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

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

Decomposition of hexamethylcyclotrisiloxane over solid oxides

The decomposition of hexamethylcyclotrisiloxane (HMCTS) has been studied at room temperature and in the range 473-673 K over the surface of basic (CaO, MgO) and acidic oxides (Al(2)O(3), SiO(2)). Alumina allows the complete removal of HMCTS from synthetic biogases at 673 K. A reactive adsorption occurs with surface silication and release of methane. The adsorption capacity of our alumina adsorbent (180 m(2) g(-1)), until saturation, at 673 K, is 0.31 g((HMCTS))g((Al2O3))(-1), which corresponds to one silicon atom per 9 A(2), i.e. the silication monolayer capacity. On the contrary, silica, which is an excellent adsorbent for siloxanes at room temperature, looses its adsorption ability at high temperature as it is typical of a molecular adsorption behavior. Basic oxides such as MgO and CaO have strong reactivity in decomposing siloxanes in the absence of CO(2), but loose reactivity when in contact with carbon dioxide because of surface carbonation.     

Acidification of a Solonetzic soil by nitrogenous fertilizers

Annual applications of (NH4)2SO4, NH4NO3 and urea on a Solonetzic soil at 112 kg N/ha for 10 consecutive years reduced pH levels from 5.6 for the check to 4.4, 4.9 and 5.3, respectively for (NH4)2SO4, NH4NO3 and urea. (NH4)2SO4 generated twice as much exchange acidity as NH4NO3 and four times as much as urea. Net extractable cations leached from the Ap horizon closely approximated the amount of exchange acidity generated by (NH4)2SO4 and NH4NO3 fertilizers. The levels of soil extractable Al and Mn were greatly enhanced by (NH4)2SO4 as were plant contents. Similar acidifying effects to that produced by the (NH4)2SO4 occurred when NH4NO3 was applied at 300 kg N/ha annually for 12 consecutive years in another field experiment on the same soil. Liming samples of the field (NH4)2SO4 acidified soils in the greenhouse, significantly increased yields and lowered the Al and Mn contents of the plants to normal levels.     

Evaluation of accelerated dechlorination of p,p'-DDT in acidic paddy soil

The reductive dechlorination and behavior of p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) was investigated in a paddy soil. Treatment with 5% (w/w) metallic iron (Fe(0)) resulted in sharp decrease of p,p'-DDT, whereas there was no extra effect when 2% (w/w) aluminum sulfate (Al(2)(SO(4))(3)) was added to the Fe(0) treatment. These results suggest that Fe(0) could effectively promote the reductive dechlorination of p,p'-DDT and its metabolites while Al(2)(SO(4))(3) did not show any effect on those processes. Furthermore, p,p'-DDT and its daughter compounds inhibited holistic soil respiration greatly at first but could be metabolized by certain species of indigenous microorganisms after a period of adaptation time in the soil. When treated with Fe(0), the polluted soil produced much less CO(2) while the addition of Al(2)(SO(4))(3) counteracted its negative effect to much extent.     

Polyacrylamide + Al2(SO4)3 and polyacrylamide + CaO remove coliform bacteria and nutrients from swine wastewater

Animal wastes are a major contributor of nutrients and enteric microorganisms to surface water and ground water. Polyacrylamide (PAM) mixtures are an effective flocculent, and we hypothesized that they would reduce transport of microorganisms in flowing water. After waste water running at 60.0 1 min(-1) flowed over PAM + Al2(SO4)3, or PAM + CaO in furrows, total coliform bacteria (TC) and fecal coliform bacteria (FC) were reduced by 30-50% at 1 and 50 m downstream of the treatments compared to the control. In a column study, PAM + Al2(SO4)3, and PAM + CaO applied to sandy, sandy loam, loam, and clay soils reduced NH4+ and ortho-P concentrations in leachate compared to the source waste water and the control. PAM + Al2(SO4)3 and PAM + CaO applied to sandy, sandy loam and loam soils reduced both total and ortho-P, concentrations in leachate compared to he source wastewater and control treatment. In a field study, PAM + Al2(SO4)3, or PAM + CaO treatments did not consistently reduce NH4+, NO3-, ortho-P, and total P concentrations in wastewater flowing over any soil compared to inflow wastewater or the control treatment. With proper application PAM + Al2(SO4)3 and PAM + CaO may be able to reduce the numbers of enteric bacteria in slowly flowing wastewater running off animal confinement areas, reducing the amount of pollutants entering surface water and groundwater.     

