Atmospheric input of elements to forest ecosystems: a method of estimation using artificial foliage placed above rain collectors

Usefulness of a method of artificial foliage was tested for estimation of total ionic inputs from the atmosphere to forest ecosystems, as well as of processes relevant to ionic fluxes through tree canopies: uptake, leaching, passive flow. The studies were performed in Norway spruce and European beech stands in Karkonosze Mountains (Poland), in 1995-97. Artificial leaves of increasing leaf area index: 0, 2, 6 and 12 m(2) m(-2 )were placed above standard rain collectors. It has been found that total atmospheric fluxes of H(+), NH(4)(+), Ca(2+), Mg(2+), Pb(2+), NO(3)(-) and SO(4)(2-) rose as surface area of the foliage increased. This was especially true for nitrate, sulphate and ammonium. No such relationship was found for K(+), Na(+), Zn(2+), Cd(2+), Cu(2+) and PO(4)(3-). The increase in anion fluxes exceeded that in neutralising cations (NH(4)(+), Na(+), K(+), Mg(2+), Ca(2+)) and led to progressive rainwater acidification with the increase in the foliage area. An analysis of net canopy exchange (atmospheric input-throughfall flux) has shown that SO(4)(2-), PO(4)(3-), Na(+), Ca(2+) and Cu(2+) flowed passively through the tree crowns; NH(4)(+), NO(3)(-), Zn(2+), Cd(2+) and occasionally Pb(2+) were efficiently absorbed, whereas K(+) was leached from the canopies. Beech was more effective in modifying ionic pool from the atmosphere than spruce. This related to H(+) (greater absorption) and Mg(2+) (greater leaching). It has been demonstrated that the results concerning trends in net canopy exchange and produced by the simple method of artificial foliage are comparable to more sophisticated techniques of the measurements. This proves the method to be useful.     

Atmospheric deposition to the edge of a spruce forest in Denmark

Atmospheric deposition was measured during 1 year at the forest edge of a Norway spruce stand in Denmark. Inside the forest the deposition of H(+), Ca(2+), Mg(2+), Na(+), K(+), Cl(-), NO(3)(-), NH(4)(2) and SO(4)(2-) with canopy throughfall varies with the distance from the forest edge. The deposition at the edge is found to be 10-20 times as high as deposition to an open field and 2-8 times as high as deposition inside the stand. An exponential decrease in deposition as a function of the distance from the forest edge is found. Increased deposition of K(+) and non-sea salt Mg(2+), which mainly originates as a result of leaching from the needles may be explained by a larger leaf area index (LAI) at the forest edge. Deposition of particulate substances, especially Na(+), Cl(-), Mg(2+) and to some extent SO(4)(2-), NH(4)(+) and NO(3)(-) is increased much more than the LAI, which we believe to be caused by changes in wind movements at the forest edge.     

Throughfall chemistry and canopy interactions in a Sitka spruce plantation sprayed with six different simulated polluted mist treatments

Throughfall chemistry was studied in a mature Sitka spruce plantation in order to investigate canopy interactions, such as nitrogen absorption, cation leaching, and neutralization of rainfall passing through the canopy. The plantation had been exposed to six different simulated mist treatments including N (NH(4)NO(3)) and S (H(2)SO(4) at pH 2.5) in four replicated blocks since 1996. Throughfall and rainfall were collected from May to September 2000. The results showed that 30-35% of the applied N was retained by the canopy. There were linear relationships between the loss of H(+) and increased K(+), Mg(2+) and Ca(2+) deposition through the canopy. However these increases in K(+), Mg(2+) and Ca(2+) deposition accounted for only about 50% of total neutralization of the acidity. The relationship between the anion deficits in throughfall and the loss of H(+) implied that weak organic acid anions were involved in the neutralization of the acidity in throughfall.     

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.     

