藻体对水环境中N、P及重金属Cu2+、Pb2+、Cd2+、Cr6+的吸附特征研究

随着全球生态环境的恶化，各国日益重视对水体中各种污染物的治理。利用藻类的吸收、富集和降解作用，可以去除污水中的营养物质、重金属离子和有机污染物，与其他物理、化学及工程的方法相比，该技术具有以下优点：成本低、能耗小、治理效果较好，对环境污染小，有利于资源化，有利于整体生态环境的改善，是治理水质污染的新途径。 本文利用几种大型海藻对富营养化海水进行处理，结果发现孔石莼、刚毛藻均有很强的吸收N、P的能力，吸收能力依次为褶曲刚毛藻>束生刚毛藻>孔石莼。水体中褶曲刚毛藻3 g/L含量，在3～5小时之内，可把中等以上富营养化海水中的N、P降低至一类海水水平。利用刚毛藻处理富营养化地下海水和养殖废水，进行海参和大菱鲆养殖试验，探索藻类净化水质和废水循环利用的新模式，使水体保持较低的营养盐状态，减轻养殖废水对环境的影响，实现了海水养殖业与环境的可持续发展。 刚毛藻在我国近海滩涂分布广泛，利用它来处理富营养化水体，并和水产养殖业相结合，既净化水体，使养殖废水能循环利用，满足水产养殖的需求，又改善水产业生态环境。同时，将回收藻体生产优质饲料、食品和药物等，实现藻类资源的高值利用。刚毛藻营养丰富，用其替代鼠尾藻作海参饲料，资源丰富，成本低，效果好，是一种值得加以开发利用的宝贵资源，具有广泛的应用前景。 生物吸附法是一种经济有效的移除废水中有害重金属离子的方法。由于藻类细胞壁中的多聚糖可提供吸附重金属的位点，廉价而蕴藏丰富的海藻对多种重金属表现出很强的吸附能力。所以本文通过分批实验，研究了非活体刚毛藻对水体中重金属Cu2+、Pb2+和Cd2+的吸附影响因子、吸附热力学、吸附动力学及吸附机理，得到了平衡等温线及动力学数据。吸附过程的最佳pH值为5.0，吸附量随温度的升高而增加，水体中常见的Na+、K+、Ca2+、Mg2+阳离子及Cl-、NO3-、SO42-、C2O42-等阴离子的存在对吸附的影响并不显著。EDTA存在时，吸附百分率大大降低。吸附等温线符合Langmuir和Freundlich方程。刚毛藻对重金属Cu2+、Pb2+和Cd2+的吸附容量很高，25℃时，对Cu2+、Pb2+和Cd2+的最大吸附容量分别为1.61 mmol/g、0.96 mmol/g和0.98 mmol/g，且吸附过程为吸热反应。刚毛藻对重金属Cu2+、Pb2+和Cd2+的吸附过程为化学吸附，在吸附过程中藻体表面的官能团可能与金属离子发生了螯合作用。吸附动力学过程符合pseudo-二级动力学模型，在初始的30min内，吸附速率很快，随后速率逐渐降低。解吸试验表明，用EDTA可以对重金属进行回收，刚毛藻可以循环利用。实验结果表明刚毛藻是一种高效、经济实用的生物吸附材料，可用来吸附回收水体中的重金属Cu2+、Pb2+和Cd2+等。 通过非活体刚毛藻对重金属Cr6+的吸附影响因子、吸附动力学、吸附机理的研究发现，刚毛藻对Cr6+具有很强的还原能力，对电镀废水中的Cr6+的还原去除提供了非常好的方法。吸附过程的最佳pH值为2～3，实际电镀废水通常在此pH范围，因此处理实际废水时，首先在原酸性条件下，对Cr6+进行还原去除，然后调废水pH至5.0，继续进行吸附，去除其他二价离子及被还原的三价Cr离子，实现了利用同一材料还原Cr6+为Cr3+，并将Cr3+和其他重金属离子同时去除。通过对机理的讨论，认为刚毛藻对Cr6+的生物吸附过程不是一个简单的“离子交换过程”，而是一个“吸附还原过程”。在海藻量足够的前提下，只要时间足够长，Cr6+可被彻底还原去除。 利用工业废弃物褐藻渣，对水体中重金属离子Cu2+、Pb2+、Cd2+及Cr6+的生物吸附特性分别进行了讨论，结果表明褐藻渣对重金属离子的吸附特性与刚毛藻一致，吸附等温线符合Langmuir和Freundlich方程，在25℃时，pH为5.0时，由Langmuir方程求出褐藻渣对Cu2+、Pb2+和Cd2+的最大吸附容量分别为4.20 mmol/g、3.13 mmol/g和2.97 mmol/g。褐藻渣对低、高浓度的重金属Cr6+都具有很强的吸附能力，且移除效果比较彻底。实际应用结果表明，褐藻渣是一种高效、经济实用的生物吸附材料，可用来吸附回收水体中的重金属离子，具有广泛的应用前景。

