Effects of dilution on the complexation of metal ions in wastewaters from a fishmeal factory

The effects of dilution on the complexation of metal ions by the organic matter dissolved in effluent from a fishmeal factory were studied at pH 6.5, 7 and 7.5. The relationship between sample dilution and complexation capacity (determined by titration with copper(II) using DPASV to measure the concentration of labile copper) was linear and with a slope apparently independent of pH.     

Experimental study of chromium adsorption on minerals in the presence of phthalic and humic acids

The effect of phthalic acid (benzene 1,2 dicarboxylic acid), a surrogate compound for natural organic matter, and of humic acid, on the adsorption of chromium to the surface of minerals was observed. In ternary systems involving phthalic acid, chromium(III) adsorption decreases on clays, probably because of aqueous Cr(III)-phthalate complexation, preventing ionic-exchange. Phthalic acid was also found to reduce chromium(VI) adsorption onto alumina, because of a competitive effect. In ternary systems involving humic acid, Cr(III) adsorption is increased in the low pH range because of the formation of surface ternary complex S-L-Cr(III) and is decreased in the high pH range because of aqueous Cr(III)-humate complexation.     

Acute toxicity of copper oxide nanoparticles to Daphnia magna under different test conditions

The acute toxicity of monodispersed 6 nm and <100 nm poly-dispersed copper oxide nanoparticles toward Daphnia magna was assessed using 48 h immobilization tests. CuSO₄ was used as a reference. Four different exposure conditions were tested, to study whether the toxicity of the nanoparticle suspensions changed in a way similar to what is known for dissolved Cu: first in ISO standard test conditions (pH 7.8), second with slight acidity (pH 6.5), third in the presence of citric acid, and fourth in the presence of humic acid. For all four exposure conditions, the toxicity of Cu employed in the three forms followed the same sequence, i.e., CuSO₄ > monodispersed 6 nm CuO ? poly-dispersed CuO. The toxicity of all Cu forms decreased from pH 6.5, ? pH 7.8, > pH 7.8 + citric acid, to ? pH 7.8 + humic acid. This pattern is in agreement with concentrations of Cu²⁺ calculated using the equilibrium model MINTEQ. These findings show that the acute toxicity of copper oxide nanoparticles is governed by test water composition and the chemical species Cu²⁺.     

鲤鱼鱼鳃微环境酸碱条件与铜形态分布模拟

用鱼鳃微环境测定装置和化学平衡计算方法,研究了在人工河水中暴露于铜的鲤鱼鳃部微环境的pH、碱度、粘液含量和铜形态分布.结果发现,鱼鳃pH平衡点为6.92,人工河水pH高于或低于此值时,鱼鳃微环境pH偏低或偏高.变化幅度约达-0.6至0.4 个pH单位.根据实测结果分别建立了计算人工河水和鱼鳃微环境碱度以及鱼鳃粘液分泌量随暴露铜含量和pH变化的定量模型.化学平衡计算结果说明,在pH6至9范围内,人工河水中优势态铜从游离态铜过渡到羟基络合态铜.由于粘液和pH差异的影响,鱼鳃微环境中生物有效态铜含量显著低于人工河水.这样的差别在酸性条件下尤为显著.     

施用城市污泥对杨树土壤化学特性及金属含量的影响

采用温室盆栽方法,研究城市污泥对杨树土壤化学特性、金属含量的影响。实验设置6个处理：4个不同用量的污泥处理：30（S1）、60（S2）、90（S3）和120 t.hm-2（S4）,以及对照（Control：不施加污泥和肥料）和无机复合肥处理（F：1.5 t.hm-2）。结果表明,施用污泥后,土壤有机质、全氮及全磷均提高,且随污泥施用量的增加而增加。S1~S4处理的土壤有机质、全氮及全磷较Control处理分别提高了32.50%~52.05%、32.00%~95.30%及75.43%~236.25%;较F处理分别提高了47.60%~69.37%、35.04%~99.70%及77.10%~239.46%。但污泥施用降低土壤pH和全钾质量分数,土壤pH较Control和F处理分别下降了0.11~0.42和0.01~0.32,但仍呈弱碱性;土壤全钾质量分数较Control和F处理分别降低了1.65%~21.51%和1.19%~21.14%。随污泥施用量的增加,土壤Cu、Zn、Ca和Na质量分数呈增加趋势,而Mn、Fe、Al、Mg质量分数呈降低趋势,其中Cu和Zn增加明显,并较Control处理分别增加了31.89%~104.36%和38.93%~358.02%,较F处理分别增加了23.10%~90.75%和37.88%~354.55%。总体而言,污泥施用于杨树后,可明显改善土壤的化学特性,但污泥施用量越大,土壤重金属Cu和Zn的质量分数残留越多。     