Effects of ozone on foliar leaching in Norway spruce (Picea abies L. Karst): confounding factors due to NOx production during ozone generation

Previous experiments with conifers fumigated with O(3), produced by air-operated electric discharge ozonators, have provided evidence that O(3) increases the leaching of NO(3)(-), NH(4)(+), K(+), Ca(2+), Mg(2+) and some other cations from needles, when the trees are treated with acid mist. This evidence has provided the foundation of the ozone-acid mist hypothesis of spruce decline. We report experiments with Norway spruce saplings fumigated with purified and unpurified O(3). The results show that the accumulation of NO(3)(-) in the needles arises from the rapid deposition of N(2)O(5) and HNO(3) formed from N(2) in the ozonator. An increase in removal of NH(4)(+), Na(+), Ca(2+), Mg(2+), Zn(2+) and Mn(2+) from the needles during soaking in H(2)SO(4), pH3, was also observed, which was related to the increase in NO(3)(-) but was independent of O(3) concentration. It is concluded that results of previous experiments cited in support of the ozone-acid mist hypothesis arose from effects which were at least partly caused by N(2)O(5) produced as a contaminant, and were incorrectly attributed to ozone. Other effects, such as growth stimulations, visible symptons, enhanced frost sensitivity, and infestation by pests or pathogens, which have been attributed to O(3) generated by electric discharge in air, should be interpreted with caution. Future experiments with ozone must eliminate this problem by either using O(2)-driven ozonators, or by purifying the output from air-driven ozonators using cold and/or water traps.     

Spatial variability of throughfall fluxes in a spruce forest

The spatial variability of throughfall deposition of H(+), Ca(2+), Mg(2+), Na(+), K(+), Cl(-), NO(3)(-), NH(4)(+), O(4)(2-) to a Norway spruce (Picea abies (L.) Karst.) forest was intensively examined during the period October 1986 to October 1987. Large systematic spatial variability of the atmospheric deposition within the forest was observed. The flux of throughfall water was higher away from the trunk compared to the flux close to the trunk. In contrast to this, the deposition of all substances was considerably higher close to the trunk compared to the deposition at the periphery of the canopy. A linear decrease in deposition as a function of the distance from the nearest tree trunk was found. Further, the deposition varied quite dramatically between trees according to their size. The observed spatial variability in throughfall may be due to variabilities in the processes taking part in altering the distribution and composition of the precipitated water as it moves through the canopy. The influence of these processes of precipitation, wash-off, dry deposition and canopy exchange is discussed, and it is found that both increased dry deposition and canopy exchange in the tree tops contribute to the higher solute fluxes found close to the tree trunk.     

Atmospheric deposition and ionic interactions within a beech canopy in the Karkonosze Mountains

A method, of artificial foliage placed above rain collectors, which enables to estimate total atmospheric inputs of elements, was employed to study processes related to ionic flow through a tree canopy. The investigations were conducted within a beech forest in the Karkonosze Mountains, in 1996-1997. An analysis of net canopy exchange (throughfall flux-atmospheric input) revealed that NH4+, NO3-, H+ had been retained in the canopy, Ca2+, Na+, Cl-, SO(2-)4, PO(3-)4 flowed passively, whereas K+ and Mg2- had been removed from the tree foliage. Ammonium absorption was more efficient than that of NO3- ions, because NH4+ was taken up from rain-waters and aerosol-gaseous fraction of the atmospheric input, whereas NO3- ions were captured primarily from the latter source. Retention of H+ was also related exclusively to the aerosol-gaseous input. Leaching losses of K+ and Mg2+ did not result from exchange reactions of these ions with retained H+, but from ionic exchange between NH4+ and K+ + Mg2+. At the same time, neutralisation of H+ in the canopy has been attributed to NO3- absorption, resulting most likely from HNO3 vapour penetration into the plants.     

Rainwater chemistry at the summit and southern flank of the Itatiaia massif, Southeastern Brazil

Wet deposition and related rainwater chemistry were studied at the Itatiaia massif, on which is settled the Itatiaia National Park (INP). Samples were simultaneously collected on a weekly basis over 12 months, using automated wet and dry samplers, at the INP-Headquarters (INP-Hq; altitude=820 m) and the Itatiaia Plateau (It-Pt; altitude=2460 m). Conductivity, pH, Na(+), K(+), Mg(2+), Ca(2+), NH(4)(+), Cl(-), NO(3)(-) and SO(4)(2-) were determined in 36 rainwater samples. Volume-weighted mean (VWM) pH was lower at the INP-Hq (4.9) than at the It-Pt (5.3). Very strong correlation between Cl(-) and Na(+) was found for the INP-Hq (r=0.99). At the Itatiaia massif, SO(4)(2-), NO(3)(-), and NH(4)(+) comprised together about 60% of the total inorganic ions and appear to exert the major control on rainwater pH.     

