Throughfall chemistry in a spruce chronosequence in southern Poland

The chemical composition of throughfall and canopy leaching, as well as the acid neutralizing capacity and alkalinity depended on the age of Norway spruce (Picea abies Karst) stands and season of the year. A higher amount of sulphur and strong acids was deposited to the soil in the older age classes. Concentrations of SO(4)(2)(-), K(+), H(+), Mn(2+), Fe(2+) and Zn(2+) in throughfall were higher than in bulk precipitation in any season. This suggests that these ions were washed out or washed from the surface of needles and/or barks. The other ions NO(3)(-), NH(4)(+), Ca(2+) and Mg(2+) were retained by the canopy, in particular Ca(2+) and Mg(2+) during the growing season in young stands. Principal component analysis identified five factors responsible for the data structure and suggested the major anthropogenic emission sources were acidic emission (SO(4)(2)(-)+NO(3)(-)), heavy metals-dust particles (Fe(2+)+Mn(2+)+Zn(2+)), ammonium (NH(4)(+)) and H(+), while the natural-origin emission was mineral dust (Na(+)+K(+)+Ca(2+)+Mg(2+)).     

腐殖酸树脂处理含Pb2+、CU2+、Ni2+废水的研究

利用泥炭为原料制备腐殖酸树脂.在动态条件下,研究了腐殖酸树脂对重金属离子Pb2+、Cu2+和Ni2+的吸附效果及吸附条件.同时探讨了腐殖酸树脂对重金属离子Pb2+、Cu2+和Ni2+的吸附与解吸再生机理,吸附机理研究表明,腐殖酸树脂对重金属离子Pb2+、Cu2+和Ni2+的主要吸附形式为离子交换吸附和络合吸附.结果表明,在废水pH值为5.0～7.0,Pb2+、Cu2+和Ni2+浓度分别为50 mg/L,经腐殖酸树脂处理,Pb2+、Cu2+和Ni2+去除率可达98%以上,且处理后废水近中性.含Pb2+、Cu2+和Ni2+电镀废水经腐殖酸树脂处理后,废水中Pb2+、Cu2+和Ni2+含量显著低于国家排放标准.     

Removal of Cu(II) from aqueous solution in a fluidized-bed reactor

In this study, a fluidized-bed reactor (FBR) was employed to treat copper-containing wastewater by mean of copper precipitation on the surface of sand grains. The conditions for optimum copper removal efficiency were also investigated. This technology was controlled so as to keep supersaturation low to induce the nucleated precipitation of copper coating on the sand surface in an FBR. The effects of relevant parameters, such as the pH value, the molar ratio of [C(T)] to [Cu(2+)], hydraulic loading and the types of chemical reagents used, were examined. The experimental results indicated that 96% copper removal efficiency could be achieved when the influent copper concentration was 10mg l(-1). The optimum chemical reagent was Na(2)CO(3); the molar ratio of [C(T)]/[Cu(2+)] was 2, and the optimal hydraulic loading was not be more than 25m h(-1). In addition, preventing homogeneous nucleation in the FBR was an important operation parameter. Homogeneous nucleation and molecular growth would lead to undesirable microparticle formation in the effluent. A good mixture of carbonate and copper in the presence of sand grains could reduce the level of homogeneous nucleation in the bottom of the reactor. Energy dispersive analysis (EDS) of X-rays provided insight into the copper coating on the sand surface, and element analysis indicated the weight percentages of CuCO(3) and Cu(OH)(2) in precipitate.     

Effect of SO4 2-/Al3+ ratio and OH-/Al3+ value on the characterization of coagulant poly-aluminum-chloride-sulfate (PACS) and its coagulation performance in water treatment

A poly-aluminum-chloride-sulfate (PACS) was prepared at various experimental conditions. It was found that the coagulation performance of PACS in water treatment was affected by the PACS particle size distribution and zeta potential value. The experimental results indicated that the PACS particle size distribution and zeta potential value were highly influenced by SO(4)(2-)/Al(3+) molar ratio and bacicities (gamma,gamma=[OH]/[Al]) value. At a fixed gamma value of 2.0, the average PACS particle size increased from 25 to 80nm with the increase of SO(4)(2-)/Al(3+) ratio from 0 to 0.1. Further increase of the SO(4)(2-)/Al(3+) ratio resulted in acute increment particle size of PACS extremely, which can be attributed to its aggregation. At a fixed SO(4)(2-)/Al(3+) ratio of 0.0664, the largest average size of PACS occurred at gamma=2.0. It was also found that the zeta potential value of PACS was strongly influenced by the SO(4)(2-)/Al(3+) ratio, gamma value and pH of the aquatic solution. The zeta potential value of PACS increased with increasing of SO(4)(2-)/Al(3+) ratio. At a fixed SO(4)(2-)/Al(3+) ratio of 0.0664, PACS achieved greatest zeta potential value at gamma value of around 2.0. The maximum positive zeta potential value of PACS was found at pH5.3. At a fixed gamma value of 2.0 and SO(4)(2-)/Al(3+) ratio of 0.0664, the PACS achieved an optimum natural organic matter and turbidity removal efficiency.     

