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.     

Formation of free cyanide and cyanogen chloride from chloramination of publicly owned treatment works secondary effluent: laboratory study with model compounds.

The potential generation of cyanide species in wastewater upon chlorination in the presence of residual ammonia (resulting in chloramine formation) was investigated in experiments with synthetic solutions and publicly owned treatment works (POTW) secondary effluent. This study demonstrated that low concentrations (approximately 5 to 25 microg/L as cyanide) of cyanogen chloride (CNCI), a highly toxic cyanide species not measured in total or free cyanide analyses, could be detected as a result of chloramination reactions in POTW secondary effluent. The potential for chloramination of nitrogen-bearing organic compounds to yield CNCl and/or free cyanide was demonstrated in experiments with synthetic solutions spiked with selected precursor organics: L-serine, benzene, catechin, and humic acid. The amino acid L-serine yielded the largest concentrations of CNCI upon chloramination. Additionally, detectable cyanide (approximately 10 microg/L) was observed in solutions of L-serine and in POTW secondary effluent that was chloraminated followed by dechlorination to prevent destruction of any free cyanide produced. Thus, chlorination of POTW secondary effluent containing residual ammonia can lead to chloramination of organic compounds and the resulting production of CNCl and free cyanide.     

Wastewater analysis for volatile organic sulfides using purge-and-trap with gas chromatography/mass spectrometry.

This paper presented a modified method for the analysis of volatile organic sulfides (VOS) simultaneously with volatile organic compounds (VOC) in wastewater using purge-and-trap with gas chromatography/ mass spectrometry. Calibration standards were prepared using filtered and nitrogen-purged VOS-free wastewater, acidified to pH 1.4. Samples were also acidified to pH 1.4. This approach minimized the oxidation of methanethiol to dimethyl disulfide (DMDS), which hampered the liquid-phase analysis of VOS. Compounds were concentrated from the liquid phase, and automated analyses were performed without additional equipment, other than that required for routine wastewater VOC analysis. The linear range was 5 to 500 microg/L, with r2 > or = 0.99. The average recovery from replicate analyses of spiked samples was 81 +/- 0.5% for methanethiol, 100 +/- 1.5% fordimethyl sulfide (DMS), and 92 +/- 1.5% for DMDS. Method detection limits were 4.8, 2.8, and 1.2 microg/L for methanethiol, DMS, and DMDS, respectively. The relative percent differences were between 0 and 8%.     

Insights to false positive total cyanide measurements in wastewater plant effluents.

Many publicly owned treatment works in North America are exceeding permitted limits for total cyanide in their wastewater treatment effluents. A recently introduced rapid, segmented, flow-injection analysis procedure using UV digestion and amperometric detection of the membrane-separated cyanide was used to investigate the various scenarios by which elevated cyanide levels might be present in wastewater treatment plant effluent. A number of significant interferences can produce false positive bias during sample analysis with the traditional acid distillation technique, but are minimized or absent with the new analytical method. However, increased levels of cyanide were found in some chlorinated wastewaters compared to the levels before chlorination, suggesting a fast reaction mechanism associated with the disinfectant and some precursor in the wastewater. In particular, the contact of chlorine with nitrite in the presence of a carbon precursor appears to contribute to cyanide formation during wastewater treatment and sample handling. This paper explores the scenarios under which cyanide can form during wastewater treatment as well as those in which a false bias for total cyanide can be obtained during sample processing and provides guidance for appropriate sample handling, screening, and processing to ensure valid analytical results.     

