Effect of humate on biological treatment of wastewater containing heavy metals

This paper presents results of investigations on the influence of humic substances (humate, HS) on the biological treatment of wastewater containing heavy metals (Cr, Cu, Fe, Mn, Ni, and Zn). Respirometric studies indicated that the investigated system complied with the Haldane model for inhibitory wastes. Chemical analyses showed that, while the soluble COD removal was high (82%), only 7% of ammonia was oxidized to nitrate. An addition of HS (500 mg L⁻¹) mitigated the inhibitory effect of the wastewater on the returned activated sludge. The system with HS complied with the Monod model for non-inhibitory wastes, and the removal of ammonia and metals was 99% and over 90%, respectively. It is suggested that an application of HS could be beneficial for treatment plants receiving wastewater streams containing heavy metals.     

氧化/吸附/混凝协同工艺处理焦化废水生物处理出水的过程及效果分析

针对焦化废水生物处理出水中继续存在多种有机污染物而影响达标及存在安全隐患的现状,基于废水中有机物的物理化学特性,构建了氧化/吸附/混凝的深度处理过程。在NaC lO投加量为40 mg/L,AC投加量为500 mg/L,PFS投加量为300 mg/L,反应时间为0.5 h,以及pH为7.0的最佳条件下,先氧化后吸附混凝,该过程可以实现COD去除率为75%以上,色度去除率80%以上,处理后的水样其COD值与色度值分别下降到60 mg/L及20倍以下;通过GC/MS方法分析处理前后水样中的有机物组分,发现水样中大部分单环芳香族化合物和多环芳香族化合物,部分含氮杂环化学物、有机氯化物以及溴化物被去除,但是,长链烷烃和部分芳香烃继续保留。研究结果证明了氧化/吸附/混凝协同工艺的效果与焦化废水生物出水中有机污染物的分子结构、存在形态形成构效关系,催化作用与氧化作用的协同是获得高效去除率的关键。     

Removal of highly polar micropollutants from wastewater by powdered activated carbon

Due to concerns about ecotoxicological effects of pharmaceuticals and other micropollutants released from wastewater treatment plants, activated carbon adsorption is one of the few processes to effectively reduce the concentrations of micropollutants in wastewater. Although aimed mainly at apolar compounds, polar compounds are also simultaneously removed to a certain extent, which has rarely been studied before. In this study, adsorption isotherm and batch kinetic data were collected with two powdered activated carbons (PACs) to assess the removal of the polar pharmaceuticals 5-fluorouracil (5-Fu) and cytarabine (CytR) from ultrapure water and wastewater treatment plant effluent. At pH?7.8, single-solute adsorption isotherm data for the weak acid 5-Fu and the weak base CytR showed that their adsorption capacities were about 1 order of magnitude lower than those of the less polar endocrine disrupting chemicals bisphenol A (BPA) and 17-α-ethinylestradiol (EE2). To remove 90 % of the adsorbate from a single-solute solution 14, 18, 70, and 87 mg?L^?1 of HOK Super is required for EE2, BPA, CytR, and 5-Fu, respectively. Effects of solution pH, ionic strength, temperature, and effluent organic matter (EfOM) on 5-Fu and CytR adsorption were evaluated for one PAC. Among the studied factors, the presence of EfOM had the highest effect, due to a strong competition on 5-Fu and CytR adsorption. Adsorption isotherm and kinetic data and their modeling with a homogeneous surface diffusion model showed that removal percentage in the presence of EfOM was independent on the initial concentration of the ionizable compounds 5-Fu and CytR. These results are similar to neutral organic compounds in the presence of natural organic matter. Overall, results showed that PAC doses sufficient to remove >90 % of apolar adsorbates were able to remove no more than 50 % of the polar adsorbates 5-Fu and CytR and that the contact time is a critical parameter.     