改性膨润土对垃圾填埋场渗滤液吸附效果

通过制备不同组分改性膨润土,研究其对苯酚的吸附效果,结果表明,十六烷基三甲基溴化铵+十二烷基磺酸钠+硫酸铝-改性膨润土>十六烷基三甲基溴化铵+十二烷基磺酸钠-改性膨润土>十六烷基三甲基溴化铵-改性膨润土。通过改性膨润土对实际复杂组分渗滤液的吸附研究,结果表明,使用活性炭改性的膨润土吸附COD和NH4+-N最为理想,单位质量COD吸附量最高为26.8 mg/g,NH4+-N最高为3.92 mg/g,其中,COD最高去除率为77.3%,氨氮为28.9%;十六烷基三甲基溴化铵+十二烷基磺酸钠+硫酸铝-改性膨润土对COD和NH4+-N均有去除效果,两者对于渗滤液实际处理工程具有应用价值。     

鼓泡反应器中液相络合催化同时脱硫脱硝的研究

在鼓泡反应器中考察了[Co(en)3]2+同时吸收去除SO2和NO的影响因素,实验结果表明,pH值和脱硫剂种类是影响乙二胺合钴同时脱除NO和SO2的最重要影响因素,烟气中的氧促进乙二胺合钴吸收NO和SO2,烟气中的SO2,CO2和NO2对乙二胺合钴吸收NO具有抑制作用。在实验条件温度为20℃,pH为13.0,[Co(en)3]2+浓度为0.025 mol/L,加入1 g NH3.H2O的脱硝率更好,连续吸收60 min,脱硝率均保持在93.5%,加入NaOH和NH3.H2O的脱硫效果最好。乙二胺合钴络合同时脱除NO和SO2完全可以在一个装置中完成。     

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.     

The MAGIC simulation of surface water acidification at, and first year results from, the Bear Brook Watershed Manipulation, Maine, USA

The catchments of East and West Bear Brooks, Maine, USA, have been hydrologically and chemically monitored for 3.5 years. Stream chemistries and hydrographs are similar. These clear water streams are low in ANC (0-70 microeq litre(-1)), with variations caused by changing concentrations of base cations, SO4, NO3 and Cl. The latter range between 90-120, 0-40 and 65-75 microeq litre(-1), respectively. The West Bear catchment is being treated with six applications per year of dry (NH4)2SO4 at 1800 eq ha(-1) year(-1). After one year of treatment, the response of the stream chemistry and the response modelled by MAGIC are similar. Retentions of NH4 and SO4 are nearly 100% and greater than 80%, respectively. The additional flux of SO4 is compensated principally by an increased Ca concentration. Episodes of high discharge in the treated catchment are now characterized by lower ANC and pH, and higher Al than prior to the manipulation. Concentrations of NO3 have increased about 10 microeq litre(-1) during the dormant season, presumably due to additional nitrification of N from NH4. Discharge-chemistry relationships indicate that changes in stream chemistry, except for NO3, are dominated by ion exchange reactions in the upper part of the soil profile.     

Polyacrylamide preparations for protection of water quality threatened by agricultural runoff contaminants

