Formiate and acetate in wet deposition at Pallanza (NW Italy) in relation to major ion concentrations

Weekly samples of wet deposition were collected at Pallanza (NW Italy) from January 1987 to December 1988. Their chemistry is characterized by high mineral acidity, with a median pH value of 4.26; only in 2 out of 62 samples was pH higher than 6.0. Sulphate, nitrate and ammonium are the main ions. Formiate and acetate showed a volume weighted average of 7 and 4 μeq L^?1, respectively; the values for the dissociated forms are 5 and 1 μeq L^?1, respectively. The contribution of formiate and acetate (dissociated form) to the total ionic concentration is about 2%, while the contribution to free hydrogenion is about 13%, mainly deriving from formic acid. Seasonal variations in concentration and the relationships between organic acid and other ions indicate that the photolysis of isoprenoid compounds released into the atmosphere from vegetation is a significant source for formic acid. In the case of acetic acid there is a contribution from anthropogenic emissions, more marked during the winter period.     

Precipitation chemistry within Kvarner Bay area,Northern Adriatic (Croatia), 1984–1991

The results of rainwater analyses collected at five sampling sites within Kvarner Bay area are presented for the period 1984–1991. The samples were collected on a daily basis in open buckets thus representing bulk samples. Although measurements are referred to as wet deposition samples, they are actually an upper limit for the wet deposition. The rainwater was initially analysed for pH, sulphate and nitrate content, while during the period March 1990 — May 1991 the analyses were extended to major ion concentrations: hydrogen, sulphate, nitrate, chloride, ammonium, sodium, potassium, calcium and magnesium. The pH frequency distribution, pH medians and precipitation weighted average (PWA) concentrations of hydrogen, sulphate and nitrate are presented, as well as wet deposition rates of sulphur (as sulphate) and nitrogen (as nitrate). The dependence of hydrogen, sulphate and nitrate mean concentrations on wind directions and seasons for Site 1 is also given. The highest precipitation acidity is obtained at urban and industrial Site 1 (city of Rijeka) because of the local washout of the atmosphere and influence of dry deposition, and at remote Site 4 (Lake Vrana) due to long-range transport. The neutralizing potential of sea salt and soil dust is responsible for partial neutralization of rainwater at other sites. The influence of sea salt on chemical composition of rainwater is observed at all sites. The estimated wet deposition rates of sulphate and nitrate are close to the values reported for Southeast Europe. The wet deposition rate for ammonium ion at Site 1 is almost double comparative regional values.     

Interaction of 15N-labelled ammonium nitrate,urea and ammonium sulphate with soil N during growth of wheat (Triticum aestivum L.) under field conditions

The effects of ¹⁵N-labelled ammonium nitrate, urea and ammonium sulphate on yield and uptake of labelled and unlabelled N by wheat (Triticum aestivum L. cv. Mexi-Pak-65) were studied in a field experiment. The dry matter and N yields were significantly increased with fertilizer N application compared to those from unfertilized soil. The wheat crop used 64.0–74.8%, 61.5–64.7% and 61.7–63.4% of the N from ammonium nitrate, urea and ammonium sulphate, respectively. The fertilizer N uptake showed that ammonium nitrate was a more available source of N for wheat than urea and ammonium sulphate. The effective use of fertilizer N (ratio of fertilizer N in grain to fertilizer N in whole plant) was statistically similar for the three N fertilizers. The application of fertilizer N increased the uptake of unlabelled soil N by wheat, a result attributed to a positive added N interaction, which varied with the method of application of fertilizer N. Ammonium nitrate, urea and ammonium sulphate gave 59.3%, 42.8% and 26.3% more added N interaction, respectively, when applied by the broadcast/worked-in method than with band placement. A highly significant correlation between soil N and grain yield, dry matter and added N interaction showed that soil N was more important than fertilizer N in wheat production. A values were not significantly correlated with added N interaction (r=0.719). The observed added N interaction may have been the result of pool substitution, whereby added labelled fertilizer N stood proxy for unlabelled soil N.     

A comparison between wet and bulk deposition at an urban site in the U.K.