镁盐和炉渣对印染废水的脱色处理

实验研究了不同pH、温度：Mg2＋投量和沉降时间下，镁盐、炉渣、镁盐＋炉渣3种处理对模拟和实际印染废水的脱色效果。结果表明，在pH为11～11．5、沉降30rain、30℃及Mg2＋投加量为500～600mg／L的最优脱色条件下，3种处理对艳红FXC模拟废水的最大脱色率分别为98．41％、98．43％和99．37％，对实际印染废水的最大脱色率分别为90．18％、89．63％和93．33％，其中，镁盐＋炉渣脱色效果最好，这可能与炉渣吸附和起到协同增强Mg（OH）2沉淀效果的作用有关。对水样的液相色谱初步检测分析表明，实际废水脱色处理前后染色基团峰高和种类发生了变化。该研究对盐田富镁卤水和炉渣等废物的资源化开发有重要参考价值。     

Effect of anions and cations on cadmium sorption kinetics from aqueous solutions by chitin: experimental studies and modeling

The effect of ions, including Na(+), Mg(2+), Ca(2+), Cl(-), SO(4)(2-) and CO(3)(2-), at various initial concentrations, on the kinetics of cadmium sorption by chitin was studied at 25 degrees C and free initial pH solution in batch conditions. The presence of these ions in solution was found to inhibit the uptake of cadmium by chitin to different degrees: sodium and chloride ions have no significant effect. For Mg(2+), Ca(2+), SO(4)(2-) and CO(3)(2-) ions, the effects ranged from a large inhibition of cadmium by Ca(2+) and CO(3)(2-) to a weak inhibition by Mg(2+) and SO(4)(2-). These results indicate that the uptake sites of these ions are the same. No ion was found to enhance cadmium uptake. The results also showed that the kinetics of sorption are best described by a pseudo second-order expression than a first or second-order model.     

Stemflow chemistry of urban street trees

pH and ion concentrations (Na(+), K(+), Mg(2+), Ca(2+), NO(-)(3)) in the stemflow of the evergreen broad-leaved tree, Ilex rotunda, planted in the median strip of a highway and nitrogen oxides concentration in the air in an urban site were compared with a suburban site in Fukuoka city, Japan. The annual average of the nitrogen oxides concentration in the air was higher and NO(-)(3) concentration in the stemflow at the urban site was higher or similar compared with the suburban site. However, the annual average of pH in the stemflow at the urban site was higher than at the suburban. The annual average cation concentrations in the stemflow at the urban site were higher than at the suburban except Na(+). In particular, K(+) and Ca(2+) were higher throughout the measurement period. Therefore, higher pH in the urban stemflow was probably due to neutralization by higher concentrations of K(+), Mg(2+) and Ca(2+).     

铁碳微电解-Fenton法预处理苯胺基乙腈生产废水

采用铁碳微电解-Fenton法对苯胺基乙腈生产废水进行预处理实验。通过静态实验确定铁碳微电解最佳条件为铁屑投加量300 g/L,Fe/C质量比为2∶3,反应75 min,不需要调节进水pH;Fenton反应最佳条件为铁碳微电解出水pH=4,30%H2O2投加量15 mL/L,在搅拌条件下反应60 min;然后沉淀反应时调节pH为9,混凝沉淀75 min。在上述条件下通过动态实验得到系统连续反应在48 h内废水的COD和苯胺去除率在50%和70%以上,可生化性BOD5/COD也保持在0.3以上,为后续生物处理创造了良好条件。     

Acid-sensitive waters of the English Lake District: a steady-state model of streamwater chemistry in the upper Duddon catchment

