Verifying the effect of acid precipitation on soil leachates: A comparison between published records and model predictions

A model for predicting the effects of acid precipitation on the acid (H⁺ + Al³⁺ + Fe³⁺- and base (Na⁺ + K + Ca²⁺ + mg²⁺)-cation losses from soils via leaching as function of time was verified by examining published results for one indoor and five outdoor lysimeter studies (with precipitation pH-values ranging from 2 to 6), and five watershed studies. In each case the predictions of the model were in acceptable (but not perfect) agreement with the observed acid and base cation losses. These studies were selected from other relevant studies because they nearly met the information requirements of the model. The prediction of the acid cation content of soil leachates is important for considering the generally negative effects of such cations (especially the dominating Al³⁺-ions) on plant growth and ground-, stream- and later water quality.     

A Critical Appraisal of Field Evidence From A Regional Survey for Acid Deposition Effects On Scottish Moorland Podzols

Samples have been collected from major horizons of 34 podzol profiles distributed throughout Scotland, all developed from granite or granitic tills and under Calluna moorland. the pH in water and calcium chloride pastes, exchangeable cations and cation exchange capacity, and extractable aluminium of the soils collected have been measured, and the results studied in relation to reported atmospheric deposition of H⁺, non-marine sulphur and nitrate. for all horizons, significant positive correlations were found between soil pH and rainfall mean pH, as might be expected when the critical load of H⁺ deposition is exceeded. Acidifying pollutant deposition also apparently increased soil extractable aluminium concentrations in the B and C horizons. However, exchangeable base cation concentrations tended to increase, rather than decrease, with increasing precipitation acidity. This effect was attributed to increases in biogeochemical cycling of base cations, increases in leaching inputs of base cations from overlying A/E horizon soils, and increases in the inputs of base cations leached from upslope. the results suggest that the simple steady state mass approach to the quantification of critical loads, as often applied, may be an oversimplification.     

Effects of Simulated Sulphuric Acid Deposition On Calluna Vulgaris/Peat Microcosms and Associated Soil Solutions

Calluna vulgaris/peat microcosms have been used in an outdoor simulated acid rain experiment to test a series of hypotheses about sulphuric acid deposition effects upon the growth of Calluna on peat soil, namely: (1) Initially, enhanced acid input will enhance base cation and ammonium concentrations in soil solution. This may enhance uptake of these species, increasing foliar concentrations of base cations and nitrogen, and possibly foliar chlorophyll a and b concentrations. (2) If changes are induced in nutritional status, they may influence plant growth. (3) in the longer term, enhanced ammonium and base cation solubility occurring as a consequence of cation exchange reactions will lead, especially in winter months, to enhanced leaching losses. Hence any positive effects upon plant nutrition will not be sustainable. (4) the peat will acidify significantly over two years, in the shorter term primarily as a consequence of an enhanced mobile anion effect. (5) Acidification may reduce the rate of mineralisation of organic phosphorus and, in a phosphorus-deficient peat soil, this may lead to reduced foliar phosphate concentration and possibly induce phosphorus deficiency.

Most of these hypotheses were supported to some extent by the experimental results. the peat soil solution pH fell immediately in response to the acid treatments, and longer-term acidification continued progressively over the two years of the experiment. in the first year, the treatments significantly influenced the calcium, magnesium, phosphorus and nitrogen status of the leaves from Calluna new shoots, whereas in the second year calcium, potassium and phosphorus were influenced. However, in both years foliar phosphate concentration was enhanced, rather than reduced, in response to increased acid load. Foliar carbon and nitrogen concentrations fell with increasing acidity of     

Trends in precipitation chemistry in Alaska, 1980–1998

Nineteen years (1980–1998) of precipitation chemistry data from a site in Alaska are examined for trends using a least squares general linear model. The annual concentrations of SO^2– ₄ show a significant decreasing trend at 0.001 level and the annual change in concentration is —0.012mg 1^–1 yr^–1. The annual concentrations of NO ^– ₃ show an increasing tendency non‐significant. The annual base cation concentrations show a clear significant decreasing trend at 0.001 level and the decrease is —0.009mg 1^–1 yr^–1. Ca²⁺ concentrations exhibit a significant decreasing trend at 0.001 level and the annual change of concentration is —0.003 mg 1^–1 yr^–1. Mg²⁺ and Na⁺ concentrations show a significant decreasing trend at 0.01 level and the annual change is —0.001 mg1^–1 yr^–1 for Mg²⁺ and —0.004 mg1^–1 yr^–1 for Na⁺. K⁺ concentrations are characterised by a decreasing trend, significant at 0.05 level. K⁺ concentrations have decreased —0.002mg1^–1 yr^–1. The strongest rates of concentration decline for base cations, Ca²⁺, Mg²⁺, K⁺ and Na⁺ occurred in fall and winter season. The annual values of pH show a decreasing trend non‐significant. The values of pH oscillate between 5.1 and 5.6 during the period considered.     

