Throughfall chemistry in a spruce chronosequence in southern Poland

The chemical composition of throughfall and canopy leaching, as well as the acid neutralizing capacity and alkalinity depended on the age of Norway spruce (Picea abies Karst) stands and season of the year. A higher amount of sulphur and strong acids was deposited to the soil in the older age classes. Concentrations of SO(4)(2)(-), K(+), H(+), Mn(2+), Fe(2+) and Zn(2+) in throughfall were higher than in bulk precipitation in any season. This suggests that these ions were washed out or washed from the surface of needles and/or barks. The other ions NO(3)(-), NH(4)(+), Ca(2+) and Mg(2+) were retained by the canopy, in particular Ca(2+) and Mg(2+) during the growing season in young stands. Principal component analysis identified five factors responsible for the data structure and suggested the major anthropogenic emission sources were acidic emission (SO(4)(2)(-)+NO(3)(-)), heavy metals-dust particles (Fe(2+)+Mn(2+)+Zn(2+)), ammonium (NH(4)(+)) and H(+), while the natural-origin emission was mineral dust (Na(+)+K(+)+Ca(2+)+Mg(2+)).     

Throughfall below grassland canopies: a comparison of conventional and ion exchange methods

Sampling of canopy fluxes (throughfall and stemflow) below low structured vegetation with a small-scale, intricate canopy architecture is difficult, and representative sampling with most methods is questionable. In the present study, two sampling methods for canopy fluxes below grassland vegetation are compared. Method I sampled canopy fluxes of moisture inefficiently, because stemflow volumes were not quantitatively included. Canopy fluxes of ions calculated with method I necessitated assumptions on equal concentrations in actually sampled throughfall and non-sampled stemflow. Method II sampled canopy fluxes of ions quantitatively, because the total volume of throughfall and stemflow percolated through a mixed bed of ion exchange resins below the canopy. Ion-specific differences between the two methods were observed. For ions with foliar leaching, such as K+ and Ca2+, higher canopy fluxes were recorded with method II than with method I. In contrast, for ions with foliar uptake, such as NH4+ and NO3-, canopy fluxes were found to be less with method II than with method I. Canopy fluxes of inorganic nitrogen below Mesobrometum grassland were 2.35 and 1.52 kmol(c) ha(-1) year(-1) for methods I and II, respectively, and 2.85 and 7.90 kmol(c) ha(-1) year(-1) for K+. It is argued that these differences result from under-estimated (foliar leaching) or over-estimated (foliar uptake) concentrations in stemflow by the first method. Canopy fluxes for SO4(2-) were not statistically different, indicating that canopy exchange of SOx was quantitatively unimportant, and that both methods estimated atmospheric input equally well.     

Seasonal variation in the atmospheric deposition of inorganic constituents and canopy interactions in a Japanese cedar forest

The seasonal changes in throughfall (TF) and stemflow (SF) chemistry and the canopy interactions of K+ and N compounds were studied in a Japanese cedar forest near the Sea of Japan. The fluxes of most ions, including non-sea-salt SO4(2-), from TF, SF, and rainfall showed distinct seasonal trends, increasing from autumn to winter, owing to the seasonal west wind, while the fluxes of NH4+ and K+ ions from TF+SF might have a large effect of canopy interactions. The contact angle (CA) of water droplets on leaves decreased with leaf aging, suggesting that surface wettability increases with leaf age. The K+ concentration in TF was negatively correlated with the CA of 1-year-old leaves, while the NH4+ concentration was positively correlated with the CA. The net fluxes of NH4+ and NO3(-) from TF were positively correlated with the CA. The increase in wettability may accelerate leaching of K+ or uptake of NH4+.     

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.     

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.     

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.     

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.     

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-).     

The contribution of ammonia emissions from agriculture to the deposition of acidifying and eutrophying compounds onto forests

In the vicinity of a large ammonia emission area, dry and wet deposition of acidifying and eutrophying compounds onto Douglas Fir forests was studied by sampling throughfall, stemflow and bulk precipitation. Deposition amounts of NH(4)(+) and SO(4)(2-) were recognised to be among the highest of Central Europe, resulting in extremely high inputs of (potential) acid to the forest soils (13.1 kEq ha(-1) year(-1)). The contribution of NH(3) emissions from agriculture to the total acid deposition to the forests was 52%. The total nitrogen deposition amounted to 115.0 kg ha(-1) year(-1), 83% originating from NH(3) emissions and 17% from NO(x) emissions. Calculated mean dry deposition velocities of NH(3) and SO(2) were much larger than reported in the literature. A synergistic effect between NH(3) and SO(2) in the process of dry deposition is suggested and evidence for this effect is discussed. When deposition models do not take this interaction into account, they will underestimate NH(3) and SO(2) deposition amounts in areas with intensive animal husbandry.     

Multivariate space analysis of the major precipitation ions over Europe, 1986-1997

The annual average concentrations (1986-1997) of the major ions SO4(2-), NO3-, Cl-, NH4+, Na+, Mg2+, Ca2+, and K+ in precipitation are analyzed for selected EMEP stations. The objective is to determine the ion patterns or typologies in precipitation by principal component analysis (PCA) combined with a cluster analysis. SO4(2-) and NO3- ions are predominant in central and eastern Europe. This area corresponds to high emissions of SO2 and NO2. Sea spray ions are predominant in coastal sites. The soil components show an important contribution in southern Europe, possibly due to the soil dust transported from northern Africa.     