聚丙烯中空纤维膜萃取水溶液中铜离子的研究

研究了聚丙烯中空纤维膜萃取二(2-乙基己基)膦酸(D2EHPA)水溶液中铜离子的工艺条件.结果表明,两相流速、膜面积对萃取率基本无影响;而水溶液的pH值和有机相初始铜离子浓度的改变使萃取率在40%-99%之间变化.整个萃取过程的传质阻力主要来源于D2EHPA和 Cu2 的界面配位络合反应阻力,铜浓度比较高时,传质阻力与铜浓度无关;而当铜浓度降低时,传质阻力随着铜浓度的降低而增大.     

香港河流沉积物中有机碳对铜的吸附特性

采用厌氧序列分批滴定装置（ＡＳＢＴ）研究了香港青山湾避风塘和屯门河、城门河、林村河感潮河段沉积物中有机碳对铜的吸附特性。结果表明,在ｐＨ１６和ｐＨ７的条件下,沉积物中有机碳对铜的吸附特性可用Ｌａｎｇｍｕｉｒ等温式描述,铜在不同河流沉积物有机碳中的分配系数差别较大,吸附容量差别较小,Ｈ＾＋可以结合沉积物有机碳的重金属结合位点,导致吸附容量和分配系数随ｐＨ增大而增大。     

铜污染土壤添加有机物质的生物效应Ⅰ. 对黑麦草生物量的影响

试验研究了泥炭和堆肥对铜污染土壤盆栽黑麦草生物量的影响。结果表明,在未添加有机物质的情况下,随着污染土壤铜含量的增加,黑麦草生物量呈明显减少的趋势（呈显著负相关）,地下部分对铜毒害的反应比地上部分更敏感;导致黑麦草生物量减产20%的土壤铜含量在200～400 mg/kg之间。添加有机物质能显著促进黑麦草尤其是其地下部分的生长,使中度、重度铜污染土壤上的三茬黑麦草生物量平均增加80%～200%,并提高了导致黑麦草严重减产的土壤铜临界浓度。堆肥的增产效果好于泥炭。在试验的9个月内,有机物质仍能维持对受铜污染的土壤上的黑麦草生长的促进作用。     

农用污泥中铜的生态安全阈值研究

本论文采用污泥和土壤外源铜的活性差异系数法研究了农用污泥中铜的生态安全阈值。首先通过比较确定不同土壤条件下污泥中铜和水溶性铜的活性差异的系数,然后利用系数法得到相应土壤条件下污泥铜HC5值(即能够保护95%物种的浓度),并建立了土壤理化性质参数与污泥铜HC5值的量化关系和预测模型。最后与我国现行污泥农用标准值进行了比较,提出了修改建议。结果表明,土壤中来源污泥的铜活性均值约为来源水溶性盐的40%左右。土壤阳离子交换量(CEC)是影响土壤中污泥源铜的毒性的主控因子,可影响污泥铜HC5值变异的84.6%,而土壤pH值和有机碳含量(OC)分别可影响污泥铜HC5值变异的8.4%和1.8%。基于土壤pH、OC和CEC的三因子模型进行预测优于基于土壤pH和CEC的两因子模型,其相关性达到94.8%。与模型预测值相比,我国现行污泥农用标准GB4284-84与CJ/T309-2009中对铜限值的规定均存在着不同程度的保护不足或保护过度问题。     

设施土壤pH值与有机质演变特征研究

设施土壤的pH、有机质与土壤环境质量及设施栽培作物生产水平密切相关。文章对云南不同区域、不同大棚种植年限、不同轮作制度的设施土壤pH与有机质的演变特征进行研究,结果表明:大棚种植年限长的地区,土壤pH、有机质变化明显;随着大棚种植年限的增长,土壤pH呈下降趋势,有机质含量则呈上升趋势;随着土壤层次的加深,大棚土壤pH逐渐升高,而有机质则逐渐降低;不同轮作方式,花-菜轮作比菜-菜轮作有利于增加有机肥对设施土壤pH的缓冲性。     

