电活化过硫酸盐去除铜绿微囊藻的效果及机理研究

为了开发微藻及藻类有机物的高效去除技术,采用电活化过硫酸盐(EC/PS)体系处理含铜绿微囊藻的水样. 通过藻细胞密度和叶绿素a含量测定以及扫描电镜观察,研究了EC/PS体系的除藻特性及影响因素;采用荧光区域积分法定量分析了除藻过程中胞内有机物(IOM)和胞外有机物(EOM)的变化特征;利用电子顺磁共振波谱仪测定了EC/PS体系中的自由基类别,并分析了EC/PS体系的除藻机理. 结果表明:①在初始藻细胞密度为1.24×107~1.30×107 cells/mL,电压为7 V,初始pH为6,初始PS浓度为4 mmol/L的条件下,当EC/PS体系处理60 min时,藻细胞和叶绿素a的去除率分别达90.80%和98.41%,明显优于单独EC体系和单独PS体系;当EC/PS体系处理10 min时,IOM的总荧光响应值降低了77.39%. 在处理过程中,以腐殖酸类物质为主的胞内有机物会大量释放. ②EC/PS体系中电化学作用对除藻的平均贡献率为54.63%;同时,除藻过程可产生大量的SO₄?·和·OH,且其随处理时间的增加而增加. 研究显示,EC/PS体系能有效去除铜绿微囊藻及藻类有机物,反应体系中的SO₄?·和·OH发挥了重要作用.      

高铁酸盐预氧化对松花江水混凝效果的影响

以高铁酸钾和硫酸铝为预氧化剂和混凝剂,考察了NH ,4-N、浊度、TOC、AOC和相对分子质量分布(Mr)等参数的变化,分析了高铁酸钾预氧化对松花江水源水性质产生的影响.结果表明,单独硫酸铝混凝时,在混凝剂投量为50mg·L-1的条件下,松花江水的UV254、浊度、TOC的去除率分别为36.7%、80.2%、31.1%.当高铁酸钾为预氧化剂,投量为1 mg·L-1,时,混凝后松花江水的UV254、浊度、TOC的去除率分别为63.3%、89.6%、37.%.铁酸盐预氧化使混凝后的NH ,4-N值上升了17%.高铁酸盐预氧化使松花江水混凝后的AOC值从998 μg·L-1升到1 241 μg·L-1,同时,使混凝后的AOC/TOC从28.4%上升到38.7%,很大程度上提高了原水中有机物的可生物降解性.这一过程中, AOC-P17所代表的醛酮类物质显著增加,达到总AOC的83%.溶解态有机物分子量分布的考察表明, Mr小于500的分子所占的百分比由单独混凝时的38.9%上升到预氧化后的65.0%,证明高铁酸钾预氧化将原水中的大分子有机物氧化成小分子有机物.分子有机物的增加引起了原水可生物降解性的提高.     

磷对四尾栅藻代谢有机物生成规律的影响

通过改变培养基中ρ(TP),并结合TOC(总有机碳)分析、考马斯亮蓝法、蒽酮硫酸法和茚三酮法研究不同ρ(TP)对水华中常见绿藻——四尾栅藻的生长规律及其IOMs(胞内有机物)和EOMs(胞外有机物)中TOC、蛋白质、碳水化合物和氨基酸代谢规律的影响. 结果表明,随着ρ(TP)的增加,四尾栅藻生长的指数期变长. ρ(TP)为0.01 mg/L时有利于四尾栅藻EOMs中碳水化合物的形成与积累,ρ(碳水化合物)在指数期达到最大,为89.25 mg/L;ρ(TP)为0.20 mg/L时则有利于四尾栅藻EOMs中氨基酸的形成,并且ρ(氨基酸)在稳定期达到最大,为13.72 mg/L. ρ(TP)为0.01 mg/L时有利于四尾栅藻IOMs中氨基酸的形成,ρ(氨基酸)在指数期达到最大值(21.85 mg/L). 利用EEM(三维荧光)对四尾栅藻的EOMs和IOMs进行表征发现,ρ(TP)的改变会对四尾栅藻IOMs和EOMs中不同物质的峰强产生影响;同时,随着藻细胞的生长,ρ(TP)也会影响四尾栅藻EOMs中的物质组成.      

