本文關(guān)鍵詞： 藍藻水華 微囊藻毒素 飲用水處理 污染調(diào)控 技術(shù)優(yōu)化　出處：《山東大學》2013年博士論文　論文類型：學位論文

【摘要】：藍藻水華引發(fā)的微囊藻毒素(Microcystins, MCs)次生污染已成為全球關(guān)注的熱點環(huán)境問題。MCs是水華藻類的次生代謝產(chǎn)物,屬于環(huán)狀多肽,細胞死亡或解體后大量釋放到水體中,危害水質(zhì)安全。MCs具有極高的細胞選擇性和專一生物毒性,機體攝入后可經(jīng)多種途徑轉(zhuǎn)移到肝臟等靶器官。毒素暴露后,肝細胞的氧化應激水平顯著提高,同時伴生有DNA損傷、細胞骨架破壞、細胞凋亡現(xiàn)象。鑒于MCs對水環(huán)境安全及人類健康的危害,控制水體藍藻水華和MCs濃度水平,確保飲用水安全供給已經(jīng)成為科學工作者重點關(guān)注的環(huán)境問題。原水除藻(物理、化學、生物方式)、化學混凝、沉淀、過濾、消毒、活性炭吸附、生物降解等工藝陸續(xù)應用于MCs的調(diào)控并且獲得了明顯的成效。但是由于技術(shù)限制和認識不足,上述各類工藝尚難以從根本上調(diào)控MCs的產(chǎn)生、釋放和毒性風險問題,仍然需要對受MCs污染的原水層層設防,逐級調(diào)控。本論文從藍藻細胞低破損去除、含藻給水污泥減量化處理、MCs消毒副產(chǎn)物鑒定與毒性評價方面,優(yōu)化了受藍藻水華污染飲用水的處理工藝,為MCs的有效調(diào)控提供新的技術(shù)支持。論文主要包括以下五部分： 論文第一章闡述了微囊藻毒素的理化特性、生成機制與污染現(xiàn)狀；歸納了微囊藻毒素典型的生物毒性、作用機制、水質(zhì)標準與檢測方法；詳細介紹了針對營養(yǎng)物質(zhì)、針對水源地藻細胞/MCs和針對給水常規(guī)/深度處理中MCs調(diào)控策略與工藝進展。在文獻綜述的基礎上分析了目前相關(guān)研究存在的問題,提出了基于藍藻細胞低破損去除、含藻給水污泥減量化處理、MCs消毒副產(chǎn)物鑒定與毒性評價研究的飲用水微囊藻毒素污染調(diào)控技術(shù)。 論文第二章針對混凝沉淀工藝過程中藍藻細胞的破損與胞內(nèi)毒素釋放問題,通過模擬混凝沉淀工藝,評價了混凝藥劑和工藝運行條件(攪拌速度、時間、靜沉時間等)對藍藻細胞及其代謝產(chǎn)物的去除效果,在此基礎上考察藍藻細胞代謝產(chǎn)物的釋放規(guī)律,闡明藍藻細胞的破損機理；并對混凝劑劑量、攪拌操作及絮體堆積時間等條件進行了優(yōu)化。在優(yōu)化后的混凝條件下(對AlCl3而言最優(yōu)條件為15mg/L,快攪250r/min、1min,慢攪20r/min、20min;對PACl而言最優(yōu)條件為4mg/L,快攪150r/min、2min,慢攪40r/min、30min),幾乎所有銅綠微囊藻細胞都可通過表面電中和被完整去除,混凝劑的投加和攪拌條件并沒有導致MCs的額外釋放。AlCl3混凝絮體中,藻細胞表面能夠形成一種有效保護層,一定程度上減弱了藻細胞的溶解。與AlCl3不同,PACl能夠打破藻細胞外的保護層,顯著加劇藻細胞的破損,使其在絮體堆置2天后即發(fā)生溶解。本研究不僅對傳統(tǒng)飲用水混凝沉淀處理工藝中有效去除藻細胞具有重要意義,對于沉淀污泥處理過程中水資源的循環(huán)利用和二次污染防治同樣具有重要的指導意義。 論文第三章在混凝沉淀凈化處理含藻原水工藝優(yōu)化的基礎上,進一步考察了含藻給水污泥真空過濾脫水過程中機械作用和理化作用對藍藻細胞穩(wěn)定性與MCs釋放特性的影響�；诓煌僮鳁l件下過濾效率(過濾時間、平均濾速)、濾液濁度、MCs濃度的變化,明確了機械作用和理化作用對藻細胞完整性的具體影響,并據(jù)此對過濾操作條件進行優(yōu)化。研究發(fā)現(xiàn)載樣量對污泥脫水特性影響顯著,污泥在過濾介質(zhì)表面逐漸堆積,不僅降低濾速且對藻細胞具有明顯的擠壓破壞,實際操作中應避免污泥層的形成,以提高濾速同時減少MCs釋放。含藻給水污泥過濾脫水時應選擇親水性過濾介質(zhì),在保證較高過濾效率的條件下盡可能降低介質(zhì)孔度。盡管正壓過濾效率略有提高,卻會造成絮體和藻細胞破損,從減少MCs釋放的角度來講,應選擇低破壞性的真空過濾技術(shù)。在合適的推動力作用下(高真空度),含藻給水污泥過濾效率較高且未增加濾液MCs濃度和濁度,應優(yōu)先選擇。污泥堆存時間的延長雖有利于提高污泥脫水效率,卻顯著提高了濾液MCs濃度和濁度。在實際給水廠含藻給水污泥減量化處理時,應控制嚴苛的堆存時間(AlCl3給水污泥要求堆存時間不超過4d, PACl給水污泥要求堆存時間不超過2d)。本研究完善了對藍藻細胞胞內(nèi)MCs的歸趨方式的認識,同時具體研究結(jié)果能夠為實際給水廠含藻給水污泥的減量化處理和含泥水資源化利用提供借鑒和參考。 論文第四章以典型毒素MCLR和MCRR作為飲用水中微囊藻毒素調(diào)控研究的契入點,通過模擬常規(guī)氯消毒工藝條件,在實現(xiàn)MCs氧化去除的同時借鑒微囊藻毒素的傳統(tǒng)制備工藝,實現(xiàn)MCs消毒副產(chǎn)物(MC-DBPs)的分離純化,并利用液相色譜-質(zhì)譜(LC/MS)、質(zhì)譜-質(zhì)譜聯(lián)用(MS/MS)等技術(shù)對MCs及MC-DBPs進行結(jié)構(gòu)對比解析,進而確定主要MC-DBPs的結(jié)構(gòu)特性與生成機制；同時在色譜制備的基礎上利用蛋白磷酸酶抑制毒性實驗建立和完善MC-DBPs環(huán)境風險的評價方法。