Influence of ozone pre-treatment on sludge anaerobic digestion: removal of pharmaceutical and personal care products

The effect of an oxidative pre-treatment with ozone on the removal of Pharmaceutical and Personal Care Products (PPCPs) during the anaerobic digestion of sewage sludge has been investigated. Besides, the digested sludge characteristics in terms of pathogens content, dewatering properties, heavy metals content and linear alkylbenzene sulfonates (LAS) were determined. During ozonation (20mg O(3)/g TSS), about 8% of volatile solids (VS) and 60% of the chemical oxygen demand (COD) were solubilized. However, no mineralization was observed. The elimination of VS and total COD during anaerobic digestion were not affected by ozone treatment with efficiencies ranging from 60% to 65%. All PPCPs considered were removed during anaerobic treatment of sludge, with efficiencies ranging from 20% to 99%. No significant influence of ozone pre-treatment was observed on PPCPs elimination except for carbamazepine. Pathogens, heavy metals and LAS contents after conventional and pre-ozonation treatment of sewage sludge were below the legal requirements. However, the dewatering properties of sludge were deteriorated when the ozone pre-treatment was applied.     

Organic micropollutants’ distribution within sludge organic matter fractions explains their dynamic during sewage sludge anaerobic digestion followed by composting

The simultaneous fate of organic matter and 4 endocrine disruptors (3 polycyclic aromatic hydrocarbons (PAHs) (fluoranthene, benzo(b)fluoranthene, and benzo(a)pyrene) and nonylphenols (NP)) was studied during the anaerobic digestion followed by composting of sludge at lab-scale. Sludge organic matter was characterized, thanks to chemical fractionation and 3D fluorescence deciphering its accessibility and biodegradability. Total chemical oxygen demand (COD) removal was 41% and 56% during anaerobic digestion and composting, respectively. 3D fluorescence highlighted the quality changes of organic matter. During continuous anaerobic digestion, organic micropollutants’ removal was 22?±?14%, 6?±?5%, 18?±?9%, and 0% for fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, and nonylphenols, respectively. Discontinuous composting allowed to go further on the organic micropollutants’ removal as 34?±?8%, 31?±?20%, 38?±?10%, and 52?±?6% of fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, and nonylphenols were dissipated, respectively. Moreover, the accessibility of PAH and NP expressed by their presence in the various sludge organic matter fractions and its evolution during both treatments was linked to both the quality evolution of the organic matter and the physicochemical properties of the PAH and NP; the presence in most accessible fractions explained the amount of PAH and NP dissipated.

     

PAH removal from spiked municipal wastewater sewage sludge using biological, chemical and electrochemical treatments

Polycyclic aromatic hydrocarbons (PAHs) have been widely studied due to their presence in all the environmental media and toxicity to life. These molecules are strongly adsorbed on the particulate matters of soils, sludges or sediments because of their strong hydrophobicity which makes them less bioavailability, thus limiting their bioremediation. Different sludge treatment processes were tested to evaluate their performances for PAH removal from sludge prealably doped with 11 PAHs (5.5mg each PAH kg(-1) of dry matter (DM)): two biological processes (mesophilic aerobic digestion (MAD) and simultaneous sewage sludge digestion and metal leaching (METIX-BS)) were tested to evaluate PAH biodegradation in sewage sludge. In parallel, two chemical processes (quite similar Fenton processes: chemical metal leaching (METIX-AC) and chemical stabilization (STABIOX)) and one electrochemical process (electrochemical stabilization (ELECSTAB)) were tested to measure PAH removal by these oxidative processes. Moreover, PAH solubilisation from sludge by addition of a nonionic surfactant Tween 80 (Tw80) was also tested. The best yields of PAH removal were obtained by MAD and METIX-BS with more than 95% 3-ring PAH removal after a 21-day treatment period. Tw80 addition during MAD treatment increased 4-ring PAHs removal rate. In addition, more than 45% of 3-ring PAHs were removed from sludge by METIX-AC and during ELECSTAB process were quiet good with approximately 62% of 3-ring PAHs removal. However, little weaker removal of 3-ring PAHs (<35%) by STABIOX. None of the tested processes were efficient for the elimination of high molecular weight (> or = 5-ring) PAHs from sludge.     