混凝-化学沉淀法处理含氰废水的实验研究

采用“分步混凝 化学沉淀”法处理苯乙腈生产过程中排放的高浓度含氰废水 ,对混凝剂种类、用量、pH、搅拌速率等因素对总氰去除效果的影响进行了探讨 ,找到了此方法处理含亚铁氰化物废水的最佳工艺条件。在最佳工艺条件下处理废水 ,出水无色透明 ,总氰降到 1mg/L以下。该方法工艺简单 ,运行费用低 ,处理效果好 ,是一种具有推广价值的新方法     

微生物制剂与玄武岩纤维联用处理城市废水

为了探索一种新型的去除水体中有机物的工艺,以模拟城市废水为研究对象,研究不同工况条件下,复合微生物制剂、组合双环玄武岩纤维填料以及复合微生物制剂与组合双环玄武岩纤维填料结合对模拟城市废水中COD的去除情况。实验结果表明,复合微生物制剂与组合双环玄武岩纤维填料结合在曝气的情况下对COD的去除能力较高。在复合微生物制剂与组合双环玄武岩纤维填料结合的条件下,对COD浓度为500 mg/L左右的模拟城市废水的去除效率可达 97.22%;影响模拟城市废水中COD去除效果的各因素的主次顺序依次为反应时间>曝气时间>投加量=pH;得出最佳工况参数是:复合微生物制剂的投加量为0.05 g/L,曝气时间为72 h,反应时间为96 h,pH为7。     

电混凝处理电镀综合废水

采用电混凝法处理酸性电镀综合废水，首先研究了不同电流密度对总氰化物、重金属和化学需氧量（COD）去除率的影响。实验结果表明，电混凝可有效去除酸性电镀综合废水中的氰化物与重金属。随着电流密度的增大，总氰化物与重金属的去除率逐渐提高。当电流密度为10mA／cm2时，废水中残留的总氰化物、Cu2＋、Ni2＋、Cr6＋和Zn2＋ 的浓度分别为23．0、25．0、4．5、0．2和0．2mg／L。为了进一步提高去除率，在电化学体系中添加H2O2，随着H2O2投量的增大，总氰化物、重金属、COD去除率不断提高。当H2O2投量为3mL／L时，处理过废水中残留总氰化物、Cu2＋、Ni2＋、Cr6＋、Zn2＋和COD的浓度分别为0．2、2．0、3．0、1．5、0．1和220mg／L。     

二氧化氯处理矿山含氰废水的实验研究

实验采用二氧化氯 ( Cl O2 )作为矿山含氰废水处理剂 ,含氰废水在 p H 8.5～ 11.5之间 ,Cl O2 /CN- ≥ 3 (质量比 )的条件下 ,搅拌反应 3 0 min后 ,氰化物去除率达 99%以上 ,p H<9,CN- <0 .5 mg/L,达到《污水综合排放标准》中的一级标准。实验表明 ,利用 Cl O2 的强氧化性处理矿山含氰废水 ,具有投药量少、使用便捷、无二次污染等优点 ,且处理效果明显优于传统次氯酸盐处理法。     

Sources and fate of nitrosodimethylamine and its precursors in municipal wastewater treatment plants.

To assess the occurrence and fate of nitrosodimethylamine (NDMA) and its precursors in wastewater treatment plants, samples from wastewater treatment plants and industrial sources were analyzed for NDMA, total NDMA precursors, and dimethylamine (DMA). The median concentration of NDMA in untreated wastewater was approximately 80 ng/L, with maximum concentrations up to 790 ng/L presumably occuring because of sources unrelated to domestic wastewater. Concentrations of DMA in untreated wastewater ranged from approximately 50 to 120 microg/L and accounted for a majority of the NDMA precursors. The removal of NDMA during secondary biological treatment exhibited considerable variability, with overall removal ranging from 0 to 75%. In contrast, removal of NDMA precursors and DMA generally exceeded 70%. The median concentration of NDMA in secondary effluent before disinfection was 46 ng/L. Although DMA was removed during secondary treatment, other NDMA precursors in wastewater effluent will result in formation of additional NDMA upon disinfection with chloramines.     

