Phenol removal from high salinity effluents using Fenton's reagent and photo-Fenton reactions

The removal of pollutants in saline medium by the Fenton's reagent needs a more detailed investigation, since the presence of chloride may inhibit or retard degradation. Phenol was used as a model pollutant and the influence of some important process variables for the removal of total organic carbon and phenol were investigated, such as FeSO4 and H2O2 concentrations, pH and salinity. The reactivity of iron cations and alternative procedures of applying UV radiation (photo-Fenton) were evaluated. Phenol was fast and completely removed by the Fenton's process even in a high saline medium (50,000mg NaCll(-1)). However, TOC was only moderately or poorly removed in saline media, depending on the salt concentration. When the photo-Fenton process was used, mineralization was improved and high TOC removals were observed in moderately saline media (NaCl concentration < or =10,000mgl(-1)). For the highest NaCl concentration tested (50,000mgl(-1)) only a moderate TOC removal was observed (50%).     

Sources of adsorbable organic halogens (AOX) in sludge of Gaza

Average concentrations of adsorbable organic halogens (AOX) in sludge from the Gaza Strip reached 600 mg kg(-1) which currently represents a major limiting factor for sludge application in agriculture. This study aims to identify the main sources of AOX in Gaza where the area is small with limited industrial activities. The results showed that the AOX in effluent sludge is formed mainly inside the treatment plant. Although the plant receives AOX wastewater of only 85 microg l(-1), this value increased five fold inside the plant to an average of 400 microg l(-1) in the effluent wastewater. On the other hand, the sludge from the first sedimentation pond showed an AOX concentration of 213 mg kg(-1) and increased in the final sedimentation pond to 500 mg kg(-1). The AOX concentration in three month old sludge was 130 mg kg(-1). The textile and detergent industries are the major AOX producing industries in Gaza, with an average AOX of 40,000 microg l(-1) in their effluent wastewater. These values do not represent a significant AOX pollution load to the treatment plant because these industries are very limited and their effluents are diluted before entering the municipal treatment plant. Industrial activity decreased in 2006 to less than 70% of the previous four years. Consequently, the AOX in the industrial effluent decreased from 150,000 to 40,000 microg l(-1) over the same time period. Sludge from these industries showed 1300 mg kg(-1) AOX for the past four years and only 400 mg kg(-1) in 2006. Moreover, the AOX in the influent wastewater discharged to the treatment plant decreased from 320 to 85 microg l(-1) for the same period. This study revealed that the major AOX is formed inside the treatment plant and especially in the anaerobic facilities. There was no correlation between the AOX concentrations in the sludge and the wastewater at the same location. Moreover, there was no correlation between the AOX in sludge/wastewater and dissolved oxygen, pH and chloride in that treatment plant.     

Degradation of azo dye Procion Red MX-5B by photocatalytic oxidation

The photocatalytic oxidation (PCO) of a monoazo dye Procion Red MX-5B under various physico-chemical conditions was investigated. Degradation of the dye by PCO was enhanced by augmentation in UV intensity, titanium dioxide and hydrogen peroxide concentrations but was inhibited by increase in initial dye concentration. The PCO process was affected by pH in a peculiar way. In the presence of 100 mg/l of TiO2 and the absence of H2O2, the highest reaction rate was observed when the initial pH was 10. With 500 mg/l of TiO2 and 10 mM of H2O2, the reaction was the fastest at initial pH of 3-5. The optimal conditions for the degradation of the dye, at an UV intensity of 17 mW/cm2, were determined to be: TiO2 concentration, 500 mg/l; initial H2O2 concentration, 10 mM; initial pH, 5.0. Monitoring of TOC loss showed that the dye was mineralized by 90% within 80 min under these conditions. Nevertheless, the persistence of a low level of TOC indicated that mineralization was not complete and dead-end product(s) which was (were) resistant to PCO might have accumulated.     