As a part of an ongoing investigation into urban acidic deposition in Greater Manchester, a wet-only collector was collocated with a bulk collector in the city centre of Manchester, one of 18 sites of an urban precipitation monitoring network. A comparison of data from these collocated bulk and wet-only collectors allowed estimates of the contribution of dry deposition to the bulk collector to be made. Dry deposition was found to contribute between 15 and 17% to elevated deposition and concentrations of non marine sulphate, nitrate and ammonium in the bulk collector. By a statistical analysis between ion concentrations with gas concentrations and an evaluation of the available literature, the form of the dry deposited material was inferred. The contribution of dry deposited Ca²⁺ to concentration and deposition in the bulk collector was found to be 46%. Calcium species are suggested as being those which reduce acidity most. Statistical analyses revealed significant differences between concentrations of ions found in the bulk and wet-only collectors. An evaluation of the data from the collocated collectors has identified possible sampling artifacts introduced by the use of bulk collectors in urban areas.     

Rainfall Concentrations and Wet Atmospheric Deposition of Phosphorus and Other Constituents in Florida,U.S.A.

Concentrations of phosphorus (P) and other constituents inweekly composited rain samples and concurrently acquired rainfallvolumes, collected from September 1992 through October 1993, wereused to estimate volume-weighted concentrations and wetatmospheric deposition rates, and compared to estimates fromprevious studies. Since this study’s purpose was to estimateregionally representative concentrations and rates of wetatmospheric deposition, sampling locations were chosen to avoidsites characterized by substantial local resuspension orrecycling phenomena. Significant differences were found in the wet deposition rates of calcium (Ca), magnesium (Mg), potassium (K), sodium (Na), hydrogen (H), and chloride (Cl) ions between sampling stationsin Florida. Consequently, statewide deposition rates and volume-weighted concentrations were estimated only for P, and fororthophosphate (PO₄), ammonium (NH₄), nitrate (NO₃) and sulfate (SO₄) ions that were not found to be spatially variable. Over the period of record, the mean rate of wet atmospheric P deposition across the state, and the mean rainfall P concentration, were found to be 25±>5 μg P M^-2 wk^-1 and 1.3±0.1 μg P L ^-1, respectively.     

Soil Acidification Induced by Ammonium Sulphate Addition in a Norway Spruce Forest in Southwest Sweden

The contributions of different acidifying processes to the total protonload (TPL) of the soil in control plots (C) and ammonium sulphate treatedplots (NS) were studied in a Norway spruce stand in Southwest Sweden during 1988–1998. The annual deposition of inorganic nitrogen and sulphate was on average 18 kg N and 20 kg S ha^-1. In addition the NS treated plots received 100 kg N and 114 kg S ha^-1 annually. The amounts of nutrients added to the ecosystem by wet and dry deposition and the leaching at 50 cm depth were calculated. The net atmosphericproton load, the proton load by nitrogen transformations in the soil, the sulphate sorption/desorption in the soil and the excess base cation accumulation in biomass were calculated. There was no leaching of inorganic nitrogen from control plots during the study period. The net atmospheric proton deposition, originating from sulphuric and nitric acid deposition, was the main contributor to TPL in control plots. The addition of ammonium sulphate increased the leaching of ammonium, nitrate, sulphate, magnesium and calcium but not of potassium. The TPL in NS plots was about ten times that in control plots. The nitrogen transformation processes were the main contributors to TPL to NS soil, in the beginning by ammonium uptake and later also by nitrification. The pH decreased by 0.4 units in the mineral soil. The between-year variation in TPL during the eleven year period in C plots (200–1500 mol_c ha^-1 yr^-1) and in NS plots (1000–13000 mol_c ha^-1 yr^-1) was mainly dependent on the sorption or release of sulphate. Both in C and NS, the TPL was buffered mainly by dissolving solid aluminium compounds, most probably some Al(OH)₃ phase.     