Effect of vegetation type on throughfall deposition and seepage flux

This paper compares different vegetation types (coniferous and deciduous forest, grassed and pure heathland) in terms of input (throughfall deposition) and output (seepage flux) in a region with intermediate nitrogen load (+/-20kg Nha(-1)y(-1) via bulk precipitation) in comparable conditions in north Belgium. Coniferous forest (two plots Pinus sylvestris and two plots Pinus nigra) received significantly higher nitrogen and sulphur throughfall deposition than deciduous forest and heathland. Grassed and pure heathland had significantly highest throughfall quantities of Ca(2+) and Mg(2+), respectively. The observed differences in throughfall deposition between the different vegetation types were not univocally reflected in the ion seepage flux. Considerable seepage fluxes of NO(3)(-), SO(4)(2-), Ca(2+) and Al(III) were only found under the P. nigra plots. We discuss our hypothesis that the P. nigra forests already evolved to a situation of N saturation, while the other vegetation types did not.     

Soil solution nitrogen and cations influenced by (NH4)2SO4 deposition in a coniferous forest

The effects of chronically enhanced (NH(4))(2)SO(4) deposition on ion concentrations in soil solution and ionic fluxes were investigated in a Picea abies plot at Grizedale forest, NW England. Soil cores closed at the base and containing a ceramic suction cup sampler were 'roofed' and watered every 2 weeks with bulk throughfall collected in the field. Treatments consisted of the inclusion of living roots from mature trees in the lysimeters and increasing (NH(4))(2)SO(4) deposition (NS treatment) to ambient + 75 kg N ha(-1) a(-1). Rainfall, throughfall and soil solutions were collected every 2 weeks during 18 months, and analysed for major cations and anions. NO(3)(-) fluxes significantly increased following NS treatment, and were balanced by increased Al(3+) losses. Increased SO(4)(2-) concentrations played a minor role in controlling soil solution cation concentrations. The soil exchange complex was dominated by Al and, during the experimental period, cores of all treatments 'switched' from Ca(2+) to Al(3+) leaching, leading to mean [Formula: see text] molar ratios in soil solution of NS treated cores of 0.24. The experiment confirmed that the most sensitive soils to acidification (through deposition or changing environmental conditions) are those with low base saturation, and with a pH in the lower Ca, or Al buffer ranges.     

Contribution of canopy leaching to sulphate deposition in a Scots pine forest

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.     

Bulk deposition in a rural area located around a large coal-fired power station, northeast Spain

This work focuses on bulk deposition in a rural area located around a large coal-fired power station in northeast Spain. Deposition chemistry was characterised by high concentrations of SO(4)(2-), Ca(2+) and NH(4)(+), which were relatively high when compared with other rural areas. Monthly bulk deposition evolution of major ions was the result of two superimposed patterns: one pattern related to the volume of precipitation and the other showed the seasonal influence of the major ionic sources. A major local origin was attributed to bulk deposition of SO(4)(2-), NH(4)(+), and Ca(2+), whereas a relatively higher contribution of an external source was deduced for NO(3)(-), Na(+) and Cl(-). The SO(4)(2-) concentrations showed a significant correlation with the local SO(2) emissions. High levels of Ca(2+) were due to the high alkalinity of soils in the study area, although an external origin was attributed to the frequent air mass intrusions from the Sahara. Sources of NH(4)(+) were related to intensive livestock farming in the area. Total suspended particles exert a marked influence over bulk deposition and neutralisation. Thus, despite the high emissions of SO(2) in the area, neutral pH values have always been attained given that the concentrations of Ca(2+) and NH(4)(+) account for the total neutralisation of NO(3)(-) and SO(4)(2-).     

