Anaerobic treatment of domestic sewage with a rotating stationary fixed-film reactor

An anaerobic reactor was developed for on-site and small scale wastewater treatment applications. The up-flow fixed-film reactor was packed with two different types of circular media: stationary and rotating. Experimental results showed the reactor can treat primary settled domestic wastewaters efficiently, under different operating conditions. At 29°C the mixing action did not improve the organic matter removal efficiencies (65% COD removal was obtained with an organic load of 1.7 kg COD m⁻³ day⁻¹ and a 6 h space time). However, at 16°C the removal efficiency was greatly dependent on the mixing conditions: a gentle agitation (5 rpm) up-graded significantly the reactor operation, but no improvement was observed beyond 15 rpm. It appears that at low temperatures liquid biofilm mass transfer is the rate limiting step when treating sewage anaerobically. Gas production was rather limited [0.11 m³ (STP) kg⁻¹ COD removed] and calculations suggest that more than 50% of the total CH₄ produced is lost due to its dissolution in the effluent. Improved effluent quality, reduced sludge production (0.11 kg TSS kg⁻¹ COD supplied), low energy requirements and low maintenance needs make this reactor a good, compact alternative to conventional household wastewater treatment processes.     

Anaerobic biological treatment of phenol at 9.5-15 degrees C in an expanded granular sludge bed (EGSB)-based bioreactor

The aims of this study were to demonstrate the (1) feasibility of psychrophilic, or low-temperature, anaerobic digestion (PAD) of phenolic wastewaters at 10–15 °C; (2) economic attractiveness of PAD for the treatment of phenol as measured by daily biogas yields and (3) impact on bioreactor performance of phenol loading rates (PLRs) in excess of those previously documented (1.2 kg phenol m⁻³ d⁻¹). Two expanded granular sludge bed (EGSB)-based bioreactors, R1 and R2, were employed to mineralise a volatile fatty acid-based wastewater. R2 influent wastewater was supplemented with phenol at an initial concentration of 500 mg l⁻¹ (PLR, 1 kg m⁻³ d⁻¹). Reactor performance was measured by chemical oxygen demand (COD) removal efficiency, CH₄ composition of biogas and phenol removal (R2 only). Specific methanogenic activity, biodegradability and toxicity assays were employed to monitor the physiological capacity of reactor biomass samples. The applied PLR was increased to 2 kg m⁻³ d⁻¹ on day 147 and phenol removal by day 415 was 99% efficient, with 4 mg l⁻¹ present in R2 effluent. The operational temperature of R1 (control) and R2 was reduced by stepwise decrements from 15 °C through to a final operating temperature of 9.5 °C. COD removal efficiencies of c. 90% were recorded in both bioreactors at the conclusion of the trial (day 673), when the phenol concentration in R2 effluent was below 30 mg l⁻¹. Daily biogas yields were determined during the final (9.5 °C) operating period, when typical daily R2 CH₄ yields of c. 3.3 l CH₄ g⁻¹ COD_removed d⁻¹ were recorded. The rate of phenol depletion and methanation by R2 biomass by day 673 were 68 mg phenol g VSS⁻¹ d⁻¹ and 12–20 ml CH₄ g VSS⁻¹ d⁻¹, respectively.     

Integrated ozone and biotreatment of pulp mill effluent and changes in biodegradability and molecular weight distribution of organic compounds

The overall effectiveness of integrating ozonation with biological treatment on the biodegradability enhancement and recalcitrant organic matter (ROM) removal from pulp mill alkaline bleach plant effluent was investigated. Ozonation was performed in a semi-batch bubble column reactor at pH of 11 and 4.5. Batch biological treatment was conducted in shake flasks. Samples obtained during the treatments were monitored for BOD₅, COD, TOC, and molecular weight distribution. At an ozone dosage of 0.7-0.8 mg O₃/mL wastewater, integrated treatment showed about 30% higher TOC mineralization compared to individual ozonation or biotreatment. Ozone treatment enhanced the biodegradability of the effluent (monitored as 21% COD reduction and 13% BOD₅ enhancement), allowing for a higher removal of pollutants. The conversion of high molecular weight (HMW) to low molecular weight (LMW) compounds was an important factor in the overall biodegradability enhancement of the alkaline effluent. The overall biodegradability of the LMW compounds did not change over the course of ozonation, but it increased from 5% to 50% (measured as COD removal) for the HMW portion. Ozonation at pH of 11 was more effective than that at pH of 4.5 in terms of generating more biodegradable compounds.     