臭氧预处理—厌氧消化工艺促进剩余污泥减量化的研究

主要研究了臭氧氧化对剩余污泥的破解效果及污泥厌氧消化效率的影响.结果表明,随着臭氧投加量的增加,悬浮物(SS)、可挥发性悬浮物(VSS)逐步减少,而剩余污泥上清液中的溶解性COD(SCOD)、总有机碳(TOC)、蛋白质和多糖则明显增加.经臭氧预处理(臭氧投加量为0.050 g(以每克SS计))后,剩余污泥中温(35℃)厌氧消化效率明显提高,经65d稳定运行后,总挥发性固体(TVS)去除率为67.58％,与未经臭氧预处理的剩余污泥相比提高50.61％;甲烷平均产率为0.303 L(以每克TVS计),与未经臭氧预处理的剩余污泥相比提高54.59％.可见,臭氧预处理能有效促进污泥厌氧消化,从而达到污泥减量的目的.     

Treatment of distillery spent-wash by ozonation and biodegradation: significance of pH reduction and inorganic carbon removal before ozonation.

This study is aimed at exploring strategies for mineralization of refractory compounds in distillery effluent by anaerobic biodegradation/ozonation/aerobic biodegradation. Treatment of distillery spent-wash used in this research by anaerobic-aerobic biodegradation resulted in overall COD removal of 70.8%. Ozonation of the anaerobically treated distillery spent-wash was carried out as-is (phase I experiments) and after pH reduction and removal of inorganic carbon (phase II experiments). Introduction of the ozonation step resulted in an increase in overall chemical oxygen demand (COD) removal, with the highest COD removals of greater than 95% obtained when an ozone dose of approximately 5.3 mg ozone absorbed/mg initial total organic carbon was used. The COD removal during phase II experiments was slightly superior compared with phase I experiments at similar ozone doses. Moreover, efficiency of ozone absorption from the gas phase into distillery spent-wash aliquots was considerably enhanced during phase II experiments.     

Treatment of pharmaceutical wastewater containing antibiotics by O3 and O3/H2O2 processes

Ozonation of three different synthetic pharmaceutical formulation wastewater containing two human antibiotics and a veterinary antibiotic has been studied to enhance the their biodegradability. The effects of pH and initial chemical oxygen demand (COD) value as well as addition of hydrogen peroxide on ozonation process were investigated. Total organic carbon (TOC), COD, biochemical oxygen demand (BOD), and aromatic content (UV254) were the parameters followed to evaluate the performance of ozonation process. Comparison of the biodegradability of selected wastewaters containing different antibiotics confirmed that the variation of biodegradability was associated with the target compound. While BOD5/COD ratio of veterinary antibiotic formulation wastewater was increased from 0.077 to 0.38 with an applied ozone dosage of 2.96 g/l, this ratio for human antibiotic I and human antibiotic II was increased from 0 to 0.1 and 0.27 respectively. Moreover the results of this investigation showed that the ozonation process is capable of achieving high levels of COD and aromaticity removals at about their natural pH values.     

