典型难生物降解污水的毒性鉴别和高效处理技术研究
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摘要
随着人类生活水平的提高和现代工业的发展，排放到环境中的污染物的种类和数量也日益增加。其中，尤为令人担忧的就是难生物降解的污水，这些污水通常具有毒性大，易生物积累等特点，如不加以妥善处理，其必然对人类的生存环境造成巨大影响。
本论文主要研究了三种典型的难生物降解污水：化工废水，老龄垃圾渗滤液和目前引起广泛关注的药品与个人护理用品污水的毒性鉴别和相关处理措施，具体可分为如下3个部分：
1.以老龄化工废水为例，创新的采用小麦根伸长抑制毒性试验和传统的大型蚤急性毒性试验，鉴别出了化工废水中的主要有毒污染物为Cl-和重金属Cu~(2+)，Pb~(2+)和Zn~(2+)。根据该废水的高盐度特点，研究发现附近泰达污水处理厂的连续间歇曝气(DAT-IAT)工艺对生活污水与化工废水混合污水的化学需氧量(COD)，总磷(TP)和总氮(TN)的去除率可达85.08%，89.29%和96.54%，处理后的污水毒性可降低到0.5TU。证明对化工废水和生活污水共处理是一种可行且成本较低的方法。
2.从常规污染物去除和生态毒性削减两方面，研究了混凝吸附联用法对垃圾渗滤液的处理效果，结果表明：聚合硫酸铁(PFS)对老龄垃圾渗滤液的处理效果最佳，在投加量为0.3gFe~(3+)/L，pH为5.5时，COD去除率为70%，浊度去除率为99%，悬浮固体(SS)去除率为93%，毒性去除率为74%。以PFS处理后的垃圾渗滤液为活性炭吸附法的进水，在活性炭剂量为10g/L，反应时间为90min时，残留COD约为407mg/L。混凝吸附联用法总的COD去除率可达86%，毒性削减率可达78%。
3.研究了Fenton法和类Fenton法对污水处理厂出水中常检测到的药品与个人护理用品(PPCPs)：对乙酰氨基芬，安替洛尔，双氯芬酸，美托洛尔，狄兰汀，已酮可可碱，咖啡因，碘普罗胺，氟西汀，甲氧卞氨嘧啶，普奈洛尔，磺胺甲恶唑，布洛芬，奈普生，二甲苯氧庚酸，避蚊胺，立痛定，氧苯酮，双酚A和阿特拉津的降解效率优化和降解动力学，以及在Fenton和类Fenton反应过程中，二级出水中有机物(EfOM)的迁移转化规律和氧化副产物，并探讨了EfOM的紫外光谱参数和荧光光谱参数与PPCPs降解率的关系，具体结论如下：
(1)综合考虑PPCPs降解效率和处理成本，Fenton法降解PPCPs的较优条件为：H_2O_2/Fe~(2+)摩尔比2.5，Fe~(2+)剂量为10mg/L，pH为3，反应时间为30min。类Fenton法降解PPCPs的较优条件为：H_2O_2/Fe~(3+)摩尔比2.5，Fe~(3+)剂量为10mg/L，pH为3，反应时间为120min。在污水总溶解有机碳(DOC)为8.287mg/L和较优条件下，PPCPs的去除率都可达到90%以上。
(2) Fenton对PPCPs的降解动力学符合联合一级反应动力学；类Fenton法对双氯酚酸，氟西汀和二甲苯氧庚酸的降解符合二级反应动力学；对其余PPCPs的降解符合一级反应动力学。
(3)采用竞争动力学模型计算了Fenton和类Fenton反应中OH氧化PPCPs的反应速率常数kPPCPs-OH，除了由于反应条件差异造成避蚊胺，甲氧卞氨嘧啶，布洛芬，双氯芬酸，咖啡因和二甲苯氧庚酸与报道值有偏差外，其余都和报道值接近，这证明了在Fenton和类Fenton反应中，PPCPs本质上是被OH氧化降解，而不是被混凝作用去除的。
(4) Fenton法和类Fenton法通过OH氧化和混凝共同作用对DOC的去除率最大可达30%和38%，分子排阻色谱(SEC)数据表明，Fenton法和类Fenton法优先去除高表观分子量的有机物，并且可以将大分子量有机物氧化分解为小分子量有机物。
(5) Fenton法和类Fenton法氧化EfOM的产物为甲酸、乙酸、草酸和浓度相对较低的甲醛、乙醛、丙醛和乙醇醛，其中，在H_2O_2/Fe~(2+)摩尔比2.5，Fe~(2+)剂量为20mg/L，pH为3，反应时间为30min的条件下，Fenton法中羧酸类有机物和醛类有机物的产率分别为11.62%和1.01%；在H_2O_2/Fe~(3+)摩尔比2.5，Fe~(3+)剂量为20mg/L，pH为3，反应时间为120min的条件下，类Fenton法中羧酸类有机物和醛类有机物的产率分别为13.2%和1.34%。
(6)随着Fenton和类Fenton试剂剂量和反应时间的增加，污水EfOM的紫外光谱逐渐降低。EfOM的差值吸光度光谱在波长265-275nm范围内有一个较明显的峰。这个峰和UV254，SUVA254值的降低可能表明Fenton法和类Fenton法会优先去除芳香族有机物。
污水的紫外吸光光谱容易受无机离子的影响，在消除干扰的情况下，对于同一种废水，在Fenton反应或类Fenton反应中，波长254nm处的吸光度的相对变化(A_(254)/A_(254)~0)与PPCPs降解，OH暴露和羧酸浓度都具有一致的关系，且该关系不受时间或剂量条件影响，说明A_(254)/A_(254)~0可以用来监测Fenton高级氧化过程中的PPCPs的降解和EfOM氧化程度。
(7)根据污水EfOM的三维荧光光谱，可将EfOM分为分为蛋白质类有机物/可溶性微生物代谢产物，腐殖酸类有机物和富里酸类有机物三种，其中，蛋白质类有机物/可溶性微生物代谢产物最容易被Fenton法和类Fenton法去除；腐殖酸类有机物的区域总荧光强度相对变化(TF0腐殖酸类/TF腐殖酸类)和峰荧光强度相对变化(PF腐殖酸类/PF0腐殖酸类)与PPCPs降解，OH暴露和羧酸浓度变化存在一致的关系，且该关系不受Fenton反应或类Fenton反应或反应条件影响。因此，该参数可用来监测高级氧化过程中PPCPs的降解和EfOM氧化。