Biodegradability of ozonation products as a function of COD and DOC elimination by the example of humic acids

Ozone pretreatment studies of humic acids were conducted to evaluate the effects of ozonation on the biodegradability of the oxidation products as a function of COD-, DOC-elimination, decrease of u.v.-absorbance and ozone consumption. A 50–60% decrease of the COD-value and a 30% decrease of the DOC-value lead to biodegradable products (BOD₅/COD = 0.4) in most cases independent of the pH-value and the initial concentration. To reach these results 3.4–4 mg ozone are consumed per mg initial DOC. With this ozone consumption complete decolorization of the solutions is achieved and the value of u.v./DOC decreases from 4 to 0.8 m² g⁻¹.     

Combined biological and ozone treatment of log yard run-off

Batch biological treatment of log yard run-off reduced biochemical oxygen demand (BOD), chemical oxygen demand (COD) and tannin and lignin (TL) concentration by 99%, 80%, and 90%, respectively. Acute (Microtox) toxicity was decreased over treatment, from an initial EC50 of 1.83% to a value of 50.4% after 48 h of treatment. Kinetics of biodegradation were determined using respirometry and fitted using the Monod and Tessier model. For the Monod model the maximum substrate uptake rate, and Ks values determined were 0.0038 mg BOD/mgVSS min, and 1.4 mg/L, respectively. The efficacy of ozone as a pre- and post- biological treatment stage was also assessed. During ozone pretreatment, TL concentration and acute toxicity were rapidly reduced by 70% and 71%, respectively. Pre-ozonation reduced BOD and COD concentration by < 10%, however a larger fraction of residual COD was non biodegradable after ozonation. Biologically treated effluent was subjected to ozonation to determine whether further improvements in effluent quality could be achieved. A reduction in COD and TL concentration was observed during ozonation, however no further improvement in toxicity was observed. Ozonation increased BOD by 38%, due to conversion of COD to BOD.     

Effect of settling on performance of the upflow anaerobic sludge bed reactors

The effects of settler volume on the start-up and steady-state performance of 41. laboratory upflow sludge bed reactors treating bean blanching waste of 10,000 mg COD l⁻¹ were determined. The rate of start-up, as well as the maximum loading rate, increased with increased settler volume and performance. A loading rate of 30 kg COD m⁻³ day⁻¹ (based on reactor volume alone) and a COD removal of 95% was obtained with a 21. settling flask and a 4 to 1 recirculation rate. Without a settler, the maximum loading rate was 10 kg COD m⁻³ day⁻¹. The sludge was flocculent rather than granular. Sludge profiles and characteristics in the reactors and settlers were determined.     

利用同步臭氧氧化实现SBR污泥减量的研究

将臭氧通入SBR反应器中进行同步臭氧氧化,考察了污泥的减量效果以及对出水水质的影响.结果表明:污泥产率随着臭氧投量的增加而减小,当臭氧投加量从零增加到O.04gO3/gSS时污泥产率从0.45 gSS/gSCOD减少到-0.04 gSS/gSCOD;同步臭氧氧化对SBR系统的出水水质没有显著影响,当臭氧投加量为0.03 gO3/gSS时系统对COD、NH4 -N、TP的去除率分别为92.5%、91.1%、80.5%.可见,同步臭氧氧化是实现污泥减量的有效方法.     

Disinfection of advanced wastewater treatment effluent by chlorine, chlorine dioxide and ozone: Experiments using seeded poliovirus

Chlorine, chlorine dioxide and ozone were tested as chemical disinfectants against seeded poliovirus and naturally-occurring fecal coliform organisms in wastewater effluent that had received secondary treatment followed by bench scale advanced wastewater treatment (AWT). The AWT sequence consisted of chemical treatment with lime or alum followed by mixed media filtration. The resulting effluent had low suspended solids concentrations but chemical oxygen demand and nitrogen concentrations only slightly lower than those of secondary effluent. Lime treatment produced greater reductions than alum treatment in virus numbers, but not in fecal coliform organisms.

