massachusetts in the Berkshire Mountains for 62 days during the summer of 1984. One purpose of this study was to determine the source regions of wet acid deposition for this northeastern U.S. location. First, to apportion the precursors (sulfate, sulfur dioxide and nitrate) to source regions, daily ambient air samples were analyzed for the precursors as well as for tracer species that are associated with particular sources. Factor and trajectory analyses were then used to deduce the contributions of the Midwest and the Northeast to these precursors. Finally, the contribution of the precursors to precipitation acidity was estimated by analyzing the chemical constituents in the rain during seven precipitation events. Averaged over the entire duration of the study, the data show that Northeast sources accounted for about 60% of the precipitation sulfate and nitrate, while Midwest sources accounted for about 30%. The balance (~ 10%) was accounted for by background sulfate. A more useful way of examining the data is according to the type of storm that caused the wet deposition. The site was affected by two basic types of storms: coastal low-pressure systems that traveled up the Atlantic Coast, and cold fronts that approached from the west. During the coastal lowpressure events, the Midwestern contribution to precipitation acidity was zero, as easterly flows from the Atlantic Ocean dominated. The cold front events, however, were all associated with southwesterly flows, and the Midwest contributions exceeded the Northeast contributions. During these events, the average Midwest contribution to precipitation acidity was about 50%. For all events, the ratio of sulfate to nitrate was approximately 2:1 on an equivalent basis. During the coastal lows, the relative nitrate contributions were the highest. It was estimated that particulate sulfate scavenging was responsible for about half of the sulfate in the rain, while the other half was due to in-cloud oxidation of gaseous sulfur dioxide.     

Directional biases in back trajectories caused by model and input data

Back trajectory analyses are often used for source attribution estimates in visibility and other air quality studies. Several models and gridded meteorological datasets are readily available for generation of trajectories. The Big Bend Regional Aerosol and Visibility Observational (BRAVO) tracer study of July to October 1999 provided an opportunity to evaluate trajectory methods and input data against tracer concentrations, particulate data, and other source attribution techniques. Results showed evidence of systematic biases between the results of different back trajectory model and meteorological input data combinations at Big Bend National Park during the BRAVO. Most of the differences were because of the choice of meteorological data used as input to the trajectory models. Different back trajectories also resulted from the choice of trajectory model, primarily because of the different mechanisms used for vertical placement of the trajectories. No single model or single meteorological data set was found to be superior to the others, although rawinsonde data alone are too sparse in this region to be used as the only input data, and some combinations of model and input data could not be used to reproduce known attributions of tracers and simulated sulfate.     

A Receptor Climatology of Trajectories Originating in New York State

Air parcel trajectories originating from three locations in New York State are calculated for a three year period using the ARL-ATAD long-range transport model. Model output consisting of a trajectory segment's end point longitude and latitude position are analyzed to describe the long-range transport climatology by computing the frequency of occurrence of segment end points terminating over 33 receptor areas comprising east-central North America and a portion of the Atlantic Ocean. Results of the frequency of occurrence data show how often air pollutants emitted at or near the origin may be expected to drift over a specific downwind region. For the New York City airshed, it was found that 26.2% of the trajectories remain over New York State for transport times of 3 h and the frequency decreases to 5.2% after 24 h of transport. Approximately 40% of all trajectories are found to be over the Atlantic Ocean after 3 h of transport. When allowances are made for losses of data over the Atlantic Ocean, up to 64% of all trajectories are over the Atlantic Ocean after 24 h of transport. This frequency of trajectories over the Atlantic Ocean was found to be in agreement with wet and dry deposition modeling results conducted for power plants in New York City.     

An analysis of the impact of the Sudbury smelters on wet and dry deposition in OntariO

Meteorological analyses of acidic deposition data were undertaken to quantify the effect of Sudbury emissions on precipitation quality and air quality in Ontario during the period 1980–1983 with particular emphasis on the Sudbury smelter shutdown period (July 1982–March 1983). The techniques used included air parcel trajectories and detailed meteorological analysis.Results indicate that the contribution of the Sudbury smelters to sulphate wet deposition in central and southern Ontario was small—less than 12 % of the wet deposition at the study sites. The smelter contribution to sulphur dry deposition was greater—possibly as high as 47 % of the total at Kapuskasing, and up to about 20–30% of the total in central Ontario, with a smaller contribution (less than 5 %) to the southwest and west of Sudbury. These percentages apply to the smelter emission rate in the early 1980s, i.e. about 0.9 million metric tons of SO₂ per year.     

