Nutrients removal and recovery by crystallization of magnesium ammonium phosphate from synthetic swine wastewater

With synthetic swine wastewater, lab-scale batch experiments were carried out to investigate the effects of pH value, magnesium dosage, calcium and carbonate concentrations on magnesium ammonium phosphate (MAP) crystallization. The morphology of the precipitates obtained was observed by using scanning electron microscopy with energy dispersive X-ray analysis, and the composition of the precipitates was analyzed with X-ray diffraction. The results show that the optimum pH value for MAP crystallization is in the range of 9.5-10.5; the phosphorus removal efficiency increases with the increase of Mg/P molar ratio; the optimum Mg/P molar ratio is 1.4, and excessive Mg dosage does not show significant effect on the efficiency improvement of MAP crystallization; the co-existing of Ca in solution disturbs the morphology and purity of the MAP product, and amorphous calcium phosphate will form when Ca increases to a certain concentration; CO3(2-) can affect the P removal efficiency, but does not obviously affect the morphology and purity of MAP.     

Effects of solution conditions on the precipitation of phosphate for recovery. A thermodynamic evaluation

To understand the effects of solution conditions on the precipitation of calcium phosphates from wastewater for recovery, a computer programme PHREEQC was employed to calculate the speciation and saturation-index (SI) with respect to hydroxyapatite of a chemically defined precipitation system, which contains phosphate of 1–200 mg P/l, with Ca/P molar ratios of one to 10 times of the stoichiometric calcium to phosphorus molar ratio of hydroxyapatite, at a pH range of 7.0–11.0. The results show that the SI is respectively the logarithmic function of the phosphate concentration and the calcium concentration, increasing with the increase of either of them; the SI is a polynomial function of the solution pH value and increases with its increase, and the effect of solution pH value is due to its influence on base uptake of the precipitation reaction and the speciation of phosphate and calcium ions; the SI is also a logarithmic function of the solution ionic strength but decreases with its increase; at the temperature range of 5–30 °C the SI increases linearly with solution temperature and the effect of temperature is also due to its influence on the speciation of phosphate and calcium ions.     

磷酸铵镁沉淀法预处理垃圾渗滤液

探讨了用磷酸铵镁沉淀法预处理垃圾渗滤液时,沉淀剂种类、pH值、物质摩尔配比和反应时间等因素对氨氮去除效果的影响。得出了处理氨氮浓度为2 677.34 mg/L的垃圾渗滤液时,在兼顾所用镁盐量尽量低和处理出水氨氮或磷酸盐的残留量都比较低的较佳实验条件为:沉淀剂种类为:MgSO4.7H2O和Na2HPO4.12H2O,反应时间为20 min,pH=9.5,n(Mg)∶n(P)∶n(N)=1.3∶1.15∶1.0。在较佳实验条件下,垃圾渗滤液的NH3-N去除率为97.05%,处理出水PO34--P含量为8.35 mg/L,NH3-N含量为75.86 mg/L。对所得沉淀物进行了成分分析和X-衍射光谱、扫描电镜表征,表明大部分沉淀物为磷酸铵镁物质。     

鸟粪石结晶法回收垃圾渗滤液氨氮研究

采用MgSO₄·7H₂O和Na₂HPO₄·12H₂O使NH₃-N生成MgNH₄PO₄·6H₂O（鸟粪石）结晶沉淀法回收渗滤液中NH₃-N。考察了pH值、反应时间、药剂配比对NH₃-N去除率的影响。结果表明,鸟粪石结晶回收NH₃-N反应的适宜pH值为9～9.5之间,过高的pH会破坏鸟粪石晶体结构,导致固定氨从MgNH₄PO₄中游离出来,不利于氨氮的去除。在pH值为9.5、反应时间为25 min、Mg²⁺∶NH⁺₄∶PO^3-₄=1.5∶1∶1.5的最佳条件下,渗滤液中NH₃-N浓度由初始3 500 mg/L,经结晶沉淀后降低至175 mg/L,去除率达95%。鸟粪石结晶沉淀过程中几乎不吸收重金属,同时回收了氨氮,其沉淀产物鸟粪石是一种优良的缓释肥原料。     

Microbial degradation of phenol in high-salinity solutions in suspensions and hollow fiber membrane contactors