With both chlorine and chlorine dioxide, in order to reduce seeded poliovirus to less than detectable levels, it was necessary to use doses comparable to those required to disinfect secondary effluent. The required contact times of 30–60 min were also comparable. Utilized ozone doses of 2–4 mg l⁻¹ were required to reduce seeded poliovirus to less than detectable levels in AWT effluent. Naturally-occurring fecal coliform organisms were unaffected at these ozone doses, but were inactivated at higher doses. Because they were more resistant than seeded poliovirus to ozone, fecal coliform organisms show promise as indicators for ozone disinfection.     

Biodegradability of ozonation products as a function of COD and DOC elimination by example of substituted aromatic substances

Ozone pretreatment studies of nonbiodegradable substituted aromatic compounds were conducted to evaluate the effects of ozonation on the biodegradability of the oxidation products as a function of COD- DOC-elimination and ozone consumption.In the case of substituted aromatic compounds a 60–70% decrease of the COD-value and a 30–40% decrease of the DOC-value lead to biodegradable products (BOD₅-/COD = 0.4) independent of the pH and the initial concentration of compounds. To reach good biodegradability of the oxidation products 3 mg ozone on average per 1 mg initial DOC are necessary.     

Upgrading a facultative pond by implanting water hyacinth

Water hyacinth was implanted in one of two existing facultative ponds and both units were operated in parallel under comparable conditions. The ponds were fed with mainly domestic wastewater after pretreatment in anaerobic ponds and operated at a BOD₅-loading of about 48 kg (ha d)⁻¹ and a detention time of 12 days. This paper covers a period of 4 months, from the implantation of the water hyacinths until no further systematic change in the treatment efficiency of the water hyacinth pond was observed. The median effluent concentrations of the facultative pond for SS, COD, TKN and TP were 55, 95, 6.4 and 1.4 mg l⁻¹, respectively. The values for the water hyacinth pond were 12, 26, 2.5 and 0.4 mg l⁻¹, respectively. The average DO effluent concentration of the water hyacinth pond was 1.2 mg l⁻¹, but this still increased slightly as compared to the influent. The study demonstrates that the implantation of water hyacinth is an appropriate option for upgrading facultative ponds. In many cases where more stringent effluent standards are imposed the method may be a suitable alternative to technical treatment processes.     

Effects of ozone pre-treatment on diclofenac: Intermediates, biodegradability and toxicity assessment

Diclofenac (DCF), a common analgesic, anti-arthritic and anti-rheumatic drug, is one of the most frequently detected compounds in water. This study deals with the degradation of diclofenac in aqueous solution by ozonation. Biodegradability (BOD₅/COD ratio and Zahn-Wellens test), acute ecotoxicity and inhibition of activated sludge activity were determined in ozonated and non-ozonated samples. Liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) was used to identify the intermediates formed in 1 h of ozonation. Eighteen intermediates were identified by these techniques and a tentative degradation pathway for DCF ozonation is proposed.Experimental results show that ozone is efficient at removing DCF: > 99% removal (starting from an initial concentration of 0.68 mmol L^− 1) was achieved after 30 min of ozonation (corresponding to an absorbed ozone dose of 0.22 g L^− 1, which is 4.58 mmol L^− 1). However, only 24% of the substrate was mineralized after 1 h of ozonation. The biodegradability, respiration inhibition in activated sludge and acute toxicity tests demonstrate that ozonation promotes a more biocompatible effluent of waters containing DCF.     

Combined γ-ray irradiation-activated sludge treatment of humic acid solution from landfill leachate

Humic acid, which is a typical microbially refractory organic substance, was extracted from a landfill leachate. The humic acid solution (COD = 367 mg 1⁻¹; TOC = 293 mg 1⁻¹; BOD = 27 mg 1⁻¹) was applied to a batch scale activated sludge treatment after the modification of its biodegradability by γ-ray irradiation. The BOD increased to 64 mg 1⁻¹ by irradiation of 15 kGy (1.5 Mrad), while the COD and TOC decreased to 231 and 230 mg 1⁻¹, respectively. When the irradiated sample was treated with an activated sludge, the BOD decreased rapidly in 2–3 h to about 15 mg 1⁻¹ which was a similar value as the unirradiated sample was treated. The elimination efficiency of TOC by the sludge treatment was approximately equal to that obtained by irradiation of 15 kGy. These facts suggest a utility of applying microbial processes after radiation treatment of microbially refractory wastewaters.     