Nonlinear regression and ARIMA models for precipitation chemistry in East Central Florida from 1978 to 1997

Continuous monitoring of precipitation in East Central Florida has occurred since 1978 at a sampling site located on the University of Central Florida (UCF) campus. Monthly volume-weighted average (VWA) concentration for several major analytes that are present in precipitation samples was calculated from samples collected daily. Monthly VWA concentration and wet deposition of H(+), NH(4)(+), Ca(2+), Mg(2+), NO(3)(-), Cl(-) and SO(4)(2-) were evaluated by a nonlinear regression (NLR) model that considered 10-year data (from 1978 to 1987) and 20-year data (from 1978 to 1997). Little change in the NLR parameter estimates was indicated among the 10-year and 20-year evaluations except for general decreases in the predicted trends from the 10-year to the 20-year fits. Box-Jenkins autoregressive integrated moving average (ARIMA) models with linear trend were considered as an alternative to the NLR models for these data. The NLR and ARIMA model forecasts for 1998 were compared to the actual 1998 data. For monthly VWA concentration values, the two models gave similar results. For the wet deposition values, the ARIMA models performed considerably better.     

The accuracy of plume trajectories forecast using the U.K. Meteorological Office operational forecasting models and their sensitivity to calculation schemes

Studies into the various errors associated with long-range 950 mb trajectories computed using the Meteorological Office numerical weather prediction suite are presented. In the absence of observational data, trajectory error is measured using a verification computed from the model analysed and short-period forecast wind fields. While it is safest to assume that errors determined in this way are the minimum to be expected in relation to “true” trajectories, they nonetheless provide a useful diagnostic of model performance under different synoptic conditions and for trajectory releases at different stages of the forecast. Absolute and directional errors are analysed and the effect of altering the trajectory calculation schemes considered. The possible implications of the results for acid precipitation control strategies are discussed in some detail.     

The MICS-Asia study: model intercomparison of long-range transport and sulfur deposition in East Asia

An intercomparison study involving eight long-range transport models for sulfur deposition in East Asia has been initiated. The participating models included Eulerian and Lagrangian frameworks, with a wide variety of vertical resolutions and numerical approaches. Results from this study, in which models used common data sets for emissions, meteorology, and dry, wet and chemical conversion rates, are reported and discussed. Model results for sulfur dioxide and sulfate concentrations, wet deposition amounts, for the period January and May 1993, are compared with observed quantities at 18 surface sites in East Asia. At many sites the ensemble of models is found to have high skill in predicting observed quantities. At other sites all models show poor predictive capabilities. Source–receptor relationships estimated by the models are also compared. The models show a high degree of consistency in identifying the main source–receptor relationships, as well as in the relative contributions of wet/dry pathways for removal. But at some locations estimated deposition amounts can vary by a factor or 5. The influence of model structure and parameters on model performance is discussed. The main factors determining the deposition fields are the emissions and underlying meteorological fields. Model structure in terms of vertical resolution is found to be more important than the parameterizations used for chemical conversion and removal, as these processes are highly coupled and often work in compensating directions.     

Trajectory analysis of acid deposition data from the new jersey pine barrens

This research provides an example of the application of a simple method for evaluating regional interrelationships using air parcel trajectory analysis. An assessment of trajectories associated with storms affecting McDonald's Branch watershed (39°50′N, 74°30′W) is presented. A simple classification system is used to examine regional contributions of acid precursors. The results of the work suggest that major regional sources of acid precursor emissions dominated precipitation acidity for the Pine Barrens region from 1978 to 1981. An incremental approach to acid precipitation policy is suggested.     