Atmospheric Deposition in a Rural Area in India - Net and Potential Acidity

Atmospheric deposition in India is generally described as alkaline and well buffered against an increase of acidifying components. Such conclusion has been based on measurements usually performed in urban or suburban areas. Our data on deposition in NE India (in the countryside N of Bhubaneswar) obtained with wet-only and bulk collectors show that: 1) the weighted mean concentrations (and wet deposition) of H⁺ and HCO₃ ^? are almost equal, with dustfall contributing a negligible amount of HCO₃ ^?, 2) the deposition of potential acidity, defined as the acidity that would give the same acidity contribution to the receiving surface as the actual deposition provided that all ammonium was converted to nitrate in the soil, could be as high as 40 mmol H⁺ m^?2 a^?1 corresponding to a pH of 4.3 in precipitation. The low buffer capacity against acidification and high potential acidity were discovered from long- term measurements in a vegetation covered rural area. Similar measurements in a nearby suburban area gave a much higher input of HCO₃ ^? both in wet deposition and dustfall. Further increase of the emission of acidifying components in the region will increase the acid deposition.     

Effects of sulphuric acid and acidifying ammonium deposition on water quality and vegetation of simulated soft water ecosystems

In a greenhouse, seven identical mini-ecosystems, simulating soft water ponds, were exposed to different types of artificial rain water. The effects of rain water containing H₂SO₄ and nitrate, and rain water containing ammonium sulphate on water quality and vegetation were studied and compared. Causal relations were established between rain water quality, water chemistry and changes in floristic composition. Ammonium sulphate deposition, particularly, strongly affected water quality and vegetation development. Although ammonium sulphate deposition was only slightly acid, due to nitrification it acted as an important acid source, causing acidification to pH=3.8. Under acidified conditions, ammonium sulphate deposition lead to a luxuriant growth ofJuncus bulbosus andAgrostis canina. In the mini-ecosystems, H₂SO₄ deposition with a pH of 3.5 only decreased the pH of the water to 5.1 within 1 yr. The acidification of water appeared to be coupled with changes in alkalinity, sulphate, Al, Cd, Ca, Mg, K and inorganic-N. It is concluded that in NH₃-affected regions in The Netherlands, the high atmospheric deposition of ammonium sulphate probably contributes to a large extent in the acidification, eutrophication and floristic changes of oligotrophic soft waters.     

Nine years of measurements of atmospheric nitrogen and sulphur deposition to Danish forest

Since 1985 measurements of gasses, aerosols, precipitation and throughfall have been carried out at three forest sites in Denmark with equal aged Norway Spruce plantations. The times series show a downward trend in the concentration of sulphur dioxide. Particulate sulphate, ammonia and particulate ammonium and the total nitrate seem to have a more constant concentration level. The wet deposition measurements show a decreasing trend in the content of acid (protons), sulphate, ammonium and nitrate, though for the nitrogen compounds it is only a slight fall. A decrease in concentrations of protons and sulphate is also seen in the throughfall measurements, in throughfall the nitrogen compounds hardly seem to decrease.     

The acidifying potential of atmospheric deposition in Canada

It is proposed that the value of ([SO₄ ^??] - [Ca⁺⁺ + Mg⁺⁺]) in precipitation is a suitable way to describe the acidifying potential (AP) of the wet desposition. In eastern North America, the AP of precipitation varies from 20 to 85% of the total sulphate, the remainder of the sulphate being neutralized H₂SO₄, sulphate from salts in dust or from sea salt. The AP ranges from 20 to 80% of the H⁺ in the wet deposition. The rest of the H⁺ is contributed by the net effect of N compounds. Ammonium and nitrate ions from ammonia and NO_Xemissions do not represent a net acidic loading to the terrestrial ecosystem if they are taken up by vegetation. However, when N leaches from watersheds in the form nitrate, it constitutes an acidifying demand on the ecosystem. Therefore, the overall net acidifying potential (NAP) applied to the terrestrial ecosystem is defined by the value of ([SO₄ ^??] - [Ca⁺⁺ + Mg⁺⁺]) in precipitation plus [NO₃ ^??] in runoff from the watershed.     