Data on deposition and streamwater chemistry, obtained for the upper catchment of the River Duddon in the 1970s and 1980s, are reviewed. These data, together with soil chemical data, are used to deduce key processes in the deposition-catchment interaction, the analysis being based on current concepts of acidification. The processes are incorporated into a steady-state model that allows streamwater compositions to be calculated. The large baseflow pH range (5-7) of Duddon streams is accounted for in the model by a range of base cation weathering rates. Other processes invoked are evapotranspiration, the uptake of nitrogen by plants, dissolution of Al(OH)(3) in the mineral soil, precipitation of Al(OH)(3) in the baserock zone and in streamwater, Al(3+) hydrolysis, and reactions of the carbonate system. Both cation exchange and sulphate adsorption are ignored, because they are assumed to influence rates-of-change between steady states, but not steady-state water compositions per se. The model can be used to estimate variations in streamwater composition with flow. Model calculations suggest that a 50% decrease in depositional acidifying components (sulphur oxides and NH(4)(+)) would result in increases of up to 1 pH unit in streamwaters with present-day baseflow pH values of 5 or less. It appears that water quality in the upper Duddon is currently more sensitive to inputs of NH(4)(+) than of H(2)SO(4). To improve the reliability of model predictions, more information is required on (a) the pH dependence of base cation weathering, (b) transformations involving nitrogen, (c) aluminium chemistry and (d) partial pressures of CO(2) in soil and baserock.     

Effect of immobilized microalgal bead concentrations on wastewater nutrient removal

A unicellular green microalga, Chlorella vulgaris, entrapped in calcium alginate as algal beads were employed to remove nutrients (N and P) from simulated settled domestic wastewater. A significantly higher nutrient reduction was found in bioreactors containing algal beads (at concentrations ranging from 4 to 20 beads ml(-1) wastewater) than the blank alginate beads (without algae). A complete removal of NH(4)(+)-N and around 95% reduction of PO(4)(3-)-P was achieved within 24 h of treatment in bioreactors having the optimal algal bead concentration (12 beads ml(-1), equivalent to 1:3 algal beads:wastewater, v/v). The NH(4)(+)-N removal was significantly lower at low (around 4 beads ml(-1)) and high (>15 beads ml(-1)) algal bead concentrations. On the other hand, the effect of bead concentration on phosphate removal was less obvious, and bead concentrations ranging from 8 to 20 beads ml(-1) showed comparable percentages of phosphate reduction. Algal uptake and adsorption on alginate gels were found to be the major processes involved in the removal of N and phosphate in the present study. In addition, NH(4)(+)-N could be lost via ammonia volatilization while PO(4)(3-)-P was removed by chemical precipitation, as alkaline pH was recorded in the immobilized microalgal treatment system.     

Evaluation of the multiple-ion competition in the adsorption of As(V) onto reclaimed iron-oxide coated sands by fractional factorial design

This study describes the competitive effects of selected ions and natural organic matter on As(V) removal using reclaimed iron-oxide coated sands (RIOCS) in the single- and multi-ion systems. A 2(7-3) factional factorial experimental design (FFD) was employed for screening main competitive factors in this adsorption process. As a result, the inhibitive competition effects of the anions on As(V) removal in the single ion system were in the following sequence: PO(4)(3-)>SiO(3)(2-)>HCO(3)(-)>humic acid (HA)>SO(4)(2-)>Cl(-), whereas the cation Ca(2+) was observed to enhance the As(V) removal. In addition, the optimum initial pH for As(V) removal in single-ion system was 5. Based on the estimates of major effects and interactions from the FFD, PO(4)(3-), SiO(3)(2-), Ca(2+) and HA were important factors on As(V) removal in the multi-ion system. The promoters for the As(V) removal were found to be Ca(2+) and, to a lesser extent, SO(4)(2-). The competitive effects of these ions on As(V) removal were in the order of PO(4)(3-), SiO(3)(2-), HA, HCO(3)(-), and Cl(-). In the single ion system, the efficiencies of As(V) removal range from 75% to 96%, much higher than those in the multi-ion system (44%) at the initial pH 5. Clearly, there were some complex anion interactions in the multi-ion system. To promote the removal of As(V) by RIOCS, it is proposed to lower the pH in the single-ion system, while in the multi-ion system, the increase of the Ca(2+) concentration, or decreases of PO(4)(3-), SiO(3)(2-) and HA concentrations is suggested.     