Synthetic olive mill wastewater treatment by Fenton’s process in batch and continuous reactors operation

Degradation of total phenol (TPh) and organic matter, (expressed as total organic carbon TOC), of a simulated olive mill wastewater was evaluated by the Fenton oxidation process under batch and continuous mode conditions. A mixture of six phenolic acids usually found in these agro-industrial wastewaters was used for this purpose. The study focused on the optimization of key operational parameters of the Fenton process in a batch reactor, namely Fe²⁺ dosage, hydrogen peroxide concentration, pH, and reaction temperature. On the assessment of the process efficiency, > 99% of TPh and > 56% of TOC removal were attained when [Fe²⁺] = 100 ppm, [H₂O₂] = 2.0 g/L, T = 30 °C, and initial pH = 5.0, after 300 min of reaction. Under those operational conditions, experiments on a continuous stirred-tank reactor (CSTR) were performed for different space-time values (τ). TOC and TPh removals of 47.5 and 96.9%, respectively, were reached at steady-state (for τ = 120 min). High removal of COD (> 75%) and BOD₅ (> 70%) was achieved for both batch and CSTR optimum conditions; analysis of the BOD₅/COD ratio also revealed an increase in the effluent’s biodegradability. Despite the high removal of lumped parameters, the treated effluent did not met the Portuguese legal limits for direct discharge of wastewaters into water bodies, which indicates that coupled chemical-biological process may be the best solution for real olive mill wastewater treatment.     

Swine wastewater treatment using attached-growth and suspended-growth two stage sequencing batch reactors with real-time control.

Two two-stage sequencing batch reactors (TSSBR), one attached-growth and one suspended-growth, were operated under three levels of wastewater concentration (approximately 4,000, 2,000 and 500 TOC mg/L), respectively, to compare the pH and ORP (oxidation-reduction potential) patterns and system performance. In both TSSBR systems, the pH and ORP profiles varied with organic loading yet exhibited consistent patterns with distinctive features suitable for real-time control. For all runs at the three levels of influent, both systems achieved similar levels of treatment for BOD5, TOC and TSS of over 97.5, 93.4, and 97.3%, respectively. The attached-growth system out performed the suspended-growth system in achieving the same levels of treatment at much shorter aeration cycle times. The treatment efficiency for NO3(-)-N and PO4(-3) was greatly affected by the carbon content in the wastewater, and the best treatment was achieved during the TOC approximately 4,000 mg/L runs with final effluent at 4.0 and 21.3 mg/L, respectively.     

Buffering processes in a boreal dissolved organic carbon-rich stream during experimental acidification

The role of organic acids on surface water acidity as well as their buffering during anthropogenic acidification and subsequent recovery was studied in a field experiment on a total organic carbon (TOC)-rich stream draining the Svartberget catchment in northern Sweden. H(2)SO(4) was added to the stream to increase SO(4)(2-) concentration by 90 microeq l(-1) for 30 h. About 60% of the added H(+) was buffered by protonation of organic acids, another 20% was buffered by base cations released from the surface of the stream channel and only ca. 20% of the added acid remained unbuffered. TOC concentrations (27 mg l(-1)), and site density of carboxylic groups--8.6 microeq (mg TOC)(-1)--remained stable during the experiment. Two models of organic acid dissociation (a triprotic model and a monoprotic pH-dependent pKa model) were fitted to the experimental results. These models explained the observed variations in organic anions, but the model parameters were quite different from those reported by studies in Northern America and Central Europe. This experiment had substantially more buffering effect of TOC between pH 4.4 and 5.3, which is an environmentally important pH range.     

Decomposition and mineralization of cefaclor by ionizing radiation: kinetics and effects of the radical scavengers