Water-soluble main ions in precipitation over the southeastern Adriatic region: chemical composition and long-range transport

Background, aim and scope  

Precipitation samples collected from 1995 to 2000 at meteorological station in the eastern outskirts of Herceg Novi (Montenegro) were analysed on Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl^–, SO₄ ^2–, NO₃ ^– and NH₄ ⁺. Four-day backward trajectory simulations were conducted during the precipitation period to investigate the regional transport of main ions and their deposition in the region of the southeastern Adriatic Sea. The air mass trajectories were classified into six trajectory categories by the origin and direction of their approach to Herceg Novi.     

Analysis of long-range transport influences on urban PM10 using two-stage atmospheric trajectory clusters

There is evidence that long-range transport of natural and/or anthropogenic particles can have a negative impact on urban air quality. Certain European cities may fail to comply with the currently implemented 24-h PM₁₀ limit value due to the additional impact of remote sources of particles, which are not controllable at local level. For that reason, reliable methodologies identifying long-range transport patterns and quantifying their contribution to urban PM₁₀ levels are required. In this study, a two-stage clustering methodology was developed and applied to back trajectories arriving in three European cities: Athens, Madrid and Birmingham, which experience large, moderate and small numbers of daily PM₁₀ episodes, respectively. The atmospheric trajectories used in this analysis were computed with HYSPLIT model (NOAA) for a 3-year period. The two-stage cluster analysis has the advantage of providing highly disaggregated trajectory clusters, which proved to correspond to significantly different PM₁₀ levels. In the case of Madrid and Birmingham, clusters of trajectories originating from North Africa and continental Europe, respectively, were strongly associated with the highest PM₁₀ levels recorded in selected monitoring stations. In Athens, long-range transport patterns and trans-boundary influences were less evident, which highlighted the more substantial impact of local emission sources. Finally, two simple statistical indexes were proposed for assessing PM₁₀ episodes associated with different clusters of trajectories. This study has established a practical methodology for examining the impact of long-range atmospheric transport on local air quality, without resorting to high resource-demanding source apportionment techniques.     

Long-term assessment of the wet precipitation chemistry in Austria (1984-1999)

The aim of the present study was to determine the long-time trends in concentrations and depositions of major ions in wet precipitation samples collected at 11 sampling sites from the Austrian precipitation chemistry network in the period 1984-1999. The analytical results were treated by the use of least square linear regression method. It is shown that a serious decrease of sulfate (between 30% and 60% for the period) and hydrogen ion (between 60% and 102% for the period) concentrations and depositions is achieved at almost all sampling sites and in most of these cases the linear trend proves to be statistically significant. Nitrogen containing ions and base cations do not reveal a distinct trend of changing and in the majority of the sites the linear models are not adequate. In principle, an overall slight concentration and deposition decrease for these major ions is observed (up to 30% for the period of observation) but some substantial exceptions are also found (site Haunsberg or site Lobau). The changes in chloride concentration and deposition, too, do not indicate significant linear trend and, in general, are decreasing for the period of monitoring. In order to give some explanation of the exceptional behaviour of some of the major ions in several sites, an additional comparison with Austrian emission data (sulfur dioxide, nitrogen oxides, ammonium) and with data from five EMEP sites from neighbouring countries is performed. A significant West-East trend of acidity increase is found as well as a good correlation with the emission trends. Therefore, both transboundary and specific local factors could be substantial factors in the wet precipitation chemistry in the region.     

Analysis of rainfall and fine aerosol data using clustered trajectory analysis for National Park sites in the Western US

We calculated daily back-trajectories using the NOAA-HYSPLIT model to analyze 7 years of precipitation and PM2.5 data from three National Park sites in the Western US. Using a k-means clustering algorithm, the trajectories were segregated into six main transport patterns. At each site, we calculated trajectory clusters for 1, 5, and 10 days to represent short, medium and long-range flow patterns. Most clusters show marked seasonality. Faster flow patterns are more prevalent in winter, and slower/stagnant patterns are more prevalent in summer. The analyses between the 1, 5, and 10-day clusters revealed that the clusters of different duration show very different predictive power for rainfall and PM2.5. We found that the 1-day clusters are a better predictor for precipitation and PM2.5 concentrations, followed by the 5-day clusters. The 10-day clusters did a poorer job of differentiating precipitation and PM2.5. This is because the 10-day clusters show the greatest variability during the first day or two of transport.     