离子交换纤维对金属氰络合物吸附性能的研究

采用强碱性离子交换纤维对含氰废水中主要离子铜氰络合物、锌氰络合物的吸附性能进行了研究。实验结果表明：含氰废水的pH在8—11范围内，纤维材料对金属氰络合物具有良好的吸附性能；纤维对铜氰络合物、锌氰络合物的吸附速率很快，4min左右就可达吸附平衡；温度对铜氰络合物、锌氰络合物吸附影响不大，纤维的这些吸附特点对工业应用非常有利。     

离子交换纤维对金属氰络合物吸附性能的研究

采用强碱性离子交换纤维对含氰废水中主要离子铜氰络合物、锌氰络合物的吸附性能进行了研究.实验结果表明:含氰废水的pH在8～11范围内,纤维材料对金属氰络合物具有良好的吸附性能;纤维对铜氰络合物、锌氰络合物的吸附速率很快,4 min左右就可达吸附平衡;温度对铜氰络合物、锌氰络合物吸附影响不大,纤维的这些吸附特点对工业应用非常有利.     

Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.     

A study on influential factors of high-phosphorus wastewater treated by electrocoagulation–ultrasound

A combined treatment of electrocoagulation and ultrasound was proposed to solve some problems which exist in the phosphorus removal processes in fine chemical industry. The intermittently discharged wastewater has the features of high initial phosphorus concentration and wide initial pH variation. The electrocoagulation–ultrasound effective performance for the removal of phosphorus was investigated. The results obtained from synthetic wastewater showed that the total phosphorus (TP) decreased from 86 to about 0.4 mg/L, and the removal efficiency reached about 99.6 %, when ultrasound was applied to the electrocoagulation cell under the optimum working conditions in 10 min. Comparatively, the TP removal efficiency of electrocoagulation group was 81.3 % and the ultrasound group has almost no change. Therefore, we can conclude that the electrocoagulation and ultrasound synergistic effect can effectively degrade high-phosphorus wastewater. We have discussed the impact of various parameters on the electrocoagulation–ultrasound based on the phosphorus removal efficiency. The results obtained from synthetic wastewater showed that the optimum working pH was found to be 6, allowing the effluent to be met the emission standards without pH adjustment. An increased current enhanced the speed of treatment significance, but higher current (>40 mA/cm²) enhanced ultrasonic cavitation effect causing flocculation ineffective. In addition, it was found that the optimum ultrasonic power was 4 W/cm² and the frequency was 20 kHz. The best ultrasound intervention and ultrasonic irradiation time were processed with electrocoagulation simultaneously. The results indicated that the electrocoagulation–ultrasound could be utilized as an attractive technique for removal of phosphate in the real wastewater.     

Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.     

Making chlorine greener: performance of alternative dechlorination agents in wastewater

The residual chlorine in chlorine-disinfected and dechlorinated wastewater was characterized using a liquid chromatograph that was switched between reversed-phase separation and flow injection analysis modes, permitting measurement of fractionated and total residual chlorine, respectively. Residuals were detected in the effluent of an operating wastewater treatment plant employing chlorine disinfection and sulfite dechlorination. Despite dechlorination, an estimated total residual chlorine of 3 microM (0.2 ppm as Cl2) was detected in the effluent. To improve dechlorination effectiveness, four alternative agents (ascorbic acid, iron, sulfite plus iodide mediator, thiosulfate) were compared to sulfite on laboratory-chlorinated wastewater. Listed in order of decreasing relative effectiveness, we found: iron metal > sulfite plus iodide approximately = thiosulfate > sulfite > ascorbic acid. Only the iron metal column was completely effective at rapidly removing all traces of residual chlorine.     

Measurement of organic nitrogen and phosphorus fractions at very low concentrations in wastewater effluents

The purpose of this study was to develop simple, accurate, and inexpensive measurement protocols for dissolved organic nitrogen (DON) and dissolved non-reactive phosphorus (DNRP) at low levels in wastewater effluents. Two protocols are presented--one to measure DON exclusively, and the other to measure DON and DNRP simultaneously. Currently, DON and DNRP are calculated indirectly by subtracting the dissolved inorganic fractions from the total dissolved concentration, resulting in significant errors. To increase the accuracy of DON measurements, effluent sample pretreatment using ion exchange to remove nitrate was applied. Spectrometric methods were selected to measure the inorganic fractions-the second derivative UV spectroscopy method for nitrate, and the malachite green method for orthophosphate. These methods, combined with the optimized persulfate digestion of the samples, can be used to measure total dissolved nitrogen and phosphorus accurately. The measurement ranges attained were 0.05 to 3 mg N/L for DON and 0.01 to 0.5 mg P/L for DNRP.     