Atmospheric input of elements to forest ecosystems: a method of estimation using artificial foliage placed above rain collectors

Usefulness of a method of artificial foliage was tested for estimation of total ionic inputs from the atmosphere to forest ecosystems, as well as of processes relevant to ionic fluxes through tree canopies: uptake, leaching, passive flow. The studies were performed in Norway spruce and European beech stands in Karkonosze Mountains (Poland), in 1995-97. Artificial leaves of increasing leaf area index: 0, 2, 6 and 12 m(2) m(-2 )were placed above standard rain collectors. It has been found that total atmospheric fluxes of H(+), NH(4)(+), Ca(2+), Mg(2+), Pb(2+), NO(3)(-) and SO(4)(2-) rose as surface area of the foliage increased. This was especially true for nitrate, sulphate and ammonium. No such relationship was found for K(+), Na(+), Zn(2+), Cd(2+), Cu(2+) and PO(4)(3-). The increase in anion fluxes exceeded that in neutralising cations (NH(4)(+), Na(+), K(+), Mg(2+), Ca(2+)) and led to progressive rainwater acidification with the increase in the foliage area. An analysis of net canopy exchange (atmospheric input-throughfall flux) has shown that SO(4)(2-), PO(4)(3-), Na(+), Ca(2+) and Cu(2+) flowed passively through the tree crowns; NH(4)(+), NO(3)(-), Zn(2+), Cd(2+) and occasionally Pb(2+) were efficiently absorbed, whereas K(+) was leached from the canopies. Beech was more effective in modifying ionic pool from the atmosphere than spruce. This related to H(+) (greater absorption) and Mg(2+) (greater leaching). It has been demonstrated that the results concerning trends in net canopy exchange and produced by the simple method of artificial foliage are comparable to more sophisticated techniques of the measurements. This proves the method to be useful.     

Effect of vegetation type on throughfall deposition and seepage flux

This paper compares different vegetation types (coniferous and deciduous forest, grassed and pure heathland) in terms of input (throughfall deposition) and output (seepage flux) in a region with intermediate nitrogen load (+/-20kg Nha(-1)y(-1) via bulk precipitation) in comparable conditions in north Belgium. Coniferous forest (two plots Pinus sylvestris and two plots Pinus nigra) received significantly higher nitrogen and sulphur throughfall deposition than deciduous forest and heathland. Grassed and pure heathland had significantly highest throughfall quantities of Ca(2+) and Mg(2+), respectively. The observed differences in throughfall deposition between the different vegetation types were not univocally reflected in the ion seepage flux. Considerable seepage fluxes of NO(3)(-), SO(4)(2-), Ca(2+) and Al(III) were only found under the P. nigra plots. We discuss our hypothesis that the P. nigra forests already evolved to a situation of N saturation, while the other vegetation types did not.     

Bulk deposition in a rural area located around a large coal-fired power station, northeast Spain

This work focuses on bulk deposition in a rural area located around a large coal-fired power station in northeast Spain. Deposition chemistry was characterised by high concentrations of SO(4)(2-), Ca(2+) and NH(4)(+), which were relatively high when compared with other rural areas. Monthly bulk deposition evolution of major ions was the result of two superimposed patterns: one pattern related to the volume of precipitation and the other showed the seasonal influence of the major ionic sources. A major local origin was attributed to bulk deposition of SO(4)(2-), NH(4)(+), and Ca(2+), whereas a relatively higher contribution of an external source was deduced for NO(3)(-), Na(+) and Cl(-). The SO(4)(2-) concentrations showed a significant correlation with the local SO(2) emissions. High levels of Ca(2+) were due to the high alkalinity of soils in the study area, although an external origin was attributed to the frequent air mass intrusions from the Sahara. Sources of NH(4)(+) were related to intensive livestock farming in the area. Total suspended particles exert a marked influence over bulk deposition and neutralisation. Thus, despite the high emissions of SO(2) in the area, neutral pH values have always been attained given that the concentrations of Ca(2+) and NH(4)(+) account for the total neutralisation of NO(3)(-) and SO(4)(2-).     

CuO/γ-Al_2O_3类Fenton试剂降解丁基黄药

CuO/γ-Al2O3类Fenton试剂是降解丁基黄药的优良试剂。该试剂与传统的Fenton试剂相比,提高了反应的pH值,可在较高pH（4~5）条件下反应,而传统的Fenton试剂的适宜pH值一般在3以下。采用单因素实验和正交实验相结合的方法研究了pH、催化剂投加量、过氧化氢投加量以及反应时间对丁基黄药降解效果的影响,并对催化剂的使用寿命进行了探讨。研究结果表明,反应的最佳条件为：pH为4~5,催化剂投加量为6 g/L,过氧化氢用量为30 mg/L,反应30min。在此反应条件下,丁基黄药的降解率达98%以上;影响丁基黄药降解效果的因素大小顺序为：pH〉反应时间〉H2O2用量〉催化剂投加量,其中pH对CuO/γ-Al2O3类Fenton试剂降解丁基黄药的影响最为显著。     