原位臭氧氧化对活性污泥系统硝化和反硝化作用的影响研究

将厌氧序批式间歇反应器(ASBR)和序批式间歇反应器(SBR)串联组成污泥减量新工艺,着重探讨了对SBR段进行原位臭氧投加时,臭氧氧化作用对系统硝化和反硝化能力的影响,并以不投加作为对照。结果表明,将臭氧原位投加到ASBR—SBR组合工艺的SBR段,臭氧投加量为0.027g(以每克MLSS计),每隔3个周期再次投加、连续运行40d,试验组SBR段臭氧投加当期出水COD去除率为86%,比对照组下降了9百分点,但臭氧氧化细胞内大量有机物进入混合液中,为反硝化作用提供了外加碳源,对污泥反硝化能力的提高起到了一定的促进作用;试验组部分硝化细菌由于臭氧的强氧化作用而失去活性,但是随着剩余污泥量的减少,系统的污泥龄延长,有利于硝化细菌的生长,使得系统的硝化能力基本未受影响;试验组臭氧投加当期SBR段出水NO2--N平均浓度比对照组的高18.9%,但经过3个周期的运行后,其SBR段出水NO2--N平均质量浓度降低至7.57mg/L,基本与对照组持平;试验组臭氧投加当期SBR段出水NO3--N的平均浓度高于对照组,但经过3个周期的运行后,试验组出水NO3--N平均浓度低于对照组;试验组臭氧投加当期SBR段出水TN和对照组的出水TN平均去除率分别为65%和75%,但试验组再经过3个周期的运行后,出水TN平均去除率可以达到72%。可见,原位投加臭氧并未对SBR段的硝化和反硝化能力产生明显的影响。     

Persistence of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge-amended soil

The application of sewage sludge as a fertilizer is a common method used to improve soil properties. However, sewage sludge may contain various organic pollutants including polycyclic aromatic hydrocarbons. In the present study, the persistence of PAHs in soils fertilized with different sewage sludge doses was compared in relation to the sewage sludge dose applied (30, 75, 150, 300 and 600 Mgha(-1)) and the content of the polycyclic aromatic hydrocarbons in them. The experiment was carried out in two blocks of experimental plots divided according to the type of plants grown: field plants and perennial-willow. Sewage sludge addition to soils resulted in an increase in the content of polycyclic aromatic hydrocarbons in these soils. This increase was proportional to the quantity of sewage sludge applied. The results obtained showed that during a 42/54-month period, more than half of the individual PAHs introduced into the soil with sewage sludge were degraded. The scope of dissipation depended on the sewage sludge dose and the use to which the area was put. In the experiment with the willow only in the case of the highest sludge dose was a decrease in the PAH content above 50% noted; whereas in the case of the experiment with the field plants, it was higher by 50% for all sewage sludge doses. In experiment with field plants the highest scope of individual PAH disappearance was observed in the soil with the sewage sludge dose amounting to 300 Mgha(-1). In experiment with willow a relatively high dissipation of individual PAHs (>50%) was found in the treatment with the highest sludge dose (600 Mgha(-1)). A wider PAH dissipation range in the experiment with field plants was conditioned by the more favourable conditions created as a result of the breeding treatments applied. Agrotechnical treatments clearly increased the disappearance of the PAHs in those soils fertilized with the lowest sewage sludge doses (30 and 75 Mgha(-1)). The results obtained showed that the preferred method of treating a light soil fertilised with sewage sludges should be a one-year system, with a sludge application of 75 Mgha(-1).     

应用表面活性剂-生物柴油微乳液去除污染土壤中多环芳烃

针对修复焦化厂高浓度多环芳烃污染土壤高成本的现实,采用以非食用性植物油、生物柴油、表面活性剂及其乳化合成的微乳液为淋洗剂,比较不同淋洗剂的淋洗效果。结果表明乳化合成的微乳液对焦化厂土壤中多环芳烃的总去除率高于单独使用表面活性剂为淋洗剂对土壤中多环芳烃的总去除率,说明生物柴油及植物油与表面活性剂乳化形成的微乳液对原污染土壤中的多环芳烃具有显著的增溶作用。1%TW-80和2.5%TW-80对土壤中多环芳烃总去除率分别为11%和14%;以2.5%TW-80为原料乳化合成的微乳液的淋洗去除率较以1%TW-80为原料乳化合成的微乳液高,总去除率分别为15%～30%和11%～18%;以生物柴油为原料乳化合成的微乳液的淋洗去除率较以植物油为原料乳化合成的微乳液高,分别为17%～30%和15%～23%,且对多环芳烃的去除率与其辛醇水分配系数(logKow)呈线性相关关系。     