Assessment of the relative uptake of added and indigenous soil nitrogen by nodulated legumes and reference plants in the 15N dilution measurement of N2 fixation: Glasshouse application of method

A method for calculating the relative uptake (R) of added N and indigenous soil N by a legume (Trifolium subterraneum) and non-legume (Lolium rigidum), growing together, was investigated in two pot experiments. In the first experiment, ¹⁵N-labelled sodium nitrate was applied to the soil surface at rates equivalent to 0.3 or 1.0kg N ha^?1. Twenty one days later, the legume had fixed about 95% of its total N and this was unaffected by N addition. There was no difference in R values between legume and non-legume at both N rates.In the second experiment using a soil of higher total N, sodium nitrate or ammonium sulphate were surface-applied at a rate equivalent to 1 kg N ha^?1 and harvests were made at 3, 6, 12 and 27 days after N addition. Fixation of atmospheric N₂ by the legume did not begin until day 12 but accounted for about 40% of the total N assimilated by the legume by day 27. There was no difference in R values between legume and non-legume throughout the growth period when sodium nitrate was applied. However, when ammonium sulphate was added to label to soil N, the uptake of added N relative to indigenous soil N was greater for the non-legume than the legume. This caused an overestimation (51 vs 43%) of the proportion on N fixed by the legume when compared with that for the control or sodium nitrate treatments.     

Wet and Dry Deposition of Sulphur at the Site Melpitz in East Germany. In memorium dedicated to Wolfgang Rolle

Sulphur concentrations in precipitation as sulphate and in air as sulphur dioxide were determined from October 1991 (May 1992), respectively, to December 1995. The total sulphur deposition was calculated from sum of the wet and dry deposition, using the concentration of sulphate and precipitation volume and the concentration and deposition velocity of sulphur dioxide, determined with the micrometeorological gradient method. The concentration of sulphur in precipitation decreased over the period by about 40% and in air about 70%. The wet deposition decreased over the period by about 30%. However there was no decrease in dry deposition despite the reduction in SO₂ concentrations because the deposition velocity varied from 0.16 cm s^-1 to 0.37 cm s^-1 during the period. Therefore no trend was observed in the total sulphur deposition.     

Observations on Gaseous and Aerosols Components of the Atmosphere and Their Relationships

Measurements of sulphur dioxide, ozone, ammonia, and soluble inorganic components of the atmospheric aerosol were made at a site in central southern England. Ammonia, ozone, and nitrate aerosol in winter were shown to exhibit significant diurnal variation. Ozone showed a typical diurnal variability, the magnitude of which was dependent upon wind speed. The lower night-time ozone concentrations at lower wind speeds were attributed to depletion inside nocturnal boundary layers by dry deposition. Ammonia, in contrast, showed a different behaviour, whereby the diurnal cycle was more pronounced at higher wind speeds, indicating that the cycle was unlikely to be the result of dry deposition at night. Ammonia concentrations showed a temperature dependence and the diurnal cycle of ammonia at this site appears to be the result of a temperature-driven emission signal. Of the total reduced nitrogen, NH_x (NH_x = NH₃ + NH₄ ⁺ aerosol), the phase was dominant and it is likely that more than 60% of the boundary layer NH_x is in this phase. The loss term of ammonia by reaction with acid sulphate aerosol is likely to be greater than that by dry deposition on a UK scale. Nitrate aerosol showed a positive correlation with sodium aerosol, once the effect of mutual correlations with sulphate and ammonium were removed. This correlation effect, in combination with evidence of a marine-oriented directional dependence of nitrate aerosol, and negative non sea-salt chloride aerosol from the same ‘marine’ sector, shows the potential importance of the formation of sodium nitrate aerosol from reaction of dinitrogen pentoxide, or possibly nitric acid or nitrogen dioxide with sodium chloride aerosol. It is likely that this provides the major route of nitrate into rain, not the scavenging of nitric acid vapour. Aerosol sulphate, nitrate, and ammonium have been measured at Harwell since 1954. Sulphate aerosol increased up until 1976 and has declined subsequently. Nitrate aerosol has increased over the whole period, whereas ammonium aerosol follows a similar pattern to that of sulphate, but with an equivocal direction of trend after 1976. Sulphate, nitrate and ammonium aerosol all show a similar statistically significant seasonality. A historical inventory of ammonia emissions shows a clear correlation with ammonium aerosol.     