Waste streams associated with a variety of agricultural runoff sources are major contributors of nutrients, pesticides and enteric microorganisms to surface and ground waters. Water soluble anionic polyacrylamide (PAM) was found to be a highly effective erosion-preventing and infiltration-enhancing polymer, when applied at rates of 1-10 g m(-3) in furrow irrigation water. Water flowing from PAM treated irrigation furrows show large reductions in sediment, nutrients and pesticides. Recently PAM and PAM + CaO and PAM + Al(SO4)3 mixtures have been shown to filter bacteria, fungi and nutrients from animal wastewater. Low concentrations of PAM [175-350 g PAM ha(-1) as PAM or as PAM + CaO and PAM + Al(SO4) mixture] applied to the soil surface, resulted in dramatic decreases (10 fold) of total, coliform and fecal streptococci bacteria in cattle, fish and swine wastewater leachate and surface runoff. PAM treatment also filtered significant amounts of NH4, PO4 and total P in cattle and swine wastewater. This points to the potential of developing PAM as a water quality protection measure in combination with large-scale animal feeding operations. Potential benefits of PAM treatment of animal facility waste streams include: (1) low cost, (2) easy and quick application. (3) suitability for use with other pollution reduction techniques. Research on the efficacy of PAM for removal of protozoan parasites and viruses and more thorough assessment of PAM degradation in different soils is still needed to completely evaluate PAM treatment as an effective waste water treatment. We will present analysis and feasibility of using PAM, PAM + Al(SO4)3, and PAM + CaO application for specific applications. Our results demonstrate their potential efficacy in reducing sediment, nutrients and microorganisms from animal production facility effluents.     

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

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

Fate of high loads of ammonia in a pond and wetland downstream from a hazardous waste disposal site

Halls Brook (eastern Massachusetts, USA) is a significant source of total dissolved ammonia (sum of NH(3) and NH(4)(+); (NH(3))(T)) to the Aberjona River, a water body listed for NH(3) impairment on the Clean Water Act section 303(d) list. We hypothesized (1) that (NH(3))(T) in Halls Brook derived from a hazardous waste site via groundwater discharging to a two-basin pond that feeds the brook; and (2) that transport of (NH(3))(T) to the Aberjona River was controlled by lacustrine and wetland processes. To test these hypotheses we measured (NH(3))(T) levels in the brook, the pond, and a wetlands directly downstream of the pond during both dry and wet weather over a ten month period. In addition, we analyzed sediment cores and nitrogen isotopes, and performed mass balance calculations. Groundwater discharge from beneath the hazardous waste site was the major source of (NH(3))(T) (20-67 kg d(-1)) and salinity to the north basin of the pond. The salty bottom waters of the north basin were anoxic on all sampling dates, and exhibited relatively stable (NH(3))(T) concentrations between 200 and 600 mg Nl(-1). These levels were >100-times higher than typical background levels, and 8-24-times above the acute effects level for (NH(3))(T) toxicity. Bottom waters from the north basin continuously spill over into the south basin contributing approximately 50% of the (NH(3))(T) load entering this basin. The remainder comes from Halls Brook, which receives (NH(3))(T) loadings from as yet unknown sources upstream. During storm events up to 50% of the mass of (NH(3))(T) was flushed from the south basin and into the wetlands. The wetlands acted as a (NH(3))(T) sink in dry weather in the growing season and a discharge-dependent (NH(3))(T) source to the Aberjona River during rainstorms.     

Simulation of stack plume opacity

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO3 (that hydrolyzes to H2SO4), HCl, and NH3, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult. We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply). Conversion of H2SO4 to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO3 emissions showed only a small effect, except if one assumes that most H2SO4 condenses on primary particles. Condensation of NH4Cl occurs only at high NH3 emission rates (about 25 ppm stack concentration).     

Removal of SO2 from simulated flue gases using non-thermal plasma-based microgap discharge

The removal of sulfur dioxide (SO2) from simulated flue gases streams (N2/O2/H2O/SO2) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al2O3) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH*) radicals were produced using the ionization of O2 and H2O to further the conversion of SO2 into sulfuric acid (H2SO4) at 120 degrees C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O2 and H2O increased the production of OH. radicals resulting in enhanced removal of SO2 from gas streams. With the test and analysis, a number of H2SO4 droplets were produced in experiment. Therefore, a new method for removal of SO2 in semidry method without ammonia (NH3) additive was found.     