Successful Treatment of Low PAH-Contaminated Sewage Sludge in Aerobic Bioreactors (7 pp) *

Background, Aims and Scope Polycyclic Aromatic Hydrocarbons (PAHs) are known for their adverse and cumulative effects at low concentration. In particular, the PAHs accumulate in sewage sludge during wastewater treatment, and may thereafter contaminate agricultural soils by spreading sludge on land. Therefore, sludge treatment processes constitute the unique opportunity of PAH removal before their release in the environment. In this study, the ability of aerobic microorganisms to degrade light and heavy PAHs was investigated in continuous bioreactors treating trace-level PAH-contaminated sludge. Methods Several aerobic reactors were operated under continuous and perfectly mixed conditions to simulate actual aerobic sludge digesters. Three sterile control reactors were performed at 35°C, 45°C or 55°C to assess PAH abiotic losses under mesophilic and thermophilic conditions. Three biological reactors were also operated at 35°C, 45°C or 55°C. Furthermore, 250 mM methanol were added in an additional mesophilic reactor (35°C). All reactors were fed with long-term PAH-contaminated sewage sludge, and PAH removal was assessed by inlet/outlet mass balance. In this study, PAH compounds ranged from 2 to 5-unsubstituted aromatic rings, i.e. respectively from Fluorene to Indeno(123cd)pyrene. Results and Discussion Significant abiotic losses were observed for the lightest PAHs (fluorene, phenanthrene and anthracene), while biodegradation occurred for all PAHs. More than 80% of the lightest PAHs were removed. Biodegradation rates inversely correlated with the increasing molecular weight, and seemed limited by the low bioavailability of the heaviest PAHs (only 50% of removal). The enhancement of PAH bioavailability by increasing the process temperature or adding methanol was tested. A temperature increase from 35°C to 45°C and then to 55°C significantly enhanced the biodegradation of the heaviest PAHs from 50% to 80%. However, high abiotic losses were observed for all PAHs at 55°C, which was attributed to volatilization. Optimal conditions were found at 45°C considering the low abiotic losses and the high PAH biodegradation rates. Similar performances were achieved by addition of methanol in the sludge. It was concluded that increasing temperatures or addition of methanol favored PAH diffusion from solids to an aqueous compartment, and enhanced their bioavailability to PAH-degrading microorganisms. Conclusion In this study, the use of long-term acclimated aerobic ecosystems showed the high potential of aerobic microorganisms to degrade a wide range of PAHs at trace levels. However, PAH biodegradation was likely controlled by their low bioavailability. Two aerobic processes have been finally proposed to achieve efficient decontamination of sewage sludge, at 45°C or in the presence of methanol. The PAH concentrations in reactor outlet were lower than the French requirements, and allow the treated sludge to be spread on agricultural land. Recommendations and Outlook The two proposed aerobic processes used physical or chemical diffusing agents. The global ecological impact of using the latter agents for treating trace level contamination must be considered. Since methanol was completely removed during the process, no additional harm is expected after treatment. However, an increase of temperature to 45°C could drastically increase the energy demand in full-scale plants, and therefore the ecological impact of the process. Moreover, since bioavailability controls PAH biodegradation, efficiency of the processes could also be influenced by the hydraulic parameters, such as mixing and aeration rates. Further experimentations in a pilot scale are therefore recommended, as well as a final assessment of the global environmental benefit of using such aerobic processes in the bioremediation of trace level compounds. - Abbreviations (PAHs): Ant – anthracene; B(a)A – benzo(a)anthracene ; B(b)F – benzo(b)fluoranthene; B(k)F – benzo(k)fluoranthene; B(ghi)P – benzo(g,h,i)perylene; B(a)P – benzo(a)pyrene; Chrys – chrysene; DB – dibenzo(a,h)anthracene; Fluor – fluoranthene; Fluo - fluorene; Ind – indeno(1,2,3-c,d)pyrene; Phe - phenanthrene; Pyr – pyrene - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Efficacy of in-situ for the remediation of PAH contaminated soils