研究表明在不同消毒模式下,MCs能夠穩(wěn)定消減至WHO規(guī)定的限值(1.0μg/L)以下,但同時氧化生成多種MC-DBPs。典型DBPs產(chǎn)物類型與分布受MCs類型和消毒劑量的影響與制約。綜合分析MC-DBPs的生成機制,不難發(fā)現(xiàn)MC主要經(jīng)歷Adda共軛二烯雙鍵加成反應和部分初級產(chǎn)物的脫水反應。蛋白磷酸酶PP1的毒性抑制實驗均證實多數(shù)MC-DBPs的生物毒性較原毒素有明顯下降,但殘余的生物毒性依然不能忽視。盡管消毒處理可有效調(diào)控MCs的濃度水平,但綜合考慮MC-DBPs的含量變化和潛在生物毒性,MC-DBPs對飲用水的二次污染同樣值得關(guān)注。本研究建立的針對MC-DBPs毒性分析評價技術(shù)并不局限于MCLR和MCRR,依據(jù)原水中MCs的分布特征,同樣適用于其它類型毒素消毒副產(chǎn)物毒性的評價與調(diào)控。本研究有助于綜合認識MCs的危害及其調(diào)控策略和提高飲用水質(zhì)量,因而具有重要實際意義和應用價值。 論文第五章對各研究部分進行了總結(jié),并分析了“飲用水處理工藝中微囊藻毒素污染調(diào)控技術(shù)的優(yōu)化研究”的優(yōu)勢與不足之處,展望了該領(lǐng)域的發(fā)展方向。本論文優(yōu)化和改進了微囊藻毒素污染原水的常規(guī)處理工藝,為MCs的有效調(diào)控提供新的技術(shù)支持與參考。
[Abstract]:Microcystins cyanobacterial blooms caused by (Microcystins, MCs) secondary pollution has become a hot.MCs global environmental concern is the secondary metabolites of algae, which belongs to the cyclic peptides, cell death or after the collapse of a large number of release into the water, water quality and safety hazards of.MCs has high selectivity and specific cell toxicity, after intake of the body through multiple channels of transfer to the liver and other organs. The toxin after exposure, the levels of oxidative stress in liver cells increased significantly, while associated with DNA damage, cytoskeleton damage, cell apoptosis. In view of the MCs on the water environment safety and human health hazards, control water cyanobacteria and MCs concentration level, to ensure the safety of drinking water supply environmental problems have become the focus of scientific workers. The raw water algae (physical, chemical and biological methods), chemical coagulation, sedimentation, filtration, disinfection, activated carbon adsorption, biological The regulation of degradation process were used in MCs and achieved remarkable results. But due to technical limitations and inadequate understanding of the various types of technology is difficult to fundamentally control the generation of MCs, and the release of toxic risk problem, still need to MCs contaminated water layer uponlayer, step by step regulation. This paper from the cyanobacterial cells with low damage the removal of algae containing water treatment, sludge reduction, MCs disinfection by-products identification and toxicity evaluation, optimizing the treatment process by cyanobacteria contaminated drinking water, to provide new technical support for effective control of MCs. The paper mainly includes the following five parts:
The first chapter expounds the physicochemical characteristics of microcystins, formation mechanism and pollution; summarizes the biological toxicity of microcystin typical mechanism, water quality standards and testing methods; introduced for nutrients, water algae /MCs and conventional water treatment for MCs / depth control strategy and process progress. On the basis of literature review of existing related research questions, put forward the cyanobacterial cells with low damage removal based on the treatment of algae containing water sludge reduction, microcystins in drinking water pollution control technology of MCs disinfection by-products identification and toxicity evaluation research.
In the second chapter, damage problems and release of toxin in cyanobacterial cells coagulation sedimentation process, through the simulation of coagulation sedimentation process, evaluation of the coagulant and operating conditions (stirring speed, time, settling time etc.) on the removal of algae and its metabolites, releasing test cyanobacteria metabolites on this basis, clarify the damage mechanism of cyanobacterial cells; and the coagulant dosage, stirring and floc accumulation time were optimized. Under the optimized conditions of coagulation (for AlCl3 optimal conditions for 15mg/L, 250r/min 1min, fast mixing, slow stirring 20r/min, 20min for PACl optimal; the condition is 4mg/L, stirring 150r/min, 2min, 40r/min, 30min), slow stirring, almost all of Microcystis aeruginosa cells by surface charge neutralization is the complete removal of coagulant and stirring conditions did not lead to the amount of MCs The release of.AlCl3 coagulation floc, the algal cell surface to form an effective protective layer, to a certain extent, weakened the dissolution of algal cells. Unlike AlCl3, PACl can break the protective layer outside the cell, significantly increases the damage of algal cells, the flocs piled up 2 days' dissolution this research not only on the traditional drinking water coagulation process in the effective removal of algal cells has important significance, also has an important guiding significance for the treatment process of sludge water resource recycling and two pollution prevention.
