Occurrence and fate of heavy metals in the wastewater treatment process

The occurrence and the fate of heavy metals (Cd, Pb, Mn, Cu, Zn, Fe and Ni) during the wastewater treatment process were investigated in the wastewater treatment plant (WTP) of the city of Thessaloniki, northern Greece, operating in the activated sludge mode. For this purpose, wastewater and sludge samples were collected from six different points of the plant, namely, the influent (raw wastewater, RW), the effluent of the primary sedimentation tank (primary sedimentation effluent, PSE), the effluent of the secondary sedimentation tank (secondary sedimentation effluent, SSE), sludge from the primary sedimentation tank (primary sludge, PS), activated sludge from the recirculation stream (activated sludge, AS), and the digested/dewatered sludge (final sludge, FS).

The distribution of metals between the aqueous and the solid phase of wastewater was investigated. Good exponential correlation was found between the metal partition coefficient, logK_p, and the suspended solids concentration. The mass balance of heavy metals in the primary, secondary and the whole treatment process showed good closures for all metal species. The relative distribution of individual heavy metals in the treated effluent and the sludge streams indicated that Mn and Cu are primarily (>70%) accumulated in the sludge, while 47–63% of Cd, Cr, Pb, Fe, Ni and Zn remain in the treated effluent.     

城市污水厂污水污泥的热值测定分析方法研究

建立热力学指标是污水生物处理过程热力学分析的基础工作，目前仍缺乏污水污泥化学能测试的标准方法。采用IKA C5000型自动热量计对某城市二级污水处理厂进水、出水、初沉污泥、剩余污泥、混合污泥和脱水污泥进行了热值测定，样品前处理采用103～105℃烘干获得干燥基，用苯甲酸进行加标回收。参照煤的发热量测定方法得到样品的高位热值。试验结果显示：出水干燥基的热值为05 kJ/g，进水干燥基的热值为4 kJ/g以上，各工艺段的污泥干燥基热值较高，基本都在12 kJ/g以上，接近右江褐煤水平。测定结果的标准偏差≤±0.452%，相对标准偏差≤±0.136%。通过同一批样品的元素分析及Dulong公式理论推算，发现2种方法可得到相似的结果。     

皮革废水经微电解-SBR处理后的综合毒性变化

选择蛋白核小球藻（Chlorella pyrenoidosa Chick）为供试藻种，采用藻类急性毒性试验考察皮革废水经微电解-SBR工艺处理后的综合毒性变化情况。结果表明，皮革废水经微电解-SBR工艺处理后，其综合毒性显著降低。分别以细胞数和活体叶绿素a含量计算得到的原水、微电解出水和SBR出水的EbC50值和EeC50值依次为16.6%、19.3%、52.6%和13.0%、15.6%和52.1%。根据Bulich提出的毒性等级划分原则，经处理后最终出水的毒性级别由原水的Ⅰ级降为Ⅱ级。     

Considerations about the enantioselective transformation of polycyclic musks in wastewater, treated wastewater and sewage sludge and analysis of their fate in a sequencing batch reactor plant

The present work consists of two distinct parts: in the first part enantioselective GC was used to separate the different enantiomeric/diastereomeric polycyclic musks, PCMs (HHCB, AHTN, AHDI, ATII and DPMI) including the main transformation product of HHCB, HHCB-lactone, in wastewater and sewage sludge. After optimization all PCMs were resolved on a cyclodextrin containing Rt-BDEXcst capillary GC column. Enantiomeric ratios of PCMs in a technical mixture were determined and compared to those obtained from enantioselective separation of wastewater and sewage sludge samples. In general, enantiomeric ratios were similar for most materials in influent, effluent and stabilized sewage sludge. However, the ratios for HHCB, AHDI and particularly ATII suggest some stereospecific removal of these compounds. In the second part, a field study was conducted on a wastewater treatment plant comprising a sequencing batch reactor. Concentrations of HHCB, AHTN, ADBI, AHDI, ATII, DPMI and HHCB-lactone were determined by non-enantioselective GC in daily samples of influent, effluent and activated sludge during one week. Mean concentrations in influent were 6900 and 1520 ng/l for HHCB and AHTN, respectively. The other PCMs exhibited contents 200 ng/l. Mean percent removal was between 61% (AHDI) and 87% (HHCB) resulting in mean effluent concentrations below 860 ng/l. HHCB-lactone concentration increased during wastewater treatment with a mean in the influent of 430 ng/l and in the effluent of 900 ng/l, respectively, indicating a degradation of HHCB.     