Phosphorous cycling and biogeochemistry in a Venezuelan-flooded savanna

In 1970, a programme of land recuperation started in Venezuelan savannas, strongly affected by the seasonality of precipitation; therefore, a network of dykes has been built to alleviate the floods and retain water throughout the dry period. Under the dyked system, the environment has been altered, allowing a change in the herbaceous vegetation towards aquatic species and an increase in primary production. It is assumed that a considerable quantity of nutrients is lost from the ecosystem through the floodgates, a situation that could be worsened with the climate change. This contribution describes the atmospheric input and total output in stream run-off of phosphorous (P) in a flooded savanna. Internal pools of the biogeochemical cycle of P associated with terrestrial compartments are described. In the flooded savanna, a large amount of P is immobilised (29.6?kg?ha^?1) in their above ground biomass by grasses, and in soil microbial biomass. The P budget was nearly balanced, as measured losses were cancelled out by the inputs in rainfall. Soils act as a sink, retaining P coming either from precipitation or from desorption/mineralisation processes. That interruption can be maximised, and losses of P and other nutrients can be minimised with an adequate management of the floodgate.     

Effects of Simulated Sulphuric Acid Deposition On Calluna Vulgaris/Peat Microcosms and Associated Soil Solutions

Calluna vulgaris/peat microcosms have been used in an outdoor simulated acid rain experiment to test a series of hypotheses about sulphuric acid deposition effects upon the growth of Calluna on peat soil, namely: (1) Initially, enhanced acid input will enhance base cation and ammonium concentrations in soil solution. This may enhance uptake of these species, increasing foliar concentrations of base cations and nitrogen, and possibly foliar chlorophyll a and b concentrations. (2) If changes are induced in nutritional status, they may influence plant growth. (3) in the longer term, enhanced ammonium and base cation solubility occurring as a consequence of cation exchange reactions will lead, especially in winter months, to enhanced leaching losses. Hence any positive effects upon plant nutrition will not be sustainable. (4) the peat will acidify significantly over two years, in the shorter term primarily as a consequence of an enhanced mobile anion effect. (5) Acidification may reduce the rate of mineralisation of organic phosphorus and, in a phosphorus-deficient peat soil, this may lead to reduced foliar phosphate concentration and possibly induce phosphorus deficiency.

Most of these hypotheses were supported to some extent by the experimental results. the peat soil solution pH fell immediately in response to the acid treatments, and longer-term acidification continued progressively over the two years of the experiment. in the first year, the treatments significantly influenced the calcium, magnesium, phosphorus and nitrogen status of the leaves from Calluna new shoots, whereas in the second year calcium, potassium and phosphorus were influenced. However, in both years foliar phosphate concentration was enhanced, rather than reduced, in response to increased acid load. Foliar carbon and nitrogen concentrations fell with increasing acidity of     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^?1) on ¹³⁷Cs adsorption–desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26–99.97%) of added ¹³⁷Cs (3.7?×?10³?7.03?×?10⁵ Bq l^?1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K _ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄ ⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K _ads and soil pH was observed. The ¹³⁷Cs adsorption–desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09–0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Modeling carbon sequestration under zero tillage at the regional scale. I. The effect of soil erosion

