The evolution of the pH in Europe (1986-1997) using panel data

The temporal evolution of pH values in precipitation over Europe during the period 1986-1997 is examined using panel data. The use of panel data techniques allows us to determine the temporal evolution of groups of stations rather than analyzing the temporal behavior of each of them. The analysis reveals three different temporal patterns: Peripheral, Central and French. We find a significant increasing trend (P < 0.00001) in both Peripheral and Central patterns. The annual increases are +0.057 pH-units yr(-1) and +0.022 pH-units yr(-1) respectively. However the French pattern is characterized by a significant decreasing trend (P < 0.004) and the annual decrease is -0.022 pH-units yr(-1). The standard errors of panel data estimates are around 47% smaller than those of classical pooling and 32% smaller than aggregate time-series regression. The use of panel data produces higher R2 values than classical pooling and aggregate data. This technique takes into account the individual heterogeneity, allows a larger number of data points and improves the efficiency of the estimates. In general, the policies of governments to reduce pollutant emissions seem to be effective.     

Linking national agrarian policy to deforestation in the Peruvian Amazon: a case study of Tambopata, 1986-1997

Amazonian deforestation rates vary regionally, and ebb and flow according to macroeconomic policy and local social factors. We used remote sensing and field interviews to investigate deforestation patterns and drivers at a Peruvian frontier during 1986-1991, when rural credit and guaranteed markets were available; and 1991-1997, when structural adjustment measures were imposed. The highest rate of clearing (1.5% gross) was observed along roads during 1986-1991. Roadside deforestation slowed in 1991-1997 (0.7% gross) and extensive regrowth yielded a net increase in forest cover (0.5%). Deforestation along rivers was relatively constant. Riverside farms today retain more land in both crops and forest than do roadside farms where pasture and successional growth predominate. Long-term residents maintain more forest on their farms than do recent colonists, but proximity to urban markets is the strongest predictor of forest cover. Future credit programs must reflect spatial patterns of development and ecological vulnerability, and support the recuperation of fallow lands and secondary forest.     

Forest health status in the Carpathian Mountains over the period 1997-2001

The results of forest health status assessments in the Carpathian Mountains from the monitoring networks developed by the European Union Scheme on the Protection of Forest Against Atmospheric Pollution (EU Scheme) and International Co-operative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP-Forests), have led to a better understanding of the impact of air pollution and other stressors on forests at the regional scale. During the period 1997-2001, forests in the Carpathian Mountains were severely affected by air pollution and natural stresses with 29.7-34.9% of the trees included in defoliation classes 2-4. The broadleaves were slightly healthier than the conifers, and European beech (Fagus sylvatica) was the least affected species. Norway spruce (Picea abies) has poor health status, with 42.9-46.6% of the trees damaged (2-4% defoliation classes). Silver fir (Abies alba) damage was also high, with 46.0-50.9% in defoliation classes 2-4. Pines (primarily Pinus sylvestris) were the least affected of the conifers, with 24.9-33.8% in defoliation classes 2-4. The results from the transnational networks (16 x 16 km) show that the Carpathian forests are slightly more damaged than the average for the entire Europe. The correlative studies performed in individual European countries show the relationships between air pollution stressors with trends in defoliation and a possible effect of natural stresses at each site. More specific, effects of tree age, drought, ozone and acid deposition critical level exceedances were demonstrated to affect crown condition.     

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.     

Trends and variability of ground-level O3 in Connecticut over the period 1981-1997

The temporal and spatial characteristics of ground-level (tropospheric) O3 measured at 10 monitoring stations in Connecticut were studied from 1981 to 1997. To detect the O3 trend caused by changes in precursor emissions, moving average filters and a linear least-squared regression model were used to eliminate the short-term variation and effects of temperature from raw time-series O3 data. The results showed a significant decrease in the number of days exceeding the National Ambient Air Quality Standards (NAAQS) and a small change in total O3 concentration. The analysis indicated that the variation of daily maximum O3, caused by changes in emissions, explained more than 10% of the total O3 variation in Bridgeport and East Hartford during the past 17 years. Meanwhile, a strong weekly cycle was also found in O3 time-series data, resulting in lower O3 concentration in urban areas than in nonurban areas, implying that land use and land cover have impacts on the spatial distribution of ground-level O3 in Connecticut.     