不同pH下低分子量有机酸对黄壤中铝活化的影响

用一次平衡的方法研究了不同pH下低分子量有机酸对黄壤中铝活化的影响.结果表明,低分子量有机酸体系可以通过质子和有机酸阴离子两个因素促进黄壤中铝的活化.当pH>4.3时,有机酸通过络合作用促进铝溶解的大小顺序为:柠檬酸>草酸>水杨酸>乳酸,与有机酸和铝形成络合物的稳定常数大小一致.有机酸阴离子可以通过自身的吸附增加土壤交换态铝的量,但质子作用对黄壤交换态铝的活化比有机酸阴离子的吸附起着更为重要的作用,随pH值的降低这种趋势更加明显.有机酸对交换态铝的活化作用随pH值的降低而增加.低分子量有机酸活化的铝主要分布在土壤表面的交换位上,但在柠檬酸和草酸体系中,当pH值分别大于4.40和4.55时,活化铝主要分布在土壤溶液中.     

Electrochemical determination of the effect of lead(II) on the photochemical degradation of the pesticide metamitron

The complexation of the pesticide Metamitron by lead(II) was investigated by polarography and stripping voltammetry. The influence of the pH on the complexation was determined and a maximum value for the conditional stability constant of the lead‐metamitron complex (logβ’ = 3.1) was obtained at pH 5.6.

An investigation into the photochemical degradation of the pesticide demonstrated that lead decreases the degradation rate of metamitron by 13% within the first 30 days, due to stabilisation by complexation.     

污染土壤添加有机物质对黑麦草吸收铜的影响

研究了泥炭和堆肥对铜污染土壤盆栽黑麦草吸收铜状况的影响。结果表明 ,黑麦草地上、地下部含铜量皆随土壤污染水平提高而增加 ,地下部的增幅远大于地上部 ;添加有机物质明显降低了黑麦草地上、地下部的含铜量 ,平均降幅近 3 0 %。泥炭降低黑麦草地上、地下部含铜量的作用随土壤污染水平的提高而逐渐变小 ,而堆肥的作用至重度污染水平仍较明显 ;在近 4 0 0mg/kg铜污染水平上 ,有机物质表现出最佳降低植株铜吸收量的效果。有机物质的控制作用与土壤pH有关 ,并在 3茬黑麦草的试验期间内得以维持     

Species of Trace Metals, Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^-1, dry weight in fulvic acid and 820μg g^-1 in humic acid) and lead (821μg g^-1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Influence of dissolved organic matter from corn straw on Zn andCusorption to Chinese loess

The interaction of Zn and Cu with dissolved organic matter (DOM) is a significant physicochemical process affecting their sorption as well as mobility in soil. The objective of this study was to examine the influence of DOM from corn straw on the sorption of Zn and Cu by loess through batch adsorption technique. The sorption isotherms of Zn and Cu could be well described by the Freundlich equation, and the partition distribution coefficient (k) in the presence of DOM was reduced by 86% for Zn and 58% for Cu, as compared to the control receiving no DOM, suggesting that DOM had a stronger inhibitory effect on Zn sorption than that of Cu. In addition, the sorption of metal increased with an increase in pH for loess, with maximum inhibition on metal sorption observed at pH > 7.6 for Zn and pH > 5.5 for Cu in the absence ofDOM but Cu sorption of DOM was suddenly decreased with an increase of pH at pH > 7.9 in the presence of DOM. At a DOM concentration of <200 mg L^?1, sorption of Zn and Cu was reduced by 46% for Zn and 32% for Cu with an increase in DOM concentration.     

The acidobasic and complexation properties of Humic acids

Complexation of Humic Acids (HA) of different origin, like Fluka, and especially those extracted from bohemian brown coal, with cadmium(II) and lead(II) was studied at pH 5.0 using differential pulse anodic stripping voltammetry. Conditions close to those present in the environment were chosen with 3‐ 10^‐4 moll^‐4 for HAs and 2. 10^‐8‐l . 10^‐5 moll^‐1 for Cd(II) and Pb(II). Stability constants evaluation was done assuming the electrode process is diffusion controlled and the complexes are labile. Obtained log K values were in the range 4.49–5.25 for Cd(II) and as expected the higher log K values 6.05–6.60 were found for Pb(II). There was no significant difference between complexation properties of HA extracted from bohemian brown coal and that of Fluka. The results obtained are in good agreement with the literature and those obtained by ISE in our laboratory.     

