Removal of Cr(VI) from aqueous solutions by larch bark

The ability of larch (Larix leptolepis Gold.) bark to remove Cr(VI) from dilute aqueous solutions was investigated. The research parameters included the solution pH, contact time, temperature and initial concentration of Cr(VI) in solution. Of the parameters studied, the solution pH was found to be the most crucial. The Cr(VI) removal decreased steadily throughout the pH range studied (pH 2–6), while the Cr adsorption peaked at pH 3. Because the chemical reduction of Cr(VI) to trivalent state occurred to lesser extents even in strong acidic media, the Cr(VI) removal was mainly governed by physico-chemical adsorption. The positive value of the heat adsorption (ΔH ⁰) indicates the endothermic nature of the Cr(VI) adsorption. The relatively slow rate and irreversible nature of the adsorption as well as the order of the magnitude of the heat adsorption value suggest that the adsorption is of a chemical type. The adsorption data obtained from the equilibrium experiments were well fitted to both the Langmuir and Freundlich isotherms.     

Study of Cr(VI) adsorption onto nitrogen-enriched activated carbon from waste medium density fiberboard

Nitrogen-enriched activated carbons were prepared from waste medium density fiberboard waste by using NaOH, K₂CO₃ and KOH. The content of nitrogen in the activated carbon was 0.92, 0.74 and 1.33 % by analysis. The influence of contact time, pH, Cr(VI) initial concentration and the amount of activated carbon on the Cr(VI) adsorption capacity were investigated. The maximum adsorption capacity of Cr(VI) could reach 89.21 mg/g at pH 2 and a contact time of 9 h. The kinetics adsorption followed nicely the pseudo-second-order rate expression. In adsorption isotherm, the Langmuir model fitted better than the Freundlich model. Pure Poplar activated carbon was also prepared as the adsorbent for Cr(VI) removal as control sample. This study indicated that the nitrogen-enriched activated carbon prepared from waste medium density fiberboard can be used effectively for the removal of Cr(VI) compound from aqueous solutions.     

Adsorption of trivalent chromium from dilute solution by conifer leaves

Summary  Chromium(III), Cr(III) adsorption capacities of the leaves of 34 conifer species were examined. Among these, Ginkgo biloba, Taxus cuspidata, Cephalotaxus harringtonia var. nana, and Taxodiaceae and Cupressaceae spp. showed large capacities to adsorb Cr(III). The adsorption capacities of conifer leaves for Cr(III) (3.12–5.09 mg Cr g⁻¹ adsorbent) compared favorably with those of commercial activated carbons (1.23–2.75 mg g⁻¹). Factors affecting Cr(III) adsorption were studied using G. biloba leaves. The factors included solution pH, contact time, temperature, and the initial concentration of Cr(III). The amount of Cr(III) adsorbed on the adsorbent increased steadily with increasing pH in a pH range from 2 to 5, with increasing contact time, and with increasing temperature ranging 20 to 40 °C. The Cr(III) adsorption was also affected by the initial concentration of Cr(III) in the solution.  A linear relationship was observed between the amount of Cr(III) adsorbed and the equilibrium concentration of Cr(III) in the solution when graphed logarithmically. The maximum capacity of G. biloba leaves was 27.5 mg Cr g⁻¹ adsorbent by column experiments. Received 13 January 1998     

Adsorption by coniferous leaves of chromium ions from effluent

The chromium adsorption ability of leaves from 34 conifer species were examined. Among them, deciduous conifer species, such asLarix, Ginkgo, Metasequia, andTaxodium, showed high ability to adsorb chromium ions. Factors affecting chromium adsorption were studied using larch (Larix leptolepis) leaves to determine the optimum adsorption conditions. The factors included solution pH, contact time, temperature, and the initial concentration of chromium ions. Maximum adsorption for Cr³⁺ was observed at pH 5, and maximum Cr⁶⁺ adsorption occurred at pH 3. The amount of Cr⁶⁺ adsorbed on the adsorbent increased rapidly during the first 4 h, then gradually increased, and finally reached equilibrium in 16 h. The adsorption rate of Cr³⁺ was somewhat slower than that of Cr⁶⁺. The adsorption isotherm for Cr⁶⁺ adsorption was composed of two straight lines, suggesting that the adsorbent could not practically reduce the concentration of Cr⁶⁺ in solution below 1.6 mg Cr/L Column experiments using larch leaf packing suggested that the practical operation could be controlled by monitoring the effluent pH.     