Treatment of coking wastewater by an advanced Fenton oxidation process using iron powder and hydrogen peroxide

In this study the treatment of coking wastewater was investigated by an advanced Fenton oxidation process using iron powder and hydrogen peroxide. Particular attention was paid to the effect of initial pH, dosage of H₂O₂ and to improvement in biodegradation. The results showed that higher COD and total phenol removal rates were achieved with a decrease in initial pH and an increase in H₂O₂ dosage. At an initial pH of less than 6.5 and H₂O₂ concentration of 0.3 M, COD removal reached 44-50% and approximately 95% of total phenol removal was achieved at a reaction time of 1 h. The oxygen uptake rate of the effluent measured at a reaction time of 1 h increased by approximately 65% compared to that of the raw coking wastewater. This indicated that biodegradation of the coking wastewater was significantly improved. Several organic compounds, including bifuran, quinoline, resorcinol and benzofuranol were removed completely as determined by GC-MS analysis. The advanced Fenton oxidation process is an effective pretreatment method for the removal of organic pollutants from coking wastewater. This process increases biodegradation, and may be combined with a classical biological process to achieve effluent of high quality.     

Significance of design and operational variables in chemical phosphorus removal

Batch and continuous experiments using model and real wastewaters were conducted to investigate the effect of metal salt (ferric and alum) addition in wastewater treatment and the corresponding phosphate removal from a design and operational perspective. Key factors expected to influence the phosphorus removal efficiency, such as pH, alkalinity, metal dose, metal type, initial and residual phosphate concentration, mixing, reaction time, age of flocs, and organic content of wastewater, were investigated. The lowest achievable concentration of orthophosphate under optimal conditions (0.01 to 0.05 mg/L) was similar for both aluminum and iron salts, with a broad optimum pH range of 5.0 to 7.0. Thus, in the typical operating range of wastewater treatment plants, pH is not a sensitive indicator of phosphorus removal efficiency. The most significant effect for engineering practice, apart from the metal dose, is that of mixing intensity and slow kinetic removal of phosphorus in contact with the chemical sludge formed. Experiments show that significant savings in chemical cost could be achieved by vigorously mixing the added chemical at the point of dosage and, if conditions allow, providing a longer contact time between the metal hydroxide flocs and the phosphate content of the wastewater. These conditions promoted the achievement of less than 0.1 mg/L residual orthophosphate content, even at lower metal-to-phosphorus molar ratios. These observations are consistent with the surface complexation model presented in a companion paper (Smith et al., 2008).     

啤酒废水常温厌氧消化启动及运行实验

采用自行设计的复合式厌氧反应器在常温下对啤酒废水进行了厌氧发酵产沼气的实验研究,将进水COD控制在5 000 mg/L左右,采取逐步缩短HRT的方法来提高进水有机负荷,结果表明,启动运行41 d之后,产气量上升速度加快,反应器成功启动运行;在稳定运行过程中,随着负荷的升高,产气量呈阶梯式渐次上升,COD去除率保持在90%以上,出水pH值维持在7.0左右,TSS去除率达到60%以上,出水水质较好,说明该反应器具有较好的厌氧消化处理有机废水的能力。     

焦化废水泡沫分离液的Fenton催化氧化预处理

以焦化废水处理过程产生的泡沫分离液为研究对象,对其进行Fenton催化氧化处理实验,考察H₂O₂用量、Fe²⁺浓度、pH和反应时间4个因素对处理效果的影响,并结合GC/MS方法比较处理前后泡沫分离液中有机物的种类及其生物降解性的变化。结果表明,采用［H₂O₂］=100 mmol/L、［Fe²⁺］=100 mg/L、pH=3、反应时间为30 min的Fenton催化氧化反应条件,可以使分离液的COD去除率达到68%以上;经Fenton处理后,分离液的B/C值由0.12提高至0.38,生物降解性明显改善;通过GC/MS的分析,基本明确分离液中含有的有机物主要为酚、胺、腈、酯类有机物及喹啉、吡啶等杂环化合物,大多数属于难降解且生物毒性较强的有机物。针对这些复杂组分共存的泡沫分离液,利用Fenton试剂较强的氧化能力能够将其含有的有毒/难降解有机物转化为低毒或无毒的小分子有机物,为其后续的生物处理创造良好的条件。     

