水体中微囊藻的超声控制技术研究
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摘要
缓流水体富营养化引起的水华是当前突出的环境问题之一，藻类的出现不仅会破坏水体的生态平衡，而且会严重影响周边城市的饮用水水质。因此，研究引起水华藻类的控制技术具有重要的学术意义和工程价值。针对超声控藻技术与作用机理存在的问题，本文以水华中常见的藻种——微囊藻为研究对象，通过对超声声场声压分布及有效作用距离、超声控制参数影响、最优控制参数、控藻动力学规律、作用机制以及超声对微囊藻生理特征影响、藻毒素释放等方面深入研究，并在此基础上探讨了超声控藻的作用机理。
水中超声声场中的声压随着距离的增加而急剧下降；同时输入的电功率越高，产生的声压越大；超声频率越高，超声能量越易被吸收，在水中衰减越快，传播距离越小，主声束越窄，但其近场与远场的分界线越大，指向性越好。论文提出了超声有效作用距离并得出：低频率超声作用有效范围比较大，在不影响其他水生动植物的情况下，适用于大水域控藻；而高频率超声近场与远场的分界线相对比较远，适用于水处理设备中应急除藻。
“超声辐射声功率容积密度”综合考虑了超声设备与作用对象这两部分的因素，能够更准确的表征超声作用的强度,可通过导纳圆图法检测计算得出。“控藻率”表征超声控藻作用的效果，考虑了藻密度生长造成的影响，可直观的表征超声控藻的效果。
超声作用强度评估实验的结果表明：低频超声产生的主要是机械作用，随着超声频率增加，空化作用越来越显著，将产生更多的自由基，化学作用也将越显著，频率增大到一定值后，产生的空化作用将趋于饱和。低强度超声（低于空化阈）主要是通过机械作用达到控藻目的，控藻效果较为一般，且对藻类造成的损伤是可修复的；而高强度超声（高于空化阈）主要是通过空化作用与机械作用共同作用达到控藻目的，且空化作用为主导作用，对藻类作用造成的损伤是永久性的；高强度超声作用时间太长，既不经济也不利于对水质；从低频到高频过程中，超声对藻类的主导作用也将由机械作用转变为空化作用。
对超声辐射声功率容积密度、超声作用时间、超声频率等超声控藻控制参数进行响应面实验优化并建立二阶回归模型，得到超声控制微囊藻最优的控制参数为频率580kHz、辐射声功率容积密度0.089W/mL、辐照时间24s，该条件下控藻率的为99.58%。超声控藻满足准一级动力学规律，反应速率常数k随着超声辐射声功率容积密度、超声频率的增大而增大，增大到一定值后，速率常数k增幅减小，并逐步趋于饱和；同时反应速率常数k随着初始浓度的增大而减小。
低于空化阈的超声作用对微囊藻细胞外表面、内囊体与气泡均会造成损伤，使得细胞活性降低，藻胆体受到破坏，光合作用系统和浮力自动调节能力受损，净光合放氧速率降低，大部分细胞受到的损伤在其耐受极限内，藻细胞产生SOD、CAT等抗氧化性酶，清除超声产生的自由基对自身产生的伤害，使藻细胞内MDA的含量保持在较低的水平，其受到的损伤得以修复，仅部分细胞出现死亡；大于空化阈的超声作用，使微囊藻内气泡与类囊体出现断裂、破碎溶解与消失，大部分细胞失去光合作用和自动调节浮力的能力，藻胆体与叶绿体受到不可修复的损伤，抗氧化酶系统作用机制失效，细胞并将最终死亡。尽管高强度超声会引起藻细胞的破坏，但是在一定的作用时间(30min)内引起的藻毒素释放在可控范围内，超声处理后藻毒素的量在《生活饮用水卫生标准》（GB5749-2006）限值1μg/L范围以内。
Algae bloom occurs in ground water due to eutrophication becomes one of theserious environmental problems. Research on algae control technology has importantacademic significance and practical value. According to the problems betweenultrasonic algae control technology and its mechanism, this paper took Microcystis sp.as research object. Acoustic pressure distribution and effective distance in ultrasonicfield, ultrasonic control parameters effects, and the optimal control parameters, kineticslaw of algae control, mechanism, effects of ultrasonic on Microcystis sp., Phycotoxinrelease were deeply studied to discuss the mechanisms of ultrasonic algae control.
Acoustic pressure in the ultrasonic field decreased sharply with increasing distance.The higher the input electric power, the greater the acoustic pressure was. The higherthe ultrasonic frequency, ultrasonic energy was absorbed more easily and attenuation inwater was quicker, also with smaller propagation distance and narrower main beam. Butthe near and far field boundary was greater and the directivity was better. This papergave the effective distance and came to such results as follows: low-frequencyultrasound with a wide effective range was suitable for large water. Whilehigh-frequency ultrasound was suitable for emergency alage remove in water treatmentas for the near and far field boundary was relatively far.