Toxicity of herbal pharmaceutical wastewater on fish--Lebistes reticulatus (Peter)

Toxic effects of herbal pharmaceutical wastewater on common fish (Lebistes reticulatus) under laboratory conditions were studied. LC50 values for raw, neutralized, and physico-chemically treated effluent for 24, 48, 72, and 96 h ranged between 3.0-9.5%, 5.0-10.5%, and 35-41%, respectively. It was evident from the studies that physico-chemical treatment reduces the toxicity by more than 30%. This article discusses in detail the bioassay evaluation of raw, neutralized, and primary treated effluent. Physico-chemically treated effluent was further subjected to biological treatment by activated sludge system. Effluent from biological treatment revealed no toxic effect even after one month of exposure.     

铬离子对SBR工艺活性污泥毒性作用研究

针对重金属铬离子对SBR工艺系统中活性污泥的毒性作用,通过检测不同初始污泥容积指数(SVI)下SBR工艺活性污泥在不同铬负荷下的COD值、挥发性污泥浓度以及受铬离子影响的污泥容积指数(SVI),研究重金属铬离子对活性污泥的毒性作用以及对SBR工艺系统处理污水的影响。研究表明,重金属铬离子会导致SBR工艺系统出水COD升高;将铬离子对活性污泥的毒性作用按照挥发性污泥(MLVSS)铬负荷可划分为耐受范围、非耐受范围、细胞失活范围以及细胞分解范围。耐受范围铬负荷低于约30 mg Cr3+/gMLVSS,此范围内铬离子对于活性污泥的毒性作用不大,不致于导致系统出水水质变差;非耐受范围铬负荷在约30~65 mg Cr3+/g MLVSS,在铬离子作用下系统出水COD值明显高于对照系统;细胞失活范围铬负荷在约70~100 mg Cr3+/gMLVSS范围内,SVI大幅下降,微生物部份死亡和失活,出水COD尽管有一些下降,但与进水COD相比差不了多少;细胞分解范围铬负荷在约100 mg Cr3+/gMLVSS以上,微生物大量死亡,部分死亡细胞分解,系统出水COD值因微生物的死亡分解而超出进水COD值,受铬离子影响的系统SVI值大幅度降低。     

城市污水石灰法深度处理工艺中有毒物质的变化规律

分别采用7-乙氧基异酚恶唑酮-脱乙基酶(EROD)活性测定法,重组人激素受体基因的酵母测试和Q67发光菌试验方法,对北京市某生活污水处理厂的进水、二沉出水以及经过石灰法深度处理后的出水中的类二恶英物质、类雌激素物质和急性毒性物质进行了分析.进水中的三类生物毒性效应物质中的急性毒性物质,可通过活性污泥法基本去除,而对类雌激素物质和类二恶英物质的去除率分别为76%和52%.经过石灰沉淀法的深度处理后,可使上述两类物质的总去除率达到95%和68%.出水中的雌激素当量水平与欧洲国家污水处理厂出水水平相当,而类二恶英物质的总浓度低于美国EPA饮用水中二恶英的最大允许浓度.展示了生物毒性测试方法在排水生态风险和工艺评价方面的应用潜力.     