There has been recent growing interest in the presence of antibiotics in different environmental sectors. One considerable concern is the potential development of antibiotic-resistant bacteria in the environment, even at low concentrations. Cefaclor, one of the beta-lactam antibiotics, is widely used as an antibiotic. Kinetic studies were conducted to evaluate the decomposition and mineralization of cefaclor using gamma radiation. Cefaclor, 30 mg/l, was completely degraded with 1,000 Gy of gamma radiation. At a concentration of 30 mg/l, the removal efficiency, represented by the G-value, decreased with increasing accumulated radiation dose. Batch kinetic experiments with initial aqueous concentrations of 8.9, 13.3, 20.0 and 30.0mg/l showed the decomposition of cefaclor using gamma radiation followed a pseudo first-order reaction, and the dose constant increased with lower initial concentrations. At a given radiation dose, the G-values increased with higher initial cefaclor concentrations. The experimental results using methanol and thiourea as radical scavengers indicated that ()OH radicals were more closely associated with the radiolytic decomposition of cefaclor than other radicals, such as e(aq)(-) or ()H. The radical scavenger effects were tested under O(2) and N(2)O saturations for the enhancement of the TOC percentage removal efficiencies in the radiolytic decomposition of cefaclor. Under O(2) saturation, 90% TOC removal was observed with 100,000 Gy. Oxygen is well known to play a considerable role in the degradation of organic substances with effective chain reaction pathways. According to the effective radical reactions, the enhanced TOC percentage removal efficiencies might be based on the fast conversion reactions of e(aq)(-) and ()H with O(2) into oxidizing radicals, such as O(2)(-) and HO(2)(), respectively. 100% TOC removal was obtained with N(2)O gas at 20,000 Gy, as reducing radicals, such as e(aq)(-) and ()H, are scavenged by N(2)O and converted into ()OH radicals, which have strong oxidative properties. The results of this study showed that gamma irradiation was very effective for the removal of cefaclor in aqueous solution. The use of O(2) or N(2)O, with radiation, shows promise as effective radical scavengers for enhancing the TOC or COD removal efficiencies in pharmaceutical wastewaters containing antibiotics. However, the biological toxicity and interactions between various chemicals during the radiolytic treatment, as well as treatments under conditions more representative of real wastewater will require further studies.     

Cu-SBA-15催化湿式过氧化氢氧化水溶液中罗丹明B

采用水热晶化法合成了不同含铜量的Cu—SBA-15介孔分子筛，并且用XRD、N2吸附、TEM以及uV—vis对所合成的样品进行表征。以Cu—SBA-15为催化剂，H2O2为氧化剂，催化湿式过氧化水溶液中的罗丹明B，主要考察H2O2浓度、催化剂用量、处理温度、初始pH等因素对罗丹明B氧化效果的影响。结果表明，在同样的处理条件下罗丹明的脱色率明显高于TOC去除率，处理温度、初始pH对罗丹明B的脱色与氧化有重要影响。在罗丹明B初始浓度100mg／L，H2O2初始浓度1．8g／L，催化剂量0．3g／L，温度60℃，pH为7．0，处理时间100min时，罗丹明B的脱色率为98．6％，TOC去除率为62．8％。     

Chromium (VI) biosorption and bioaccumulation by chromate resistant bacteria

In this study, strains that are capable of bioaccumulating Cr(VI) were isolated from treated tannery effluent of a common effluent treatment plant. The Cr(VI) concentration in this treated effluent was 0.96 mg/l, much above the statutory limit of 0.1 mg/l for discharge of industrial effluents into inland surface waters in India. In addition to the bioaccumulation, biosorption capabilities of living and dead cells were analysed. Two strains, identified as Bacillus circulans and Bacillus megaterium were able to bioaccumulate 34.5 and 32.0 mg Cr/g dry weight, respectively and brought the residual concentration of Cr(VI) to the permissible limit in 24 h when the initial concentration was 50 mg Cr(VI)/l. Our experimental design accounts for initial as well as final residual concentration of heavy metal while selecting heavy metal accumulating strains during batch studies. Biosorption of Cr(VI) was shown by B. megaterium and an another strain, B. coagulans. Living and dead cells of B. coagulans biosorbed 23.8 and 39.9 mg Cr/g dry weight, respectively, whereas, 15.7 and 30.7 mg Cr/g dry weight was biosorbed by living and dead cells of B. megaterium, respectively. Biosorption by the dead cells was higher than the living cells. This was due to prior pH conditioning (pH 2.5 with deionized water acidified with H2SO4) of the dead cells.     