Decolorization and decomposition of organic pollutants for reactive and disperse dyes using electron beam technology: effect of the concentrations of pollutants and irradiation dose

Dyeing wastewater was known to have strong color and refractory organic pollutants. In this study irradiation alone was used for dyes wastewater treatment. This paper studies the effect of the concentrations of pollutants to its removal at various dosages using electron beam technology. Irradiation was effective in removing the highly colored and refractory organic compounds. The color removal for initial concentrations of 255 CU, 520 CU, 990 CU and 1900 CU treated using irradiation at 0.5kGy were 61%, 48%, 28% and 16%, respectively. However, at the dose of 108kGy and higher, the color removal between 87% and 96% were recorded with no apparent trend. COD removal also reported similar trend but at relatively lower removal percentage. The COD removal at 0.5kGy for initial COD concentrations of 57mg/l and 515mg/l were 10% and 0%, respectively. At irradiation dose of 108kGy, the removal for initial COD concentrations of 57mg/l and 515mg/l were 37% and 13%, respectively. This showed that concentrations of pollutants and dose of irradiation applied to remove color and COD were dependent to each other.     

二氧化氯催化氧化处理难降解废水技术的研究

研究了二氧化氯化学氧化体系和二氧化氯催化氧化体系。实验结果表明 :单用二氧化氯化学氧化处理COD为 35 0 0mg/L的酸性大红染料配制废水时 ,最佳反应pH值为 6— 8,氧化剂经济用量为 10 0 0mgClO2 /L废水 ,反应时间为 6 0min ,COD去除率可达 5 0 %左右 ,氧化指数 (COD削减量∶ClO2 投加量 ) =2 .3。当二氧化氯与自制催化剂所组成的催化氧化体系用于对酸性大红染料配制废水的处理时 ,最佳反应pH值为 2左右 ,氧化剂经济用量为 80 0mgClO2 /L废水 ,反应时间为4 5— 6 0min ,COD去除率可达 80 %以上 ,氧化指数 =3.5 ,去除每kgCOD氧化剂费用为 3.7元人民币 ,并且废水的可生化性有很大的提高 ,效果明显优于二氧化氯化学氧化。经济技术评估表明 ,二氧化氯催化氧化法是一种新型高效的处理难降解废水的技术 ,有着广阔的应用前景     

UASB performance for bleached and unbleached kraft pulp synthetic wastewater treatment

This paper presents the performance of two bench scale Upflow Anaerobic Sludge Blanket reactors (UASB) used for the treatment of synthetic substrates that simulate bleached and unbleached cellulose pulp plant wastewaters. The control reactor was fed with diluted black liquor and the treatment reactor with the same substrate plus a mixture of chlorinated organics. The total concentration of the chlorinated compounds was gradually increased from 2.5 mg l-1 to 15.0 mg l-1. The average COD removal efficiency during the last phase of the experiment was 81% in the control reactor and 76% in the treatment reactor. These results indicate the capability of UASB reactors to treat this kind of wastewater and the low impact of the chlorinated organics on COD removal efficiency. The minimum overall chlorinated organics removal efficiency was 71% and the maximum was 99.7%. The experiment indicates that under the conditions used in this research the presence of chlorinated organics does not negatively impact the treatment process.     

Effects of nitrosation on the formation of cyanide in publicly owned treatment works secondary effluent.