With the improvement of people’s living standard and development of modernindustry, the variety and quantity of the pollutants discharged into the environment iscontinuously increasing. Among them, the non-degradable wastewater attracted moreand more attention. The non-degradable wastewater is characterized by biologicalaccumulation and high toxicity to ecosystem; it may cause severe damage toecosystem and environment without appropriate treatment.
This research mainly studied the treatment methods of three typicalnon-degradable wastewater: chemical industrial wastewater, old landfill leachate andthe secondary effluent with pharmaceutical and personal care products (PPCPs)frequently detected, which attracted widely attention. And this research can beclassified to3parts:
1. Took old chemical industrial wastewater for example, emploied wheat rootelongation inhibition toxicity experiment for the first time and conventional daphniamagna toxicity experiment and identified the major toxic pollutants were Cl-andheavy metal Cu~(2+), Pb~(2+)and Zn~(2+).
Based on the high salinity characterization of the wastewater, co-treatment ofmunicipal wastewater and chemical industrial wastewater by the demand aerationtank-intermittent aeration tank (DAT-IAT) process used in TEDA wastewatertreatment plant was evaluated, and the chemical oxygen demand (COD), totalphosphorus (TP) and total nitrogen (TN) removal efficiency of the mixed wastetwatercan reach up to85.08%,89.29%and96.54%, the toxicity unit of the wastewater aftertreatment was0.5TU. This result demonstrated that co-treatment of municipalwastewater and chemical industrial wastewater is a feasible and cost effectivemethod.
2. Based on the conventional pollutants removal and toxicity reduction, thetreatment efficiency of old landfill leachate by the combined process of coagulationand powder active carbon adsorption was evaluated. Polyferric sulfate (PFS)(dosage 0.3g Fe~(3+)/L) showed the best treatment efficiency, with the removal of COD, turbidity,solid suspension (SS) and toxicity up to70%,99%,93%and74%at pH5.5. UsingPFS coagulated wastewater as the influent of adsorption and after powder activatedcarbon (PAC) adsorption (10g/L) treatment for90min, the residual COD was about407mg/L. The total COD and toxicity removal efficiency of this combined processwas86%and78%, respectively.