Dry deposition, ionic species measured and source interpretation during seasonal cycle at offshore areas near Taiwan Strait

The characterization for water-soluble species of total suspended particulate (TSP), dry deposition flux, and dry deposition velocity (V(d)) were studied at Taichung Harbor (TH) and Wuchi traffic sampling sites at offshore sampling site near Taiwan Strait of central Taiwan during March 2004-January 2005. The average concentrations of TSP and dry deposition flux at the TH sampling site were higher than at the WT sampling site during the sampling period. The samples collected were analyzed by a ion chromatography (DIONEX-100) for the ionic species (Cl(-), SO(4)(2-), NO(3)(-), NH(4)(+), Na(+), Ca(2+), and Mg(2+)) analysis. The dominant ionic species for TSP are SO(4)(2-), NO(3)(-), and NH(4)(+) of the total mass of the inorganic ions at both sampling sites. In addition, the results indicated that the NH(4)(+), NO(3)(-) and SO(4)(2-) showed higher concentrations in winter and lower in summer for both TH and Wuchi sampling sites. Statistical methods such as correlation coefficient and principal component analysis were also used to identify the possible pollutant source.     

Chemical characterization of rainwater at Singapore

A short term study of the chemical composition of rainwater was carried out from November 1999 to October 2000 in Singapore. The rainwater was typically acidic with a mean pH of 4.2. Sulfate was the most abundant ion and comparable to the results reported for other industrialized regions. The concentrations of major ions (NH(4)(+), Ca(2+), K(+), Na(+), Mg(2+), SO(4)(2+), NO(3)(2-), Cl(-), HCOO(-), CH(3)COO(-)) varied monthly. Results show that local meteorological conditions influence the chemical compositions to a significant extent. The pollutants in rainwater were derived from long range and local (industry and traffic) sources.     

Effect of anions and cations on cadmium sorption kinetics from aqueous solutions by chitin: experimental studies and modeling

The effect of ions, including Na(+), Mg(2+), Ca(2+), Cl(-), SO(4)(2-) and CO(3)(2-), at various initial concentrations, on the kinetics of cadmium sorption by chitin was studied at 25 degrees C and free initial pH solution in batch conditions. The presence of these ions in solution was found to inhibit the uptake of cadmium by chitin to different degrees: sodium and chloride ions have no significant effect. For Mg(2+), Ca(2+), SO(4)(2-) and CO(3)(2-) ions, the effects ranged from a large inhibition of cadmium by Ca(2+) and CO(3)(2-) to a weak inhibition by Mg(2+) and SO(4)(2-). These results indicate that the uptake sites of these ions are the same. No ion was found to enhance cadmium uptake. The results also showed that the kinetics of sorption are best described by a pseudo second-order expression than a first or second-order model.     

Characterization of atmospheric PM10 and related chemical species in southern Taiwan during the episode days

The concentrations of atmospheric PM10 on days with episodes of pollution were examined at four different sampling sites (CC, DL, LY, and HK) in southern Taiwan. The related to particulates water-soluble ionic species (Na+, K+, Mg2+, Ca2+, NH4+, Cl-, NO3-, SO4(2-)), carbonaceous species (EC and OC) and metallic species (Zn, Ni, Pb, Fe, Mn, Al, Si, V) were also analyzed. On the episode days of this study, the PM10 mass concentration ranged from 155 to 210 microgm(-3), from 150 to 208 microgm(-3), from 182 to 249 microgm(-3), and from 166 to 228 microgm(-3) at CC, DL, LY, and HK, respectively. The results indicate that the dominant water-soluble species were SO4(2-), NO3-, NH4+, and Cl- at the four sampling sites on these days. Moreover, the high sulfate and nitrate conversion values (SOR and NOR) presented herein suggest that secondary formations from SO2 to SO4(2-) and from NO2 to NO3- are present in significant quantities in the atmosphere of southern Taiwan on episode days. In particular, high SOR and NOR verified that both SO4(2-) and NO3- dominated the increase of atmospheric PM10 concentration in southern Taiwan on episode days.     

Ionic composition of PM(10) in the area of Thessaloniki,Greece

Airborne particulate matter (PM(10)) was collected from July 1997 to July 1998 at three locations in the city of Thessaloniki. PM(10) samples were analyzed for Cl(-), NO3(-), SO4(2-), Ca(2+), Mg(2+), Na(+), K(+) and NH4(+). The average PM(10) concentrations were found similar in all three sites with higher values in cold period. The ionic content comprised the 17-23% of the PM(10) mass and sulfate made up the 35-38% of the PM(10) ionic content with an average concentration of 4.80-7.26 microg m(-3). Good correlation was found for SO4(2-) and NO3(-) with Ca(2+), Mg(2+) and Cl(-). Two factors were found to influence the variance of ionic constituents in PM(10) by using factor analysis. Data evaluation considering wind direction showed that higher PM(10) and other ionic concentrations are associated with calm conditions, suggesting influences of local sources.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): concentrations and solubilities of PM(2.5) trace elements and their implications for source apportionment and health research