高藻水臭氧预氧化过程有机物转化及消毒副产物生成势

研究了高藻水预氧化处理过程中,不同臭氧氧化程度及不同pH值条件下,藻类有机物释放与转化规律以及氯化消毒副产物(DBPs)的生成特性.结果表明,臭氧投加量为28.92 mg·L-1时藻去除率达36%.随着臭氧投加量的增加,藻的去除率进一步增加,类腐殖酸先增加后持续减少,溶解性微生物代谢产物、类富里酸和类芳香蛋白物质持续减少;低投加量的臭氧对二氯乙腈(DCAN)、三氯乙腈(TCAN)生成势有明显的控制作用,但会增加三氯硝基甲烷(TCNM)以及1,1,1-三氯丙酮(1,1,1-TCP)前体物,随臭氧投加量增大,DBPs生成势显著增大.酸性条件下臭氧对藻的去除效果最好,UV254以及总有机碳(DOC)均随pH的增大有所上升,但变化较小;臭氧氧化可降解溶解性微生物代谢产物,降解效果受pH影响较小,类腐殖酸有机物随pH值增大而减少;DCAN、TCAN生成势随pH增大有所降低,TCNM生成势在pH=10条件下最高,1,1,1-TCP生成势在pH=7条件下最高.     

水中藻类溶解性有机物特性研究

试验从分子量分布、三维荧光光谱和亲疏水特性3个方面研究了水中藻类(鱼腥藻、小球藻和小环藻)溶解性有机物(AOM)的特性。结果表明,3种AOM有机物在分子量分布上大分子和中小分子有机物各占一定比例。鱼腥藻AOM和小球藻AOM均表现出大分子和小分子有机物所占比例较大,中等分子有机物所占比例较小;小环藻AOM所含大分子有机物的比例相对较小,中小分子有机物是小环藻AOM的主要组成部分。荧光光谱分析得出,鱼腥藻AOM的大分子有机物主要是大分子蛋白类和腐植酸类有机物,中小分子有机物主要是小分子糖类和大分子疏水性腐殖类有机物的分解产物。小球藻AOM大分子有机物以大分子蛋白质类为主,中小分子有机物含有较多的蛋白类和腐殖酸类物质。而小环藻AOM大分子有机物主要以大分子腐殖酸类为主,中小分子有机物腐殖酸类物质含量也较多。亲疏水性分析表明,藻类AOM呈现较强的亲水特性,其SUVA值较低,主要是由亲水性的多糖和蛋白类有机物组成,疏水性腐殖类有机物质的含量相对较少。     

预压力混凝沉淀除藻工艺中DOC变化规律研究

为了探讨预压力混凝沉淀除藻工艺是否会使藻细胞破裂,导致水中溶解性有机物(DOC)增加,进而优化压力作用方式,得到安全、高效的预压力除藻工艺,实验研究了预压力、预氧化技术处理含藻水时DOC的变化,以及水中相对分子质量分布,并研究了混凝沉淀后藻类、浊度、DOC的去除效果.结果表明,在0.5~0.8 MPa压力作用后,水中DOC没有增加,反而减少,且有机物相对分子质量减小.而高锰酸钾与次氯酸钠预氧化均会导致DOC增加,相对分子质量分布没有明显变化.预压力混凝沉淀后藻类去除率96.23%;DOC去除率29.11%,高于预氧化混凝沉淀工艺10%~30%.     