Zero tillage is recognized as a potential measure to sequester carbon dioxide in soils and to reduce CO₂ emissions from arable lands. An up-scaling approach of the output of the Environmental Policy Integrated Climate (EPIC) model with the information system SLISYS-BW has been used to estimate the CO₂-mitigation potential in the state of Baden-Württemberg (SW-Germany). The state territory of 35,742 km² is subdivided into eight agro-ecological zones (AEZ), which have been further subdivided into a total of 3976 spatial response units. Annual CO₂-mitigation rates where estimated from the changes in soil organic carbon content comparing 30 years simulations under conventional and zero tillage. Special attention was given to the influence of tillage practices on the losses of organic carbon through soil erosion, and consequently on the calculation of CO₂-mitigation rates. Under conventional tillage, mean carbon losses through erosion in the AEZ were estimated to be up to 0.45 Mg C ha⁻¹ a⁻¹. The apparent CO₂-mitigation rate for the conversion from conventional to zero tillage ranges from 0.08 to 1.82 Mg C ha⁻¹ a⁻¹ in the eight AEZ, if the carbon losses through soil erosion are included in the calculations. However, the higher carbon losses under conventional tillage compared to zero tillage are composed of both, losses through enhanced CO₂ emissions, and losses through intensified soil erosion. The adjusted net CO₂-mitigation rates of zero tillage, subtracting the reduced carbon losses through soil erosion, are between 0.07 and 1.27 Mg C ha⁻¹ a⁻¹ and the estimated net mitigation rate for the entire state amounts to 285 Gg C a⁻¹. This equals to 1045 Gg CO₂-equivalents per year with the cropping patterns in the reference year 2000. The results call attention to the necessity to revise those estimation methods for CO₂-mitigation which are exclusively or predominantly based on the measurements of differential changes in total soil organic carbon without taking into account the tillage effects on carbon losses through soil erosion.     

A novel polyacrylonitrile–zeolite nanocomposite to clean Cs and Sr from radioactive waste

Radioactive wastes containing Cs⁺ and Sr²⁺ are among the most dangerous environmental pollutants. Therefore, removing Cs⁺ and Sr²⁺ from environmental media is needed. Removal can be done by nanocrystalline ion exchangers. Nanocrystalline ion exchangers are studied in depth for the treatment of nuclear wastes because these exchangers have high exchange capacity and fast kinetics. However, operating the columns of these exchangers is very difficult. This issue may be overcome by the preparation and use of nanocomposites. Here, we prepared a novel polyacrylonitrile–zeolite nanocomposite for the removal of Cs⁺ and Sr²⁺ in a fixed-bed column operation. We studied the effect of influent flow rate, nanocomposite bed height and initial concentrations. Experimental data were analysed using the Thomas model and the bed-depth service time model. The results reveal that total adsorbed ion and bed capacity increased with increasing initial ions concentration and bed height; and decreased with increasing influent flow rate. The maximum bed capacity was 0.085 meq/g for Cs⁺ and 0.128 meq/g for Sr²⁺. The critical bed height (Z ₀) was 4.35 cm for Cs⁺ and 2.89 cm for Sr²⁺. These findings demonstrate that the new nanocomposite is suitable for removal of Cs⁺ and Sr²⁺.     

Phosphorus Losses to Water from Lowland Rice Fields under Rice–Wheat Double Cropping System in the Tai Lake Region

To assess P losses to surface water by runoff during the rice season and by drainage flow during the winter wheat season, serial field trials were conducted in different types of paddy soils in the Tai Lake Region (TLR) during 2000 and 2001. Four P application rates were set as 0 (CK), 30, 150, and 300 kg P/hm² for flooded rice trials and 0 (CK), 20, 80, 160 kg P/hm² for winter wheat trials respectively. Field experiments were done in two locations with a plot size of 30 m² and four replications in a randomized complete block design. A simplified lysimeter was installed for each plot to collect all the runoff or drainage flow from each event. Total P (TP) losses to surface water during rice season by runoff flow from four treatments were 150 (CK), 220 (T30), 395 (T150), 670 (T300) g P/hm² in year 2000, and 298, 440, 1828, 3744 g P/hm² in year 2001 respectively in Wuxi station, here the soil is permeable paddy soil derived from loam clay deposit. While the losses were 102, 140, 210, 270 in year 2000, and 128, 165, 359, 589 g P/hm² in year 2001 respectively in Changshu station, here the soil is waterlogged paddy soil derived from silt loam deposit. During the winter wheat season, total P lost from the fields by drainage flow in the four treatments were 253 (CK), 382 (T20), 580 (T89), 818 (T160) g P/hm² in year 2000–2001, and 573.3, 709.4, 1123.2, 1552.4 g P/hm² in year 2001–2002 at the Wuxi station. While these were 395.6, 539.1, 1356.8, 1972.1 g P/hm² in year 2000–2001, and 811.5, 1184.6, 3001.2, 5333.1 g P/hm² in year 2001–2002 at the Changshu station. Results revealed that P fertilizer application rates significantly affected the TP concentrations and TP loads in runoff during the rice season, and by drainage flow during the winter wheat season. Both TP loads were significantly increased as the P application rate increases. The data indicate that TP losses to surface water were much higher during the winter wheat season than during the rice season in two tested sites. The data also reveal that the annual precipitation and evaporation rate affected the soil P losses to surface water significantly. Year 2000 was relatively dried with higher evaporation thus P losses to water by both runoff and drainage flow were less than in year 2001 which was a relatively wet year with lower evaporation. Results indicate that texture, structure of the soil profile, and field construction (with or without ridge and deep drains) affected soil P losses to surface water dramatically. Annual possible TP lost to water at the application rate of 50 kg P/hm² year tested in TLR were estimated from 97 to 185 tones P from permeable paddy soils and 109–218 tones P from waterlogged paddy soils. There was no significant difference of TP lost between the CK and the T50 treatments in both stations, which indicate that there is no more TP lost in field of normal P fertilizer application rate than in control field of no P fertilized. Much higher TP lost in runoff or drainage flow from those other P application rates treatments than from the T50 treatment, which suggest that P losses to surface water would be greatly increasing in the time when higher available P accumulation in plough layer soil in this region.     