3. Optimized the degradation efficiency and studied the degradation kinetics ofPPCPs frequently detected in secondary wastewater, including acetaminophen,atenolol, diclofenac, metoprolol, dilantin, pentoxifylline, caffeine, iopromide,fluoxetine, trimethoprim, propranolol, sulfamethoxazole, ibuprofen, naproxen,gemfibrozil, DEET, carbamazepine, oxybenzone, bisphenol-A, atrazine, by Fentonand Fenton-like process; Transformation and oxidation byproducts of effluent organicmatter (EfOM) in Fenton and Fenton-like process was also quantified, and thefeasibility of absorbance and fluorescence surrogates used to predict PPCPsdegradation and EfOM oxidation was also explored, the conclusions are as following:
(1) Considering the degradation efficiency of PPCPs and treatment cost, theoptimal conditions for Fenton process were: molar ratio of H_2O_2/Fe~(2+)of2.5, Fe~(2+)dosage of10mg/L, pH3, reaction time of30min; the optimal conditions forFenton-like process were: molar ratio of H_2O_2/Fe~(3+)of2.5, Fe~(3+)dosage of10mg/L,pH3, reaction time of120min. Under these conditions and the initial dissolvedorganic matter (DOC) of8.287mg/L, the removal efficiency of PPCPs can reach upto90%.
(2) The degradation of PPCPs by Fenton process follows combined first orderreaction kinetic; the degradation of diclofenac, fluoxetine and gemfibrozil byFenton-like process follows second order reaction kinetic, and the degradation ofother PPCPs by Fenton-like process follows first order reaction.
(3) The reaction constants of PPCPs and OH (kPPCPs-OH) calculated based on thecompetition kinetic model were close with the previously reported values, except thatthe values for DEET, trimethoprim, ibuprofen, diclofenac, caffeine and gemfibrozilwere a little different from reported values because of the different reaction condition.This confirmed that PPCPs was removed by OH oxidation during Fenton and Fenton-like reaction other than coagulation effect.
(4) Fenton and Fenton-like reaction caused30%and38%of DOC removal byOH oxidation and coagulation. Size exclusion chromatography (SEC) datademonstrated that Fenton and Fenton-like process preferentially remove highmolecular weight EfOM molecules and break them down into smaller fragments.
(5) The oxidation byproduct of EfOM by Fenton and Fenton-like process wereformate, acetate, oxalate and less prominently, formaldehyde, acetaldehyde,propionaldehyde and glycolaldehyde. The yields of carboxylic acids and aldehydes ascarbon were11.62%and1.01%of the initial DOC by Fenton process under thereaction condition of molar ratio of H_2O_2/Fe~(2+)of2.5, Fe~(2+)dosage of20mg/L, pH3,reaction time of30min; The yields of carboxylic acids and aldehydes as carbon were13.2%and1.34%of the initial DOC by Fenton-like process under the reactioncondition of molar ratio of H_2O_2/Fe~(3+)of2.5, Fe~(3+)dosage of20mg/L, pH3, reactiontime of120min.
(6) The UV absorbance of EfOM decreases with the increase of theFenton/Fenton-like reagent dosage and reaction time. The differential absorbancespectra show a prominent feature at wavelength265-275nm. This feature, and thedecrease of UV254, SUVA254value may demonstrate the preferential removal ofaromatic organic matter.
The UV absorbance spectra were sensitive to the inorganic matter. Aftereliminating the interference, the relative changes of absorbance at254nm (donated as
A_(254)/A_(254)~0) were strongly correlated with PPCPs removal, OH exposure and theconcentration of carboxylic acids irrespective of whether the wastewater was treatedwith Fenton process or Fenton-like process at any Fe doses and treatment times. Thisdemonstrated that A_(254)/A_(254)~0could be used as a surrogate to predict the PPCPsdegradation and EfOM oxidation extent in advanced oxidation processes.
(7) According to the three dimension fluorescence spectra, EfOM can beclassified as protein-like species/soluble microbial products, humic-like species andfulvic-like species. Protein-like species/soluble microbial products are the mostreadily removed part by Fenton and Fenton-like processes.
The total integrated fluorescence relative change (TFhumic/TFhumic0) and peak intensity relative change (PFhumic/PFhumic0) of humic-like species were stronglycorrelated with PPCPs degradation, OH exposure and carboxylic acid concentrationirrespective of whether the wastewater was treated with Fenton process or Fenton-likeprocess at any Fe doses and treatment times. This demonstrated that TFhumic/TFhumic0and PFhumic/PFhumic0could be used as surrogates to predict the PPCPs degradationand EfOM oxidation extent in advanced oxidation process.