塑料管材输配水过程中有机物释放规律研究

研究了目前给水管网中常用的3种塑料管材,未增塑聚氯乙烯(uPVC),聚乙烯(PE)和无规共聚聚丙烯(PPR)管在输配水过程中有机物的释放规律.通过静态管段实验模拟给水管网中不同输配水状态,选取总有机碳(TOC)为综合评价指标,考察了不同塑料管材中有机物随时间的迁移释放特性,并分析了管材有机物释放对管网水中余氯消耗的影响.随着管材输配水次数的增加,uPVC管释放至水中的TOC浓度和TOC释放速率分别在0.03mg/L和0.04μg/(d?cm2)以下,而PE管和PPR管在输配水过程中TOC的释放浓度和释放速率在初期最大[PE: 0.19mg/L,0.25μg/(d?cm2);PPR:0.07mg/L,0.09μg/(d?cm2)],且后期递减并趋于平稳[PE:0.03~0.08mg/L,0.05~0.10μg/(d?cm2);PPR:0.01~0.03mg/L, 0.01~0.04μg/(d?cm2)].随着水力停留时间的增加,不同管材释放的有机物浓度持续升高.不同管材有机物的释放能力排序为:PE>PPR>uPVC.各管材的有机物释放特性直接影响管网水的余氯消耗特性,且管材的有机物释放量越多,管网水的余氯消耗越快.PE管的使用易引起水体有机污染问题.本研究明确了3种常用塑料管材的有机物释放规律,将进一步为与塑料管材安全性能评价相关的国家标准的修订提供理论依据.     

垃圾填埋场渗滤液有机物成分分析及蒸发处理研究

采用GC-MS对某垃圾填埋场渗滤液中的有机物成分进行检测分析。结果表明:渗滤液中至少含有50种有机污染物,相对含量最高的有机污染物是尼古丁和3-甲酚。研究真空度、蒸发温度和pH值对渗滤液蒸发过程中冷凝液的COD、TOC和氨氮浓度的影响,并对冷凝液进行有机物成分检测,结果表明:蒸发速率和冷凝液COD值均随蒸发温度和真空度的增加呈增加趋势,蒸发温度和真空度对冷凝液TOC值影响不大,随蒸发温度升高冷凝液中氨氮含量整体呈下降趋势;在蒸发温度60～120℃范围内,冷凝液的有机物成分以烷烃类有机物和尼古丁为主;烷烃类有机物的析出仅与蒸发温度有关,苯酚类有机物的析出与真空度和蒸发温度均有关;在酸性条件下蒸发冷凝液的COD值和TOC值均远大于在中性和碱性条件下的数值,但氨氮含量相反;酸性条件下冷凝液有机物成分主要为有机酸和烷烃类有机物。     

HPSEC-UV-TOC联用技术测定有机物相对分子质量分布

采用在线高效凝胶色谱仪(HPSEC)和紫外检测器以及TOC检测仪联用测定有机物相对分子质量分布.通过同步测定样品中大范围相对分子质量区间的UV254和TOC,更深入和准确地了解有机物的结构特性,特别是一些不含共轭双键和芳香度的有机物.结果显示,TOC检测仪能够简单快捷地检测出水中所有有机物的相对分子质量分布,包括蔗糖、海藻酸钠等对紫外响应较低的亲水性有机物;样品进样量与TOC响应线性正相关,进样量越大,响应越强;离子强度从0升至0.2mol.L-1,峰面积仅减小1.2%,离子强度对有机物相对分子质量分布测定影响较小;样品pH值在中性或酸性时不影响测定结果,pH值为碱性时,TOC响应异常;采用流动相配定的样品较超纯水配定的样品,相对分子质量分布曲线中干扰峰明显减小,出峰效果更好;该联用技术可以很好地表征湘江原水及其4种亲疏水性组分的相对分子质量分布.     