Effects of ozone on foliar leaching in Norway spruce (Picea abies L. Karst): confounding factors due to NOx production during ozone generation

Previous experiments with conifers fumigated with O(3), produced by air-operated electric discharge ozonators, have provided evidence that O(3) increases the leaching of NO(3)(-), NH(4)(+), K(+), Ca(2+), Mg(2+) and some other cations from needles, when the trees are treated with acid mist. This evidence has provided the foundation of the ozone-acid mist hypothesis of spruce decline. We report experiments with Norway spruce saplings fumigated with purified and unpurified O(3). The results show that the accumulation of NO(3)(-) in the needles arises from the rapid deposition of N(2)O(5) and HNO(3) formed from N(2) in the ozonator. An increase in removal of NH(4)(+), Na(+), Ca(2+), Mg(2+), Zn(2+) and Mn(2+) from the needles during soaking in H(2)SO(4), pH3, was also observed, which was related to the increase in NO(3)(-) but was independent of O(3) concentration. It is concluded that results of previous experiments cited in support of the ozone-acid mist hypothesis arose from effects which were at least partly caused by N(2)O(5) produced as a contaminant, and were incorrectly attributed to ozone. Other effects, such as growth stimulations, visible symptons, enhanced frost sensitivity, and infestation by pests or pathogens, which have been attributed to O(3) generated by electric discharge in air, should be interpreted with caution. Future experiments with ozone must eliminate this problem by either using O(2)-driven ozonators, or by purifying the output from air-driven ozonators using cold and/or water traps.     

焦化废水泡沫分离液的Fenton催化氧化预处理

以焦化废水处理过程产生的泡沫分离液为研究对象，对其进行Fenton催化氧化处理实验，考察H₂O₂用量、Fe²⁺浓度、pH和反应时间4个因素对处理效果的影响，并结合GC/MS方法比较处理前后泡沫分离液中有机物的种类及其生物降解性的变化。结果表明，采用［H₂O₂］=100 mmol/L、［Fe²⁺］=100 mg/L、pH=3、反应时间为30 min的Fenton催化氧化反应条件，可以使分离液的COD去除率达到68%以上；经Fenton处理后，分离液的B/C值由0.12提高至0.38，生物降解性明显改善；通过GC/MS的分析，基本明确分离液中含有的有机物主要为酚、胺、腈、酯类有机物及喹啉、吡啶等杂环化合物，大多数属于难降解且生物毒性较强的有机物。针对这些复杂组分共存的泡沫分离液，利用Fenton试剂较强的氧化能力能够将其含有的有毒/难降解有机物转化为低毒或无毒的小分子有机物，为其后续的生物处理创造良好的条件。     

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature,pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO(2) (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 gl(-1); while the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure oxygen, an optimal flow rate was observed at 300 ml min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 (+/-0.6) kJ mol(-1).     

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.     

Enhanced degradation of polycyclic aromatic hydrocarbons by biodegradation combined with a modified Fenton reaction

A study has been conducted to enhance degradation of a mixture of polycyclic aromatic hydrocarbons (PAHs) by combining biodegradation with hydrogen peroxide oxidation in a former manufactured gas plant (MGP) soil. An active bacterial consortium enriched from the MGP surface soil (0-2 m) biodegraded more than 90% of PAHs including 2-, 3-, and 4-ring hydrocarbons in a model soil. The consortium was also able to transform about 50% of 4- and 5-ring hydrocarbons in the MGP soil. As a chemical oxidant, Fenton's reagent (H2O2 + Fe2+) was very efficient in the destruction of a mixture of PAHs (i.e., naphthalene (NAP), fluorene (FLU), phenanthrene (PHE), anthracene (ANT), pyrene (PYR), chrysene (CHR), and benzo(a)pyrene (BaP)) in the model soil; noticeably, 84.5% and 96.7% of initial PYR and BaP were degraded, respectively. In the MGP soil, the same treatment destroyed more than 80% of 2- and 3-ring hydrocarbons and 20-40% of 4- and 5-ring compounds. However, the low pH requirement (pH 2-3) for optimum Fenton reaction made the process incompatible with biological treatment and posed potential hazards to the soil ecosystem where the reagent was used. In order to overcome such limitation, a modified Fenton-type reaction was performed at near neutral pH by using ferric ions and chelating agents such as catechol and gallic acid. By the combined treatment of the modified Fenton reaction and biodegradation, more than 98% of 2- or 3-ring hydrocarbons and between 70% and 85% of 4- or 5-ring compounds were degraded in the MGP soil, while maintaining its pH about 6-6.5.