Source and Budget of Sulfate in Precipitation From Central Alberta,Canada

Rain, hail, and snow samples collected in central Alberta have been analyzed for sulfate and chloride content using a conductometric titration method. The mean values of sulfate concentration in rain and hail collected in the region of sulfur extraction gas plants were 2.7 mg/l and 2.9 mg/l respectively. The mean value of the sulfate content of a large number of hail samples collected from one severe storm well removed from a major SO₂ source was only 0.6 mg/l. Several snow samples collected in Alberta and southern British Columbia had a mean sulfate content of less than 0.5 mg/l. These results are discussed in terms of the efficiency with which SO₂ is removed from the atmosphere by the different precipitation processes. The results strongly suggest that most of the sulfate found in central Alberta precipitation is of local industrial origin.

By comparing the sulfate deposition in precipitation around one isolated gas plant with the known SO₂ emission rate, a local atmospheric sulfur budget is derived. This budget indicates that the summertime convective storms are a very efficient mechanism for removing the SO₂ from the atmosphere, with between 32 and 46% of the sulfur emitted as SO₂ arriving at the ground as sulfate sulfur within a radius of 25 miles of the source. In contrast snow is a very inefficient removal mechanism, since in winter less than 2% of the sulfur emission is deposited in the snowfall near the source.     

Origin and distribution of trace elements in high-elevation precipitation in southern China

Introduction

During a 2009 investigation of the transport and deposition of trace elements in southern China, 37 event-based precipitation samples were collected at an observatory on Mount Heng, China (1,269?m asl).

Methods

Concentrations of trace elements were analyzed using inductively coupled plasma?Cmass spectrometry and the wet deposition fluxes were established. A combination of techniques including enrichment factor analysis, principal component analysis, and back trajectory models were used to identify pollutant sources.

Results

Trace element concentrations at Mount Heng were among the highest with respect to measured values reported elsewhere. All elements were of non-marine origin. The elements Pb, As, Cu, Se, and Cd were anthropogenic, while Fe, Cr, V, Ba, Mn, and Ni were of mixed crustal/anthropogenic origin. The crustal and anthropogenic contributions of trace elements were 12.8 % (0.9?~?17.4 %) and 87.2 % (82.6?~?99.1 %), with the maximum crustal fraction being 17.4 % for Fe. Coal combustion, soil and road dust, metallurgical processes, and industrial activities contributed to the element composition.

Conclusions

Summit precipitation events were primarily distant in origin. Medium- to long-range transport of trace elements from the Yangtze River Delta and northern China played an important role in wet deposition at Mount Heng, while air masses from south or southeast of the station were generally low in trace element concentrations.     

Long-term relationships between mercury wet deposition and meteorology

Daily-event precipitation samples collected in Underhill, VT from 1995 to 2006 were analyzed for total mercury and results suggest that there were no statistically significant changes in annual mercury wet deposition over time, despite significant emissions reductions in the Northeast United States. Meteorological analysis indicates that mercury deposition has not decreased as transport of emissions from major source regions in the Midwest and East Coast have consistently contributed to the largest observed mercury wet deposition amounts over the period. In contrast, annual volume-weighted mean (VWM) mercury concentration declined slightly over the 12-years, and a significant decrease was observed from CY 2001 to 2006. An increase in the total annual precipitation amount corresponded with the decline in annual VWM mercury concentration. Analysis suggests that the increase in precipitation observed was strongly related to changes in the amount and type of precipitation that fell seasonally, and this departure was attributed to a response in meteorological conditions to climate variability and the El Niño-Southern Oscillation (ENSO) cycle. Increased amounts of rainfall and mixed precipitation (mixture of rainfall and snowfall), particularly in the spring and fall seasons, enhanced annual precipitation amounts and resulted in declining VWM mercury concentrations during these periods. Thus, declines in concentration at the more remote Underhill site appear to be more directly linked to local scale meteorological and climatological variability than to a reduction in emissions of mercury to the atmosphere.     