水网藻(Hydrodicty on reticulatum)对富营养化水样中氮磷去除能力的研究

研究了水网藻在天然水体水样中的生长及对氮磷(N，P)的去除能力，结果表明水网藻在富营养化水库水及重营养化的湖水水样中均生长良好；富营养化水库水(含TN 3.34—5.15mg/L、TP 0.10—0.19mg/L)及重营养化湖水(含TN33.86mg/L、TP 1.939mg/L)经水网藻(1g/L)处理2d、4d、6d后，对氨氮(NH4N)、总氮、总磷去除率均在70%以上.     

紫外辐射对小球藻混凝效果作用途径探讨

针对藻类在常规水处理过程中难以被有效去除的现状,采用紫外辐射对藻类混凝过程进行强化处理.结果表明,随着紫外照射时间的增加,混凝后对藻细胞和浊度的去除均呈先上升后下降的趋势,并在照射50 min时达到最大值.PAC(聚合氯化铝)投加量为5 mg·L~(-1)时,照射样的除藻率和去浊率达到最大,分别比空白样高20.1%和18%左右.pH值在6~9范围内,紫外辐射强化混凝效果的变化较小.溶液pH=8、紫外照射50 min,混凝后的除藻率和去浊率分别达到了93.5%和90.6%.此时,藻细胞Zeta电位最大,同时释放出藻黏液,有利于混凝沉降.而当紫外照射超过60 min后,出现细胞膜破裂,胞内有机物渗出,使得溶液中的有机物浓度急剧上升,Zeta电位开始下降,不利于后续混凝的进行.     

高锰酸钾预氧化强化混凝去除绿藻的研究

以小球藻为对象,研究不同高锰酸钾投加量下小球藻胞外有机物分子量的分布、Zeta电位和胞外有机物浓度变化,并观察细胞结构,探讨预氧化强化混凝的机理.研究发现,当高锰酸钾浓度≤2 mg·L-1时,氧化前后藻液中的有机物组成基本不变,胞外分泌物(EOM)部分被氧化;在预氧化初期,EOM在高锰酸钾诱导下释放,胞外有机物浓度升高;藻的表面电位先下降后上升,藻活性由于高锰酸钾氧化受到抑制,但藻细胞结构保持完整,氧化后生成的MnO2附着在藻细胞表面,增加了藻细胞的比重,有利于后续的混凝沉降除藻.高锰酸钾浓度≥3 mg·L-1时,细胞壁被破坏,藻液中出现大分子的有机物,胞外有机物浓度上升,Zeta电位下降,这些都不利于后续的混凝除藻.结果表明,当高锰酸钾投加量为2 mg·L-1,预氧化1h后,PAC投加量为40 mg.L-1时,除藻效率达到92％,去除效果远好于直接混凝除藻.     

Fouling of nanofiltration membrane by effluent organic matter： Characterization using different organic fractions in wastewater

The UF membrane with molecular weight cutoff (MWCO) ranging from 2 kDa to 100 kDa and XAD-8 resin were employed to identify the characteristic of molecular weight (MW) distribution of wastewater effluent organic matter (EfOM) in terms of TOC and UV254, as well as the amounts of the hydrophilic/hydrophobic organic fractions in different MW ranges. Then, the nanofiltration (NF) membrane fouling experiments were carried out using the above fractionated water to investigate the effect of MW distribution and hydrophilic/hydrophobic characteristics of EfOM on the membrane flux decline using the fractionated water samples above. The experimental results have shown that 45.61% of the total organics belongs to the low MW one, among which the percentage of the hydrophilic organics with low MW (less than 2 kDa) was up to 28.07%, while that of the hydrophobic organics was 17.54%. In particular, the hydrophilic fraction was found to be the most abundant fraction in the effluents. MW distribution has a significant effect on the membrane fouling. When the MW was less than 30 kDa, the lower the MW, the larger was the specific flux decline, while in the case of MW higher than 30 kDa, the higher the MW, the larger was the specific flux decline, and the decline degree of low MW organics was larger than the high MW one. With the same MW distribution range, specific flux decline of the hydrophilic organic was considerably slower than that of the hydrophobic organic, which indicated that the hydrophobic organic fractions dominantly contribute to the flux decline.     