Passives Monitoring von Stickstoffeinträgen in Kiefernforsten mit dem Rotstengelmoos (Pleurozium schreberi (Brid.) Mitt.)

Investigations in 23 pine stands, a widespread type of forest on sandy soils in Northern Germany, were made to compare the concentration of the total N in pine needles, the overall rates and concentrations of nitrogen in precipitation water (NH₄?N+NO₃?N) to concentrations of total N in shoots ofPleurozium schreberi (Brid.) Mitt., a common bryophyte in these forests. Within the investigation period from 1996 to 1998, a total deposition of nitrogen in a range from 10 to 32 kg ha^?1a^?1 and mean values of nitrogen concentrations in the precipitation water between 2.8 and 6.9 ppm were observed. N concentrations in both bryophytes and pine needles also varied in a large scale from 1.3 to 2.3% d.wt. High correlations between concentrations of total N in moss tissue and total N concentrations in pine needles (r²=0.75, p<0.001) as well as N concentrations in the precipitation water (r²=0.81, p<0.001) were found. Lower correlations of N concentrations inPleurozium with overall rates of nitrogen calculated for the year before moss sampling in 1997 until 1999 can be attributed to temporary variations of N concentrations in precipitation due to different amounts of rainfall. Comparing the results of only one year (1998), the correlation was higher (r²=0.86). The role of other effects, e.g. growth rate and dry deposition, is discussed as well. Aside from the monitoring of heavy metals and organic compounds,Pleurozium schreberi is seen to be a useful indicator for estimating the amount of N deposition.     

Movement and transformation of35S-labelled sulphate in the soil of a heavily polluted site in the Northern Czech Republic

Changes in chemistry and vertical distribution of³⁵S were investigated in column experiments using intact topsoil and repacked mineral soil horizons 1 to 20 weeks after tracer application (901 kBq³⁵S-SO₄ ^2– per column 6.5 cm in diameter). Horizons O, A, AE and Bvs of an Orthic Podzol were incubated at 20°C and wetted twice a week with 11 mm of natural throughfall precipitation (38.5 mg S0₄ ^2– L^–1-, pH 3.3). The top 35 cm of the soil contained 1,290 kg S ha^–1, or 18 times more than is the annual atmospheric S input (71.4 kg S ha^–1 yr^–1). Of this amount, 17.8 % was stored as inorganic sulphate S, 4.6 % as reduced inorganic S, and 77.6 % as organic S. In O + A and AE, free sulphate was the most abundant³⁵S form, while in Bvs the 35S activity of free and adsorbed sulphate was similar. The proportion of adsorbed sulphate increased with depth, averaging 23, 30 and 47 % of total inorganic sulphate³⁵S in O + A, AE and Bvs, respectively. Total specific activity of chemically transformed³⁵S (i.e., of reduced inorganic S and organic S) constituted 3.4, 3.8 and 105 % of inorganic sulphate³⁵S activity in O + A, AE and Bvs, respectively, in averaged weeks 2–4, and 7.5, 6.4 and 39.6 % in averaged weeks 11–13 in O+A, AE and Bvs, respectively. The turnover time of C-bonded³⁵S was shorter than that of ester sulphate³⁵S. An increase in FeS_2– ³⁵S with time indicated anaerobic conditions suitable for bacterial sulphate reduction. After 13 weeks, 68 % of the tracer was found deeper than 8 cm below soil surface.     