“Volume density of ultrasonic power radiation” took the two factors of ultrasoundequipment and effective object into account, which could characterize the ultrasoundintensity more accurately and could be calculated through the admittance circle diagrammethod. Considering the influence of ultrasound intensity, algae control rate intuitivelycharacterized the effect of ultrasonic sound on algae control.
From Calorimetry and Iodometric method analysis, low-frequency ultrasoundmainly generated the mechanical action. With the ultrasonic frequency increased, thecavitation and chemical reaction increased significantly, producing more free radicals.Cavitation tended to be saturated as frequency increasing to a certain value.Low-intensity ultrasound (below the cavitation threshold) had a common effect on algaecontrol by mechanical action, while the damage to algae was repairable. High-intensityultrasound (above the cavitation threshold) achieved algae control by the combinedeffects of cavitation and mechanical action. As cavitation for the leading role, thedamage to algae was permanent. High-intensity ultrasonic was neither conducive toeconomy nor to water quality with long time’s treatment. From low frequency to high frequency process, the dominant role of ultrasound on algae would also be transformedfrom mechanical action into cavitation.
Response surface experimental optimization and two-stage regression model weremade on such algae control parameters as volume density of ultrasonic power radiation,ultrasonic time, ultrasonic frequency and so on, obtaining the optimal controlparameters for frequency of580kHz, volume density of ultrasonic power radiation0.089W/mL, irradiation time24s and the best algae removal rate of99.58%. Algaeremoval met the pseudo-first order kinetics law, reaction rate constant k increasedwith volume density of ultrasonic power radiation and ultrasonic frequency increasing.When reaction rate constant k increased to a certain value, its increase amplitudedecreased and reached a saturation value. The reaction rate constant decreased with theincrease of initial concentration.
Ultrasound below the cavitation threshold caused damage to the surface, thylakoidand bubble of Microcystis sp., and cell activity, phycobilisome, photosynthetic systems,buoyancy auto regulating ability were damaged, the net photosynthetic oxygenevolution rate decreased. But the damages were within the limits of its tolerance. Algaecells produced SOD, CAT and other antioxidant enzyme to clear free radicals’ damageto itself generated by ultrasound, so that the MDA content maintained at a lower level,the damage could be repaired, only part of the cell died. Ultrasound above the cavitationthreshold made the thylakoid and bubble of Microcystis sp. fracturing, breaking todissolve and disappearing. Most cells lost the photosynthesis and buoyancy autoregulating ability. Damages to phycobilisome and Chloroplast were unreparable, and themechanism of antioxidant enzyme lost, the cell died finally. High-intensity ultrasoundacted on Microcystis sp. for certain time (<30min), Phycotoxin release was under controland its concentration was under1μg/L of Standards for Drinking Water Quality.
水中超声声场中的声压随着距离的增加而急剧下降；同时输入的电功率越高，产生的声压越大；超声频率越高，超声能量越易被吸收，在水中衰减越快，传播距离越小，主声束越窄，但其近场与远场的分界线越大，指向性越好。论文提出了超声有效作用距离并得出：低频率超声作用有效范围比较大，在不影响其他水生动植物的情况下，适用于大水域控藻；而高频率超声近场与远场的分界线相对比较远，适用于水处理设备中应急除藻。
“超声辐射声功率容积密度”综合考虑了超声设备与作用对象这两部分的因素，能够更准确的表征超声作用的强度,可通过导纳圆图法检测计算得出。“控藻率”表征超声控藻作用的效果，考虑了藻密度生长造成的影响，可直观的表征超声控藻的效果。
超声作用强度评估实验的结果表明：低频超声产生的主要是机械作用，随着超声频率增加，空化作用越来越显著，将产生更多的自由基，化学作用也将越显著，频率增大到一定值后，产生的空化作用将趋于饱和。低强度超声（低于空化阈）主要是通过机械作用达到控藻目的，控藻效果较为一般，且对藻类造成的损伤是可修复的；而高强度超声（高于空化阈）主要是通过空化作用与机械作用共同作用达到控藻目的，且空化作用为主导作用，对藻类作用造成的损伤是永久性的；高强度超声作用时间太长，既不经济也不利于对水质；从低频到高频过程中，超声对藻类的主导作用也将由机械作用转变为空化作用。
对超声辐射声功率容积密度、超声作用时间、超声频率等超声控藻控制参数进行响应面实验优化并建立二阶回归模型，得到超声控制微囊藻最优的控制参数为频率580kHz、辐射声功率容积密度0.089W/mL、辐照时间24s，该条件下控藻率的为99.58%。超声控藻满足准一级动力学规律，反应速率常数k随着超声辐射声功率容积密度、超声频率的增大而增大，增大到一定值后，速率常数k增幅减小，并逐步趋于饱和；同时反应速率常数k随着初始浓度的增大而减小。
低于空化阈的超声作用对微囊藻细胞外表面、内囊体与气泡均会造成损伤，使得细胞活性降低，藻胆体受到破坏，光合作用系统和浮力自动调节能力受损，净光合放氧速率降低，大部分细胞受到的损伤在其耐受极限内，藻细胞产生SOD、CAT等抗氧化性酶，清除超声产生的自由基对自身产生的伤害，使藻细胞内MDA的含量保持在较低的水平，其受到的损伤得以修复，仅部分细胞出现死亡；大于空化阈的超声作用，使微囊藻内气泡与类囊体出现断裂、破碎溶解与消失，大部分细胞失去光合作用和自动调节浮力的能力，藻胆体与叶绿体受到不可修复的损伤，抗氧化酶系统作用机制失效，细胞并将最终死亡。尽管高强度超声会引起藻细胞的破坏，但是在一定的作用时间(30min)内引起的藻毒素释放在可控范围内，超声处理后藻毒素的量在《生活饮用水卫生标准》（GB5749-2006）限值1μg/L范围以内。