Fouling of nanofiltration membrane by e uent organic matter: Characterization using di erent organic fractions in wastewater

The UF membrane with molecular weight cuto (MWCO) ranging from 2 to 100 kDa and XAD-8 resin were employed to identify the characteristic of molecular weight (MW) distribution of wastewater e uent organic matter (EfOM) in terms of TOC and UV254, as well as the amounts of the hydrophilic/hydrophobic organic fractions in di erent MW ranges. Then, the nanofiltration (NF) membrane fouling experiments were carried out using the above fractionated water to investigate the e ect of MW distribution and hydrophilic/hydrophobic characteristics of EfOM on the membrane flux decline using the fractionated water samples. The experimental results have shown that 45.61% of the total organics belongs to the low MW one, among which the percentage of the hydrophilic organics with low MW (less than 2 kDa) was up to 28.07%, while that of the hydrophobic organics was 17.54%. In particular, the hydrophilic fraction was found to be the most abundant fraction in the e uents. MW distribution has a significant e ect on the membrane fouling. When the MWwas less than 30 kDa, the lower the MW, the larger was the specific flux decline, while in the case of MW higher than 30 kDa, the higher the MW, the larger was the specific flux decline, and the decline degree of low MW organics was larger than the high MW one. With the same MW distribution range, specific flux decline of the hydrophilic organic was considerably slower than that of the hydrophobic organic, which indicated that the hydrophobic organic fractions dominantly contribute to the flux decline.     

Characterization of refuse landfill leachates of three di erent stages in landfill stabilization process

Landfill leachates with di erent ages (mature leachate, 11 years; semi-mature leachate, 5 years; fresh leachate, under operation) were collected from Laogang Refuse Landfill, Shanghai to characterize the colloid size distribution and variations of leachate. These leachates were separated using micro-filtration and ultra-filtration into specific size fractions, i.e., suspended particles (SP) (> 1.2 m), coarse colloids (CC) (1.2–0.45 m), fine colloids (FC) (0.45 m, 5 kDa/1 kDa molecular weight (MW)), and dissolved organic matters (DM, < 5 kDa/1 kDa MW). The specific colloids in each size fraction were quantified and characterized through chemical oxygen demands (COD), total solid (TS), pH, NH4 +-N, total organic carbon (TOC) and fixed solid (FS). It was found that COD, NH4 +-N and TS in leachate decreased significantly over ages, while pH increased. The dissolved fractions (< 5 kDa/1 kDa) dominated (over 50%) in three leachates in terms of COD, and the organic matter content in dissolved fraction of leachates decreased and the inorganic matter increased as the disposal time extended, with the TOC/COD ratio 30%–7%. Dissolved fractions decreased from 82% to 40% in terms of TOC as the disposal time extended, suggested that the organic matter remained in leachate would form into middle molecular weight substances during the degradation process.     

Enhancing the total organic carbon measurement efficiency for water samples containing suspended solids using alkaline and ultrasonic pretreatment methods

In this study,we investigated the effect of sample pretreatments(ultrasonication and alkaline extraction) on total organic carbon(TOC) measurements for water samples containing suspended solids(SS) of four different origins(algae,soil,sewage sludge,and leaf litter) to more clearly assess the impact of particulate organic carbon(POC) in water.The effects each of ultrasonication(power,pulse,etc.) and alkaline extraction condition(concentration,time,etc.) on the TOC recovery and precision were investigated,and the results were compared with those of a new sample pre treatment method combining both methods.Alkaline treatment(0.01 mol/L NaOH) showed higher precision than ultrasonication(100/5 on/off pulse),and notably,the differences among the measured TOC values in samples of different origins were also further reduced in the alkaline treatment.This suggests that the ultrasonic pretreatment results can be mainly attributed to the increase in POC recovery through particle size reduction,whereas the alkaline treatment results are achieved through the enhancement of POC solubilization.It is also particularly noteworthy that a higher TOC recovery of 87.6%±7.4% with a higher precision of 8.4%could be obtained using the combined method,compared to each treatment(ultrasonic:TOC recovery 34.7%,relative standard deviation 63.1%;alkaline:49.6% and 23.0%,respectively).Thus,simultaneous pretreatment with ultrasonication and alkaline extraction is expected to increase the oxidation rate of organic matter and the homogeneity of the samples,minimizing the loss of POC measurement values,and thereby improving the reliability of the TOC measurements of water samples containing SS.     