Effects of operating parameters on advanced oxidation of diuron by the Fenton's reagent: a statistical design approach

Advanced oxidation of diuron in aqueous solution by Fenton's reagent using FeSO(4) as source of Fe(II) was investigated in the absence of light. Effects of operating parameters namely the concentrations of pesticide (diuron), H(2)O(2) and Fe(II) on oxidation of diuron was investigated by using Box-Behnken statistical experiment design and the surface response analysis. Diuron oxidation by the Fenton reagent was evaluated by determining the total organic carbon (TOC), diuron, and adsorbable organic halogen (AOX) removals. Concentration ranges of the reagents resulting in the highest level of diuron oxidation were determined. Diuron removal increased with increasing H(2)O(2) and Fe(II) concentrations up to a certain level. Diuron concentration had a more profound effect than H(2)O(2) and Fe(II) in removal of diuron, TOC and AOX from the aqueous solution. Nearly complete (98.5%) disappearance of diuron was achieved after 15min reaction period. However, only 58% of diuron was mineralized after 240min under optimal operating conditions indicating formation of some intermediate products. Optimal H(2)O(2)/Fe(II)/diuron ratio resulting in the maximum diuron removal (98.5%) was found to be 302/38/20 (mgl(-1)).     

絮凝-Fenton试剂氧化处理印染废水

采用Fenton试剂对某染袜厂2种印染废水(印染红和印染蓝)进行处理。考察了硫酸亚铁投加量、双氧水投加量、反应时间及pH值对印染废水的色度及COD去除率的影响,通过正交实验确定了Fenton试剂处理该废水的最佳操作条件为:反应时间30 min、双氧水(30%)投加量4 mL/L、硫酸亚铁投加量300 mg/L、pH值为4左右。在最佳条件下,印染蓝废水经氧化处理后COD去除率大于80%,色度去除率95%以上;印染红废水需经絮凝预处理后再用Fenton试剂氧化处理,其脱色率达到了99.6%,COD去除率为91.2%,出水COD浓度为96 mg/L,可达标排放。     

Swine wastewater treatment in a two stage sequencing batch reactor using real-time control

A laboratory scale two-stage sequencing batch reactor (TSSBR) was used to study the effectiveness of pH as a real-time control parameter in swine wastewater treatment. A Ringlace media was inserted into the A/O (Anoxic/Oxic) reactor for bacteria immobilization. The TSSBR was subjected to three levels of organic loading. The pH and ORP (Oxidation Reduction Potential) patterns obtained were consistent with distinct features, enabling the real-time control strategy to effectively set a flexible aeration time pending on influent concentration, hence resulting in flexible cycle time and HRT (Hydraulic Retention Time) for the system. The real-time process ensured a removal efficiency of over 99% and 95%, respectively, for ammonia and TOC (Total Organic Carbon). For NO3(-)-N and PO4(-3), the run with influent TOC = 4,000 mg/L yielded the most efficient removal of 61% and 95%, respectively. Test results suggest that pH can be a viable tool for on-line real-time control of a biological treatment process.     

Swine wastewater treatment in a two stage sequencing batch reactor using real‐time control

Abstract

A laboratory scale two‐stage sequencing batch reactor (TSSBR) was used to study the effectiveness of pH as a real‐time control parameter in swine wastewater treatment. A Ringlace media was inserted into the A/O (Anoxic/Oxic) reactor for bacteria immobilization. The TSSBR was subjected to three levels of organic loading. The pH and ORP (Oxidation Reduction Potential) patterns obtained were consistent with distinct features, enabling the real‐time control strategy to effectively set a flexible aeration time pending on influent concentration, hence resulting in flexible cycle time and HRT (Hydraulic Retention Time) for the system. The real‐time process ensured a removal efficiency of over 99% and 95%, respectively, for ammonia and TOC (Total Organic Carbon). For NO₃ ^‐‐N and PO₄ ^‐3, the run with influent TOC = 4,000 mg/L yielded the most efficient removal of 61% and 95%, respectively. Test results suggest that pH can be a viable tool for on‐line real‐time control of a biological treatment process.     

Application of Klebsiella oxytoca immobilized cells on the treatment of cyanide wastewater

