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.     

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+)).     

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.     

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.     

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.     

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 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.     

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.     

Development and validation of a terrestrial biotic ligand model predicting the effect of cobalt on root growth of barley (Hordeum vulgare)

A Biotic Ligand Model was developed predicting the effect of cobalt on root growth of barley (Hordeum vulgare) in nutrient solutions. The extent to which Ca(2+), Mg(2+), Na(+), K(+) ions and pH independently affect cobalt toxicity to barley was studied. With increasing activities of Mg(2+), and to a lesser extent also K(+), the 4-d EC50(Co2+) increased linearly, while Ca(2+), Na(+) and H(+) activities did not affect Co(2+) toxicity. Stability constants for the binding of Co(2+), Mg(2+) and K(+) to the biotic ligand were obtained: logK(CoBL)=5.14, logK(MgBL)=3.86 and logK(KBL)=2.50. Limited validation of the model with one standard artificial soil and one standard field soil showed that the 4-d EC50(Co2+) could only be predicted within a factor of four from the observed values, indicating further refinement of the BLM is needed.     

Development of a biotic ligand model (BLM) predicting nickel toxicity to barley (Hordeum vulgare)

A biotic ligand model (BLM) was developed to predict nickel toxicity, affecting root growth of barley (Hordeum vulgare), in nutrient solutions. The extent to which Ca(2+), Mg(2+), Na(+), K(+) ions and pH each influenced nickel toxicity was determined. Higher activities of Mg(2+) linearly increased the 4d EC50 Ni (2+) , while Ca(2+), Na(+), K(+) and H(+) activities did not significantly influence Ni(2+) toxicity. Stability constants for the binding of Ni(2+) and Mg(2+) to the biotic ligand were obtained: logK(NiBL)=5.27 and logK(MgBL)=3.47. Further, it was calculated that on average 57% of the biotic ligand sites needed to be occupied by nickel to induce 50% root growth inhibition. Auto-validation of the BLM indicated that predicted EC50s differed from the observed EC50s by a factor of less than 2, indicating that the BLM concept may also be used to predict metal toxicity to terrestrial plants.     

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.     

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.     

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.     

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.     

Chemical composition of fresh snow from Gulmarg, North India

The chemical composition and pH of 30 fresh snow samples collected during December 1986 to May 1987 at Gulmarg (34 degrees 03' N, 74 degrees 24' E, 2655 m above mean sea level), a remote place in north India, were studied. The snow samples were, by and large, alkaline in nature and were largely influenced by non-marine aerosols. The concentrations of cations (Ca(2+), K(+) and Mg(2+)) were more than the anions (SO(2-)(4) and NO(-)(3)). Factor analysis indicated that most of the ionic components were transported into the region during the period of measurements. The transport of ionic components could be attributed to the passage of western disturbances over this region. The comparison of concentrations of anions and cations in the snow samples at Gulmarg with those reported from a few countries in the west revealed that the composition of Gulmarg snow largely differs in the concentrations of cations rather than anions. Among the cations, the concentration of Ca(2+) was high at Gulmarg and this could be responsible for buffering the pH of snow in the alkaline range.     

Study on the photocatalytic degradation of glyphosate by TiO(2) photocatalyst

In this paper, the photocatalytic degradation of glyphosate selected as the deputy of organic pollutant in aqueous solution with TiO(2) powder as a photocatalyst has been studied. The effects of various parameters, such as the amount of the photocatalyst, illumination time, initial pH value, electron acceptors, metal ions, and anions on the photocatalytic degradation of glyphosate were investigated. From the studies, the best condition for the effect of the parameters on the photocatalytic degradation of glyphosate was obtained. The results show that the optimum amount of the photocatalyst used is 6.0 g l(-1) for the photocatalytic reactions. The photodegradation efficiency of glyphosate increases with the increase of the illumination time. With the addition of Fe(3+), Cu(2+), H(2)O(2), K(2)S(2)O(8) or KBrO(3), the photocatalytic degradation of glyphosate is accelerated. However, with the addition of Na(+), K(+), Mg(2+), Ca(2+), Zn(2+), Co(2+) and Ni(2+), or with the addition of trace amounts of Cl(-), Br(-), SO(4)(2-), there are no obvious effects on the reactions. Acidic or alkaline mediums are favorable for the photocatalytic degradation of glyphosate. The possible roles of the additives on the reactions and the possible mechanisms of effect were discussed.     

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-).     

Ions species size distribution in particulate matter associated with VOCs and meteorological conditions over an urban region

Airborne particulate matter (PM10, PM2.5, PM1) and volatile organic compounds (benzene, toluene, m,p-xylene, o-xylene) samples were collected during winter and summer seasons of 2005 at two sites, representing an urban and a suburban region of the Greater Athens Area. Urban site traffic emissions were the major contributor to the concentration of PM2.5, PM10, toluene, and xylenes, while benzene and PM1 concentrations were presented in significant spatial variations. K+, Na+, Mg2+, Ca2+, NO3-, Cl- and SO42- ions were analyzed for the chemical characterization of the collected PM samples. The results showed that Na+ cations and SO42- anions were the dominant species, during winter and summer, respectively, in both sites. The analysis of the synoptic scale and mesoscale atmospheric circulation during the experimental periods demonstrated that the meteorological conditions play a key role, not only in the variation but also in the distribution of the ionic concentrations at the three fractions of particulates and the dominant character (alkaline/acidic/neutral) of the particulates at the two sampling sites.     

The dissolution kinetics of major elements in municipal solid waste incineration bottom ash particles

Leaching and tracer experiments in batches at L/S 20 were performed with 3-month-old MSWI bottom ash separated into eight different particle sizes. The time-dependent leaching of major elements (Ca(2+), K(+), Na(+), Cl(-) and SO(4)(-2)) was monitored for up to 747 h. Physical properties of the particles, the specific surface (BET), pore volume and pore volume distribution over pore sizes (BJH) were determined for all particle classes by N(2) adsorption/desorption experiments. Some common features of physical pore structure for all particles were revealed. The specific surface and the particle pore volume were found to be negatively correlated with particle size, ranging from 3.2 m(2)/g to 25.7 m(2)/g for the surface area and from 0.0086 cm(3)/g to 0.091 cm(3)/g for the pore volume. Not surprisingly, the specific surface area was found to be the major material parameter that governed the leaching behavior for all elements (Ca(2+), K(+), Na(+), Cl(-) and SO(4)(-2)) and particle sizes. The diffusion resistance was determined independently by separate tracer (tritium) experiments. Diffusion gave a significant contribution to the apparent leaching kinetics for all elements during the first 10-40 h (depending on the particle size) of leaching and surface reaction was the overall rate controlling mechanism at late times for all particle sizes. For Ca(2+) and SO(4)(-2), the coupled effect of diffusion resistance and the degree of under-saturation in the intra particle pore volume was found to be a major rate limiting dissolution mechanism for both early and late times. The solubility control in the intra particulate porosity may undermine any attempt to treat bottom ash by washing out the sulfate. Even for high liquid/solid ratios, the solubility in the intra-particular porosity will limit the release rate.     

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.