本论文主要研究了三种典型的难生物降解污水：化工废水，老龄垃圾渗滤液和目前引起广泛关注的药品与个人护理用品污水的毒性鉴别和相关处理措施，具体可分为如下3个部分：
1.以老龄化工废水为例，创新的采用小麦根伸长抑制毒性试验和传统的大型蚤急性毒性试验，鉴别出了化工废水中的主要有毒污染物为Cl-和重金属Cu~(2+)，Pb~(2+)和Zn~(2+)。根据该废水的高盐度特点，研究发现附近泰达污水处理厂的连续间歇曝气(DAT-IAT)工艺对生活污水与化工废水混合污水的化学需氧量(COD)，总磷(TP)和总氮(TN)的去除率可达85.08%，89.29%和96.54%，处理后的污水毒性可降低到0.5TU。证明对化工废水和生活污水共处理是一种可行且成本较低的方法。
2.从常规污染物去除和生态毒性削减两方面，研究了混凝吸附联用法对垃圾渗滤液的处理效果，结果表明：聚合硫酸铁(PFS)对老龄垃圾渗滤液的处理效果最佳，在投加量为0.3gFe~(3+)/L，pH为5.5时，COD去除率为70%，浊度去除率为99%，悬浮固体(SS)去除率为93%，毒性去除率为74%。以PFS处理后的垃圾渗滤液为活性炭吸附法的进水，在活性炭剂量为10g/L，反应时间为90min时，残留COD约为407mg/L。混凝吸附联用法总的COD去除率可达86%，毒性削减率可达78%。
3.研究了Fenton法和类Fenton法对污水处理厂出水中常检测到的药品与个人护理用品(PPCPs)：对乙酰氨基芬，安替洛尔，双氯芬酸，美托洛尔，狄兰汀，已酮可可碱，咖啡因，碘普罗胺，氟西汀，甲氧卞氨嘧啶，普奈洛尔，磺胺甲恶唑，布洛芬，奈普生，二甲苯氧庚酸，避蚊胺，立痛定，氧苯酮，双酚A和阿特拉津的降解效率优化和降解动力学，以及在Fenton和类Fenton反应过程中，二级出水中有机物(EfOM)的迁移转化规律和氧化副产物，并探讨了EfOM的紫外光谱参数和荧光光谱参数与PPCPs降解率的关系，具体结论如下：
(1)综合考虑PPCPs降解效率和处理成本，Fenton法降解PPCPs的较优条件为：H_2O_2/Fe~(2+)摩尔比2.5，Fe~(2+)剂量为10mg/L，pH为3，反应时间为30min。类Fenton法降解PPCPs的较优条件为：H_2O_2/Fe~(3+)摩尔比2.5，Fe~(3+)剂量为10mg/L，pH为3，反应时间为120min。在污水总溶解有机碳(DOC)为8.287mg/L和较优条件下，PPCPs的去除率都可达到90%以上。
(2) Fenton对PPCPs的降解动力学符合联合一级反应动力学；类Fenton法对双氯酚酸，氟西汀和二甲苯氧庚酸的降解符合二级反应动力学；对其余PPCPs的降解符合一级反应动力学。
(3)采用竞争动力学模型计算了Fenton和类Fenton反应中OH氧化PPCPs的反应速率常数kPPCPs-OH，除了由于反应条件差异造成避蚊胺，甲氧卞氨嘧啶，布洛芬，双氯芬酸，咖啡因和二甲苯氧庚酸与报道值有偏差外，其余都和报道值接近，这证明了在Fenton和类Fenton反应中，PPCPs本质上是被OH氧化降解，而不是被混凝作用去除的。
(4) Fenton法和类Fenton法通过OH氧化和混凝共同作用对DOC的去除率最大可达30%和38%，分子排阻色谱(SEC)数据表明，Fenton法和类Fenton法优先去除高表观分子量的有机物，并且可以将大分子量有机物氧化分解为小分子量有机物。
(5) Fenton法和类Fenton法氧化EfOM的产物为甲酸、乙酸、草酸和浓度相对较低的甲醛、乙醛、丙醛和乙醇醛，其中，在H_2O_2/Fe~(2+)摩尔比2.5，Fe~(2+)剂量为20mg/L，pH为3，反应时间为30min的条件下，Fenton法中羧酸类有机物和醛类有机物的产率分别为11.62%和1.01%；在H_2O_2/Fe~(3+)摩尔比2.5，Fe~(3+)剂量为20mg/L，pH为3，反应时间为120min的条件下，类Fenton法中羧酸类有机物和醛类有机物的产率分别为13.2%和1.34%。
(6)随着Fenton和类Fenton试剂剂量和反应时间的增加，污水EfOM的紫外光谱逐渐降低。EfOM的差值吸光度光谱在波长265-275nm范围内有一个较明显的峰。这个峰和UV254，SUVA254值的降低可能表明Fenton法和类Fenton法会优先去除芳香族有机物。
污水的紫外吸光光谱容易受无机离子的影响，在消除干扰的情况下，对于同一种废水，在Fenton反应或类Fenton反应中，波长254nm处的吸光度的相对变化(A_(254)/A_(254)~0)与PPCPs降解，OH暴露和羧酸浓度都具有一致的关系，且该关系不受时间或剂量条件影响，说明A_(254)/A_(254)~0可以用来监测Fenton高级氧化过程中的PPCPs的降解和EfOM氧化程度。
(7)根据污水EfOM的三维荧光光谱，可将EfOM分为分为蛋白质类有机物/可溶性微生物代谢产物，腐殖酸类有机物和富里酸类有机物三种，其中，蛋白质类有机物/可溶性微生物代谢产物最容易被Fenton法和类Fenton法去除；腐殖酸类有机物的区域总荧光强度相对变化(TF0腐殖酸类/TF腐殖酸类)和峰荧光强度相对变化(PF腐殖酸类/PF0腐殖酸类)与PPCPs降解，OH暴露和羧酸浓度变化存在一致的关系，且该关系不受Fenton反应或类Fenton反应或反应条件影响。因此，该参数可用来监测高级氧化过程中PPCPs的降解和EfOM氧化。