Estimate of treatment plant effluent impact on chloride concentrations and oyster environment within the murderkill river estuary

The Murderkill River is a partially tidal body of water with summer-time 50-percentile freshwater flows ranging from 17.9 to 27.6ft³s⁻¹ (0.5 to 0.77m³s⁻¹) at a point coincident with the effluent discharge from the Kent County Regional Wastewater Treatment Plant (start-up late 1972). Chloride concentrations were determined over six summers to characterize river conditions prior to start-up of the 10-million gal day⁻¹ (37.850 m³ day⁻¹) (design) plant. Use of a one-dimensional steadystate model for a conservative substance shows that chloride values would be reduced by up to 20% at low water slack (LWS) periods for wastewater flows of 10 million gal day⁻¹ (37,850 m³ day⁻¹). The LWS chloride concentrations in the area of oyster production would be reduced to 3–6 ppt (5.9–10.8 ppt salinity) for wastewater loadings greater than 10 million gal day⁻¹ (37,850 m³ day⁻¹) . It is suggested that chloride additions in the treatment plant effluent be implemented to maintain minimum summertime low-water-slack levels of 5.6 ppt chloride (10 ppt salinity), consistent with a proper environment for oyster development.     

Mechanisms and products of ozonolysis of aniline in aqueous solution containing nitrite ion

The presence of nitrite ions (1 × 10⁻⁴ M) in the reaction medium affected the aqueous reaction of aniline (1 × 10⁻⁴ M) and ozone (2.07–2.15 × 10⁻⁴ M) at pH 6.25–10.65; o-, m- and p-nitroaniline were formed in addition to reaction products reported earlier. The combined yield of o- and p-nitroaniline was as high as 8%. Their yields were significantly higher at pH 6.25 and 7.25 than at pH 10.65 and carbonate species-inhibited their formation. The reaction mechanisms for the formation of the nitroanilines involves pernitrous acid, hydroxyl radical and nitrogen dioxide radical as the important intermediates.     

A comparison of fenuron degradation by hydroxyl and carbonate radicals in aqueous solution

A comparative study of the transformation of the herbicide fenuron (1,1-dimethyl-3-phenylurea) by hydroxyl radicals and carbonate radicals in aqueous solution (pH 7.2-phosphate buffer) has been undertaken. Hydroxyl radical was generated by the well-known photolysis of hydrogen peroxide at 254 nm and carbonate radical was formed by photolysis of Co(NH₃)₅CO₃⁺ at 254 nm. Competitive kinetic experiments were performed with atrazine used as the main competitor for both processes. Accordingly, the second-order rate constant of reaction between fenuron and carbonate radical was found to be (7−12±3)×10⁶ M⁻¹ s⁻¹ [(7±1)×10⁹ M⁻¹ s⁻¹ for hydroxyl radical]. The formation of degradation products was studied by LC-MS in the two cases and a comparison has been performed. The reaction with carbonate radical leads to the formation of a quinone-imine derivative which appears as the major primary product together with ortho and para hydroxylated compounds. These two compounds represent the major products in the reaction with hydroxyl radicals. The reaction of both radicals also leads to the transformation of the dimethylurea moiety.     

Removal of saxitoxins from drinking water by granular activated carbon, ozone and hydrogen peroxide--implications for compliance with the Australian drinking water guidelines

In a laboratory-scale trial, we studied the removal of saxitoxins from water by ozone, granular activated carbon (GAC) and H₂O₂, and considered the implications of residual toxicity for compliance with the Australian drinking water standards. Cell-free extracts of Anabaena circinalis were added to raw, untreated drinking water obtained from a water supply reservoir to provide a toxicity of 30 μg (STX equivalents) l⁻¹. Ozone alone, or in combination with H₂O₂, failed to destroy the highly toxic STX and GTX-2/3, and only partially destroyed dc-STX, and the low-toxicity C-toxins and GTX-5. In all cases, the toxicity of the water was reduced by less than 10%. GAC removed all of the STX, dc-STX and GTXs, but only partially removed the C-toxins. However, the residual toxicity was reduced to the suggested Australian drinking water guideline concentration of 3 μg (STX equivalents) l⁻¹ without O₃ pre-treatment. Modelling the spontaneous chemical degradation of residual C-toxins following treatment shows that residual toxicity could increase to 10 μg l⁻¹ after 11 d due to formation of dc-GTXs and would then gradually decay. In all, residual toxicity would exceed the Australian drinking water guideline concentration for a total of 50 d.     