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment. (C) 1998 Elsevier Science Ltd. All rights reserved.

Biosorption of Cr(VI) from aqueous solutions by nonliving green algae Cladophora albida

Biosorption of Cr(VI) from aqueous solutions by nonliving green algae Cladophora albida was investigated in batch experiments. The influence of pH, algal dosage, initial Cr(VI) concentration, temperature and coexisting anions on removal efficiencies of C. albida was studied. Cr(VI) removal process was influenced significantly by the variation of pH, and the optimum pH was chosen at a range of 1.0-3.0. The optimum algal dosage 2 g/L was used in the experiment. The removal rate of Cr(VI) was relatively rapid in the first 60 min, but then the rate decreased gradually. Removal mechanism was studied by analyzing Cr(VI) and total Cr in the solution. Biosorption and bioreduction were involved in the Cr(VI) removal. Biosorption of Cr(VI) was the first step. followed by Cr(VI) bioreduction and Cr(III) biosorption on the algal biomass. Actual industrial wastewater was used to evaluate the practicality of the biomass C. albida. From a practical viewpoint, the abundant and economic biomass C. albida could be used for removal of Cr(VI) from wastewater by the reduction of toxic Cr(VI) to less toxic Cr(III). (C) 2008 Elsevier Ltd. All rights reserved.

Biosorption of copper(II) from aqueous solutions by green alga Cladophora fascicularis

Biosorption is an effective means of removal of heavy metals from wastewater. In this work the biosorption behavior of Cladophora fascicularis was investigated as a function of pH, amount of biosorbent, initial Cu2+ concentration, temperature, and co-existing ions. Adsorption equilibria were well described by Langmuir isotherm models. The enthalpy change for the biosorption process was found to be 6.86 kJ mol(-1) by use of the Langmuir constant b. The biosorption process was found to be rapid in the first 30 min. The presence of co-existing cations such as Na+, K+, Mg2+, and Ca2+ and anions such as chloride, nitrate, sulfate, and acetate did not significantly affect uptake of Cu2+ whereas EDTA substantially affected adsorption of the metal. When experiments were performed with different desorbents the results indicated that EDTA was an efficient desorbent for the recovery of Cu2+ from biomass. IR spectral analysis suggested amido or hydroxy, C=O, and C-O could combine strongly with Cu2+.

Biosorption of copper (II) and lead (II) from aqueous solutions by nonliving green algae Cladophora fascicularis: Equilibrium, kinetics and environmental effects

Biosorption of Cu2+ and Pb2+ by Cladophora fascicularis was investigated as a function of initial pH, initial heavy metal concentrations, temperature and other co-existing ions. Adsorption equilibriums were well described by Langmuir and Freundlich isotherm models. The maximum adsorption capacities were 1.61 mmol/ g for Cu2+ and 0.96 mmol/ g for Pb2+ at 298K and pH 5.0. The adsorption processes were endothermic and biosorption heats calculated by the Langmuir constant b were 39.0 and 29.6 kJ/ mol for Cu2+ and Pb2+, respectively. The biosorption kinetics followed the pseudo- second order model. No significant effect on the uptake of Cu2+ and Pb2+ by co-existing cations and anions was observed, except EDTA. Desorption experiments indicated that Na(2)EDTA was an efficient desorbent for the recovery of Cu2+ and Pb2+ from biomass. The results showed that Cladophora fascicularis was an effective and economical biosorbent material for the removal and recovery of heavy metal ions from wastewater.

Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and its application for determination of amines by high performance liquid chromatography with fluorescence detection and identification with mass spectroscopy/atmospheric pressure chemical ionization

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC-HCI) as the dehydrant with fluorescence detection has been developed. Amines were derivatized to their acidamides with labeling reagent 2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA). Studies on derivatization conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum at lambda(ex) 260nm and an emission maximum at lambda(em) 380nm. The labeled derivatives exhibited high stability and were enough to be efficiently analyzed by high-performance liquid chromatography. Identification of derivatives was carried out by online post-column mass spectrometry (LC/APCI-MS/MS) and showed an intense protonated molecular ion corresponding m/z [MH](+) under APCI in positive-ion mode. At the same time, the fluorescence properties of derivatives in various solvents or at different temperature were investigated. The method, in conjunction with a gradient elution, offered a baseline resolution of the common amine derivatives on a reversed-phase Eclipse XDB-C-8 column. LC separation for the derivatized amines showed good reproducibility with acetonitrile-water as mobile phase. Detection limits calculated from 0.78 pmol injection, at a signal-to-noise ratio of 3, were 3.1-18.2 fmol. The mean intra- and inter-assay precision for all amine levels were < 3.85% and 2.11%, respectively. Excellent linear responses were observed with coefficients of > 0.9996. The established method for the determination of aliphatic amines from real wastewater and biological samples was satisfactory. (c) 2006 Elsevier B.V. All rights reserved.

污水生化处理过程仿真及在A~2/O工艺改进中的应用

基于国际水协会IWA发布的国际评价基准Benchmark,建立了与污水处理厂实际特性相近的标准仿真平台。对污水处理传统A2/O工艺做了合理改进,在不影响出水水质的情况下,取消内回流。应用该平台分别对晴天、雨天与暴雨三种天气的工艺过程模拟,验证了工艺改进的合理性。仿真结果表明,与传统A2/O工艺相比,出水指标差别不大,但污泥泵能耗降低约50%。

A/O工艺城市污水生化处理过程建模与优化控制研究

可持续发展的要求增强了人类有效利用资源和环境保护的意识，而城市污水处理过程是水环境保护的一项重要内容。本文针对我国城市污水处理系统能耗高、出水水质不稳定以及工业毒水经常入侵的现状，以A/O工艺城市污水生化处理过程为研究对象，研究通过建模、控制和优化手段提高污水处理系统运行性能和降低运行降耗的理论和方法。论文工作是在国际水协会发布的典型工艺与污水处理厂实际运行环境相结合的基础上完成，内容主要涉及活性污泥模型简化、基于简化模型的工艺改进与过程模拟、仿真平台的建立、关键控制回路设计、工业毒水诊断与应对系统开发以及优化控制方法与应用研究。具体内容包括： (1) 基于国际评价基准benchmark实现了污水生化处理过程的稳态模拟和动态模拟，对A2/O工艺的改进进行了仿真研究和分析，结果表明在保证出水水质稳定达标的前提下，改进工艺由于取消了内回流，大大节约了回流泵的能耗。 (2) 在国际水协会活性污泥模型ASM1模型的基础上，结合我国污水处理过程特点，并充分考虑我国污水处理厂现场测量信息严重不足的现状，对ASM1模型的组分和反应过程进行简化，建立了简化的活性污泥模型，研究了难以测量的模型组分浓度与易测的常规水质指标的转换方法，针对温度对反应速率的影响，研究了模型参数的校正方法。在此基础上，开发了A/O工艺污水生化处理过程模拟与仿真平台，并对辽宁某污水处理厂的实际运行过程进行了模拟，取得了较好的模拟结果。 (3) 建立了完整的城市污水处理过程控制系统设计框架，引入入水有机负荷和比耗氧速率分别表征微生物（活性污泥）的“食物”（有机物）数量和微生物活性，进行了系统动态特性分析，在此基础上完成了入水流量串级控制、污泥浓度前馈－反馈控制、溶解氧前馈－串级控制三个控制回路的设计。针对溶解氧控制过程采用了仿人智能控制方法，在实际应用中取得了较好的控制效果。 (4) 针对城市污水处理厂经常遇到的工业毒水侵入的问题，开发了基于专家经验的工业毒水诊断与应对系统，编写了较为完备的专家规则，系统能够在毒水侵入时及时发出警报，并采取相应的应对措施，最大程度的降低污水处理厂的损失，该系统在辽宁某污水处理厂取得了较好的应用效果。 (5) 在优化控制方面，针对污水处理过程能耗过高的问题，设计了A/O工艺城市污水处理过程的优化控制策略。建立了只考虑底物与微生物两种组分的简化活性污泥模型，以溶解氧浓度和污泥排放量为决策变量，以污水处理厂日运行费用为性能指标，以物料平衡、水质排放标准等限制为约束条件，建立了完整的优化控制模型，实现了污水处理过程的最优控制，采用基于最优步长参数动态搜索的改进型梯度法进行最佳运行工况寻优。通过对辽宁某城市污水处理厂的优化，获得了当前溶解氧浓度设定值和污泥排放量的最优值，在保证出水水质稳定达标的前提下，污水处理厂日运行费用显著降低，为污水处理厂的实际操作提供了指导。