With the improvement of people’s living standard and development of modernindustry, the variety and quantity of the pollutants discharged into the environment iscontinuously increasing. Among them, the non-degradable wastewater attracted moreand more attention. The non-degradable wastewater is characterized by biologicalaccumulation and high toxicity to ecosystem; it may cause severe damage toecosystem and environment without appropriate treatment.
This research mainly studied the treatment methods of three typicalnon-degradable wastewater: chemical industrial wastewater, old landfill leachate andthe secondary effluent with pharmaceutical and personal care products (PPCPs)frequently detected, which attracted widely attention. And this research can beclassified to3parts:
1. Took old chemical industrial wastewater for example, emploied wheat rootelongation inhibition toxicity experiment for the first time and conventional daphniamagna toxicity experiment and identified the major toxic pollutants were Cl-andheavy metal Cu~(2+), Pb~(2+)and Zn~(2+).
Based on the high salinity characterization of the wastewater, co-treatment ofmunicipal wastewater and chemical industrial wastewater by the demand aerationtank-intermittent aeration tank (DAT-IAT) process used in TEDA wastewatertreatment plant was evaluated, and the chemical oxygen demand (COD), totalphosphorus (TP) and total nitrogen (TN) removal efficiency of the mixed wastetwatercan reach up to85.08%,89.29%and96.54%, the toxicity unit of the wastewater aftertreatment was0.5TU. This result demonstrated that co-treatment of municipalwastewater and chemical industrial wastewater is a feasible and cost effectivemethod.
2. Based on the conventional pollutants removal and toxicity reduction, thetreatment efficiency of old landfill leachate by the combined process of coagulationand powder active carbon adsorption was evaluated. Polyferric sulfate (PFS)(dosage 0.3g Fe~(3+)/L) showed the best treatment efficiency, with the removal of COD, turbidity,solid suspension (SS) and toxicity up to70%,99%,93%and74%at pH5.5. UsingPFS coagulated wastewater as the influent of adsorption and after powder activatedcarbon (PAC) adsorption (10g/L) treatment for90min, the residual COD was about407mg/L. The total COD and toxicity removal efficiency of this combined processwas86%and78%, respectively.