Study of Cr(VI) adsorption onto nitrogen-containing activated carbon preparation from bamboo processing residues

Nitrogen-containing bamboo charcoals were prepared using bamboo processing residues, and modified by melamine or urea. The iodine value of the products we obtained was analyzed, and two samples were chosen for the Cr(VI) adsorption. The experimental results show that under the KOH and carbon ratio of 3:1 (w₁/w₂), activation temperature 800 °C and activation time 1 h, the activated carbons modified by melamine boasted the iodine value of 1144 mg/g and the activated carbons modified by urea boasted the iodine value of 1263 mg/g. In addition, the equilibrium adsorption capacity is 95.3 mg/g for the activated carbons modified by melamine with the adsorbent dosage of 1.0 g/L at an initial pH 2 in the presence of 100 mg/L K₂Cr₂O₇ at 30 °C for 180 min and it is 94.2 mg/g for the activated carbons modified by urea in the same reaction condition. The pseudo-second-order kinetic model can better reflect the two kinds of nitrogen-containing activated carbons adsorption kinetic process of Cr(VI). The adsorption process conforms to the Langmuir model, indicating that the process is single molecular layer adsorption.     

Sorption of copper and lead by citric acid modified wood

The sorption characteristics of citric acid modified wood to remove copper and lead ions from aqueous solution under batch conditions have been investigated. Sorption was pH dependent with increasing uptake at higher pH values. The kinetics of sorption for both ions was rapid with 90% sorption taking place within the first 60 min regardless of its initial concentration. Sorption can be explained by a second-order kinetics model from which the rate constant, the equilibrium sorption capacity and the initial rate were calculated. From these parameters, the predictive models for Cu and Pb sorbed (q _t) in time t and at an initial concentration (C _o) are given by q _t=C _o t[0.31C _o–2.29+(0.04C _o+5.19)t] and q _t=C _o t/[0.06C _o–6.59+(0.01C _o+4.48)t] for Cu and Pb, respectively. Using these models the predicted and experimental uptakes of Cu and Pb were compared and discussed. Maximum sorption capacities of modified wood under present experimental conditions were 23.70 and 82.64 mg/g for Cu and Pb, respectively. However, for untreated wood the corresponding values were 2.56 and 7.71 mg/g indicating a tenfold increase in sorption upon citric acid modification. Ethylene diamine tetraacetic acid and nitrilotriacetic acid complexed with both ions render sorption less favorably. However, salicylic acid had little influence. In a binary system, Pb ions were more favorably sorbed than Cu ions which could be due to the larger ionic radius of the former ions.     

Removal of Cu<Superscript>2+</Superscript> ions from aqueous solution by amino-functionalized magnetic sawdust composites

In this study, amino-functionalized magnetic γ-Fe₂O₃/sawdust composites (MSC-NH₂) were investigated as biological absorption materials for removing Cu²⁺ ions from aqueous solution. These composites were fabricated by precipitated γ-Fe₂O₃ nanoparticles on sawdust substrate and then functionalized with 1,6-hexanediamine. Characterization of MSC-NH₂ was performed by means of SEM, TEM, XRD, FTIR, BET, MPMS and XPS analysis to discuss the uptake mechanism. As a result, the amino groups are grafted upon the sawdust surfaces. The MSC-NH₂ could be effectively used to remove Cu²⁺ from aqueous solution and be separated conveniently from the solution with the help of an external magnet. Batch experiments show that the adsorption equilibrium is achieved in 150 min, and the adsorption capacity is 7.55 mg/g at pH 6 and room temperature. The isotherm analysis indicates that the sorption data could be represented by Langmuir isotherm models. The kinetics is evaluated utilizing the Lagergren pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion models. Thermodynamic parameters reveal the spontaneous, endothermic and chemical nature of adsorption.     