污泥处理经济评价和污泥堆肥中氧气监测与动态分析

With the continually increase both in the amount of wastewater disposal and in the treatment rate, more and more sewage sludge has been produced. An economic estimate was taken on the different sewage sludge disposal and treatment technologies, and led to the conclusion that compost is an effective way to make sewage sludge harmless, stable and resourceable. Normally, there are several ways to treat sewage sludge, such as landfill, compost, incineration and so on. These technologies will cost 300-1000 Y per ton of sludge. Among those ways, landfill is the cheapest one and operates easily, however, it just postpones the pollution instead of eventually eliminating the pollution; The amount of the sludge will reduce dramatically after incineration, while incineration will take a very high investment in the beginning, at the same time, it's very hard to maintain running; Sewage sludge will be resourceful after composting treantment, thus makes up the treatment cost, makes composting is the most economical way. Compost production is safe when correctly used, compost is a important way to treat sewage sludge. Oxygen is an important control factor in aerobic composting that has great effects on temperature and microorganisms. The gas gathering and transfering system of an online oxygen monitoring system for composting were bettermented to prolong the monitoring system's running period. The oxygen concentration changes in various aerobic composting stage were studied, and conclusions came to that oxygen concentration changes much faster in the oxygen concentration increasing stage than that in the declining stage; the better the aerobic condition is, the sooner the monitoring system starts to work. The minimal oxygen concentration during a ventilation cycle often falls at the beginning, then ascends in the composting period; at the same time, oxygen concentration changes fast in the early composting stage(temperature increasing stage), much slower in the middle stage(continouns thermophilic stage),and seldom changes in the late composting stage(temperature declining stage). With the help of the oxygen realtime-online monitoring system, oxygen concentrations was measured. During the composting period, water contents was analyzed after sampled. It's found that water contents (WC) and Oxygen concentration can both influence the composting process, and the control rule varies in the various composting stages. Essentially, the rule that water and oxygen control the composting process comes from water counterchecks the oxygen transferring to the composting substrate. The most influential factor to the WC and to the oxygen is the components in the composting pile. In the temperature increasing stage, seldom microorganisms exist in the composting pile with low activity, thus oxygen can meet with microorganisms' need, and WC is the dominant factor. In the high temperature (continouns thermophilic) stage, composting process is controlled by WC and oxygen, essentially by WC, at the same time, their influence somehow is not remarkable. In the temperature declining stage, WC and oxygen influence the composting process little. It's also found that the composting process will differ even if under the same components, thus to equably mix the components can avoid WC focusing in some place and let the composting pile to be aerobic. In one sentence, aerobic state is the most important factor in the composting process, suitable bulking material will be useful to the composting control.

污水处理厂工艺运行分析及模拟优化技术研究——以沈阳北部污水处理厂为例

2002年12月，国家环保总局颁布了《城镇污水处理厂污染物排放标准》(GB18918-2002)，对我国城镇污水处理厂的出水水质，尤其是对出水的氮、磷指标提出了更加严格的要求。这不仅对污水处理厂的工艺设计提出了挑战，而且对其运行工艺提出了更高要求，因此污水处理厂面临着进行工艺优化及达标改造以满足新的污水排放标准的问题。 本文以沈阳北部污水处理厂为研究对象，结合国际水质协会（IWA）开发推荐的活性污泥模型(ASM2D)，按照设备评估和分析、数据收集和分析、活性污泥模型的设计和校正、方案评估及改造建议4个阶段对该污水处理厂进行了工艺优化分析及模拟优化技术研究，并运用收集到的原始数据对活性污泥模型（ASM2D）进行了校正。随后，在模型校正成功基础上，对北部污水处理厂三种可能的污水设计处理工艺（A2/O工艺、5段式 Bardenpho工艺、组合工艺）进行了预测及筛选，选定了组合工艺作为北部污水处理厂的最佳脱氮除磷改造方案，确保了沈阳北部污水处理厂污水排放稳定达标。同时，为沈阳市其它城市污水处理厂的污水排放达标改造提供了借鉴。 该研究对提高城市污水处理厂设计和运行管理水平，减少投资和运行成本，提高处理效果，逐渐缩小我国在模型研究和应用方面与国外的差距，在实际应用方面及理论研究方面都具有重要意义。