Acid neutralization of precipitation in Northern China

There is an increasing concern over the impact of human-related emissions on the acid precipitation in China. However, few measurements have been conducted so far to clarify the acid-neutralization of precipitation on a regional scale. Under a network of 10 sites across Northern China operated during a 3-year period from December 2007 to November 2010, a total of 1118 rain and snow samples were collected. Of this total, 28% was acid precipitation with pH < 5.6. Out of these acid samples, 53% were found heavily acidic with pH value below 5.0, indicating significantly high levels of acidification of precipitation. Most of the acidity of precipitation was caused by H2SO4 and HNO3, their relative contribution being 72% and 28%, respectively. However; the contribution of HNO3 to precipitation acidity will be enhanced due to the increasing NO(x) and stable SO2 emissions in future. Neutralization factors for K+, NH4+, Ca2+, Na+, and Mg2+ were estimated as 0.06, 0.71, 0.72, 0.15, and 0.13, respectively. The application of multiple regression analysis further quantified higher NH4+ and Ca2+ contribution to the neutralization process, but the dominant neutralizing agent varied from site to site. The neutralization was less pronounced in the rural than urban areas, probably due to different levels of alkaline species, which strongly buffered the acidity. Presence of high concentrations of basic ions was mainly responsible for high pH of precipitation with annual volume-weighted mean (VWM) values larger than 5.6 at several sites. It was estimated that in the absence of buffering ions, for the given concentration of SO4(2-) and NO3-, the annual VWM pH of precipitation would have been recorded around 3.5 across Northern China. This feature suggested that emissions of particles and gaseous NH3 played very important role in controlling the spatial variations of pH of precipitation in the target areas.     

Field intercomparison of throughfall measurements performed within the framework of the Pan European intensive monitoring program of EU/ICP Forest

A 6-month field intercomparison study on throughfall measurements was performed at Speulder forest near the west coast in The Netherlands. Twenty throughfall sampling systems were evaluated on accuracy, sampling strategy and performance under field conditions. Throughfall fluxes of NO3-, K+ and Kjeldahl-N generally could be determined with a larger accuracy than fluxes of SO4(2-), NH4+, Na+, Cl-, Mg2+, Ca2+, and alkalinity. Throughfall fluxes of H+ generally had the lowest accuracy. Only 20% of the sampling systems differed more than 20% from the best estimate, whereas 45% of the systems stayed within a 10% range from the best estimate. The difference from the best estimate was mainly caused by aspects related to sampling strategy, like, for example, collecting area, sampler placement. The inaccuracy induced by the sampling system appeared to be much larger than that resulting from the analysis of the samples by different laboratory as determined by ring-tests. The field intercomparison described in this article gave a good insight in the different aspects contributing to the overall accuracy of the measurements. However, performing a future field intercomparison is recommended for throughfall and stemflow in order to also take in account other aspects that might influence the performance of the different measurement systems (e.g. tree species, climate zone, summer/winter period).     

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.     

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.     

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.     

Field intercomparison of precipitation measurements performed within the framework of the Pan European Intensive Monitoring Program of EU/ICP Forest

A 6-month field intercomparison study on precipitation measurements was performed at Schagerbrug near the west coast in the Netherlands. Twenty bulk sampling systems and two wet-only samplers were evaluated on accuracy, sampling strategy and performance under field conditions. Bulk precipitation fluxes of NO3-, NH4+, H+ and Kjeldahl-N generally could be determined with a greater accuracy than bulk precipitation fluxes of SO4(2-), Na+, Cl-, Mg2+, Ca2+, Alkalinity and H+. Bulk precipitation fluxes of K+ generally had the lowest accuracy. Only 20% of the sampling systems differed less than 10% from the best estimate, whereas most systems (60%) differed more than 20% from the best estimate. The inaccuracy induced by the sampling system appeared to be much larger than that resulting from the analysis of the samples by different laboratories as determined by ring-tests.     

森林降水化学的变化特征和机理

研究并比较了湖南酸雨区韶山小集水区林内降水的化学特征，结果表明，与大气降水相比，穿冠水和地表穿透水中的富集的离子浓度除了NO3^-和Na^ 外均明显增加，到达地表的降水离子增加倍数最高达34．3倍；离子总量最高倍数为8．1倍，乔木树冠层的离子富集作用大于灌木层。韶山的大气降水、穿冠水和地表穿透水的年均pH分别为4．61、5．54和5．85。持续大量的降水对森林上空的污染物有较高的清除效果。     

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.     

Stemflow chemistry of urban street trees

pH and ion concentrations (Na(+), K(+), Mg(2+), Ca(2+), NO(-)(3)) in the stemflow of the evergreen broad-leaved tree, Ilex rotunda, planted in the median strip of a highway and nitrogen oxides concentration in the air in an urban site were compared with a suburban site in Fukuoka city, Japan. The annual average of the nitrogen oxides concentration in the air was higher and NO(-)(3) concentration in the stemflow at the urban site was higher or similar compared with the suburban site. However, the annual average of pH in the stemflow at the urban site was higher than at the suburban. The annual average cation concentrations in the stemflow at the urban site were higher than at the suburban except Na(+). In particular, K(+) and Ca(2+) were higher throughout the measurement period. Therefore, higher pH in the urban stemflow was probably due to neutralization by higher concentrations of K(+), Mg(2+) and Ca(2+).     

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.