THE USE OF BULK COLLECTORS IN MONITORING WET DEPOSITION AT HIGH-ALTITUDE SITES IN WINTER

Concentrations of dissolved ions from samples collected by wet/dry collectors were compared to those collected by bulk collectors at Halfmoon Creek and Ned Wilson Lake in western Colorado to determine if bulk collectors can be used to monitor wet deposition chemistry in remote, high-altitude regions in winter. Hydrogen-ion concentration was significantly lower (p <0.05) in the bulk collectors. All other ion concentrations were significantly higher (p <0.05) in the bulk collectors except for ammonium (p >0.05) at Halfmoon Creek. Wet deposition concentrations were predicated from bulk deposition concentrations through linear regression analysis. Results indicate that anions (chloride, nitrate and sulfate) can be predicted with a high degree of confidence. Lack of significant differences between seasonal (winter and summer) ratios of bulk to wet deposition concentrations indicates that at sites where operation of a wet/dry collector during the winter is not practical, wet deposition concentrations can be predicted from bulk collector samples through regression analysis of wet and bulk deposition data collected during the summer.     

不同氮肥形态的氨挥发损失比较

利用从德国引进的农田土壤氨挥发风洞法测定系统,对不同N肥形态的肥料进行对比实验。结果表明,在相同施N量条件下,硝酸铵、硝酸铵钙、硫硝酸铵的氨挥发损失分别比尿素减少22.5%、3.2%和8.3%,不同N肥的氨挥发损失差异很大。相同条件下,尿素的氨挥发损失为25.7%,添加DMPP后氨挥发损失为27.6%;硫硝酸铵的氨挥发损失为18.6%,添加DMPP后为20.6%;添加DMPP对尿素和硫硝酸铵的氨挥发影响不显著。     

Contribution of dissolved organic nitrogen deposition to total dissolved nitrogen deposition under intensive agricultural activities

For elucidating the atmospheric deposition contribution of dissolved organic nitrogen (DON) to the total dissolved nitrogen (TDN) deposition rate, dissolved inorganic nitrogen (DIN: NH₄ ⁺ + NO₃ ^–) and DON deposition rates were annually and monthly estimated during 4 and half-yr monitoring period in an experimental multi-farm under intensive agricultural activities of N fertilizer use and animal husbandry in Central Japan. Annual NH₄ ⁺, DON and NO₃ ^– deposition rates in bulk and wet deposition data accounted for 48%, 32% and 20% of TDN deposition, respectively, which indicated that this area is strongly affected by the intensive agricultural activities. The DIN and DON deposition rates were respectively estimated at 21.6 and 10.1 kg N ha^?1 yr^?1, which ranked high in a worldwide regional data set. Consequently, this area has been exposed to a large amount of N deposition including DON with N fertilizer input. The difference between bulk and wet deposition rates (NH₄ ⁺ and DON) is one of important factors controlling the N deposition in this area. Monthly DON deposition showed positive correlations with DIN and NH₄ ⁺ deposition rates, respectively, with a significant linear regression curve. The linear regression curve of our monthly data (n = 127) indicates the same trend as the worldwide annual data set (n = 31).     

Measurement Uncertainty of Sulphur and Nitrogen Containing Inorganic Compounds By 1-Stage and 2-Stage Filter-pack Methods

The sampling and analysis properties of 1-stage and 2-stage filter-pack methods were studied in detail in monitoring of sulphur and nitrogen containing inorganic gases and particles (sulphur dioxide, sulphate, sum of nitric acid and nitrate and total ammonium). The limit of detection and the limit of quantitation for 24-h samples were estimated using the results of a short-term field experiment completed with available data from long-term monitoring and internal quality assurance. Furthermore, the combined expanded measurement uncertainty including sampling and analysis (U_tot) was estimated for filter-pack methods in order to give a tool for distinguishing long-term trends in air quality from the measurement variability. U_tot was found to be very near the analytical uncertainty when measuring higher air concentration levels, being ± 4.0% for sulphur concentrations?>?1.0 μg m^?3, ± 3.0% for sulphate concentrations?>?0.5 μg m^?3, ± 3.5% for the sum of nitrate and nitric acid concentrations?>?0.3 μg m^?3 and ± 4.5% for total ammonium concentrations?>?0.8 μg m^?3. At the lower air concentration range U_tot increases significantly due to the field blank values. The precision of the 24-h filter-pack sample results expressed by means of modified median absolute difference (M.MAD) and coefficient of variance (CoV) gave 8.3% for sulphur dioxide and 5.4% for particulate sulphate. For the sum of gaseous nitric acid and particulate nitrate the CoV was 5.5% and for total ammonium 4.3%. In addition the suitability of the 24-h filter-pack methods in weekly sampling was proved.     