Klebsiella oxytoca, isolated from cyanide-containing industrial wastewater, has been shown to be able to biodegrade cyanide to non-toxic end products. The technology of immobilized cells can be applied in biological treatment to enhance the efficiency and effectiveness of biodegradation. In this study, potassium cyanide was used as the target compound and both alginate and cellulose triacetate techniques were applied for the preparation of immobilized cells. Results from this study show that KCN can be utilized as the sole nitrogen source by K. oxytoca. The free suspension systems reveal that the cell viability was highly affected by initial KCN concentration and pH. Results show that immobilized cell systems could tolerate a higher level of KCN concentration and wider ranges of pH. In the batch experiments, the maximum KCN removal efficiencies using alginate and cellulose triacetate immobilized beads were 0.108 and 0.101mM h(-1) at pH 7, respectively. Results also indicate that immobilized system can support a higher biomass concentration. Complete KCN degradation was observed after the operation of four consecutive degradation experiments with the same batch of immobilized cells. This suggests that the activity of immobilized cells can be maintained and KCN can be used as the nitrogen source throughout KCN degradation experiments. The maximum KCN removal rates using alginate and cellulose triacetate immobilized beads in continuous-column system were 0.224 and 0.192mMh(-1) with initial KCN concentration of 3mM, respectively. Results indicate that the immobilized cells of K. oxytoca would be applicable to the treatment of cyanide-containing wastewaters.     

Formation of chlorinated disinfection by-products in viticulture

Background, aim and scope  The use of sodium hypochlorite (HYP) in viticulture results in effluents which are contaminated with halogenated substances. These disinfection by-products (DBPs) can be quantified as group parameter ‘adsorbable organic halogens’ (AOX) and have not been determined in effluents of viticulture yet. The substances that are detected as AOX are unknown. The AOX can be composed of harmless substances, but even toxic contaminants. Thus, it is impossible to assess ecological impacts. The aim of this study is to determine the quantification of AOX and DBPs after the use of HYP. This will be helpful to reduce environmental pollution by AOX. Materials and methods  The potential of HYP to generate AOX was determined in laboratory-scale experiments. Different model solutions were treated with HYP according to disinfection processes in viticulture and conditions of AOX formation in effluents were simulated. AOX were quantified using the flask-shaking method and identified DBPs were investigated by gas chromatography–mass spectrometry. Results  Treatment with HYP resulted in the formation of AOX. The percentage conversion of HYP to AOX was up to 11%. Most important identified DBPs in viticulture are chloroform, dichloroacetic acid and trichloroacetaldehyde. In addition, the formation of carbon tetrachloride (CT), 1,1,1-trichloropropanone, 2,4-dichlorobenzoic acid and 2-chloro-/2,4-dichlorophenylacetic acid was investigated. It was demonstrated that reaction temperature, concentration of HYP and type of organic matter have important influence on the formation of chlorinated DBPs. Discussion  The percentage conversion of HYP to AOX was similar to other published studies. Although a correlation of single compounds and AOX is difficult, chloroform was the predominant AOX. Generation of the volatile chloroform should be avoided due to possible adverse effects. The generation of dichloroacetic acid is of minor importance on account of biodegradation. Trichloroacetaldehyde and 1,1,1-trichloropropanone are weak mutagens and their formation should be avoided. Conclusions  The generation of AOX and chlorinated DBPs can be minimised by reducing the concentrations of the organic materials in the effluents. The removal of organic matter before disinfection results in a decreased formation of AOX. HYP is an effective disinfectant; therefore, it should be used at low temperatures and concentrations to reduce the amount of AOX. If possible, disinfection should be accomplished by the use of no chlorine-containing agents. By this means, negative influences of HYP on the quality of wine can also be avoided. Recommendations and perspectives  Our results indicate that HYP has a high potential to form AOX in effluents of viticulture. The predominant by-products are chloroform, dichloroacetic acid and trichloroacetaldehyde. In further research, wastewaters from a winery and the in- and outflows of two sewage treatment plants were sampled during vintage and analysed. These results will be discussed in a following paper.     

不同来源废水COD、TOC与Cl-的关系

通过对含盐化工废水(A)、受潮汐影响的河流水(B)、城市生活污水处理厂排水(C)、采油废水(D)4种不同来源废水进行为期15 d的采样监测,测定了其COD、TOC和Cl-浓度,分析比较了3种废水指标之间的关系,其中COD分别使用重铬酸钾法、氯气校正法和碘化钾碱性高锰酸钾法3种方法进行测定.实验结果表明,4种废水Cl-浓...     

Efficient biosorption of chromium(VI) ion by dry Araucaria leaves

Background

In this paper, batch removal of hexavalent chromium from aqueous solutions by Araucaria heterophylla leaves was investigated. The batch experiments were conducted to study the adsorption of metal species and effect of different pH, contact time, metal concentration, biosorbent concentration, and adsorption capacity.