A microporous polypropylene (PP) hollow fiber membrane contactor was used as a bioreactor to degrade phenol in aqueous solutions by Pseudomonas putida BCRC 14365 at 30 degrees C. The fibers were pre-wetted by ethanol to make them more hydrophilic. The initial cell density was fixed at 0.025 gl(-1). The effects of added NaCl concentration (0-1.78 M) and pH (3-8) in substrate solution on the biodegradation were studied. The experimental results by suspended cells were discussed. It was shown that the cells in microporous hollow fibers were unable to tolerate substrate solution pH to a larger range than those in suspensions. The suspended cells grew well on 100 mg l(-1) of phenol only at NaCl concentrations below 0.44 M. However, the cells in microporous hollow fibers could completely degrade 500 mg l(-1) of phenol in solutions containing NaCl concentration up to 1.52 M, which was due to the enhanced tolerance limit to salinity effect by the membrane-attached biofilms and the sufficiently slow mass transfer of NaCl through the membrane pores.     

Effect of fluoride on pH, organic matter and solubility of elements in soils

The effect of NaF addition on pH, organic matter and the solubilities of fifteen elements was investigated on twenty-eight surface soil samples. Four concentrations of NaF were added: 0, 10(-2.7), 10(-1.7) and 10(-1.0)m F in solution. Addition of NaF increased the pH and the solubility of organic matter for all soils. The magnitude of these increases was higher for acid than for alkaline soils. Aluminum, Fe and Ca showed the greatest increases in solubility while Mg, K, Mn and P showed intermediate increases. The elements Cd, Cr, Ni, Cu, Zn, B, Mo and Ba showed only slight increases in solubility. Another experiment was conducted to test whether the effects of NaF on pH, organic matter and the solubilities of various elements were due to F or Na. Four levels of NaCl similar to those for NaF were added to three acid and two alkaline soils. The results confirmed the effects of F on soil pH, organic matter and the solubilities of all elements investigated except those of K, Ca and Mg. Addition of Na as NaF resulted in release of K, Ca and Mg from the exchange sites on solid surfaces into solution.     

Characteristics of leachate from pyrolysis residue of sewage sludge

The pyrolysis residue (SP) of sewage sludge (SS) produced at 500 degrees C was subjected to batch and column leaching tests to investigate the release of its organic and inorganic constituents and metals. For comparison, incineration ash (SI) obtained from a SS incinerator was also tested. Pyrolysis and incineration reduced organic matter of SS from 0.78 kg kg(-1)-dry SS to 0.16 and 0.01 kg kg(-1)-dry SS, respectively. Heavy metals remained in SP without being volatilized, although Cd and Pb were transferred into the off-gas during incineration. In the batch leaching test with the leaching liquid-to-solid mass ratio (L/S)=10, the pH of the SS, SP, and SI filtrates was 6.3, 7.9, and 11.0, respectively. The total organic carbon concentrations were in the order SS (877 l mg l(-1))>SP (99 mg l(-1))>SI (26 mg l(-1)). The SP and SI filtrates met the landfill standard for the Cd and Pb concentrations (<0.3 mg l(-1)). In the column tests, although the SP contained more organic matter than that of SI, its carbon discharge into the leachate under aerobic conditions was similar to that of SI under anaerobic conditions. The leaching of heavy metals, such as Cd, Cr, Pb, and Zn, was also suppressed in SP during the active decomposition of organic matter. We demonstrated that pyrolysis reduces the potential release of pollutants from sewage sludge in landfill, making it a promising method of treating sewage sludge before landfilling.     

Interaction of pH with mercuric chloride toxicity to penaeid prawns from a tropical estuary, East Coast of India: enhanced toxicity at low pH