Trends in atmospheric ammonium concentrations in relation to atmospheric sulfate and local agriculture

Ammonium (NH(4)(+)) concentrations in air and precipitation at the Institute of Ecosystem Studies (IES) in southeastern New York, USA declined over an 11-year period from 1988 to 1999, but increased from 1999 to 2001. These trends in particulate NH(4)(+) correlated well with trends in particulate SO(4)(2-) over the 1988-2001 period. The NH(4)(+) trends were not as well correlated with local cattle and milk production, which declined continuously throughout the period. This suggests that regional transport of SO(4)(2-) may have a greater impact on concentrations of NH(4)(+) and subsequent deposition than local agricultural emissions of NH(3). Ammonium concentrations in precipitation correlated significantly with precipitation SO(4)(2-) concentrations for the 1984-2001 period although NH(4)(+) in precipitation increased after 1999 and SO(4)(2-) in precipitation continued to decline after 1999. The correlation between NH(4)(+) and SO(4)(2-) was stronger for particulates than for precipitation. Particulate NH(4)(+) concentrations were also correlated with particulate SO(4)(2-) concentrations at 31 of 35 eastern U.S. CASTNet sites that had at least 10 years of data. Air concentrations of NH(4)(+) and SO(4)(2-) were more strongly correlated at the sites that were located within an agricultural landscape than in forested sites. At most of the sites there was either no trend or a decrease in NH(4)(+) dry deposition during the 1988-2001 period. The sites that showed an increasing trend in NH(4)(+) dry deposition were generally located in the southeastern U.S. The results of this study suggest that, in the northeastern U.S., air concentrations of NH(4)(+) and subsequent deposition may be more closely linked to SO(4)(2-) and thus SO(2) emissions than with NH(3) emissions. These results also suggest that reductions in S emissions have reduced NH(4)(+) transport to and NH(4)(+)-N deposition in the Northeast.     

Characterization of major chemical components of fine particulate matter in North Carolina

This paper presents measurements of daily sampling of fine particulate matter (PM2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM2.5 is organic matter, and the major soluble components are sulfate (SO4(2-)), ammonium (NH4(+)), and nitrate (NO3(-)). NH4(+) is neutralized mainly by SO4(2-) rather than by NO3(-), except in winter when SO4(2-) concentration is relatively low, whereas NO3(-) concentration is high. The equivalent ratio of NH4(+) to the sum of SO4(2-) and NO3(-) is < 1, suggesting that SO4(2-) and NO3(-) are not completely neutralized by NH4(+). At both rural and urban sites, SO4(2-) concentration displays a maximum in summer and a minimum in winter, whereas NO3(-) displays an opposite seasonal trend. Mass ratio of NO3(-) to SO4(2-) is consistently < 1 at all sites, suggesting that stationary source emissions may play an important role in PM2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM2.5 mass concentrations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

Formation of leadhillite and calcium lead silicate hydrate (C-Pb-S-H) in the solidification/stabilization of lead contaminants

In this study, we have investigated the structure of Pb-doped solidified waste forms (SWF) for assessment of lead fixation. A large quantity of lead precipitates produced during the S/S, based upon the results of cement-water solution analysis, X-ray diffraction and electron probe microanalysis/electron dispersive spectroscopy investigations, have been shown to be principally leadhillite (lead carbonate sulfate hydroxide, Pb(4)SO(4)(CO(3))(2)(OH)(2)), lead carbonate hydroxide hydrate (3PbCO(3).2Pb(OH)(2).H(2)O) and two other unidentified lead salts. In the long curing, the lead species dissolved from the lead precipitates are fixed into the cement matrix, forming a gelling calcium lead silicate hydrate during cement-based solidification. On leaching the lead precipitates such as leadhillite were markedly dissolved/released and some dissolved lead species were adsorbed to silicate-rich surface of leached SWF with the subsequent formation of mainly amorphous gel of calcium lead silicate hydrate.     

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

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

Adsorption of aluminium by stream particulates

An experimental study was made of the adsorption of aluminium by fine particulates from Whitray Beck, a hill stream in NW England. Adsorption increased with Al(3) activity, pH and concentration of particles, and could be quantitatively described by the empirical equation: [Formula: see text] [particles] where square brackets indicate concentrations, curly brackets, activities, and alpha, beta and gamma are constants with values of 5.14x10(-10) (mol litre(-1))(2.015) (g particles litre(-1))(-1), 0.457, and 1.472, respectively. For the experimental data, the equation gave a correlation ratio of 0.99. The equation accounts reasonably well for the adsorption of Al by particulates from seven other streams. In applying the equation, it must be borne in mind that the desorption kinetics of Al depend on pH, and rapid reversibility (<15min) can only be assumed for pHor=10%) of total monomeric Al.     

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.