Biosorption of Ce(III) onto modified Pinus brutia leaf powder using central composite design

The biosorption of Ce(III) from aqueous solution by citric acid-modified Pinus brutia leaf powder was studied in a batch system as a function of initial pH, temperature, initial concentration of adsorbate, and contact time. Central composite design method was used in the experiments. Thermodynamic parameters such as standard enthalpy (ΔH ⁰), entropy (ΔS ⁰), and free energy (ΔG ⁰) were calculated, and the results indicated that biosorption was exothermic. The biosorption of Ce(III) on modified Pinus brutia leaf powder was investigated by Freundlich, Langmuir, and Dubinin-Radushkevich (D-R) isotherms. The results show that Ce(III) adsorption can be explained by Langmuir isotherm model, and monolayer capacity was found as 62.1?mg/g. The results suggested that the modification process enhances the biosorption capacity of the adsorbent, and modified Pinus brutia leaf powder may find promising applications for the recovery of Ce(III) from aqueous effluents.     

Veterinary antibiotic sorption to agroforestry buffer,grass buffer and cropland soils

The potential of veterinary antibiotics (VAs) to impact human and environmental health requires the development and evaluation of land management practices that mitigate VA loss from manure-treated agroecosystems. Vegetative buffer strips (VBS) are postulated to be one management tool that can reduce VA transport to surface water resources. The objectives of this study were to (1) investigate oxytetracycline (OTC) and sulfadimethoxine (SDT) sorption to agroforestry buffer, grass buffer, and cropland soils, (2) evaluate differences in VA sorption to soils collected from different vegetative management and soil series, and (3) elucidate relationships between soil properties and VA sorption. Sorption/extraction isotherms for OTC were well-fitted by the Freundlich isotherm model (r ² > 0.86). OTC was strongly adsorbed by all soils and the VA was not readily extractable. OTC and SDT solid to solution partition coefficients (K _d) values are significantly greater for soils planted to VBS relative to grain crops. Significant differences in OTC and SDT K _d values were also noted among the soil series studied. Linear regression analyses indicate that clay content and pH were the most important soil properties controlling OTC and SDT adsorption, respectively. Results from this study suggest that agroforestry and grass buffer strips may effectively mitigate antibiotic loss from agroecosystems, in part, due to enhanced antibiotic sorption properties.     

Epichlorohydrin and aspartic acid incorporated into sawdust and application as sorbent for methylene blue

In this paper, a new cation exchanger is prepared by activating sawdust with epichlorohydrin, followed by coupling the epoxy-activated sawdust with aspartic acid. The sawdust cation exchanger (SCE) was investigated for its methylene blue (MB) removal capacity from aqueous solution. The removal experiments were performed under various conditions such as different initial pH, SCE dosage, dye concentration, ionic strength, and contact time in a batch system. The highest sorption capacity of MB was obtained beyond pH 4. The 2.0 g/l or more of SCE could remove above 95% of MB from 250 mg/l of dye solution. Increasing the ionic strength of the solution caused decline of MB sorption. The sorption isotherm conformed well to the Langmuir model. The sorption process could be described by the pseudo-second-order kinetic model.     

Effects of chronic nitrogen application on the growth and nutrient status of a Japanese cedar (Cryptomeria japonica) stand

To investigate the potential effects of nitrogen (N) deposition on Japanese forests, a chronic N-addition experiment that included three treatments (HNO₃, NH₄NO₃, and control) was carried out in a 20-year-old Japanese cedar (Cryptomeria japonica D. Don) stand in eastern Japan over 7 years. The amount of N applied was 168 kg N ha⁻¹ year⁻¹ on the HNO₃ plots and 336 kg N ha⁻¹ year⁻¹ on the NH₄NO₃ plots. Tree growth, current needle N concentration, and soil solution chemistry were measured. Nitrogen application decreased the pH and increased NO₃ ⁻, Ca²⁺, Mg²⁺, and Al concentrations in the soil solution. The needle N concentration increased in both of the N plots during the first 3 years. Nevertheless, the annual increments in height and in the diameter at breast height of the Japanese cedars were not affected by N application, and no visible signs of stress were detected in the crowns. Our results suggest that young Japanese cedar trees are not deleteriously affected by an excess N load.     