Toxicity tests were conducted to study the interaction of pH and the response of two size groups of penaeid prawns i.e. Penaeus monodon and Penaeus indicus to different sets of five concentrations of HgCl2 (0.01-0.09 mg l(-1)) under a broad range of pH conditions (5-9). Behavioural responses varied according to test solution concentration and nominated values of pH. Abnormality was detected in the higher concentrations with lower pH in smaller size group of P. monodon. High mortality was observed at higher concentration of test solution with low pH. Irrespective of species and size group LC50 demonstrated similar trend of variation with respect to time period. At pH 9 the threshold limit for 65-75 mm size group of P. monodon and P. indicus was 0.043 and 0.049 mg l(-1) respectively while it was 0.041 and 0.035 mg l(-1) respectively at pH 8; and 0.038 and 0.044 mg l(-1) respectively at pH 7. Relative toxicities were significantly varied except for bigger size groups in the studied pH ranges. The result was pronounced at pH 5 with maximum 1.61 times for inter-hour relative toxicity in contrast to all. At pH below 7 of mercury resulted more toxic compared to high pH range (>7) might be due to acid toxicity itself. At each pH smaller size groups were sensitive while bigger shown tolerant. P. monodon were more sensitive than P. indicus. The toxic order of pH effect was 9<8<7<6<5. Toxicity increased significantly (p>0.01) in acidic medium compared to alkaline.     

The distribution, solid-phase speciation, and desorption/dissolution of As in waste iron-based drinking water treatment residuals

Arsenic concentrations and solid-phase speciation were assessed as a function of depth through Fe-media beds for two commercially available products (Granular Ferric Hydroxide-GFH and Bayoxide E33-E33) from pilot-scale water treatment field tests. These results were compared with data from solution (de-ionized water-DI-H2O) concentrations of As equilibrated with Fe-media in an anoxic environment at 4 degrees C. The materials had a high capacity for As (GFH media 9620 mg kg(-1) As, E33 Media 5246 mg kg(-1)). Arsenic concentrations decreased with bed depth. For E33, X-ray absorption near-edge spectroscopy results showed that As(V) was the dominant solid-phase species. For GFH, As(III) was detected and the proportion (relative to As(V)) of As(III) increased with bed depth. Arsenic concentrations in DI-H2O equilibrated with the media were low (35 microg l(-1)) over a period of 50 d. Arsenic concentrations in the equilibrated solutions also decreased with depth. Results from tests on soluble As speciation show that As in solution is in the form of As(V). Kinetic desorption experiments carried out at different pH values (3, 5, 7, 8, and 9) show that the media exhibit some acid/base neutralization capacity and tend to bind As sufficiently. Concentrations of As in the pH desorption experiments were in the same order of magnitude as the toxicity characteristic leaching procedure extractions (tens of microgl(-1)) except at low pH values. For the GFH media tested at a pH of three, As increases in solution and is mainly associated with colloidal (operationally defined as between 0.1 and 1.0 microm) iron.     

Sorption of lead in soil as a function of pH: a study case in México

Reactions of lead sorption onto soil are largely affected by properties and composition of soil and its solution. In this study, the lead sorption onto regosol eutric soil from Francisco I. Madero, Zacatecas, Mexico is evaluated at different pH values. Soil samples were suspended in lead solutions of 10, 25, 50, 100, 150, 200, 300, and 400 mg/l (as Pb(NO3)2). The pH was adjusted at 2, 3, 4, and 5.5 with nitric acid for each of the lead solution concentrations. In all the cases the ionic strength was I=0.09 M with calcium nitrate. The solid-liquid-ratios were fixed in 1:100 and 1:200 g/ml. The results show that lead sorption increases when pH increases. Experimental isotherms were adjusted by both Langmuir and Freundlich models. The Langmuir affinity parameter, K, indicates that the lead sorption capacity of Francisco I. Madero soils is largely perceptible to pH changes.     

Fluoride removal performance of a novel Fe-Al-Ce trimetal oxide adsorbent

A trimetal oxide was developed as a fluoride adsorbent by coprecipitation of Fe(II), Al(III) and Ce(IV) salt solutions with a molar ratio of 1:4:1 under alkaline condition. The material retained amorphous structure and maintained relatively stable fluoride adsorption performance at calcination temperatures lower than 600 degrees C. The optimum pH range for fluoride adsorption was 6.0-6.5 and the adsorbent also showed high defluoridation ability around pH 5.5-7.0, which is preferable for actual application. A high fluoride adsorption capacity of 178 mg g(-1) was acquired under an equilibrium fluoride concentration of 84.5 mg l(-1), adsorbent dose of 150 mg l(-1) and pH 7.0. The adsorption isotherm could be better described by the two-site Langmuir model than the one-site model, suggesting the existence of two types of active sites on the adsorbent surface. Coexistence of high concentrations of phosphate or arsenate only led to partial inhibition of fluoride adsorption, which further suggests the existence of heterogeneous adsorption sites. Sulfate and chloride did not affect fluoride adsorption, and nitrate influenced it only when the concentration of NO(3)(-)-N exceeded 50 mg l(-1). A high desorption efficiency of 97% was achieved by treating fluoride loaded Fe-Al-Ce oxide with NaOH solution at pH 12.2. A column experiment using the adsorbent fabricated into 1mm pellets was performed at an initial fluoride concentration of 5.5 mg l(-1), space velocity of 5h(-1) and pH of 5.8, and 2240 bed volumes were treated with the effluent fluoride under 1.0 mg l(-1).     

Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

Recovery of phosphates from wastewater using converter slag: Kinetics analysis of a completely mixed phosphorus crystallization process

A phosphorus crystallization process for recovering phosphates was developed using a completely mixed reactor and powdered converter slag as a seed crystal. This completely mixed phosphorus crystallization process achieved a stable and high phosphorus recovery: the average PO4-P removal efficiency during 200 d of operation was 87%, with a range of 70-98%. The apparent volume of the slag doubled due to crystal growth during the long-term phosphorus-removal experiments. The Ca2+ concentration, slag dosage, and temperature were found to govern the phosphorus recovery system for a given condition of pH and hydraulic retention time. The equations for the rate constant and reaction order were obtained by evaluating the model parameters. The model developed in this study was observed to successfully simulate the behavior of effluent PO4-P in a completely mixed phosphorus crystallization reactor over a wide variety of operating conditions of temperature, Ca2+ concentration, and influent PO4-P. Model investigations of design factors suggest that the completely mixed phosphorus crystallization process with influent PO4-P concentrations of less than 10 mg l(-1) could ensure effluent PO4-P concentrations of less than 0.5 and 1.0 mg l(-1) during summer and winter in Korea, respectively.     

Simulated Effects of Acidic Solutions on Element Dynamics in Monsoon Evergreen Broad-leaved Forest at Dinghushan,China - Part 1: Dynamics of K,Na, Ca,Mg and P (7 pp)

Background, Aim and Scope Acid deposition has become a concern in south China in recent years. This phenomenon has increased to a dramatic extent with the large use of cars and coal- fueled power plants. As a consequence, soils are becoming acidified and their element dynamics will change. A decrease in the nutrient availability will lead to slower plant growth and maybe to a change in the forest type with current species being replaced by new ones with less nutrient requirements. Because of these reasons, it is important to understand how the dynamics of elements will change and what mechanism is part of the process. This knowledge is important for modeling the acidification process and either finding ways to counter it or to predict its consequences. The primary purpose of this study was to provide information about how the dynamics of K, Na, Ca, Mg and P are affected by acid deposition in a typical forest in southern China. Materials and Methods: Experimental soils and saplings were collected directly from the monsoon evergreen broad-leaved forest in Dinghushan. All saplings were transplanted individually into ceramic pots in August 2000 and placed in an open area near their origin site. Pot soils were treated weekly from October, 2000 to July, 2002 with an acidic solution at pH 3.05, pH 3.52, pH 4.00 or pH 4.40, or with tap water as a control. The concentrations of SO42-, NO3-, K+, Na+, Ca2+, Mg2+ and available P and the pH were measured in soil and leachate samples taken at different times. The sapling leaves were collected and their element concentrations were measured at the end of the experiment. Results: Concentrations of soil exchangeable Ca and Mg decreased quickly over time, although only Ca showed changes with the acidic solution treatment and soil exchangeable K was stable because of soil weathering. Leaching of K, Mg and Ca was dependent upon the treatment acidity. Soil available P decreased slowly without any correlation with the acidity of the treatment. All the NO3- added by the treatment was taken up by the plants, but the SO42- added accumulated in the soil. Discussion: Amongst the plant species, Schima superba was little affected by the treatment, the leaf P content was affected in Acmena acuminatissima plants and Cryptocarya concinna was the most susceptible species to soil acidification, with a marked decrease of the leaf K, Ca and Mg concentrations when the treatment acidity increased. Conclusions: Simulated acid deposition affected the dynamics of K, Ca and Mg in the monsoon evergreen broad-leaved forest. The dynamics of Ca in the soil and of K, Mg and Ca in the soil leachates were affected by the acidic solution treatment. If such a soil acidification occurs, Cryptocarya concinna will be amongst the first affected species, but Schima superba will be able to sustain a good growth and mineral nutrition. Recommendations and Perspectives: Acid deposition will lead to imbalance the nutrient elements in the evergreen broad-leaved forest because of accelerated leaching losses of soil exchangeable Ca and Mg. Measures should be developed to slow down soil acidification or nutrient decrease.     