Spatial analysis of extreme precipitation in Sweden 1961-2000

Extreme daily precipitation in Sweden for the years 1961-2000 is analyzed with respect to spatial scale, regional variations and associated weather types. Correlograms based on a lag distance of 30 km estimated the spatial scale of variation of the annual mean precipitation, the 99th percentile of daily precipitation and the average of annual maximum daily precipitation to 100 km, 60-100 km and 40-70 km, respectively. Regions of correlation with respect to precipitation at 82 stations during days of extreme events are identified through Maximum-Likelihood Factor Analysis. Eleven factors are found to provide the optimum factor solution. Weather types for the days of extreme events are determined by an objective classification scheme, based on daily sea level pressure, which is modified by subjective inclusion of fronts. In total, 63% of the extreme events occurred during cyclonic weather types, 32% during frontal, 3% during directional and 2% during anticyclonic types. The frequency of the weather types during extreme events varied between the regions however.     

Ionic composition of wet precipitation over the southern slope of central Himalayas,Nepal

Severe atmospheric pollution transported to Himalayas from South Asia may affect fragile ecosystem and can be harmful for human health in the region. In order to understand the atmospheric chemistry in the southern slope of central Himalayas, where the data is limited, precipitation has been sampled at four sites: Kathmandu (1,314 m), Dhunche (2,065 m), Dimsa (3,078 m), and Gosainkunda (4,417 m) in Nepal for over a 1-year period characterized by an urban, rural, and remote sites, respectively. HCO₃ ^? is the dominant anion, while the NH₄ ⁺ is the dominant cation in precipitation at the four sites. Generally, most of ions (e.g., SO₄ ^2?, NO₃ ^?, NH₄ ⁺, HCO₃ ^?, and Ca²⁺) have higher concentrations in urban site compared to the rural sites. Neutralization factor calculation showed that precipitation in the region is highly neutralized by NH₄ ⁺ and Ca²⁺. Empirical orthogonal function and correlation analysis indicated that the precipitation chemistry was mostly influenced by crustal, anthropogenic, and marine sources in Nepal. Among different sites, urban area was mostly influenced by anthropogenic inputs and crustal dusts, whereas remote sites were mostly from marine and crustal sources. Seasonal variations show higher ionic concentrations during non-monsoon seasons mainly due to limited precipitation amount. On the other hand, lower ionic concentrations were observed during monsoon season when higher amount of precipitation washes out aerosols. Thus, precipitation chemistry from this work can provide a useful database to evaluate atmospheric environment and its impacts on ecosystem in the southern slope of central Himalayas, Nepal.     

Hydrogen behaviour and ion concentrations in precipitation of Europe and the United States

Hydrogen ions in precipitation vary primarily with (SO4 + NO3) concentration. However the slope of the H: (SO4 + NO3) relation for high concentrations (0.60 and 0.61) is twice that at low concentrations (0.32 and 0.22) in European and US samples respectively. Sulphuric and nitric acid dominate precipitation in the US. Precipitation in Europe, although nearly equally acid, is dominated by NH4+, Ca2+, and Mg2+ salts at total ionic concentrations 2 and 3 times higher. Ion concentrations in precipitation, other than H, are proportional to their respective emission fluxes.     

Multivariate analysis of photo-Fenton degradation of the herbicides tebuthiuron, diuron and 2,4-D

The degradation of herbicides in aqueous solution by photo-Fenton process using ferrioxalate complex (FeOx) as source of Fe2+ was evaluated under blacklight irradiation. The commercial products of the herbicides tebuthiuron, diuron and 2,4-D were used. The multivariate analysis, more precisely, the response surface methodology was applied to evaluate the role of FeOx and hydrogen peroxide concentrations as variables in the degradation process, and in particular, to define the concentration ranges that result in the most efficient degradation of the herbicides. The degradation process was evaluated by the determination of the remaining total organic carbon content (TOC), by monitoring the decrease of the concentrations of the original compounds using HPLC and by the chloride ion release in the case of diuron and 2,4-D. Under optimized conditions, 20 min were sufficient to mineralize 93% of TOC from 2,4-D and 90% of diuron, including oxalate. Complete dechlorination of these compounds was achieved after 10 min reaction. It was found that the most recalcitrant herbicide is tebuthiuron, while diuron shows the highest degradability. However, under optimized conditions the initial concentration of tebuthiuron was reduced to less than 15%, while diuron and 2,4-D were reduced to around 2% after only 1 min reaction. Furthermore, it was observed that the ferrioxalate complex plays a more important role than H2O2 in the photodegradation of these herbicides in the ranges of concentrations investigated.     