Algae bloom occurs in ground water due to eutrophication becomes one of theserious environmental problems. Research on algae control technology has importantacademic significance and practical value. According to the problems betweenultrasonic algae control technology and its mechanism, this paper took Microcystis sp.as research object. Acoustic pressure distribution and effective distance in ultrasonicfield, ultrasonic control parameters effects, and the optimal control parameters, kineticslaw of algae control, mechanism, effects of ultrasonic on Microcystis sp., Phycotoxinrelease were deeply studied to discuss the mechanisms of ultrasonic algae control.
Acoustic pressure in the ultrasonic field decreased sharply with increasing distance.The higher the input electric power, the greater the acoustic pressure was. The higherthe ultrasonic frequency, ultrasonic energy was absorbed more easily and attenuation inwater was quicker, also with smaller propagation distance and narrower main beam. Butthe near and far field boundary was greater and the directivity was better. This papergave the effective distance and came to such results as follows: low-frequencyultrasound with a wide effective range was suitable for large water. Whilehigh-frequency ultrasound was suitable for emergency alage remove in water treatmentas for the near and far field boundary was relatively far.
“Volume density of ultrasonic power radiation” took the two factors of ultrasoundequipment and effective object into account, which could characterize the ultrasoundintensity more accurately and could be calculated through the admittance circle diagrammethod. Considering the influence of ultrasound intensity, algae control rate intuitivelycharacterized the effect of ultrasonic sound on algae control.
From Calorimetry and Iodometric method analysis, low-frequency ultrasoundmainly generated the mechanical action. With the ultrasonic frequency increased, thecavitation and chemical reaction increased significantly, producing more free radicals.Cavitation tended to be saturated as frequency increasing to a certain value.Low-intensity ultrasound (below the cavitation threshold) had a common effect on algaecontrol by mechanical action, while the damage to algae was repairable. High-intensityultrasound (above the cavitation threshold) achieved algae control by the combinedeffects of cavitation and mechanical action. As cavitation for the leading role, thedamage to algae was permanent. High-intensity ultrasonic was neither conducive toeconomy nor to water quality with long time’s treatment. From low frequency to high frequency process, the dominant role of ultrasound on algae would also be transformedfrom mechanical action into cavitation.
Response surface experimental optimization and two-stage regression model weremade on such algae control parameters as volume density of ultrasonic power radiation,ultrasonic time, ultrasonic frequency and so on, obtaining the optimal controlparameters for frequency of580kHz, volume density of ultrasonic power radiation0.089W/mL, irradiation time24s and the best algae removal rate of99.58%. Algaeremoval met the pseudo-first order kinetics law, reaction rate constant k increasedwith volume density of ultrasonic power radiation and ultrasonic frequency increasing.When reaction rate constant k increased to a certain value, its increase amplitudedecreased and reached a saturation value. The reaction rate constant decreased with theincrease of initial concentration.
Ultrasound below the cavitation threshold caused damage to the surface, thylakoidand bubble of Microcystis sp., and cell activity, phycobilisome, photosynthetic systems,buoyancy auto regulating ability were damaged, the net photosynthetic oxygenevolution rate decreased. But the damages were within the limits of its tolerance. Algaecells produced SOD, CAT and other antioxidant enzyme to clear free radicals’ damageto itself generated by ultrasound, so that the MDA content maintained at a lower level,the damage could be repaired, only part of the cell died. Ultrasound above the cavitationthreshold made the thylakoid and bubble of Microcystis sp. fracturing, breaking todissolve and disappearing. Most cells lost the photosynthesis and buoyancy autoregulating ability. Damages to phycobilisome and Chloroplast were unreparable, and themechanism of antioxidant enzyme lost, the cell died finally. High-intensity ultrasoundacted on Microcystis sp. for certain time (<30min), Phycotoxin release was under controland its concentration was under1μg/L of Standards for Drinking Water Quality.
引文
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