In the third chapter, based on the coagulation treatment of raw water containing algae precipitation purification process optimization, to further investigate the effects of the mechanical process of algae containing water supply sludge dewatering by vacuum filter and physicochemical effects on the release characteristics of cyanobacterial cells. MCs stability and filtration efficiency under different operating conditions (based on the filtration time, average filtration rate). The filtrate turbidity, the MCs concentration, the effect of mechanical and physicochemical effects of specific effects on algal cell integrity, and thus to optimize the filter operation conditions. It is found that the effect of loading amount of sludge dewatering characteristics of sludge was gradually accumulated on the surface of the filter media, not only reduce the filtration rate and has obvious damage to the extrusion the algal cells, prevent the formation of sludge layer should be in the actual operation, in order to improve the filtering speed and reduce the release of MCs. The water containing algae sludge dewatering should choose hydrophilic filter media, in order to ensure a The high filtration efficiency as much as possible under the condition of reducing medium porosity. Despite the positive pressure filtration efficiency increased slightly, it will cause the flocs and cell damage, reduce the release of MCs from the point of view, should choose the low destructive vacuum filtration technology. In the driving force under suitable (high vacuum), algae containing water sludge with high filtration efficiency without increasing the filtrate MCs concentration and turbidity, should be preferred. Although the time prolonged sludge storage can improve sludge dewatering efficiency, but significantly improved the filtrate MCs concentration and turbidity. The water containing algae sludge reduction in the actual water supply plant, should control the stockpiling time demanding (AlCl3 water supply sludge requirements storage time is not more than 4D, PACl requirements of water supply sludge stockpiling time not more than 2D). This study was to improve the cyanobacteria cells MCs the fate of understanding of the way, at the same time the research result can actually give water containing algae The reduction and treatment of water sludge and the utilization of mud water resources provide reference and reference.
In the fourth chapter, taking the typical MCLR toxin and MCRR as the study of microcystins in drinking water regulation point, through the simulation of conventional chlorine disinfection process conditions, while achieving the MCs oxidation removal of microcystins from the traditional preparation process, the realization of MCs disinfection by-products (MC-DBPs) separation and purification, and the use of liquid chromatography mass spectrometry (LC/MS), MS (MS/MS) of the comparison and analysis of the structure of MCs and MC-DBPs technology, structure characteristics and formation mechanism and to determine the main MC-DBPs; at the same time based on the chromatographic preparation of protein phosphatase enzyme inhibition toxicity evaluation method to establish and perfect the MC-DBPs study showed that in the environmental risk. The different disinfection mode, MCs can stabilize the provisions of cut to the WHO limit value (1 g/L), but at the same time the oxidation of various MC-DBPs. typical DBPs product types and distribution by MCs type and dose of disinfection The impacts and constraints. The formation mechanism of MC-DBPs comprehensive analysis, it is not difficult to find MC mainly through Adda conjugated diene double bond addition reaction and dehydration reaction. Part of the primary products of protein phosphatase PP1 toxicity inhibition experiment confirmed the biological toxicity of most of the MC-DBPs was lower than that of the original toxin, but the toxicity of residual disinfection although still can not be ignored. Treatment can effectively control the concentration of MCs level, but considering the MC-DBPs content changes and potential biological toxicity, MC-DBPs two pollution of drinking water is also worthy of attention. This study established for MC-DBPs toxicity analysis evaluation technology is not limited to MCLR and MCRR, according to the distribution characteristics of MCs in raw water, the same for evaluation and regulation in other types of toxin DBPs toxicity. This study is helpful to harm and control strategy of a comprehensive understanding of MCs and improve the quality of drinking water, which is heavy It is of practical significance and applied value.
The fifth chapter summarizes the research, and analysis of the "optimization" of drinking water treatment of microcystin pollution control technology in the process of the advantages and disadvantages of the future development direction of this field. This thesis optimized and improved the conventional treatment process of microcystin contamination of raw water, provide technical support with the new reference for effective control of MCs.

【學位授予單位】：山東大學
【學位級別】：博士
【學位授予年份】：2013
【分類號】：TU991.2

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