Fluxes of ions in precipitation, throughfall and stemflow in an urban forest in Kuala Lumpur, Malaysia

A study was carried out to determine the chemical composition of bulk precipitation, throughfall and stemflow in an urban forest in Kuala Lumpur, Malaysia. The mean weekly rainfall recorded during the period of study was 63.2 mm. Throughfall, stemflow and canopy interception of incident precipitation were 77.1%, 1.2% and 21.7% respectively. Bulk precipitation, througfall and stemflow were acidic, the pH recorded being 4.37, 4.71 and 4.15 respectively. In all cases the dominant ions were NO3, SO4, Cl, NH4, K, Ca and Na. Of the ions studied Ca, K, Cl, SO4, Mg and Mn showed net increases in passing through the forest canopy, while NH4, Na, NO3, Zn, H and Fe showed net retention. This study shows that the urban environment of Kuala Lumpur contributes considerable amounts of materials to the atmosphere, as reflected by the high ionic contents in bulk precipitation, throughfall and stemflow.     

Chemical composition of aerosols during a major biomass burning episode over northern Europe in spring 2006: Experimental and modelling assessments

The long-range transported smokes emitted by biomass burning had a strong impact on the PM_2.5 mass concentrations in Helsinki over the 12 days period in April and May 2006. To characterize aerosols during this period, the real-time measurements were done for PM_2.5, PM_2.5–10, common ions and black carbon. Moreover, the 24-h PM₁ filter samples were analysed for organic and elemental carbon (OC and EC), water-soluble organic carbon (WSOC), ions and levoglucosan. The Finnish emergency and air quality modelling system SILAM was used for the forecast of the PM_2.5 concentration generated by biomass burning. According to the real-time PM_2.5 data, the investigated period was divided into four types of PM situations: episode 1 (EPI-1; 25–29 April), episode 2 (EPI-2; 1–5 May), episode 3 (EPI-3; 5–6 May) and a reference period (REF; 24 March–24 April). EPI-3 included a local warehouse fire and therefore it is discussed separately. The PM₁ mass concentrations of biomass burning tracers—levoglucosan, potassium and oxalate—increased during the two long-range transport episodes (EPI-1 and EPI-2). The most substantial difference between the episodes was exhibited by the sulphate concentration, which was 4.9 (±1.4) μg m⁻³ in EPI-2 but only 2.4 (±0.31) μg m⁻³ in EPI-1 being close to that of REF (1.8±0.54 μg m⁻³). The concentration of particulate organic matter in PM₁ was clearly higher during EPI-1 (11±3.3 μg m⁻³) and EPI-2 (9.7±4.0 μg m⁻³) than REF (1.3±0.45 μg m⁻³). The long-range transported smoke had only a minor impact on the WSOC-to-OC ratio. According to the model simulations, MODIS detected the fires that caused the first set of concentration peaks (EPI-1) and the local warehouse fire (EPI-3), but missed the second one (EPI-2) probably due to dense frontal clouds.     

Changes in the wet precipitation of sodium and chloride over the continental United States, 1984–2006

Data on wet-only precipitation from the National Atmospheric Deposition Program/National Trends Network were analysed for trends in the sodium and chloride fluxes over the United States between 1 January 1984 and 31 December 2006. The data were first checked for consistency and for ionic balance. It was necessary to correct for changes in bicarbonate due to changes in atmospheric CO₂ levels over the study period, in order to obtain a balance. The fluxes were calculated and the trends determined by linear regression in the log domain. The significance of the trends was checked using both F- and t-tests. At 154 sites having reasonably continuous records over the assessment period, the sodium flux fell significantly at 139 and increased significantly at only one. The chloride flux similarly fell significantly at 140 and increased significantly at the same one as the sodium flux increased. At coastal sites the chloride to sodium ratio was the same as that in sea water, within experimental limits. Further from the coast the ratio changed apparently due to changes in the entire aerosol chemistry. The findings are discussed in terms of the simplicity and robustness of the methodology employed to determine the trends; the oceanic origin of most observable sodium even in the interior of the continent, probably because it occurs as a fine (<1 micron) aerosol which is poorly scavenged by precipitation; and the possibility that the drop in sodium and chloride fluxes might be driven by climate change.     