Polycyclic aromatic hydrocarbons (PAHs) are of environmental concern because many PAHs are either carcinogens or potential carcinogens. Petroleum products are a major source of PAHs. The occurrence of PAH contamination is widespread and novel treatment technologies for the remediation of contaminated soils are necessary.Ozone has been found to be extremely useful for the degradation of PAHs in soils. For these compounds, the reaction with molecular ozone appears to be the more important degradation pathway. Greater than 95% removal of phenanthrene was achieved with an ozonation time of 2.3 h at an ozone flux of 250 mg h⁻¹. After 4.0 h of treatment at an ozone flux of 600 mg h⁻¹, 91 % of the pyrene was removed. We have also found that the more hydrophobic PAHs (e.g. chrysene) react more slowly than would be expected on the basis of their reactivity with ozone, suggesting that partitioning of the contaminant into soil organic matter may reduce the reactivity of the compound. Even so, after 4 h of exposure to ozone, the chrysene concentration in a contaminated Metea soil was reduced from 100 to 50 mg kg⁻¹ .Ozone has been found to be readily transported through columns packed with a number of geological materials, including Ottawa sand, Metea soil, Borden aquifer material and Wurtsmith aquifer material. All of these geological materials exerted a limited (finite) ozone demand, i.e. the rate of ozone degradation in soil columns is very slow after the ozone demand is met. Moisture content was found to increase the ozone demand, most likely owing to the dissolution of gaseous ozone into the pore water. As once the initial ozone demand is met, little degradation of ozone is observed, it should be possible to achieve ozone penetration to a considerable distance away from the injection well, suggesting that in-situ ozonation is a feasible means of treating uncontaminated unsaturated soils. This is substantiated by two field studies where in-situ ozonation was apparently successful at remediating the sites.     

The enhancement of the biodegradability of phenolic solution using preozonation based on high ozone utilization

In this research, the effects of preozonation on the biodegradability of 4-cresol, 4-nitrophenol and 2-chlorophenol solutions were investigated using a new gas-inducing reactor with high ozone utilization rate. The extent of preozonation may be monitored by determining the characteristic ozonation behaviors of preozonized phenolic solutions, such as residual phenolic concentration, ADMI value and ozone gas outlet concentration. Experimental results showed that as the initial phenolic compounds decomposed completely, the ozone gas outlet concentration rapidly increases. In addition, at pH 7, a peak ADMI value appears during the preozonation of 4-cresol and 2-chlorophenol, while for 4-nitrophenol the ADMI value decreases monotonically. Based on the characteristic ozonation behaviors and the ozone utilization rate, three characteristic times were chosen in order to have better control on the extent of preozonation. The effect of preozonation on the biodegradability of preozonized phenolic solution was studied based on these characteristic times. The intermediate products during the preozonation were also identified. The variation of BOD5 is strongly dependent on the accumulation of intermediate products. It is suggested that the best characteristic time is as the rapid increase of ozone gas outlet concentration in this study. The biodegradability (BOD5/COD) of preozonized 4-cresol, 2-chlorophenol and 4-nitrophenol solutions increase to 0.18, 0.26 and 0.33, respectively, for the best characteristic time.     

The fate of chlorobenzenes and permethrins during anaerobic sewage sludge digestion

Mixed primary sewage sludge was incubated anaerobically with and without azide addition to prevent biological activity. The behaviour of 1,3-, 1,4- and 1,2-dichlorobenzene, 1,3,5-, 1,2,4- and 1,2,3-trichlorobenzene, 1,2,3,4- and 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, and cis- and trans-permethrin was examined to determine their potential removal during anaerobic digestion. All the chlorobenzenes were removed to varying extents over 32 days of incubation, ranging from 25% removal for 1,3,5-trichlorobenzene to 80% removal for 1,4-dichlorobenzene. Biodegradation may have been responsible for the reductions in 1,3- and 1,4-dichlorobenzene and 1,2,4- and 1,2,3-trichlorobenzene as there was no significant removal of these compounds in azide treated sludge. The removal over 32 days of cis- and transpermethrin was 87% and 96% respectively. These removals were attributed to a chemical or physical process.     