Reproductive impairment of sea urchins upon chronic exposure to cadmium. Part I: Effects on gamete quality

Successful reproduction is a determining factor for species survival. Pollution may impair reproductive success of adults through effects on gamete quality. Reproductive impairment of the sea urchin Anthocidaris crassispina upon chronic (4 weeks) exposure to 0.01 and 0.1 mg l-1 Cd2+ was investigated. Criteria used for assessing gamete quality included sperm motility, egg morphology, fertilization rate and dynamics of first cleavage. A dose-response relationship was found between Cd2+ levels and changes in sperm motility, and percentage fertilization. Sperm motility, measured by computer-assisted sperm analysis, indicated that percent motile sperm, velocities, and percent sperm with normal trajectory were significantly affected by chronic exposure to > or = 0.1 mg l-1 Cd2+. A decline in sperm motility was also accompanied by a decrease in fertilization success of sea urchin sperm. Width/height ratio of sea urchin eggs was not affected by cadmium, but larger egg sizes were found when sea urchins were exposed to 0.1 mg l-1 Cd2+. Male sea urchins exposed to Cd2+ produced poorer quality sperm, as indicated by a lower percent fertilization and lower cleavage rate, implying that male sea urchins were more sensitive than females to chronic Cd2+ exposure. Results of the present study provide an explanation of reproductive impairment in marine invertebrates upon chronic exposure to Cd2+.     

Integrated catalytic wet air oxidation and aerobic biological treatment in a municipal WWTP of a high-strength o-cresol wastewater

This study examines the feasibility of coupling a Catalytic Wet Air Oxidation (CWAO), with activated carbon (AC) as catalyst, and an aerobic biological treatment to treat a high-strength o-cresol wastewater. Two goals are pursued: (a) To determine the effect of the main AC/CWAO intermediates on the activated sludge of a municipal WasteWater Treatment Plant (WWTP) and (b) To demonstrate the feasibility of coupling the AC/CWAO effluent as a part of the influent of a municipal WWTP. In a previous study, a high-strength o-cresol wastewater was treated by AC/CWAO aiming to establish the distribution of intermediates and the biodegradability enhancement. In this work, the biodegradability, toxicity and inhibition of the most relevant intermediates detected in the AC/CWAO effluent were determined by respirometry. Also, the results of a pilot scale municipal WWTP study for an integrated AC/CWAO-aerobic biological treatment of this effluent are presented. The biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) of main AC/CWAO intermediates allowed the classification of the intermediates into readily biodegradable, inert or toxic/inhibitory compounds. This detailed study, allowed to understand the biodegradability enhancement exhibited by an AC/CWAO effluent and to achieve a successful strategy for coupling the AC/CWAO step with an aerobic biological treatment for a high-strength o-cresol wastewater. Using 30%, as COD, of AC/CWAO effluent in the inlet to the pilot scale WWTP, the integrated AC/CWAO-biological treatment achieved a 98% of total COD removal and, particularly, a 91% of AC/CWAO effluent COD removal without any undesirable effect on the biomass.     

The effect of wastewater cations on activated sludge characteristics: effects of aluminum and iron in floc.

Wastewater samples collected from seven wastewater treatment plants (WWTPs) were characterized to assess the impacts of wastewater cations on the activated sludge process. The cations included in this study were sodium (Na+), potassium, ammonium, calcium, magnesium, aluminum (Al), and iron (Fe). Among the selected cations, Al and Fe were of most interest to this study because their role in bioflocculation has not been extensively studied and remains largely unknown. The data showed that WWTPs contained highly varying concentrations of Na+, Al, and Fe in the wastewater and that these cations were responsible for differences between WWTPs as to sludge dewatering rates and effluent quality. In general, a high influent Na+ concentration caused poor sludge dewatering and effluent characteristics. However, when sufficient Al and Fe were present in floc, the deleterious effects of Na+ were offset. The data associated with Al further revealed that waste activated sludge with low Al contained high concentrations of soluble and colloidal biopolymer (protein + polysaccharide), resulting in a high effluent chemical oxygen demand, high conditioning chemical requirements, and poor sludge dewatering properties. These results suggest that Al will improve activated sludge effluent quality by scavenging organic compounds from solution and binding them to floc.     