3. Optimized the degradation efficiency and studied the degradation kinetics ofPPCPs frequently detected in secondary wastewater, including acetaminophen,atenolol, diclofenac, metoprolol, dilantin, pentoxifylline, caffeine, iopromide,fluoxetine, trimethoprim, propranolol, sulfamethoxazole, ibuprofen, naproxen,gemfibrozil, DEET, carbamazepine, oxybenzone, bisphenol-A, atrazine, by Fentonand Fenton-like process; Transformation and oxidation byproducts of effluent organicmatter (EfOM) in Fenton and Fenton-like process was also quantified, and thefeasibility of absorbance and fluorescence surrogates used to predict PPCPsdegradation and EfOM oxidation was also explored, the conclusions are as following:
(1) Considering the degradation efficiency of PPCPs and treatment cost, theoptimal conditions for Fenton process were: molar ratio of H_2O_2/Fe~(2+)of2.5, Fe~(2+)dosage of10mg/L, pH3, reaction time of30min; the optimal conditions forFenton-like process were: molar ratio of H_2O_2/Fe~(3+)of2.5, Fe~(3+)dosage of10mg/L,pH3, reaction time of120min. Under these conditions and the initial dissolvedorganic matter (DOC) of8.287mg/L, the removal efficiency of PPCPs can reach upto90%.
(2) The degradation of PPCPs by Fenton process follows combined first orderreaction kinetic; the degradation of diclofenac, fluoxetine and gemfibrozil byFenton-like process follows second order reaction kinetic, and the degradation ofother PPCPs by Fenton-like process follows first order reaction.
(3) The reaction constants of PPCPs and OH (kPPCPs-OH) calculated based on thecompetition kinetic model were close with the previously reported values, except thatthe values for DEET, trimethoprim, ibuprofen, diclofenac, caffeine and gemfibrozilwere a little different from reported values because of the different reaction condition.This confirmed that PPCPs was removed by OH oxidation during Fenton and Fenton-like reaction other than coagulation effect.
(4) Fenton and Fenton-like reaction caused30%and38%of DOC removal byOH oxidation and coagulation. Size exclusion chromatography (SEC) datademonstrated that Fenton and Fenton-like process preferentially remove highmolecular weight EfOM molecules and break them down into smaller fragments.
(5) The oxidation byproduct of EfOM by Fenton and Fenton-like process wereformate, acetate, oxalate and less prominently, formaldehyde, acetaldehyde,propionaldehyde and glycolaldehyde. The yields of carboxylic acids and aldehydes ascarbon were11.62%and1.01%of the initial DOC by Fenton process under thereaction condition of molar ratio of H_2O_2/Fe~(2+)of2.5, Fe~(2+)dosage of20mg/L, pH3,reaction time of30min; The yields of carboxylic acids and aldehydes as carbon were13.2%and1.34%of the initial DOC by Fenton-like process under the reactioncondition of molar ratio of H_2O_2/Fe~(3+)of2.5, Fe~(3+)dosage of20mg/L, pH3, reactiontime of120min.
(6) The UV absorbance of EfOM decreases with the increase of theFenton/Fenton-like reagent dosage and reaction time. The differential absorbancespectra show a prominent feature at wavelength265-275nm. This feature, and thedecrease of UV254, SUVA254value may demonstrate the preferential removal ofaromatic organic matter.
The UV absorbance spectra were sensitive to the inorganic matter. Aftereliminating the interference, the relative changes of absorbance at254nm (donated as
A_(254)/A_(254)~0) were strongly correlated with PPCPs removal, OH exposure and theconcentration of carboxylic acids irrespective of whether the wastewater was treatedwith Fenton process or Fenton-like process at any Fe doses and treatment times. Thisdemonstrated that A_(254)/A_(254)~0could be used as a surrogate to predict the PPCPsdegradation and EfOM oxidation extent in advanced oxidation processes.
(7) According to the three dimension fluorescence spectra, EfOM can beclassified as protein-like species/soluble microbial products, humic-like species andfulvic-like species. Protein-like species/soluble microbial products are the mostreadily removed part by Fenton and Fenton-like processes.
The total integrated fluorescence relative change (TFhumic/TFhumic0) and peak intensity relative change (PFhumic/PFhumic0) of humic-like species were stronglycorrelated with PPCPs degradation, OH exposure and carboxylic acid concentrationirrespective of whether the wastewater was treated with Fenton process or Fenton-likeprocess at any Fe doses and treatment times. This demonstrated that TFhumic/TFhumic0and PFhumic/PFhumic0could be used as surrogates to predict the PPCPs degradationand EfOM oxidation extent in advanced oxidation process.
引文
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