Cyanide has been detected in the effluents of some publicly owned treatment works (POTWs) at levels exceeding the influent concentration. The presence of nitrite ion (NO2-) as a common constituent in domestic wastewater effluents may play an important role in the formation of cyanide through reaction with certain kinds of organic compounds, especially aromatic compounds. Laboratory studies with seven organic compounds (aniline. p-toluidine, phenol, 1,2,4-trihydroxybenzene, L-serine, glycine, and benzoic acid) revealed that cyanide can be formed by reaction of nitrite with some of these compounds. The most substantial free cyanide (HCN. CN-) production observed at 25 degrees C was 0.15 mg/L from reaction of 0.01 mM 1.2.4-trihydroxybenze with 5 mg/L nitrite for 72 hours. Substantial free cyanide formation was also observed at pH 2-4 in experiments with POTW effluents when reactive organics and nitrite were both added to wastewater. Formation of cyanide through nitrosation was strongly pH dependent, being most significant at low pH (2 to 4) and negligible at neutral-to-high pH. This result points to nitrous acid (HNO2) as being more reactive than the dissociated NO2- ion. The reaction of these nitrite species with organics also occurs in conventional analyses for total cyanide which involve distillation under strongly acidic conditions. Sufficient sample pretreatment with sulfamic acid at the time of sampling, not at the time of analysis. is highly recommended to prevent biasing analytical measurement of total cyanide in POTW effluents.     

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.     

The double-edged sword of humic substances: contrasting their effect on respiratory stress in eastern rainbow fish exposed to low pH

High amounts of humic substances (HS) are commonly found in natural acidic waterways and have been suggested to offer some protection against low pH. This study investigated the ability of HS to decrease respiratory stress in eastern rainbowfish (Melanotaenia splendida splendida) exposed to decreases in pH (range of 7–3.5) in soft and hard water. Repeated measures ANOVA revealed a significant difference in respiration (time taken for ten operculum movements) between pH and HS treatments, with a significant interaction between pH and HS present in 5/6 trials. Respiratory stress was shown to increase with increasing acidity, but significantly decreased in treatments with HS (10 and 20 mg/L) compared to those without. The fish exposed to pH treatments without HS also displayed increased hyperactivity, larger operculum movements and increased mucous production. Increased morbidity was shown in HS treatments at pH 3.5 (soft water) and at pH 4 (hard water) compared to treatment without HS. This indicates that HS is helpful in ameliorating the effects of decreased pH on respiration at sublethal pH levels; however, as pH decreases further, it seems that HS increases the toxicity (morbidity) of the low pH.     

造纸中段废水的混凝-臭氧氧化深度处理研究

就混凝-臭氧氧化组合工艺对造纸中段废水生物处理出水的净化效果进行了研究.结果表明,Ca(OH)2对废水色度、TOC、COD和254 nm的紫外吸收值(UV254)的去除效果均优于聚合氯化铝/聚丙烯酰胺(PAC/PAM);Ca(OH)2-O3组合工艺的处理效果也优于PAC/PAM-O3工艺.当Ca(OH)2投加量为1 g/L、臭氧投加量为50 mg/L时,废水色度降低至10倍以下,COD小于150 mg/L.经Ca(OH)2混凝处理后,相对分子量在0.5～1.0 ku和10.0 ku以上的有机物显著减少;进一步臭氧氧化处理后,除0.5 ～1.0 ku范围的有机物大幅度增加外,其余分子量有机物显著减少.由于对色度贡献很大的大分子量物质的去除,废水的色度显著下降直至无色.     

电子工业光致抗蚀剂乳化废水预处理试验研究

研究了光致抗蚀剂乳化废水用硫酸和含钙辅助破乳分离出有机物沉淀的预处理工艺。确定了最合适的预处理工艺参数和流程；用GC／MS法分析了废水的组成和浓度，并探讨了有机物的去除机理。试验结果表明，pH值控制在3，辅助剂A的浓度为300mg/L、静置时间为60min时，是最合适的工艺条件，废水的CODcr值从15600mg/L下降到3542mg/L，CODcr的去除率达77.4%，投加辅助剂后既提高了有机物的去除率，又改善了沉淀物的过滤性能，从而有利于降低后续工艺的处理成本。     