Atmospheric sulfur and nitrogen in West Java

Wet-only rainwater composition on a weekly basis was determined at four sites in West Java, Indonesia, from June 1991 to June 1992. Three sites were near the extreme western end of Java, surrounding a coal-fired power station at Suralaya. The fourth site was ～100 km to the east in the Indonesian capital, Jakarta. Over the 12 months study period wet deposition of sulfate at the three western sites varied between 32–46 meq m^?2 while nitrate varied between 10–14 meq m^?2. Wet deposition at the Jakarta site was systematically higher, at 56 meq m^?2 for sulfate and 20 meq m^?2 for nitrate. Since sulfate and nitrate wet deposition fluxes in the nearby and relatively unpopulated regions of tropical Australia are both only ～5 meq m^?2 anthropogenic emissions of S and N apparently cause significant atmospheric acidification in Java. It is possible that total acid deposition fluxes (of S and N) in parts of Java are comparable with those responsible for environmental degradation in acid-sensitive parts of Europe and North America.     

Influence of nitrite accumulation in association with seasonal patterns and mineralization of soil nitrogen in a semi-arid pine forest

To identify factors that influence the relatively high productivity of a semi-arid pine afforestation system in southern Israel, we investigated inorganic nitrogen deposition and mineralization for more than 2 years. To this end, we measured bulk and dry deposition, in situ N-mineralization over the seasonal cycle, and the potential activity of nitrifying microorganisms by soil slurry incubations. There was a small increase in bulk N deposition in the forest, compared with shrubland, but no change in dry deposition. An unexpected rapid increase in nitrite concentration in the forest soil was observed after soil rewetting by the first winter rains, which could not be explained by deposition. This was accompanied by a decrease in ammonium and only a slight increase in nitrate concentrations. Only a small increase in nitrite and a rapid increase in nitrate concentration in the mineral soil were observed in the surrounding shrubland. Soil slurry incubations from the forest sites exhibited significant delay in nitrite, compared with nitrate accumulation (up to 50 h under lab conditions) in samples taken in the dry season, but not in the wet season. This indicated different rates of ammonium and nitrite oxidation that are most likely linked to differential activation of different microbial populations after the summer stress. The initial oxidation process of ammonia to nitrate, upon soil rewetting in semi-arid environments, appears to occur as a partially uncoupled two-step process, as opposed to a rapid continuous one in wetter environments. This may have implications for the synchronization of nitrate availability to plants and therefore for high forest productivity and nitrogen use efficiency. Forest productivity in the semi-arid regions, in turn, is becoming increasingly more important with persistent predictions of warming and drying trends over the entire Mediterranean basin and other regions.     

Time trend of wet deposition acidifying potential at five ecological monitoring sites in eastern Canada 1981–1993

The Acidifying Potential (AP) of wet deposition has been previously defined by the expression AP = SO₄ ^?-[Ca⁺⁺ + Mg⁺⁺]. The time series over the period 1981 to 1993 for sulphate, calcium plus magnesium and AP concentrations are examined at five ecological monitoring research sites in the eastern half of Canada. At all sites there was a reduction in the concentrations of all 3 parameters over the whole period. As a result the reduction in AP was between 70 and 80% of the sulphate reduction at the 4 sites where precipitation acidity is highest. The annual wet deposition of AP showed a substantial decline in the first half of the period, but has levelled off in the second half, in spite of continuing sulphate decline. In assessing the impact of acidic deposition on surface water systems it is, thus, important to account for the counteraction of sulphate decreases by base cation decreases. This is particularly important for simulation modelling, either diagnostic using past data, or predictive using future sulphur dioxide emission scenarios, where in general cations have been assumed to remain constant.