The EDTA effect on phytoextraction of single and combined metals-contaminated soils using rainbow pink (Dianthus chinensis)

Rainbow pink (Dianthus chinensis), a potential phytoextraction plant, can accumulate high concentrations of Cd from metal-contaminated soils. The soils used in this study were artificially added with different metals including (1) CK: original soil, (2) Cd-treated soil: 10 mg Cd kg(-1), (3) Zn-treated soil: 100 mg Zn kg(-1), (4) Pb-treated soil: 1000 mg Pb kg(-1), (5) Cd-Zn-treated soil: 10 mg Cd kg(-1) and 100 mg Zn kg(-1), (6) Cd-Pb-treated soil: 10 mg Cd kg(-1) and 1000 mg Pb kg(-1), (7) Zn-Pb-treated soil: 100 mg Zn kg(-1) and 1000 mg Pb kg(-1), and (8) Cd-Zn-Pb-treated soil: 10 mg Cd kg(-1), 100 mg Zn kg(-1), and 1000 mg Pb kg(-1). Three concentrations of 2Na-EDTA solutions (0 (control), 2, and 5 mmol kg(-1) soil) were added to the different metals-treated soils to study the influence of applied EDTA on single and combined metals-contaminated soils phytoextraction using rainbow pink. The results showed that the Cd, Zn, Pb, Fe, or Mn concentrations in different metals-treated soil solutions significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). The metal concentrations in different metals-treated soils extracted by deionized water also significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). Because of the high extraction capacity of both 0.005 M DTPA (pH 5.3) and 0.05 M EDTA (pH 7.0), applying EDTA did not significantly increase the Cd, Zn, or Pb concentration in both extracts for most of the treatments. Applying EDTA solutions can significantly increase the Cd and Pb concentrations in the shoots of rainbow pink (p<0.05). However, this was not statistically significant for Zn because of the low Zn concentration added into the contaminated soils. The results from this study indicate that applying 5 mmol EDTA kg(-1) can significantly increase the Cd, Zn, or Pb concentrations both in the soil solution or extracted using deionized water in single or combined metals-contaminated soils, thus increasing the accumulated metals concentrations in rainbow pink shoots. The proposed method worked especially well for Pb (p<0.05). The application of 2 mmol EDTA kg(-1) might too low to enhance the phytoextraction effect when used in silty clay soils.     

工艺条件对鸟粪石法回收磷耗碱量的影响及其理论计算

通过分析磷回收过程中存在的各种耗碱因素,推导出耗碱量的理论计算公式,计算出了不同工艺条件下的理论耗碱量,并与小型连续搅拌反应-沉淀磷回收过程的实验实测值进行比较。结果表明,耗碱量的理论计算值与实验测定值的平均相对误差为13.20%,说明计算方法可用于耗碱量的工程估算;耗碱量随出水pH值的增大而急剧增加,随废水中氨氮含量和磷初始浓度的增加都近似于线性增加,但随镁磷比的增加基本不变。因此,从节约废水处理成本的角度看,磷回收过程中pH值应控制在9.2-9.3,氮磷比控制在3.0-5.0,镁磷比控制在1.1-1.2为佳。磷回收过程的药剂消耗量与废水中磷的浓度和工艺条件有关,以磷初始浓度为124 mg/L,N/Mg/P=5∶1.2∶1,出水pH值为9.20的回收过程为例,处理毎吨废水需消耗片碱0.5313 kg,成本约为1.328元,需消耗氯化镁（含六个结晶水）0.9758 kg,成本约为0.634元。因此,处理每吨废水的药剂成本约为1.962元,其中耗碱约占67.7%。     