Ozonation of the purified hydrolyzed azo dye Reactive Red 120 (CI)

The combination of chemical and biological water treatment processes is a promising technique to reduce recalcitrant wastewater loads. The key to the efficiency of such a system is a better understanding of the mechanisms involved during the degradation processes. Ozonation has been applied to many fields in water and wastewater treatment. Especially for effluents of textile finishing industry ozonation can achieve high color removal, enhance biodegradability, destroy phenols and reduce the COD. However, little is known about the reaction intermediates and products formed during ozonation. This work focuses on the oxidative degradation of purified (>90%), hydrolyzed Reactive Red 120 (Color Index), a widely used azo dye in the textile finishing processes with two monochlorotriazine anchor groups. Ozonation of the dye in ultra pure water was performed in a laboratory scale cylindrical batch reactor. Decolorization, determined by measuring the light absorbance at the maximum wavelength in the visible range (53 5 nm), was almost complete after 150 min with an ozone concentration of 12.8 mg/l. The TOC/TOC0 ratio was about 74% and the COD was diminished to 46% of the initial value. The BOD5/COD ratio increased from 0.01 to 0.14. To obtain detailed information on the reaction processes during ozonation and the resulting oxidation products organic and inorganic anions were analyzed. Oxidation and cleavage of the azo group yielded nitrate. Cleavage of the sulfonic acid groups of aromatic rings caused an increase in the amount of sulfate. Formic acid and oxalic acid were identified as main oxidation products by high performance ion chromatography (HPIC). The concentrations of these major products were monitored at defined time intervals during ozonation.

Preservação de germoplasma vegetal, com ênfase na conservação in vitro de variedades de mandioca.

O melhoramento genético de plantas tem contribuído sobremaneira para o aumento da produção em diversas espécies de grande importância econômica e/ou social, beneficiando bilhões de pessoas, especialmente de menor poder aquisitivo, que vivem em países em desenvolvimento distribuídos por todo o mundo. Esses aumentos na produção resultam da obtenção de novos genótipos, que apresentam rendimentos mais elevados, adaptados a diversas condições ecológicas, muitas das vezes adversas, e resistentes a pragas e doenças. No entanto, para a geração desses materiais melhorados, torna-se necessário que características de interesse sejam incorporadas às novas cultivares, dentro de programas de melhoramento genético bem definidos, de forma que possam ser, ao final de todo o processo, exploradas comercialmente.

Armadilha CNPMF: nova técnica para o controle de brocas-da-haste da mandioca.

2009

Recomendação de calagem e adubação para o cultivo da mandioca.

A mandioca (Manihot esculenta Crantz) é cultivada em todas as regiões do Brasil, desempenhando papel importante na alimentação humana e animal, como matéria-prima para vários produtos industriais e na geração de emprego e de renda. O Brasil ocupa a segunda posição na produção mundial de mandioca (12,7% do total), com área cultivada de cerca de 1,7 milhões de hectares, produção da ordem de 22,6 milhões de toneladas de raízes e produtividade média de 13,3 t/ha. Dentre os principais estados produtores destacam-se: Pará (18,0%), Bahia (16,3%), Paraná (12,5%), Rio Grande do Sul (5,0%) e Amazonas (4,3%), que respondem por 56,1% da produção do país. Estima-se que, nas fases de produção primária e no processamento de farinha e fécula, gera-se em torno de um milhão de empregos diretos e que a atividade mandioqueira proporciona receita bruta anual equivalente a 2,5 bilhões de dólares e uma contribuição tributária de 150 milhões de dólares; a produção que é transformada em farinha e fécula gera, respectivamente, receitas equivalentes a 600 milhões e 150 milhões de dólares. A Região Nordeste destaca-se com uma participação de 36,8% da produção nacional; as demais regiões participam com 28,7% (Norte), 19,7% (Sul), 8,8% (Sudeste) e 6,0% (Centro-Oeste).