非生长季刺槐林土壤CH4通量的变化特征及其影响因子

[目的]探讨在非生长季不同天气条件下45年生刺槐林土壤CH₄通量的日变化和季节变化特征,并确定其主要影响因子.[方法]2014年10月-2015年4月(非生长季),在华北低山丘陵区黄河小浪底森林生态系统定位研究站,利用基于离轴积分腔输出光谱技术的土壤CH₄通量自动观测系统,对土壤CH₄通量进行连续观测,同步观测林内大气温度和相对湿度、5 cm深处土壤温度和土壤湿度、林内总辐射以及降雨量,分析各因子间的相互关系并确定影响土壤CH₄通量的主要因子.[结果]表明:(1)在非生长季,刺槐人工林土壤为大气CH₄重要的汇,变化范围为-0.15~-2.34 nmol·m^-2·s^-1 .晴天的林地土壤吸收CH₄能力 (-0.78 nmol·m^-2·s^-1) 明显高于阴天(-0.61 nmol·m^-2·s^-1)、降雨或降雪天气 (-0.58 nmol·m^-2·s^-1),而且呈"V"型日际变化特征;在2014年11月-2015年1月,土壤吸收CH₄能力逐渐下降,并维持相对较低的水平,直至2015年3月达到最大值 (-2.34 nmol·m^-2·s^-1);(2)土壤CH₄通量与大气温度、5 cm深处土壤温度呈显著负相关,与相对湿度呈正相关;在2015年1月,土壤CH₄通量与总辐射呈正相关;(3)在生长末期土壤上冻阶段和冬季土壤冻结阶段,大气温度和相对湿度为影响土壤CH₄通量的主要因子;而在生长季初期,主要的影响因子为大气温度和5 cm深处土壤温度.[结论]非生长季刺槐林土壤表现为大气CH₄的汇,在非生长季初期土壤吸收CH₄的能力最弱,主要受大气温度和相对湿度的影响,而在非生长季末期土壤吸收CH₄的能力逐渐增加,主要受大气温度和土壤温度的影响.     

The performance of selected leaf mulches in temperature reduction and moisture conservation in the upper soil stratum

This paper reports on the effect of the leaf mulches of Leucaena leucocephala, Gliricidia sepium and Flemingia macrophylla on moisture content and temperature in the first 5 cm of the soil. The mulches were applied at a standard quantity of 5,000 kg ha^–1 DM.In order to characterise a mulch material two parameters are distinguished; the initial impact (I _i ) and the effective lifetime (T _e ) of a mulch material. I is expressed in terms of percentage surplus moisture or degrees Celsius average temperature reduction. T quantifies the duration of the effect. Of the three mulch materials that of Flemingia macrophylla performs best in terms of moisture retention and lowering soil temperatures as well as in terms of longevity of the effect. Leucaena leucocephala mulch shows the smallest impact, over the shortest period.     

Consumption of O<Subscript>2</Subscript>, evolution of CO<Subscript>2</Subscript> and reduction of Cr(VI) during fixation of chromium based wood preservatives in wood

Norway spruce dust was impregnated with aqueous solutions of chromated copper wood preservatives. Immediately after treatment, observation of CO₂ evolution and O₂ consumption were performed. Significant quantities of CO₂ were released during reaction of chromium (K₂Cr₂O₇) containing solutions with wood or brown rotted wood. Nevertheless, during reaction of cellulose with these preservatives we did not observe evolution of CO₂. The presence of copper did not influence on concentration of CO₂. Opposite to CO₂ evolution, treatment of wood and brown rotted wood resulted in O₂ consumption. The oxygen concentration decrease in the measuring chamber was approximately 5 times greater than increase of concentration of carbon dioxide. Electron paramagnetic resonance (EPR) observations of chromium fixation showed that chromium is reduced from Cr(VI) to Cr(III) with Cr(V) as an intermediate on wood, brown rotted wood and cellulose. However, the reduction on wood and brown rotted wood was faster than the reduction on cellulose, as determined from changes of Cr signals in EPR spectra. So, evolution of CO₂ and consumption of O₂ as well as EPR signals of Cr species thus indicate that brown rotted wood, consisting of lignin and hemicelluloses in contact with Cr(VI) reacts more intensively than cellulose, and possibly, oxidation mechanisms of lignin and cellulose with Cr(VI) are different. Received: 20 July 2000     