Removal of As(III) and As(V) from water using a natural Fe and Mn enriched sample

The arsenic removal capacity of a natural oxide sample consisting basically of Mn-minerals (birnessite, cryptomelane, todorokite), and Fe-oxides (goethite, hematite), collected in the Iron Quadrangle mineral province in Minas Gerais, Brazil, has been investigated. As-spiked tap water and an As-rich mining effluent with As-concentrations from 100 μg L⁻¹ to 100 mg L⁻¹ were used for the experiments. Sorbent fractions of different particle sizes (<38 μm to 0.5 mm), including spherical material (diameter 2 mm), have been used. Batch and column experiments (pH values of 3.0, 5.5, and 8.5 for batch, and about pH 7.0 for column) demonstrated the high adsorption capacity of the material, with the sorption of As(III) being higher than that of As(V). At pH 3.0, the maximum uptake for As(V) and for As(III)-treated materials were 8.5 and 14.7 mg g⁻¹, respectively. The Mn-minerals promoted the oxidation of As(III) to As(V), for both sorbed and dissolved As-species. Column experiments with the cFeMn-c sample for an initial As-concentration of 100 μg L⁻¹ demonstrated a very efficient elimination of As(III), since the drinking water limit of 10 μg L⁻¹ was exceeded only after 7400 BV total throughput. The As-release from the loaded samples was below the limit established by the toxicity characteristic leaching procedure, thus making the spent material suitable for discharge in landfill deposits.     

Formation of mutagens from the aqueous reactions of ozone and anilines

Azobenzenes, azoxybenzenes and benzidines were the products of interest obtained from the aqueous reactions of anilines with ozone. The reaction mechanisms for their formation are discussed. Conditions favoring ozone decomposition and the presence of carbonate species increased the yield of these polyaromatic nitrogen compounds. Fulvic acid inhibited the formation of azobenzene without decreasing the amount of aniline degraded. The effects of pH and inorganic buffers on the formation of N-substituted polyaromatic compounds from aniline can be explained by the decomposition of ozone by OH⁻ and OOH⁻, scavenging of the hydroxyl radical and suppression of ozone decomposition by carbonate species, and selective oxidation of aniline by carbonate radicals.     

Study of catalyzed ozonation for advanced treatment of pulp and paper mill effluents

Ozonation and catalytic ozonation (TOCCATA process) were used as tertiary treatments of wastewaters from three different pulp and paper mills. Laboratory batch experiments were conducted to assess the efficiency of each oxidation system for removal of organic matter. The investigations measured ozone consumption rate, variations in chemical oxygen demand (COD), total organic carbon (TOC), suspended solids (SS) and molecular weight distribution with contact time. For conventional ozonation, ozone consumption rate was dependent on the nature of the effluent. Organic matter elimination occurred both by oxidation and precipitation. Precipitation played a major role on TOC removal varying with the effluent, and was responsible for production of high final SS concentrations. However, the effluent type did not affect the ozone consumption rate for TOCCATA-catalyzed reactions. Using TOCCATA, it was shown that organic matter was removed through steady conversion of organic carbon to carbon dioxide. Finally the two oxidation systems were compared with respect to their impact on molecular weight distribution. A total removal of the two initial fractions of compounds (high and low molecular weights) was observed with two effluents. With the third effluent, only the initial fraction of low molecular weight compounds was removed by the two oxidizing systems. The results showed that ozonation and TOCCATA-catalyzed ozonation could achieve removals of COD of 36-76%. Depending on the effluent type, the amount of ozone consumed per gram of COD removed was lower for conventional or for catalytic ozonation.     

Ozone and the Formation of Bromate in Water Treatment

The ozonation of water is widely used within the drinking-water industry. The improvement of the performance of the Barcombe water-treatment works is envisaged. An ozonation stage and granular activated carbon filtration are being considered as an addition to the existing plant. As part of the investigation work, the influence of ozone on bromate formation was studied using a 3 m³/h pilot plant. The bromate production was found to depend upon (a) the applied ozone dose, (b) the contact period, and (c) the pH.
Using ozone in an appropriate way will be of benefit to the treatment process as well as meeting the new World Health Organization health guidelines for drinking water.