Method

Freundlich and Langmuir??s isotherm model were used to describe the adsorption behavior, and the experimental results fitted Freundlich model well.

Results

The adsorption efficiency observed for all chromium concentrations, i.e., 1, 3, 5, and 10?mg/L was 100% and the equilibrium was achieved in 30?min for 1 and 3?mg/L, whereas for 5 and 10?mg/L, it was less than 60?min. FTIR spectra was taken to identify functional groups involved in the biosorption.

Conclusion

Thus, Araucaria leaves can be considered as one of the cheap and efficient biosorbent for toxic hexavalent chromium removal from natural or wastewaters.     

Influence of sediment on the fate and toxicity of a polyethoxylated tallowamine surfactant system (MON 0818) in aquatic microcosms

The fate and toxicity of a polyethoxylated tallowamine (POEA) surfactant system, MON 0818, was evaluated in water-sediment microcosms during a 4-d laboratory study. A surfactant solution of 8 mg l(-1) nominal concentration was added to each of nine 72-l aquaria with or without a 3-cm layer of one of two natural sediments (total organic carbon (TOC) 1.5% or 3.0%). Control well water was added to each of nine additional 72-l aquaria with or without sediment. Water samples were collected from the microcosms after 2, 6, 24, 48, 72, and 96 h of aging to conduct 48-h toxicity tests with Daphnia magna and to determine surfactant concentrations. Elevated mortality of D. magna (43-83%) was observed in overlying water sampled from water-only microcosms throughout the 96-h aging period, whereas elevated mortality (23-97%) was only observed in overlying water sampled from water-sediment microcosms during the first 24h of aging. Measured concentrations of MON 0818 in water-only microcosms remained relatively constant (4-6 mg l(-1)) during the 96-h period, whereas the concentrations in overlying water from microcosms containing either of the two types of sediment dissipated rapidly, with half-lives of 13 h in the 3.0% TOC sediment and 18 h in the 1.5% TOC sediment. Both toxicity and the concentration of MON 0818 in overlying water decreased more rapidly in microcosms containing sediment with the higher percent TOC and clay and with a higher microbial biomass. Mortality of D. magna was significantly correlated with surfactant concentrations in the overlying water. These results indicate that the toxicity of the POEA surfactant in water rapidly declines in the presence of sediment due to a reduction in the surfactant concentration in the overlying water above the sediment.     

Investigation of acute toxicity of cadmium chloride (CdCl2 . H2O) metal salt and behavioral changes it causes on water frog (Rana ridibunda Pallas, 1771)

The 96-h LC(50) value of cadmium chloride (CdCl(2).H(2)O), a metal salt widely used in industry, was determined in the water frog (Rana ridibunda Pallas, 1771). The experiments were conducted in two series and a total of 140 frogs were used to determine acute toxicity. In addition, behavioral changes in the water frog were determined for each cadmium chloride concentration. Data obtained from the cadmium chloride investigation were evaluated by using the probit analysis statistical method and the 96 h LC(50) value for water frog was estimated to be 51.2 mg/l.     

Biodegradation of phenol in refinery wastewater by pure cultures of Pseudomonas aeruginosa NCIB 950 and Pseudomonas fluorescence NCIB 3756

The potential of microorganisms to catabolise and metabolise xenobiotic compounds has been recognised as a potentially effective means of toxic and hazardous wastes disposal. Phenol and its derivatives have long been recognised as some of the most persistent chemicals in petroleum refinery wastewaters, with high toxicity even at low concentrations. Biodegradation of these compounds has been recognised as a potential solution for their disposal owing to its cost effectiveness and simplicity. Two species of pseudomonas, P. aeruginosa and P. fluorescence, were studied for their biodegradation potential on phenol present in a refinery wastewater under a batch fermentation process. Phenol was successfully degraded by both species, and there was high positive correlation between phenol biodegradation and microbial growth. The maximum specific growth rate were obtained for both species from the Haldane model. The study revealed the high potential of these local strains, with P. aeruginosa being more effective, and the possibility of using them in bioremediation of petroleum refinery wastewaters.