臭氧-紫外预处理对高有机物原水混凝效果的影响

以腐殖酸为模型污染物,分别考察了臭氧氧化、紫外照射及臭氧-紫外联合预处理过程对高有机物原水混凝性能的影响.结果表明,3种预处理方式均对原水中的溶解性腐殖酸具有明显的矿化作用.紫外及臭氧-紫外联合预处理还对后续的混凝过程具有强化作用.随着臭氧投量的增加和紫外照射时间的延长,混凝过滤出水的TOC和浊度呈明显下降趋势.当臭氧浓度(O3/C)达到9.0 mg/mg时,预处理对腐殖酸的去除率可以达到47%,过滤出水TOC含量为3.5 mg/L,浊度为2.6 NTU;紫外光照射3 h可去除原水中52%的溶解性有机物,其出水TOC为2.0 mg/L,浊度低于1.0 NTU.臭氧-紫外联合预处理后的混凝效果要明显优于二者单独作用的系统.在联合预处理系统中,当预臭氧浓度(O3/C)为1.0 mg/mg紫外照射时间为1 h时,过滤出水TOC为2.6 mg/L,且浊度低于1.0 NTU.不同预处理条件下的矿化作用主要是通过.OH实现的,同时.OH还对溶解性腐殖酸的团聚结构产生破坏作用,使其稳定性降低,从而促进了混凝过程对有机物的去除.     

蛋白类有机质在水厂各处理单元中的去除特性

蛋白类有机质（pDOM）广泛存在于天然水体中,是非常重要的含氮消毒副产物前驱物.近年来,其在饮用水处理过程中的去除和控制逐渐受到广泛关注.本文以两个实际饮用水厂不同工段进出水为研究对象,通过高效尺寸排阻色谱联合紫外、荧光及有机碳检测器的分析方法,对水样中pDOM不同分子量组分的去除特性及变化规律进行探究.同时,选取混凝和活性炭吸附两种水处理技术进行小试实验,进一步探究pDOM组分在常规处理单元的去除规律.结果表明,pDOM在不同水处理单元具有不同的去除特性,预氧化能够有效分解类色氨酸和类酪氨酸型高分子组分,且随着氧化剂氧化作用增强,更多的高分子组分被氧化分解为小分子,但一些分子量较大的脂肪族蛋白等组分则难以被氧化分解;混凝沉淀对高分子组分有良好去除效果,尤其是类色氨酸型pDOM,且混凝过程可能存在一定量pDOM组分的释放,多为小分子及疏水性组分;活性炭过滤易去除分子量较低及疏水性较强的组分,但炭砂滤池长期运行可能存在微生物滋生,因此造成出水部分pDOM组分浓度增加;紫外消毒在一定程度上提高了小分子组分的去除效率.由于实际水厂运行过程中水质条件变化复杂且微生物活动不可控,故各处理单元对pDOM的去除并没有展现协同作用.且相比于腐殖质类物质,pDOM组分受水质变化影响较大,从整体工艺流程来看,去除效果有限.因此在水厂未来运行中,应加强进出水中pDOM各组分的监测,及时对各处理单元运行参数进行调整,同时考虑结合臭氧-生物活性炭工艺,或增加纳滤等膜过滤单元,严格控制pDOM组分的去除.