The behaviors and fate of polycyclic aromatic hydrocarbons (PAHs) in a coking wastewater treatment plant

The occurrence, behaviors and fate of 18 PAHs were investigated in a coking wastewater treatment plant in Songshan coking plant, located in Shaoguan, Guangdong Province of China. It was found that the target compounds occurred widely in raw coking wastewater, treated effluent, sludge and gas samples. In raw coking wastewater, high molecular weight (MW) PAHs were the dominant compounds, while 3-6 ring PAHs predominated in the final effluent. The dominant compounds in gas samples were phenathrene, fluoranthene and pyrene, while they were fluoranthene, pyrene, chrysene and benzo[k]fluoranthene for sludge. The process achieved over 97% removal for all the PAHs, 47-92% of eliminations of these target compounds in liquid phase were achieved in biological stage. Different behaviors of PAHs were observed in the primary tank, anaerobic tank, aerobic tank, hydrolytic tank and coagulation tank units, while heavier and lower ones were mainly removed in anaerobic tank and aerobic tanks, respectively. Regarding the fate of PAHs, calculated fractions of mass losses for low MW PAHs due to transformation and adsorption to sludge accounted for 15-50% and 24-49%, respectively, while the rest was less than 1%. For high MW PAHs, the mass losses were mainly due to adsorption to sludge and separation with tar (contributing 56-76% and 22-39%, respectively), and the removal through transformation was less.     

Overcoming the toxicity effects of municipal wastewater sludge and biosolid extracts in the Yeast Estrogen Screen (YES) assay

For nearly two decades, the Yeast Estrogen Screen (YES) has been used as a valuable tool for determining the total estrogenic potency of various environmental samples, including influent and effluent streams at municipal wastewater plants. However, applying the YES assay to wastewater sludges and stabilized biosolids has been problematic. This is due to co-extracted compounds from the solids either proving toxic to the yeast or masking the presence of estrogenic substances. The present research describes the development and validation of sample preparation steps that mitigate the toxicity effects of municipal wastewater sludge and biosolid samples in the YES assay, while allowing for reliable dose-dependent expression of estrogenic activity. A copper work-up for sulfur removal and chromatographic cleanup with silica and alumina were required in addition to solid-phase extraction to adequately remove interfering compounds. Sample stabilization methods such as autoclaving, lyophilization and formaldehyde treatment were found to be detrimental to the assay. Hence, heat-drying is recommended to prevent cytotoxicity and the degradation of estrogenic substances.     

Vegetable and synthetic tannins induce hormesis/toxicity in sea urchin early development and in algal growth

Mimosa tannin and phenol-based synthetic tannin (syntan) were tested for toxicity to sea urchin (Paracentrotus lividus and Sphaerechinus granularis) early development and to marine algal growth (Dunaliella tertiolecta). Sea urchin embryogenesis was affected by vegetable tannin and syntan water extracts (VTWE and STWE) at levels >or=1mg/L. Developmental defects were significantly decreased at VTWE and STWE levels of 0.1 and 0.3mg/L when control cultures displayed suboptimal quality, i.e. <70% "viable" (normal or retarded) larvae. Fertilization success of sea urchin sperm was increased up to 0.3 mg/L STWE or VTWE, then was inhibited by increasing tannin levels (1-30 mg/L). Offspring abnormalities, following sperm exposure to VTWE or STWE, showed the same shift from hormesis to toxicity. Cell growth bioassays in D. tertiolecta exposed to VTWE or STWE (0.1-30 mg/L) showed non-linear concentration-related toxicity. Novel criteria are suggested in defining control quality that should reveal hormetic effects.     

Petroleum refinery stripped sour water treatment using the activated sludge process

A pilot study was performed over 91 days to determine if the activated sludge process could treat a segregated stripped sour water (SSW) stream from a petroleum refinery. The study was performed in two periods. The first period was terminated after 19 days, as a result of excessive sludge bulking. The elimination of sludge bulking during the 70-day second period is attributed to operational changes, which included aerating the influent to oxidize reduced sulfur, adjusting the influent pH, and adding micronutrients to satisfy biological requirements. The pilot plant provided a chemical oxygen demand (COD) removal of up to 93%. Nitrification was achieved, with effluent ammonia values < 1 mg-N/L. These results indicate that direct treatment of SSW with the activated sludge process is possible and has direct application to full-scale petroleum refinery wastewater plant upgrades.     