盐碱地农-渔开发对土壤环境的影响

在东北苏打盐碱地进行了稻-鱼-苇-蒲开发试验,并探讨了该模式对盐碱土壤环境的影响。结果表明,开发后土壤有机质含量增加96.8%(平均值,以下同),盐分含量下降43.6%,全量和速效N、P、K质量分数分别增加142.8%和188.2%;阳离子交换量、盐基总量分别增加8.21%及27.71%;土壤腐殖质以富里酸为主,w(HA)/w(FA)比值提高36.15%;养鱼稻田的土壤微生物总量明显高于未养鱼田(P<0.01);优势种为放线菌。土壤酶活性进一步加强。系统废水的盐分质量浓度降至1.0 g/L左右,碱浓度低于水源(7.0~10.0 mmol/L)。该模式不会造成土壤次生盐碱化。     

Characteristics of mass distributions of aerosol particle and its inorganic water-soluble ions in summer over a suburb farmland in Beijing

Agricultural activity is one of the most important sources of aerosol particles. To understand the mass distribution and sources of aerosol particles and their inorganic water-soluble ions in a suburb farmland of Beijing, particle samples were collected using a microorifice uniform deposit impactor (MOUDI) in the summer of 2004 in a suburb vegetable field. The distribution of the particles and their inorganic water-soluble ions in the diameter range of 0.18–18 μm were measured. The dominant fine particle ions were SO₄ ^2?, NO₃ ^?, and NH₄ ⁺. The association of day-to-day variation of the concentration of these ions with temperature, humidity, and solar radiation suggested that they are formed by the reaction of NH₃ released from the vegetable field with the acid species produced from photochemical reactions. Fine particle K⁺ is likely from vegetation emission and biomass burning. Coarse particles like Ca²⁺, Mg²⁺, NO₃ ^?, and SO₄ ^2? are suggested to come from the mechanical process by which the soil particle entered the atmosphere, and from the reaction of the acid species at the surface of the soil particle. The results show that fertilizer and soil are important factors determining the aerosol particle over agricultural fields, and vegetable fields in suburban Beijing contribute significantly to the aerosol particle.     

镉对北京城郊土壤潜在硝化速率的影响

采集北京城郊5个区县的3种土壤褐土、潮土和山地棕壤,通过急性毒性实验,研究了外源添加镉(Cd)对土壤潜在硝化速率(PNR)的影响。结果表明,5个采样点土壤的PNR分别随土壤中总Cd和有效态Cd含量呈先增后减的趋势。所有处理土壤的有效态Cd含量与PNR的相关关系(R2=0.42,p0.001)优于土壤总Cd含量与PNR的相关关系(R2=0.27,p=0.001)。在土壤总Cd含量和PNR的逐步回归分析中,引入土壤有机质和阳离子交换量(CEC)2个变量可提高其相关性。基于土壤总Cd的EC50(PNR降低至对照50%时的土壤Cd浓度)和有效态Cd的EC50的最大值与最小值之间分别相差2.3倍和3.3倍,而EC10(PNR降低至对照10%的土壤Cd浓度)的最大值与最小值之间分别相差8.5倍和10.8倍。基于总Cd的EC50最低值出现在CEC最小的丰台土壤,而最高值出现在有机质含量最多的灵山土壤,但这2个EC50值未达到显著性差异,表明5个采样点的土壤有机质和CEC虽然在一定程度上影响Cd对PNR的毒性,但不足以引起EC50的显著变化。     

Nitrogen Export from an Agriculture Watershed in the Taihu Lake Area, China

Temporal changes in nitrogen concentrations and stream discharge, as well as sediment and nitrogen losses from erosion plots with different land uses, were studied in an agricultural watershed in the Taihu Lake area in eastern China. The highest overland runoff loads and nitrogen losses were measured under the upland at a convergent footslope. Much higher runoff, sediment and nitrogen losses were observed under upland cropping and vegetable fields than that under chestnut orchard and bamboo forest. Sediment associated nitrogen losses accounted for 8–43.5% of total nitrogen export via overland runoff. N lost in dissolved inorganic nitrogen forms (NO ₃ ^– -N + NH ₄ ⁺ -N) accounted for less than 50% of total water associated nitrogen export. Agricultural practices and weather-driven fluctuation in discharge were main reasons for the temporal variations in nutrient losses via stream discharge. Significant correlation between the total nitrogen concentration and stream discharge load was observed. Simple regression models could give satisfactory results for prediction of the total nitrogen concentrations in stream water and can be used for better quantifying nitrogen losses from arable land. Nitrogen losses from the studied watershed via stream discharge during rice season in the year 2002 were estimated to be 10.5 kg N/ha using these simple models.     