Metal speciation in sediments of polluted and non‐polluted lakes

A five‐step extraction procedure for metal speciation studies (copper, lead, nickel, manganese and zinc) was applied to the analysis of lake sediments characterised by different environmental features. A different partition of metals into the several metal forms was observed. Both the metal fraction sorbed or co‐precipitated on hydrous Mn‐oxides (especially lead and zinc) and that bound to organic matter (especially copper) are high in some samples. A prevalently anthropogenic origin of these metals may be hypothesised on the basis of existing knowledge of the equilibrium and change phenomena occurring among water, particulate and sediments. Conversely, the non‐solubilised forms of metals are abundant in the sediments of lakes that are certainly not polluted. The concentration of manganese is very high in the sediments of Antarctic lakes; sequential extractions show its lithogenic origin. In conclusion, a knowledge of the different types of metal associations in sediments and their percentage can facilitate understanding of both natural and anthropogenic metal enrichment of aquatic systems.     

Species of Trace Metals,Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Abstract

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^?1, dry weight in fulvic acid and 820μg g^?1 in humic acid) and lead (821μg g^?1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Ionic dye adsorption by zinc oxide nanoparticles

The adsorption behaviour of Basic Red 12, Acid Orange 7 and Acid Blue 1 on zinc oxide nanoparticles (ZNP) has been investigated to understand the physicochemical process involved and to explore the possible use of nanoparticles in the treatment and management of textile waste matter. The dye removal capacity of ZNP towards Basic Red 12, Acid Orange 7 and Acid Blue 1 was found to be 15.64, 6.78 and 6.38 mg g^?1, respectively. The adsorption process was pH dependent and optimum pH values of 9.0, 2.0 and 4.0 were obtained for Basic Red 12, Acid Orange 7 and Acid Blue 1, respectively. Equilibrium was established after 1.0 h for all dyes. Langmuir, Freundlich and Temkin isotherm models were applied to the system. The adsorbent ZNP was characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) and Fourier transform infrared (FTIR) techniques. SEM analysis revealed the noticeable nanoporous morphology of the material. The results of FTIR spectroscopy showed that the process is driven by an electrostatic complexation mechanism. XRD studies revealed the nanocrystalline structure of ZNP. BET surface area measurement suggested a high pore volume and large surface area for the adsorbent. The kinetic measurements suggested pseudo-second-order kinetic processes with high regression coefficients and smaller standard error of estimate values and lower residual sum of squares. The thermodynamic measurements suggested that all processes were exothermic and accompanied by negative values for Δ G⁰, Δ S⁰ and Δ H⁰.     

SOMPROF: A vertically explicit soil organic matter model

Most current soil organic matter (SOM) models represent the soil as a bulk without specification of the vertical distribution of SOM in the soil profile. However, the vertical SOM profile may be of great importance for soil carbon cycling, both on short (hours to years) time scale, due to interactions with the soil temperature and moisture profile, as well as on long (years to centuries) time scale because of depth-specific stabilization mechanisms of organic matter. It is likely that a representation of the SOM profile and surface organic layers in SOM models can improve predictions of the response of land surface fluxes to climate and environmental variability. Although models capable of simulating the vertical SOM profile exist, these were generally not developed for large scale predictive simulations and do not adequately represent surface organic horizons. We present SOMPROF, a vertically explicit SOM model, designed for implementation into large scale ecosystem and land surface models. The model dynamically simulates the vertical SOM profile and organic layer stocks based on mechanistic representations of bioturbation, liquid phase transport of organic matter, and vertical distribution of root litter input. We tested the model based on data from an old growth deciduous forest (Hainich) in Germany, and performed a sensitivity analysis of the transport parameters, and the effects of the vertical SOM distribution on temporal variation of heterotrophic respiration. Model results compare well with measured organic carbon profiles and stocks. SOMPROF is able to simulate a wide range of SOM profiles, using parameter values that are realistic compared to those found in previous studies. Results of the sensitivity analysis show that the vertical SOM distribution strongly affects temporal variation of heterotrophic respiration due to interactions with the soil temperature and moisture profile.