Removal and formation of chlorinated triclosan derivatives in wastewater treatment plants using chlorine and UV disinfection

Triclosan, a common antimicrobial agent, may react during the disinfection of wastewater with free chlorine to form three chlorinated triclosan derivatives (CTDs). This is of concern because the CTDs may be photochemically transformed to tri- and tetra-chlorinated dibenzo-p-dioxins when discharged into natural waters. In this study, wastewater influent, secondary (pre-disinfection) effluent, and final (post-disinfection) effluent samples were collected on two occasions each from two activated sludge wastewater treatment plants, one using chlorine disinfection and one using UV disinfection. Concentrations of triclosan and three CTDs were determined using ultra performance liquid chromatography-triple quadrupole mass spectrometry with isotope dilution methodology. Triclosan and the CTDs were detected in every influent sample at levels ranging from 453 to 4530 and 2 to 98 ng L⁻¹, respectively, though both were efficiently removed from the liquid phase during activated sludge treatment. Triclosan concentrations in the pre-disinfection effluent ranged from 36 to 212 ng L⁻¹, while CTD concentrations were below the limit of quantification (1 ng L⁻¹) for most samples. In the treatment plant that used chlorine disinfection, triclosan concentrations decreased while CTDs were formed during chlorination, as evidenced by CTD levels as high as 22 ng L⁻¹ in the final effluent. No CTDs were detected in the final effluent of the treatment plant that used UV disinfection. The total CTD concentration in the final effluent of the chlorinating treatment plant reached nearly one third of the triclosan concentration, demonstrating that the chlorine disinfection step played a substantial role in the fate of triclosan in this system.     

Comparison of the occurrence of antibiotics in four full-scale wastewater treatment plants with varying designs and operations

The occurrence of ciprofloxacin, sulfamethoxazole, tetracycline, and trimethoprim antibiotics in four full-scale wastewater treatment plants (WWTPs) that differ in design and operating conditions was determined. The WWTPs chosen utilized a variety of secondary removal processes, such as a two stage activated sludge process with a nitrification tank, extended aeration, rotating biological contactors, and pure oxygen activated sludge. Several of the WWTPs also employed an advanced treatment process, such as chlorination and UV radiation disinfection. The detected concentrations (microg/l) ranged from 0.20 to 1.4 for ciprofloxacin, 0.21 to 2.8 for sulfamethoxazole, 0.061 to 1.1 for tetracycline, and 0.21 to 7.9 for trimethoprim. The overall percent difference in the concentrations of the antibiotics in the effluent and influent of these antibiotics differed between plants and ranged from 33% to 97%. Based on these four full-scale WWTPs evaluated, the apparent removal of organic micropollutants in wastewater is dependent on a combination of biological and physico-chemical treatment processes and operating conditions of the treatment system.     

Removal of organic compounds during treating printing and dyeing wastewater of different process units

Wastewater in Shaoxing wastewater treatment plant (SWWTP) is composed of more than 90% dyeing and printing wastewater with high pH and sulfate. Through a combination process of anaerobic acidogenic [hydraulic retention time (HRT) of 15h], aerobic (HRT of 20h) and flocculation-precipitation, the total COD removal efficiency was up to 91%. But COD removal efficiency in anaerobic acidogenic unit was only 4%. As a comparison, the COD removal efficiency was up to 35% in the pilot-scale upflow anaerobic sludge bed (UASB) reactor (HRT of 15h). GC-MS analysis showed that the response abundance of these wastewater samples decreased with their removal of COD. A main component of the raw influent was long-chain n-alkanes. The final effluent of SWWTP had only four types of alkanes. After anaerobic unit at SWWTP, the mass percentage of total alkanes to total organic compounds was slightly decreased while its categories increased. But in the UASB, alkanes categories could be removed by 75%. Caffeine as a chemical marker could be detected only in the effluent of the aerobic process. Quantitative analysis was given. These results demonstrated that GC-MS analysis could provide an insight to the measurement of organic compounds removal.     