Combined chemical and biological treatment of oil contaminated soil

Combined chemical (Fenton-like and ozonation) and biological treatment for the remediation of shale oil and transformer oil contaminated soil has been under study. Chemical treatment of shale oil and transformer oil adsorbed in peat resulted in lower contaminants' removal and required higher addition of chemicals than chemical treatment of contaminants in sand matrix. The acidic pH (3.0) conditions favoured Fenton-like oxidation of oil in soil. Nevertheless, it was concluded that remediation of contaminated soil using in situ Fenton-like treatment will be more feasible at natural soil pH. Both investigated chemical processes (Fenton-like and ozonation) allowed improving the subsequent biodegradability of oil. Moderate doses of chemical oxidants (hydrogen peroxide, ozone) should be applied in combination of chemical treatment (both, Fenton-like or ozonation) and biotreatment. For remediation of transformer oil and shale oil contaminated soil Fenton-like pre-treatment followed by biodegradation was found to be the most efficient.     

Performance change during long-term ozonation aimed at augmenting denitrification and decreasing waste activated sludge

Partial ozonation of return activated sludge for waste sludge minimization and soluble COD production was examined. Two nitrifying sequencing batch reactors, one control and one ozonated, were operated under alternating anoxic/aerobic conditions. During the first steady-state period of 95-136 d of ozonation, the amount of wasted solids decreased with the ozone dose up to 25%, generating soluble COD by cell lysis. However, during a subsequent period of 190-232 d of continuous ozonation, the effect of solids destruction and COD production decreased by 50%. The investigations of extracellular polymers content and floc shape analyses showed that, after prolonged daily ozone treatment, sludge floc structure becomes stronger, denser, and more ozone-resistant. The findings suggest that, for prolonged operation of partial sludge ozonation, an increase in ozone doses may be required to continuously maintain the expected solids destruction level. This in turn will increase the operational costs of the treatment.     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

臭氧对活性污泥特性影响研究

探讨了臭氧对于污水生物处理中活性污泥特性的影响。结果显示 ,随着臭氧化的进行 ,促进了活性污泥生物量的减少 ,并有一定量的生物污泥被无机化 ,并且污泥的活性和存活性降低了。其中臭氧投加量低于 0 .1gO3 /gSS时污泥活性即大幅下降 ,而后污泥浓度才随着臭氧量的增加而显著降低。     

Changes of polycyclic aromatic hydrocarbons during composting of sewage sludges with chosen physico-chemical properties and PAHs content

The aim of the experiment was to determine changes in the PAH content during sewage sludge composting. The extent was evaluated to which sewage sludge properties influences on PAHs losses during composting. Five municipal sewage sludges were studied from sewage treatment plants located in the south-east of Poland, i.e. in Stalowa Wola, Kra?nik, Lublin, Zamo?? and Bi?goraj. The treatment plants selected were characterised by their differentiation with catchments area as well as the industrial character of the areas. Sludge composting was carried out in aerobic conditions in plastic containers for a period of 76 days. The content of 14 polycyclic aromatic hydrocarbons (PAHs) and some physical-chemical (TOC, Nt, TOC/Nt, CEC, BS, TEB, pH, available potassium and phosphorus, total forms of cations) sewage sludge properties were monitored. In the present study correlations between PAHs losses (during various phases of composting) and physical-chemical properties of sewage sludges and composts were also evaluated. The sewage sludges were characterised both by differentiated properties and by PAH content. The total PAH content (the sum of 14 PAHs from the EPA List with exception of naphthalene and acenaphthene) in the sludges ranged from 3674 to 11236 microg kg(-1). Four- and three-ring compounds were predominant in the sewage sludges. Almost all of the sludges were characterised by differentiated content levels of both individual PAHs groups and PAHs sum. After 76 days of composting, a significant lowering of the PAH content was observed in all sludges as compared to the beginning of the experiment. The range of total observed PAH losses was from 15.8% to 48.6%, depending on the sewage sludge. The largest lowering of the PAH content was observed in the sludge with the lowest concentration of the xenobiotics studied. The largest losses in individual PAHs were observed in the case of five- and six-rings compounds, and were probably related to strong pollutant binding by other components of the sewage sludge. The few significant relationships showed that PAH losses during composting were only slightly determined by the analysed physical-chemical properties.     