Phytoaccumulation of chromium by some multipurpose-tree seedlings

A pot culture experiment was conducted in green house to study the potential of chromium (Cr) phytoaccumulatory capabilities of four promising agroforestry tree species viz., Albizia amara, Casuarina equisetifolia, Tectona grandis, and Leucaena luecocephala. Possibility of enhancement of Cr uptake by chemical (citric acid) and biological vesicular arbuscular mycorrhizal fungi (VAM) amendments were also tried. Biologically stable speciation of Cr trivalent (Cr(III) and hexavalent Cr(VI) were used. Cr(VI) was more toxic to the tree growth in terms of collar diameter (CD) increment in all the tree species than Cr(III). In general, roots accumulated more Cr than shoots in all the tree species. There was more than 10 fold increase in root Cr content in comparison with shoot Cr content in all the trees at all the concentration of Cr and all sources of Cr. Citric acid significantly increased the Cr content in the tissues of roots in all the species under both speciation of Cr. The highest increase in Cr content brought by 20 mM citric acid addition was in A. amara. Unlike citric acid, VAM treatment did not bring about a significant increase in the Cr content of all the tree species studied. Results suggest that Albizia amara is a potential Cr accumulator with citric acid as soil amendment. The potential of this tree as a Cr phytoaccumulator may be investigated in long-term studies.     

Effects of the absorption of artificial acidic solutions on the root systems of Japanese red cedar (Cryptomeria japonica D. Don) cutting and saplings

The effects of the absorption of artificial acidic solutions only from below-ground parts on root systems were examined for 60 days in summer and 72 days in fall using cuttings and saplings of Japanese red cedar (Cryptomeria japonica D. Don). Cuttings and saplings absorbed the solutions through the potted soils from the reservoir of an autoirrigator and/or a simplified-autoirrigator. Nitric acid solutions of pH 2.0, 4.0 and 6.0 and distilled water (control) were used in summer, mixtures of H₂SO₄ and HNO₃ solutions of pH 2.0, 3.0 and 4.0, HNO₃ solution of pH 3.0, H₂SO₄ solution of pH 3.0 and distilled water (control) were used in fall. Although no detrimental effects of acidic solutions on saplings were observed, the rooting rate of cuttings treated at pH 2.0 in summer was significantly lower than that of the control. Root lengths and root dry weight per cutting at pH 2.0 in summer and fall were smaller than those of the control, and the difference in fall was significant. The present study revealed that the acidic treatment only from below-ground parts had detrimental effects on the root systems of cuttings, suggesting the importance of quantification of the effects on below-ground parts, as well as on above-ground parts, to evaluate the effects of acidic precipitation on trees.     

Effects of elevated CO2 concentration on the respiratory behavior of the branches of field-grown hinoki cypress (Chamaecyparis obtusa)

The effects of elevated atmospheric CO₂ concentrations on the nighttime respiration were examined for two sample branches of a hinoki cypress tree (Chamaecyparis obtusa) growing in the field with an open gas exchange system for a one-year period from July 1994 to June 1995. The branches were of a similar size and located at a similar position within the crown. One branch was subjected to an elevated CO₂ concentration of 800 μmol mol⁻¹ and the other was subjected to ambient air which had a CO₂ concentration of about 370 μmol mol⁻¹. Nighttime respiration rate was higher in elevated CO₂ level than in ambient CO₂ level. The relationship between nighttime respiration and the corresponding nighttime air temperature was fitted by the exponential function in every month of the year. The segregation of regression lines between the two CO₂ treatments increased gradually as the seasons progressed during the treatment period. TheQ ₁₀ values for nighttime respiration were lower in elevated CO₂ (1.9 ≤Q ₁₀ ≤ 3.7) than in ambient CO₂ (2.4 ≤Q ₁₀ ≤ 4.5) in every month of the year. TheQ ₁₀ was inversely related to the monthly mean nighttime air temperature in both elevated and ambient CO₂. The estimated daily nighttime respiration rate under both CO₂ treatments had a similar seasonal pattern, which almost synchronized with the temperature change. The respiration ratio of elevated CO₂ to ambient CO₂ increased gradually from 1.1 to 1.6 until the end of the experiment. Our results indicate that the CO₂ level and the temperature have a strong interactive effect on respiration and suggest that a potential increase in respiration of branches will occur when ambient CO₂ increases.     