2001-2012年天津市大气降水特征及化学成分分析

为了解天津市大气降水特征及化学成分变化规律,对2001-2012年天津市酸雨监测资料进行了统计分析.结果表明:2001-2012年,天津市降水pH在波动中总体升高,但升高趋势不显著;酸雨率则呈显著下降趋势;降水pH从春季到冬季呈直线下降趋势,酸雨率从春季到冬季总体呈上升趋势;2008-2012年,pH在6.0～7.5的降水样本较多,在这区间,平均降水量越大,则降水pH越低,酸性越强,平均电导率和平均降水量则表现出明显负相关,即平均降水量较小时平均电导率较高;2001-2012年,天津市降水中各离子当量浓度(当量浓度=质量浓度×原子价/化学结构式量)所占比例为SOi-＞Ca2+ ＞NH4+ ＞NO3-＞C1-＞Mg2+ ＞Na+ ＞F-＞K+;对天津市降水起主导中和作用的阳离子为Ca2+,贡献率在56.4％～77.9％,贡献率春季最高,夏季最低,NHt的贡献率在28.4％～44.0％,夏季最高,冬季最低;从2001-2012年天津市降水的SO42-、NO3-当量浓度之比的变化来看,该市酸雨类型经历了从硫酸型或燃煤型到混合型的过渡过程.     

Spatial and temporal trends of precipitation chemistry in the United States, 1985-2002

A Seasonal Kendall Trend (SKT) test was applied to precipitation-weighted concentration data from 164 National Atmospheric Deposition Program National Trends Network (NADP/NTN) sites operational from 1985 to 2002. Analyses were performed on concentrations of ammonium, sulfate, nitrate, dissolved inorganic nitrogen (DIN, sum of nitrogen from nitrate and ammonium), and earth crustal cations (ECC, sum of calcium, magnesium, and potassium). Over the 18-year period, statistically significant (p< or =0.10) increases in ammonium concentrations occurred at 93 sites (58%), while just three sites had statistically significant ammonium decreases. Central and northern Midwestern states had the largest ammonium increases. The generally higher ammonium concentrations were accompanied by significant sulfate decreases (139 sites, 85%), and only one significant increase which occurred in Texas. In the west central United States there were significant nitrate increases (45 sites, 27%), while in the northeastern United States there were significant decreases (25 sites, 15%). Significant DIN decreases were observed in the northeastern United States (11 sites, 7%); elsewhere there were significant increases at 75 sites (46%). ECC decreased significantly at 65 sites (40%), predominantly in the central and southern United States, and increased at 11 sites (7%). The concentrations of sulfate, nitrate, and ammonium in precipitation have changed markedly over the time period studied. Such trends indicate changes in the mix of gases and particles scavenged by precipitation, possibly reflecting changes in emissions, atmospheric chemical transformations, and weather patterns.     

Influence of contamination on the analysis of precipitation samples

Liquid precipitation samples, collected in a standard open gauge, are often contaminated by biological debris, which can give rise to unusually high ammonium ion concentrations. In order to prevent this kind of contamination a 1-mm fibreglass teflon coated grid was mounted in the neck of the collection bottle. Collection characteristics of this gauge were compared with a standard open gauge by a parallel sampling of precipitation in the two gauges. 34 parallel samples were collected during 6 months (May–October. 1979) in a rural area. The results indicate that biological contamination has no effect on the concentration of chloride, nitrate, and sulphate ion in the liquid precipitation samples. As expected, biological contamination has a very strong influence on concentrations of ammonium ion, strong acid, and on pH.     

Simulation of aerosols and gas-phase species over Europe with the Polyphemus system. Part II: Model sensitivity analysis for 2001

This paper presents a multi-pollutant sensitivity study of an air quality model over Europe with a focus on aerosols. Following the evaluation presented in the companion paper, the aim here is to study the sensitivity of the model to input data, mathematical parameterizations and numerical approximations. To that end, 30 configurations are derived from a reference configuration of the model by changing one input data set, one parameterization or one numerical approximation at a time. Each of these configurations is compared to the same reference simulation over two time periods of the year 2001, one in summer and one in winter. The sensitivity of the model to the different configurations is evaluated through a statistical comparison between the simulation results and through comparisons to available measurements. The species studied are ozone (O₃), nitrogen dioxide (NO₂), sulfur dioxide (SO₂), ammonia (NH₃), coarse and fine aerosol particles (PM_c and PM_2.5), sulfate, nitrate, ammonium, chloride and sodium.For all species, the modeled concentrations are very sensitive to the parameterization used for vertical turbulent diffusion and to the number of vertical levels. For the other configurations considered in this work, the sensitivity of the modeled concentration to configuration choice varies with the species and the period of the year. O₃ is impacted by options related to boundary conditions. PM_c is sensitive to sea-salt related options, to options influencing deposition and to options related to mass transfer between gas and particulate phases. PM_2.5 is sensitive to a larger number of options than PM_c: sea-salt, boundary conditions, heterogeneous reactions, aqueous chemistry and gas/particle mass transfer. NO₂ is strongly influenced by heterogeneous reactions. Nitrate shows the highest variability of all species studied. As with NO₂, nitrate is strongly sensitive to heterogeneous reactions but also to mass transfer, thermodynamic related options, aqueous chemistry and computation of the wet particle diameter. While SO₂ is mostly sensitive to aqueous chemistry, sulfate is also sensitive to boundary conditions and, to a lesser extent, to heterogeneous reactions. As with nitrate, ammonium is largely impacted by the different configuration choices, although the sensitivity is slightly lower than for nitrate. NH₃ is sensitive to aqueous chemistry, mass transfer and heterogeneous reactions. Chloride and sodium are impacted by sea-salt related options, by options influencing deposition and by options concerning the aqueous-phase module.     