Microbial degradation of metal complexed cyanides and thiocyanate from mining wastewaters

A microbiological examination of the soil from a cyanide wastewater storage basin was carried out. The storage basin contained water from the cyanidation process of gold extraction, and it was composed principally of simple cyanide, metal complexed cyanide, mainly cuprocyanide, ferro-ferricyanides and thiocyanate. Pseudomonas species were the principal bacteria identified in the soil. Using the storage basin soil as a seed sludge, its potential for the biodegradation of all the cyanide complexes in the mining wastewater was studied in the laboratory, using batch, fed-batch and continuous processes. The ammonia and sulphate produced were quantified. The presence of intermediate products was suspected. In the continuous process, total degradation of all cyanide was observed at a dilution rate of 0.066 day(-1).     

变频控制DO下SBR硝化反应控制参数及节能的中试研究

根据微生物好氧反应的需氧量调节曝气量在当今能源紧缺的形势下具有十分重要的意义.为了研究曝气量大小对SBR实时控制参数pH、DO的影响,采用变频器调节曝气量以控制系统不同的DO浓度,以60 m3中试SBR反应器处理北京市北小河污水处理厂城市污水,考察了硝化过程中pH值、DO与有机物去除及硝化过程的相关性,并引入了新的控制参数--变频频率f.试验结果表明,控制溶解氧浓度较低时,pH值不能作为硝化结束的控制参数,但可根据变频频率f的特征点判断硝化反应的结束;控制溶解氧为3.0 mg/L和4.0 mg/L时,DO、pH值、变频频率f都可作为硝化结束的控制参数,同时,变频控制可有效降低单位时间内风机的能耗.     

Evaluating the vulnerability of surface waters to antibiotic contamination from varying wastewater treatment plant discharges

Effluents from three wastewater treatment plants with varying wastewater treatment technologies and design were analyzed for six antibiotics and caffeine on three sampling occasions. Sulfamethoxazole, trimethoprim, ciprofloxacin, tetracycline, and clindamycin were detected in the effluents at concentrations ranging from 0.090 to 6.0 microg/L. Caffeine was detected in all effluents at concentrations ranging from 0.19 to 9.9 microg/L. These findings indicate that several conventional wastewater management practices are not effective in the complete removal of antibiotics, and their discharges have a large potential to affect the aquatic environment. To evaluate the persistence of antibiotics coming from the wastewater discharges on the surrounding surface waters, samples were collected from the receiving streams at 10-, 20- and 100-m intervals. Ciprofloxacin, sulfamethoxazole, and clindamycin (0.043 to 0.076 microg/L) were found as far as 100 m from the discharge point, which indicates the persistence of these drugs in surface waters.     

Determination of beta-adrenergic receptor blocking pharmaceuticals in United States wastewater effluent

Beta adrenergic receptor antagonists (beta-Blockers) are frequently prescribed medications in the United States and have been identified in European municipal wastewater effluent, however no studies to date have investigated these compounds in United States wastewater effluent. Municipal wastewater effluent was collected from treatment facilities in Mississippi, Texas, and New York to investigate the occurrence of metoprolol, nadolol, and propranolol. Propranolol was identified in all wastewater samples analyzed (n = 34) at concentrations < or = 1.9 microg/l. Metoprolol and nadolol were identified in > or = 71% of the samples with concentrations of metoprolol < or = 1.2 microg/l and nadolol < or = 0.36 microg/l. Time course studies at both Mississippi plants and the Texas plant indicate that concentrations of propranolol, metoprolol, and nadolol remain relatively constant at each sampling period. This study indicates that beta-Blockers are present in United States wastewater effluent in the ng/l to microg/l range.