2株漂白废水高效降解菌的选育

用含氯漂白废水驯化城市污水处理厂的好氧污泥 ,从中分离出两株高效去除有机氯的菌 ,并对其适应条件进行了研究。结果表明 ,当pH为 7.0、废水浓度为 5 0 %、加入 0 .4g/L葡萄糖、2mL菌液时 ,处理效果较好 ,有机氯的去除率最高可达 74 .8%。     

SBR处理高浓度养猪废水工艺条件

以养猪场废水作为研究对象,采用序列间歇式活性污泥法SBR,通过实验研究了供气量、pH、排泥量、原水稀释倍数、水力停留时间（HRT）对SBR出水水质的影响。结果表明,供气量为375 L/（min·m³）、pH为8.0,并添加排泥100 mL的操作,可使SBR处理效果明显提高,COD、磷和凯氏氮去除率最高分别可达96.37%、94.14%、99.38%。逐步降低进水稀释倍数有利于培养出处理高浓度有机养猪废水的活性污泥,可将平均COD、磷和凯氏氮含量高达9 161.24、33.41和1 502.77 mg/L的养猪废水处理至出水的490.11、5.35和17.84 mg/L。降低HRT对SBR去除率影响不大。     

BM二代菌去除电镀废水中重金属离子的效果研究

BM菌是一种能够高效去除电镀废水中重金属离子的新型功能菌群,实验研究了BM二代菌对Cr6+、Ni2+的最佳去除条件,结果表明:当水温为10~30℃,pH=2,Cr6+浓度为100 mg/L,反应10 min,菌废比为1∶200时废水中Cr6+的去除率达到98%以上;当水温为10~30℃,pH=8.5,Ni2+浓度为100 mg/L,反应10 min,菌废比为1∶200时废水中Ni2+的去除率达到96%以上;在相同条件下实际电镀废水中Cr6+和Ni2+的去除率均高于99%。     

直接驯化嗜盐菌处理高盐废水的研究

从大连旅顺盐场底泥中筛选出适合高盐度的嗜盐菌,在序批式间歇反应器(SBR)中对其进行3.5%(质量分数)盐度的驯化,污泥混合液悬浮固体(MLSS)平均质量浓度达600mg/L。污泥比耗氧速率(SOUR)测量结果显示,内源呼吸阶段污泥SOUR为10.36mg/(g.h),外源呼吸阶段污泥SOUR达到29.09mg/(g.h),表明所筛选的嗜盐菌培养的污泥具有较高活性。利用培养的污泥进行高盐模拟废水处理试验,结果表明,对盐度为3.5%、COD为240～340mg/L的高盐废水,在每周期12h、曝气量0.6L/min、污泥MLSS为600mg/L、污泥龄为18d条件下,COD去除率达95%以上,NH4+-N去除率达61%,TP去除率达55%。改变进水有机负荷对出水COD去除影响不大,该系统耐有机负荷冲击能力较强;盐度负荷的改变对COD的去除影响不大,而NH4+-N去除率有明显变化,在3.5%和5.0%的盐度下,NH4+-N去除率分别为61%和31%。     

二级Fenton氧化高浓度有机硅废水研究

采用二级Fenton氧化技术对可生化性差的高浓度有机硅废水进行处理,考察了不同因素对COD去除率的影响,对比了一级氧化和二级氧化的效果。结果表明对于COD为9 600 mg/L的高浓度有机硅废水,pH为3,[H2O2]/[Fe2+]=2∶1为最佳的反应条件,COD去除率随着H2O2的投加量的增大先增大而后减小,每200 mL水样中先投加20%的硫酸亚铁12 mL,然后分2次投加30%的H2O2各4 mL,氧化完成后调整pH值为7~8静止沉淀,COD去除率达89.2%。对于某绝缘电器厂的生产废水经二级Fenton氧化处理后,出水有机物浓度显著降低,可生化性提高,Fenton二级氧化可以作为高浓度有机硅废水的预处理工艺。