温度对大叶桃花心木(Swietenia macrophylla King)幼苗叶片的光合影响

本文研究了大叶桃花心木（Swietenia macrophylla King）一年生幼苗在经过夜温处理后的光响应曲线和在饱和光强下的CO2反应曲线.结果表明:在大气CO2浓度下,叶片的最佳光合作用温度在25-31℃之间,而在饱和CO2浓度下为31-35℃.在25℃以下光合速率开始降低,主要是由于羧化效率的降低,而当温度超过31℃时,光合速率下降,是因为羧化效率的降低和呼吸速率的增加.CO2浓度对光合的促进作用在低温下受到抑制,这意味着未来在CO2浓度增高的情况下,高浓度的CO2对热带常绿植物光合的促进在冬天低温情况下表现不十分明显.图4参23.     

南亚热带杉木人工成熟林密度对土壤养分效应研究

[目的]研究5种不同密度林分土壤剖面养分含量的变化规律。[方法]以广西大青山37年生杉木密度试验林为研究对象,测定了A(1 667株·hm-2)、B(3 333株·hm-2)、C(5 000株·hm-2)、D(6 667株·hm-2)、E(10 000株·hm-2)5种密度下0 100 cm土层土壤养分含量。利用单因素方差分析和多重比较判断不同密度和不同土层土壤养分含量的差异。[结果]表明:(1)杉木人工成熟林大多数土层土壤有机质、全氮、碱解氮、全磷、有效性铁含量在A、B等低密度林分中最高,并且在0 30 cm的土壤中,随密度的增加表现出总体下降的变化趋势,而土壤pH值与全钾、速效钾随密度的增加而上升,交换性钙与交换性镁含量受密度影响不明显;(2)土壤有机质、全氮、碱解氮、有效磷、速效钾、交换性钙、交换性镁和有效性铁含量均随土层深度的增加而明显下降,0 30 cm表层土壤的降幅较大,密度对不同土壤深度养分含量的变化具有一定影响。[结论]初植密度对杉木人工成熟林土壤养分含量影响明显,低初植密度更有利于杉木人工林土壤肥力的长期维持,南亚热带杉木林密度对土壤养分的影响深度可达60 cm。     

Temperature-dependent functional response of two aphid parasitoids, Aphidius colemani and Aphidius matricariae (Hymenoptera: Aphidiidae), on the cotton aphid

The functional response of two aphid parasitoids, Aphidius colemani Viereck and Aphidius matricariae (Haliday) (Hymenoptera: Aphidiidae), on the cotton aphid, Aphis gossypii Glover (Homoptera: Aphididae), was examined. Five constant temperatures (10, 15, 20, 25, and 30°C) and six host densities (2, 4, 8, 16, 32, and 64) were used during a 24-h period. At each temperature, 2–64 third-instar nymphs of A. gossypii were exposed to individual wasp mating pairs. A type II functional response model for both parasitoid wasps was fit separately for each temperature. The results showed that instantaneous attack rate (a) in A. colemani increased linearly as the temperature increases from 10 to 30°C, but in A. matricariae, (a) increased almost linearly with temperature to reach a maximum at 25°C, and then decreased at 30°C, displaying an asymmetrical dome-shaped pattern. The highest instantaneous attack rate for A. colemani and A. matricariae were calculated 0.940 ± 0.144 day⁻¹ at 30°C and 0.687 ± 0.157 day⁻¹ at 25°C, respectively. Handling time (T _h) for A. colemani was inversely proportional to temperature and ranged from 0.093 ± 0.026 day at 10°C to 0.032 ± 0.004 day at 30°C, but in A. matricariae, (T _h) was between 0.078 ± 0.015 day at 10°C and 0.036 ± 0.014 day at 20°C. A. colemani achieved higher parasitism rate than A. matricariae at higher temperatures. This observation suggests that A. colemani maybe more effective for biological control of the cotton aphid during warmer periods.