氧化亚铁硫杆菌浸铜作用研究

为研究氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,简称A.f)对铜浸出的作用,从某煤堆积水中分离得到A.f菌,利用该菌对铜进行浸出实验,设置3个处理,3个处理的浸出液分别为9 K培养基(简称S),成熟菌液(简称MS)和过滤除菌液(简称FS)。结果表明,3个处理中铜都得到了浸出,浸出铜浓度按S、FS和MS依次递增分别为4 433、5 377和6 296 mg/L;浸出初期,MS中的铜,浸出速度最快,过滤除菌液中次之,而培养基中的速度比较稳定,比前两者均慢,24 h后三者浸铜速度趋近一致;三者中pH、Eh变化相似,pH均先升高至3.4左右保持相对稳定,Eh均先迅速下降至280 mV后保持稳定。由实验可知,氧化亚铁硫杆菌主要在浸出初期促进了铜的浸出,且菌液中溶解氧氧化Fe2+以及酸性条件下氧化Cu0对铜的浸出作用不容忽视。     

Major inorganic ions in North Pole snow samples

Major inorganic ions, pH, total N and P were analyzed in eight arctic snow samples collected in March, April and May 1984 during an expedition in the North Pole region (N83₀18′ W73₀06′ - N89.960₀). The concentrations of the ions in different samples were close to each other and the values obtained seem to be representative for mean concentrations in the snow. In the sample taken from the North Pole the pH value was 5.00 while the H⁺-, SO^2?₄- and NO^?₃-concentrations were 0.24, 6.2 and 4.3 μmol/l, respectively. The concentrations are exceedingly low and agree very well with earlier results from arctic snow samples.     

Influence of some additives to aluminium species distribution in aluminium coagulants

Aluminium ions hydrolyse and polymerise into different species in water. Main aluminium species in aluminium coagulant solutions are monomeric Al species (Al1) and polymeric Al species Al13O4(OH)24(7+) (Al13). The aluminium species distribution in coagulant solutions can be influenced by many parameters. This paper studies influences of concentrations of total aluminium species (Al(t)) and other species--OH-, polysilicic acid and ferric species, which were added in aluminium coagulant solutions, on the aluminium species distribution through 27Al nuclear magnetic resonance (NMR) analysis. Results show that only Al1 and no Al13 exist in coagulant solutions at higher Al(t) concentrations (over 1 mol l(-1)), while both species exist at lower Al(t) concentrations (0.1 mol l(-1)). The increase of OH/Al value (molar ratio) increases the concentration of Al13 in coagulant solutions, while the addition of polysilicic acid and ferric species decreases the concentration of Al13.     

Effects of acid rain on growth and nutrient concentrations in Scots pine and Norway spruce seedlings grown in a nutrient-rich soil

The effects of artificially applied acid precipitation on growth and nutrient concentrations of Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies [L.] Karst.) seedlings were investigated in a long-term acid irrigation experiment in field conditions. Seedlings of northern and southern origin were planted in boxes containing peat and composted soil rich in nutrients, and sprinkler irrigated with water acidified with nitric and sulphuric acids to pH 3 or pH 4 for periods varying from two to three and a half growing seasons during 1986-1989. Water irrigated (pH 5.4-7.6) and non-irrigated groups of seedlings were also included in the experiment. At the end of the experiment needles, main and lateral shoots and roots were collected from the seedlings for the determination of height growth and biomass partitioning, and for the analysis of S, N, Mg, P, K, Ca, Mn and Fe concentrations. The treatment effects compared to the irrigated control were studied using multivariate analyses of variance and covariance. In the pine seedlings the total dry matter production increased by 25-70% compared with the irrigated controls when the total wet deposition to the seedlings exceeded 67 kg S ha(-1) and 36 kg N ha(-1) (e.g. after two growing seasons' exposure of the pH 3 treatment). The increase was mainly due to an increase in needle dry weight (54-72% greater at pH 3) and root weight (20-65% greater at pH 3), whereas the height growth or shoot weight growth were less affected. The northern provenance pine seedlings responded more clearly to the pH 3 irrigation than the southern ones. The treatments had no consistent effects on any of the growth variables studied in the spruce seedlings, however. The pines had higher root and foliage Ca concentrations as a result of the acid irrigation, whereas in spruce, acid rain decreased the Ca concentration in needles and shoots. Root Mn and Fe concentrations were higher in both species as a result of the pH 3 treatment. A higher soil conductivity and Ca concentration resulted from the prolonged pH 3 treatment. The results strongly support the hypothesis that the long-term growth and nutrient allocation response of conifers to acid precipitation is dependent both on the tree species and on the nutritional status of the soil.