Atmospherically deposited major and trace elements in the winter snowpack along a gradient of altitude in the Central Pyrenees: The seasonal record of long-range fluxes over SW Europe

The chemistry of high mountain snowpacks is a result of the long-range atmospheric transport and deposition of elements. Pyrenean snowpacks contain information about the fluxes of elements over SW Europe in winter. Here we analysed Al, Ti, Mn, Fe, Ni, Cu, Zn, As, Se, Cd and Pb in the 2004–05 winter snowpack in the Central Pyrenees, at an altitude range of 1820–3200 m a.s.l. Ni, As, Se and Cd were not detected in most cases. The concentrations of the remaining elements were comparable to those found in other high mountain areas in Europe and North America considered representative of regional background of atmospheric deposition in populated areas. In contrast, our measurements were higher than those of polar areas, which represent the global background. Single measurements of concentrations and snow accumulation were subject to considerable spatial variability, which may be attributable to strong wind drift and other post-depositional processes. The major ions chemistry of the snow indicated three possible origins for the solutes: terrigenous dust, sea salt spray and polluting S and N aerosols. We found no association between Cu, Zn and Pb and any of these possible sources. This observation therefore indicates that these elements were not preferentially bound to any particular kind of aerosol. Snow collected at altitudes of up to 2050 m a.s.l. presented higher concentrations of several elements than snow above this altitude, thereby indicating a local influence. Snow collected above 2300 m a.s.l. was therefore more representative of broad regional inputs. At these higher altitudes, snow was not enriched in Al, Ti, Mn, Fe or As compared with the composition of the upper continental crust and the local lithology, and these elements (except Mn) appeared almost exclusively in the particulate fraction. This observation indicates that Al, Ti, Mn, Fe and As were present mainly as part of dust particles of terrigenous origin. In contrast, Cu, Zn, and Pb presented medium to high enrichment factors and showed a higher proportion of soluble forms, thereby indicating their polluting character.     

Deposition of sulphur,nitrogen and acidity in precipitation over Ireland: chemistry,spatial distribution and long-term trends

The chemical composition of pollutant species in precipitation sampled daily or weekly at 10 sites in Ireland for the five-year period, 1994–1998, is presented. Sea salts accounted for 81% of the total ionic concentration. Approximately 50% of the SO₄²⁻ in precipitation was from sea-salt sources. The proportion of sea salts in precipitation decreased sharply eastwards. In contrast, the concentration of NO₃⁻ and the proportion of non-sea-salt SO₄²⁻ increased eastwards reflecting the closer proximity to major emission sources. The mean (mol_c) ratio of SO₄²⁻:NO₃⁻ was 1.6 for all sites, indicating that SO₄²⁻ was the major acid anion.The spatial correlation between SO₄²⁻, NO₃⁻ and NH₄⁺ concentrations in precipitation was statistically significant. The regional trend in NO₃⁻ concentration was best described by linear regression against easting. SO₄²⁻ concentration followed a similar pattern. However, the regression was improved by inclusion of elevation. Inclusion of northing in the regression did not significantly improve any of the relationships except for NH₄⁺, indicating a significant increase in concentrations from northwest to southeast.The spatial distribution of deposition fluxes showed similar gradients increasing from west and southwest to east and northeast. However, the pattern of deposition shows the influence of precipitation volume in determining the overall input. Mean depositions of sulphur and nitrogen in precipitation were ≈30 ktonnes S yr⁻¹ and 48 ktonnes N yr⁻¹ over the five-year period, 1994–1998, for Ireland.Least-squares linear regression analysis indicated a slight decreasing trend in precipitation concentrations for SO₄²⁻ (20%), NO₃⁻ (13%) and H⁺ (24%) and a slight increasing trend for NH₄⁺ (15%), over the period 1991–1998.