铁炭内电解-厌氧-好氧工艺处理阿维菌素废水的试验研究

血清瓶毒性试验表明 ,AVM对厌氧消化产生强烈的抑制作用。AVM废水经铁炭内电解预处理后 ,COD和AVM的去除率分别达到 19.5 %和 6 8.5 % ,可大大降低废水的毒性。预处理出水再经UASB +生物接触氧化反应器进一步处理 ,当生化系统进水COD为 6 0 0 0— 6 5 0 0mg/L时 ,出水COD为 2 5 0— 2 80mg/L ,总COD去除率达到 95 .6 % ,出水达到生物制药行业排放标准     

Simultaneous nitrification-denitrification and clarification in a pseudoliquified activated sludge system.

This paper describes results from a pilot study of a novel wastewater treatment technology, which incorporates nutrient removal and solids separation to a single step. The pseudoliquified activated sludge process pilot system was tested on grit removal effluent at flowrates of 29.4 to 54.7 m3/d, three different solid residence times (SRT) (15, 37, and 57 days), and over a temperature range of 12 to 28 degrees C. Despite wide fluctuations in the influent characteristics, the system performed reliably and consistently with respect to organics and total suspended solids (TSS) removals, achieving biochemical oxygen demand (BOD) and TSS reductions of > 96% and approximately 90%, respectively, with BOD5 and TSS concentrations as low as 3 mg/L. Although the system achieved average effluent ammonia concentrations of 2.7 to 3.2 mg/L, nitrification efficiency appeared to be hampered at low temperatures (< 15 degrees C). The system achieved tertiary effluent quality with denitrification efficiencies of 90 and 91% total nitrogen removal efficiency at a total hydraulic retention time of 4.8 hours and an SRT of 12 to 17 days. With ferric chloride addition, effluent phosphorous concentrations of 0.5 to 0.8 mg/L were achieved. Furthermore, because of operation at high biomass concentrations and relatively long biological SRTs, sludge yields were over 50% below typical values for activated sludge plants. The process was modeled using activated sludge model No. 2, as a two-stage system comprised an aerobic activated sludge system followed by an anoxic system. Model predictions for soluble BOD, ammonia, nitrates, and orthophosphates agreed well with experimental data.     

Acidic pharmaceuticals in domestic wastewater and receiving water from hyper-urbanization city of China (Shanghai): environmental release and ecological risk

The occurrence, behavior, and release of five acidic pharmaceuticals, including ibuprofen (IBP), naproxen (NPX), ketoprofen (KEP), diclofenac (DFC), and clofibric acid (CA), have been investigated along the different units in a tertiary-level domestic wastewater treatment plant (WWTP) in hyper-urbanization city of China (Shanghai). IBP was the most abundant chemicals among the measured in raw wastewater. The loads of the acidic pharmaceuticals in the WWTP influent ranged from 7.5 to 414 mg/day/1,000 inh, which were lower than those reported in the developed countries suggesting a less per capita consumption of pharmaceuticals in Shanghai. IBP obtained by highest removal (87 %); NPX and KEP were also significantly removed (69–76 %). However, DFC and CA were only moderately removed by 37–53 %, respectively. Biodegradation seemed to play a key role in the elimination of the studied pharmaceuticals except for DFC and CA. An annual release of acidic pharmaceuticals was estimated at 1,499 and 61.7 kg/year through wastewater and sludge, respectively, from Shanghai. Highest pharmaceuticals concentrations were detected in the effluent discharge point of the WWTP, indicating that WWTP effluent is the main source of the acidic pharmaceuticals to its receiving river. Preliminary results indicated that only DFC in river had a high risk to aquatic organisms. Nevertheless, the joint toxicity effects of these chemicals are needed to further investigate.