The elemental compositions of the water-soluble and acid-digestible fractions of 24-hr integrated fine particulate matter (PM(2.5)) samples collected in Steubenville, OH, from 2000 to 2002 were determined using dynamic reaction cell inductively coupled plasma-mass spectrometry. The water-soluble elemental compositions of PM(2.5) samples collected at four satellite monitoring sites in the surrounding region were also determined. Fe was the most abundant but least water soluble of the elements determined at the Steubenville site, having a mean ambient concentration of 272 ng/m3 and a median fractional solubility of 6%. Fe solubility and its correlations with SO4(2-) and temperature varied significantly by season, consistent with the hypothesis that secondary sulfates may help to mobilize soluble Fe under suitable summertime photochemical conditions. Significantly higher ambient concentrations were observed at Steubenville than at each of the four satellite sites for 10 of the 18 elements (Al, As, Ca, Cd, Fe, Mg, Mn, Na, Pb, and Zn) determined in the water-soluble PM(2.5) fraction. Concentrations of Fe, Mn, and Zn at Steubenville were substantially higher than concentrations reported recently for larger U.S. cities. Receptor modeling identified seven sources affecting the Steubenville site. An (NH4)2SO4-dominated source, likely representing secondary PM(2.5) from coal-fired plants to the west and southwest of Steubenville, accounted for 42% of the PM(2.5) mass, and two sources likely dominated by emissions from motor vehicles and from iron and steel facilities in the immediate Steubenville vicinity accounted for 20% and 10%, respectively. Other sources included an NH4NO3 source (15%), a crustal source (6%), a mixed nonferrous metals and industrial source (3%), and a primary coal combustion source (3%). Results suggest the importance of very different regional and local source mechanisms in contributing to PM(2.5) mass at Steubenville and reinforce the need for further research to elucidate whether metals such as Fe, Mn, and Zn play a role in the PM(2.5) health effects observed previously there.     

Sulphur dioxide adsorption in Scots pine canopies exposed to high ammonia emissions near a Cu-Ni smelter in SW Finland

Since 1994 the nickel-processing plant at the Cu-Ni smelter at Harjavalta, south-west Finland, has emitted considerable amounts of NH(3) into the atmosphere. The effects of NH(3) emissions on nitrogen and sulphur deposition in throughfall and the foliar nutrient status were investigated in a Scots pine stand at 0.5 km distance. Bulk deposition, stand throughfall and percolation water (20 cm depth) samples were collected at 4-week intervals during 1992-1998. pH and the Ca, Mg, K, NH(4) and SO(4) concentrations were determined on the samples. NH(3) emissions have strongly increased the scavenging of SO(2) from the air in the pine stand, and the increased levels of N and S deposition were clearly evident as increased foliar N and S concentrations and larger needle size. The increased input of SO(4) into the forest floor was not associated with an increase in the leaching of Ca and Mg from the surface soil layers.     

Precipitation chemistry in the coast of the Metropolitan Region of Rio de Janeiro, Brazil

Precipitation chemistry was studied in the Metropolitan Region of Rio de Janeiro (MRRJ). This study reveals that rainwater in the MRRJ is affected by emissions of air pollutants and provides essential data for future estimates of regional biogeochemical cycles and the impacts of acid deposition on tropical ecosystems. The volume-weighted mean (VWM) pH was 4.77, varying from 3.50 to 6.85. Sea-salt aerosols were the dominant sources of the Na+, Cl- and Mg2+. Excess SO4(2-), Ca2+ and K+ comprised 82, 91, and 87% of their total VWM concentrations, respectively. There were very strong correlations (r > 0.75, P > 0.01) for NO3- and H+, NO3- and excess(exc-)SO4(2-), NH4+ and exc-K+, and exc-SO4(2-) and exc-Ca2+, suggesting causal relationships between these ion pairs. The VWM concentrations of all major ions, except H+, were higher in the dry season, with dry to wet VWM concentration ratios varying from 1.1 (NH4+) to 4.7 (for total K+).