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.     

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.     

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 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.     

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.     

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+)).     

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.     

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.     

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.     

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-).     

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

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

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.     

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.     

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+).     

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.     

The effects of excess nitrogen deposition on young Norway spruce trees. Part II the vegetation

The effects of wet-deposited nitrogen on soil acidification and the health of Norway spruce were investigated in a pot experiment using an open-air spray/drip system. Nitrogen was applied as ammonium ((NH(4))(2)SO(4)) or nitrate (HNO(3)/NaNO(3)) in simulated rain to either the soil or the foliage. Symptoms of forest decline as observed in the field were not reproduced, and there was no evidence of direct toxicity. Treatments did, however, have significant effects on tree nutrition. Both NH(+)(4) and NO(-)(3) treatment applied to the foliage lowered foliar K concentrations. NH(+)(4) to a greater extent. Soil-applied NH(+)(4) reduced foliar Mg concentrations and increased foliar Al and Fe. Soil-applied NO(-)(3) significantly reduced foliar P concentrations, and at high doses prevented the alleviation of P deficiency by fertiliser. These effects could be important in some field situations. Ammonium deposition is predicted to be more damaging than nitrate deposition, although the latter may be critical for forests where P status is marginal, such as in parts of the British uplands.     

Source identifications of PM10 aerosols depending on hourly measurements of soluble components characterization among different events in Taipei Basin during spring season of 2004

Continuous measurements of hourly PM10 soluble ions were performed by the in situ IC technology in order to assess the impact of Asian outflows on local air quality. The intensive aerosol observation was carried in Taipei from 11 February 22:00 to 7 April 19:00, 2004. Concentrations of the water-soluble ions (Cl(-), NO(-)(2), NO(-)(3), SO(2-)(4), Na(+), NH(+)(4), K(+), and Ca(2+)) were measured in a total of 3,300 samples. The characteristics of air pollutant events in Taipei Basin were classified as frontal dust, dust, northeast monsoon, south wind and sea/land breeze according to the hourly meteorology and air pollutant concentrations. Factor analysis was conducted based on hourly data for 13 variables to find the group of variables with similar behavior. According to the source characteristics of high loading species, the possible sources of PM10 aerosols in each group were identified. Three to four factors were identified for each event. The total variances of frontal dust, dust, northeast trade, south wind, and sea/land breeze events were explained about 85%, 86%, 76%, 77%, and 80%, respectively, indicating that the identified factors were satisfactory.     

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.     

Effects of various ions on the dechlorination kinetics of hexachlorobenzene by nanoscale zero-valent iron

The effect of several anions and cations normally co-present in soil and groundwater contamination sites on the degradation kinetics and removal efficiency of hexachlorobenzene (HCB) by nanoscale zero-valent iron (NZVI) particles was examined. The degradation kinetics was not influenced by the HCO(3)(-), Mg(2+), and Na(+) ions. It was enhanced in the presence of the Cl(-) and SO(4)(2-) ions due to their corrosion promotion. The NO(3)(-) competes with HCB so it inhibits the degradation reaction. The Fe(2+) ions would inhibit the degradation reaction due to passivation layer formed, while it was enhanced in the presence of Cu(2+) ions resulted from the reduced form of copper on NZVI surfaces. These observations lead to a better understanding of HCB dechlorination with NZVI particles and can facilitate the remediation design and prediction of treatment efficiency of HCB at remediation sites.     

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.