Clean Air Corridors: A Geographic and

Meteorological factors, pollutant emissions, and geographic regions related to transport of low optical extinction coefficient air to Grand Canyon National Park were examined. Back trajectories were generated by two models, the Atmospheric Transport and Dispersion Model (ATAD) and an approach using the Nested Grid Model output for a Lagrangian particle transport model (NGM/ CAPITA). Meteorological information along the trajectories was analyzed for its relationship to visibility at the Grand Canyon. Case studies considered days with anomalously clean air from the southwest and dirty air from the northwest. Clean air was most frequently from the north and northwest, rarely from the south. Low emissions, high ventilation and washout by precipitation was associated with clean air. All clean days with transport from the Los Angeles area had upper-level low pressure over the region with high ventilation and usually abundant precipitation. The dirtiest days with transport from the northwest were affected by forest fires.     

Composition of wet deposition in Kaynarca,Turkey

In this work, composition of wet deposition in Kaynarca, Turkey is studied by collecting precipitation samples during more than a 2-year period. August 1993-November 1995. Concentrations of the main cations Na+, Mg2+, Ca2+, K+, NH4+ and the main anions Cl-, NO3- and SO4(2-) together with pH were studied. The average pH value at Kaynarca was near neutral, 5.59. Results indicated that SO4(2-) concentration in precipitation was very high, as was Ca2+, neutralizing the acidity. Acidic wet deposition samples were generally obtained in winter. Enrichment factors for sea and soil indicate the strong effects of sea and soil, specifically limestone on the composition of precipitation. Non-sea salt fractions of SO4(2-) were found to range from 0.955 to 0.980, showing the effect of non-sea sources, especially emissions from fossil-fuel combustion, on the pH of samples. Trajectory analysis showed that cyclones originating from northwestern, central and eastern parts of Europe have generally high sulfate and nitrate concentrations and low pH.     

Numerical studies of acidification processes within and below clouds with a flow-through chemical reactor model

A flow-through chemical reactor model has been exercised to assess the importance of various oxidation reactions and cloud processes on wet removal and redistribution of atmospheric pollutants and to investigate the effect of in-cloud acidification on precipitation chemistry at the surface. Preliminary results indicate that in-cloud acidification accounts for more than 60% of the wet deposited acids derived from acidification of initial SO₂, that 42–57% of water-soluble, non-reactive NH₃ and HNO₃ are removed by wet deposition. The pseudo-first-order conversion rate of SO₂ to SO₄²⁻ ranges from 3 to 25% h ⁻¹ depending on initial and boundary conditions.Sensitivity studies have been carried out to test the importance of time evolution of clouds on partitioning of pollutants in the atmosphere and to investigate the variability of precipitation chemistry due to changes in rate constants. The distributions of NH₃ and HNO₃ are found to be dependent largely on the cloud microphysical parameters, while the distributions of H₂O₂ and SO₂ depend largely on initial conditions of both species. Individual physical and chemical mechanisms can determine the overall rate of sulfate wet deposition at different stages of cloud evolution.     

Regional trends in wet deposition of sulfate in the United States and SO2 emissions from 1980 through 1995

Regional trends of seasonal and annual wet deposition and precipitation-weighted concentrations (PWCs) of sulfate in the United States over the period 1980–1995 were developed from monitoring data and scaled to a mean of unity. To reduce some effects of year to year climatological variability, the unitless regional deposition and PWC trends were averaged (hereafter termed CONCDEP). The SO₂ emissions data over the same period from the United States, Canada, and northern Mexico, aggregated by state and province, were weighted appropriately for each deposition region in turn to produce scaled trends of the emissions affecting each region. The emission-weighting factors, which were held constant year to year, were estimated by exercise of a regional transport model. The sulfate CONCDEP regional trends are generally similar to those of regionally weighted SO₂ emissions, although the latter trends are less steep and the former trends have more year to year variability. In eastern regions, sulfate CONCDEPs and SO₂ emissions patterns both generally show an initial decrease, an essentially trendless middle period, and a final decrease as reductions mandated by the Acid Rain Provisions of the 1990 Clean Air Act Amendments began. Linear regressions of regional sulfate CONCDEPs on corresponding regionally weighted SO₂ emissions produced statistically significant relationships in all regions. The analysis indicated that although regional sulfate CONCDEPs decreased relatively faster than did SO₂ emissions during the period in all regions except the Great Plains, in general the slopes were not significantly different from unity.