Migration of polycyclic aromatic hydrocarbons (PAHs) in urban treatment sludge to the air during PAH removal applications

In the present study, the amounts of polycylic aromatic hydrocarbons (PAHs) penetrating into air during PAH removal applications from the urban treatment sludge were investigated. The effects of the temperature, photocatalyst type, and dose on the PAH removal efficiencies and PAH evaporation were explained. The sludge samples were taken from an urban wastewater treatment plant located in the city of Bursa, with 585,000 equivalent population. The ultraviolet C (UV-C) light of 254 nm wavelength was used within the UV applications performed on a specially designed setup. Internal air of the setup was vacuumed through polyurethane foam (PUF) columns in order to collect the evaporated PAHs from the sludge during the PAH removal applications. All experiments were performed with three repetitions. The PAH concentrations were measured by gas chromatography–mass spectrometry (GC-MS). It was observed that the amounts of PAHs penetrating into the air were increased with increase of temperature, and more than 80% of PAHs migrated to the air consisted of 3-ring compounds during the UV and UV-diethylamine (DEA) experiments at 38 and 53 °C. It was determined that 40% decrease was ensured in Σ₁₂ (total of 12) PAH amounts with UV application and 13% of PAHs in sludge penetrated into the air. In the UV-TiO₂ applications, a maximum 80% of Σ₁₂ PAH removal was obtained by adding 0.5% TiO₂ of dry weight of sludge. The quantity of PAH penetrating into air did not exceed 15%. UV-TiO₂ applications ensured high levels of PAH removal in the sludge and also reduced the quantity of PAH penetrating into the air. Within the scope of the samples added with DEA, there was no increase in PAH removal efficiencies and the penetration of PAHs into air was not decreased. In light of these data, it was concluded that UV-TiO₂ application is the most suitable PAH removal alternative that restricts the convection of PAH pollution.

Implications: Polycyclic aromatic hydrocarbon (PAH) evaporation rates from sludge samples obtained from an urban wastewater treatment plant were investigated here for the first time by employing removal applications. TiO₂ and diethylamine were used as photocatalysts in this study. A special device was designed and successfully used in this study. Treatment sludge can be a significant source of PAHs for the atmosphere. The data highlight the need for removal of PAHs in treatment sludge via methods limiting their evaporation to the air. It was observed that UV-TiO₂ application was the most suitable PAH removal alternative that restricts the convection of PAH pollution.     

Enhanced sludge solubilization by microbubble ozonation

A microbubble ozonation process for enhancing sludge solubilization was proposed and its performance was evaluated in comparison to a conventional ozone bubble contactor. Microbubbles are defined as bubbles with diameters less than several tens of micrometers. Previous studies have demonstrated that microbubbles could accelerate the formation of hydroxyl radicals and hence improve the ozonation of dyestuff wastewater. The results of this study showed that microbubble ozonation was effective in increasing ozone utilization and improving sludge solubilization. For a contact time of 80 min, an ozone utilization efficiency of more than 99% was obtained using the microbubble system, while it gradually decreased from 94% to 72% for the bubble contactor. The rate of microbial inactivation was obviously faster in the microbubble system. At an ozone dose of 0.02 g O₃ g⁻¹ TSS, about 80% of microorganisms were inactivated in the microbubble system, compared with about 50% inactivation for the bubble contactor. Compared to the bubble contactor, more than two times of COD and total nitrogen, and eight times of total phosphorus content were released from the sludge into the supernatant by using the microbubble system at the same ozone dosage. The application of microbubble technology in ozonation processes may provide an effective and low cost approach for sludge reduction.