Atmospheric Sulfur Deposition onto Different Ecosystems Over China

The regional acid deposition model system (RegADMS) was applied to simulate the air sulfur deposition onto different landuse types over China, in which the dry deposition velocities of SO₂ and sulfate aerosol (SO ₄ ^2– ) were estimated by use of a big leaf resistance analogy model and the wet scavenging coefficients were parameterized in terms of precipitation rate. Investigations show that the annual total sulfur deposition over mainland China is 7.24 mt (1 mt = 10⁶ ton) , in which dry deposition and wet deposition accounts for 56 and 44%, respectively. The sulfur deposition onto agriculture land, grass land, and forest land is 1.09, 3.6 and 1.41 mt, respectively, which sums 6.1 mt and accounts for 84% of the total sulfur deposition. The modeled sulfur deposition was in agreement with the measurement conducted at farmland in Yingtan, a typical read soil region in Jiangxi province of China, during the period of November 1998–October 1999. The total sulfur deposition at the Yingtan site is about 10.3 gm^–2 year^–1 of which 83% is dry deposition. The modeling sulfur deposition at the same site is 8.4 gm^–2 year^–1. Furthermore, the comparison between RegADMS and RAINS-ASIA on modeling regional sulfur deposition shows the consistence of the two models. The correlation coefficient between the simulated sulfur deposition at the medium-large cities reaches 0.72.     

Application of Zr(IV) tungstate for removal of metal ions from aqueous solutions

A heteropolyacid Zr(IV) tungstate-based cation exchanger has been synthesized. An amorphous sample, prepared at pH 1.2 and having a Na⁺ ion exchange capacity of 0.92?meq?g^?1, was selected for further studies. Its physicochemical properties were determined using Fourier transform infrared spectrometer, X-ray diffraction, thermogravimetric, and scanning electron studies. To understand the cation exchange behavior of the material, distribution coefficients (K _d) for metal ions in various solvent systems were determined. Some important binary separations of metal ions, namely Mg²⁺–Bi³⁺, Cd²⁺–Bi³⁺, Fe³⁺–Bi³⁺, Th⁴⁺–Bi³⁺, and Fe³⁺–Zn²⁺, were achieved on such columns. The practical utility of these separations was demonstrated by separating Fe³⁺ and Zn²⁺ ions quantitatively in commercial pharmaceutical formulation. The cation exchanger has been successfully applied also for the treatment of industrial wastewater and a synthetic mixture. All the results suggests that Zr(IV) tungstate has excellent potential for the removal of metals from aqueous systems using packed columns of this material.     

Use of zeolitized coal fly ash in the simultaneous removal of ammonium and phosphate from aqueous solution

Discharge of wastewater containing nitrogen and phosphate can cause eutrophication. Therefore, the development of an efficient material for the immobilization of the nutrients is important. In this study, a low calcium fly ash and high calcium fly ash were converted into zeolite using the hydrothermal method. The removal of ammonium and phosphate that coexist in aqueous solution by the synthesized zeolites were studied. The results showed that zeolitized fly ash could efficiently eliminate ammonium and phosphate at the same time. Saturation of zeolite with Ca²⁺ rather than Na⁺ favored the removal of both ammonium and phosphate because the cation exchange reaction by the NH₄ ⁺ resulted in the release of Ca²⁺ into the solution and precipitation of Ca²⁺ with PO₄ ^3? followed. An increase in the temperature elevated the immobilization of phosphate whereas it abated the removal of ammonium. Nearly 60% removal efficiency for ammonium was achieved in the neutral pH range from 5.5 to 10.5, while the increase or decrease in pH out of the neutral range lowered the adsorption. In contrast, the removal of phosphate approached 100% at a pH lower than 5.0 or higher than 9.0, and less phosphate was immobilized at neutral pH. However, there was still a narrow pH range from 9.0 to 10.5 favoring the removal of both ammonium and phosphate. It was concluded that the removal of ammonium was caused by cation exchange; the contribution of NH₃ volatilization to immobilization at alkaline conditions (up to pH level of 11.4) was limited. With respect to phosphate immobilization, the mechanism was mainly the formation of precipitate as Ca₃(PO₄)₂ within the basic pH range or as FePO₄ and AlPO₄ within acidic pH range.