Extending the diffuse layer model of surface acidity constant behaviour: II. Estimation of intrinsic acidity and electrolyte ion site binding constants

Abstract

The main objective of this work was to study the capacity of bioaccumulation of copper in an upflow anaerobic sludge blanket (UASB) reactor, for the treatment of acid mine drainages (AMD). UASB reactor of 0.8 L was fed with sodium acetate, the organic loading rate (OLR) was set at 2.0gCOD/Ld, and experiments were performed in the reactor during 115 days. After 30 days, the COD removal efficiency was 90%. In the stationary stage, the higher production methane was 0.253 L/Ld. The reactor was added with 20 mgCu(II)/L during 30 days. The copper bioaccumulation was 98% and it was accumulated gradually in sludge until reaching a 61.6 mgCu(II)/gTS. The toxicity study demonstrated that the copper concentration at which the level of specific methanogenic activity (SMA) of the biogranules was reduced to 50% of the control (IC₅₀), was 280 mgCu(N)/L     

Lead removal through biological sulfate reduction process

The feasibility of lead removal through biological sulfate reduction process with ethanol as electron donor was investigated. Sulfide-rich effluent from biological process was used to remove lead as lead sulfide precipitate. The experiments were divided into two stages; Stage I startup and operation of sulfidogenic process in a UASB reactor and Stage II lead sulfide precipitation. In Stage I, the COD:S ratio was gradually reduced from 15:1 to 2:1. At the COD:S ratio of 2:1, sulfidogenic condition was achieved as identified by 80-85% of electron flow by sulfate reducing bacteria (SRB). COD and sulfate removal efficiency were approximately 78% and 50%, respectively. In Stage II, the effluent from UASB reactor containing sulfide in the range of 30-50 mg/L and lead-containing solution of 45-50 mg/L were fed continuously into the precipitation chamber in which the optimum pH for lead sulfide precipitation of 7.5-8.5 was maintained. It was found that lead removal of 85-95% was attained.     

Principal component analysis and quantitative image analysis to predict effects of toxics in anaerobic granular sludge

Principal component analysis (PCA) was applied to datasets gathering morphological, physiological and reactor performance information, from three toxic shock loads (SL1 - 1.6 mg(detergent)/L; SL2 - 3.1mg(detergent)/L; SL3 - 40 mg(solvent)/L) applied in an expanded granular sludge bed (EGSB) reactor. The PCA allowed the visualization of the main effects caused by the toxics, by clustering the samples according to its operational phase, exposure or recovery. The aim was to investigate the variables or group of variables that mostly contribute for the early detection of operational problems. The morphological parameters showed to be sensitive enough to detect the operational problems even before the COD removal efficiency decreased. As observed by the high loadings in the plane defined by the first and second principal components. PCA defined a new latent variable t[1], gathering the most relevant variability in dataset, that showed an immediate variation after the toxics were fed to the reactors. t[1] varied 262%, 254% and 80%, respectively, in SL1, SL2 and SL3. The high loadings/weights of the morphological parameters associated with this new variable express its influence in shock load monitoring and control, and consequently in operational problems recognition.     

Anaerobic treatment of a chemical synthesis-based pharmaceutical wastewater in a hybrid upflow anaerobic sludge blanket reactor

In this study, performance of a lab-scale hybrid up-flow anaerobic sludge blanket (UASB) reactor, treating a chemical synthesis-based pharmaceutical wastewater, was evaluated under different operating conditions. This study consisted of two experimental stages: first, acclimation to the pharmaceutical wastewater and second, determination of maximum loading capacity of the hybrid UASB reactor. Initially, the carbon source in the reactor feed came entirely from glucose, applied at an organic loading rate (OLR) 1 kg COD/m(3) d. The OLR was gradually step increased to 3 kg COD/m(3) d at which point the feed to the hybrid UASB reactor was progressively modified by introducing the pharmaceutical wastewater in blends with glucose, so that the wastewater contributed approximately 10%, 30%, 70%, and ultimately, 100% of the carbon (COD) to be treated. At the acclimation OLR of 3 kg COD/m(3) d the hydraulic retention time (HRT) was 2 days. During this period of feed modification, the COD removal efficiencies of the anaerobic reactor were 99%, 96%, 91% and 85%, and specific methanogenic activities (SMA) were measured as 240, 230, 205 and 231 ml CH(4)/g TVS d, respectively. Following the acclimation period, the hybrid UASB reactor was fed with 100% (w/v) pharmaceutical wastewater up to an OLR of 9 kg COD/m(3) d in order to determine the maximum loading capacity achievable before reactor failure. At this OLR, the COD removal efficiency was 28%, and the SMA was measured as 170 ml CH(4)/g TVS d. The hybrid UASB reactor was found to be far more effective at an OLR of 8 kg COD/m(3) d with a COD removal efficiency of 72%. At this point, SMA value was 200 ml CH(4)/g TVS d. It was concluded that the hybrid UASB reactor could be a suitable alternative for the treatment of chemical synthesis-based pharmaceutical wastewater.     

Performance of anaerobic contact filter in series for treating distillery spentwash

Investigations were carried out by using rigid polyurethane foam as a packing material in the anaerobic contact filter (series) to treat distillery spentwash. The effect of hydraulic retention time (HRT) in treatment efficiency of reactor (I) and (II) was evaluated at different initial substrate concentrations ranging from 1500 mg/l to 19,000 mg/l. The effect of toxic parameters such as sulphate present in the distillery spentwash and the corresponding parameters such as total sulphide and un-ionized hydrogen sulphide generated during digestion of wastewater were evaluated to assess the reactor performance. The results showed that at 4 d HRT the overall COD removal percent ranged from 98% to 73% for an influent COD of 1500 mg/l to 19,000 mg/l. The overall performance of COD removal percent in reactor (I) and (II) at 2, 3 and 4 d HRT's were investigated. At 3 d HRT the reactor (II) showed a higher COD removal percent when compared to reactor (I), which clearly shows the role of hydraulic retention time in degradation of the organic matter present in the wastewater above an influent COD concentration of 5000 mg/l.     

Nutrient removal from slaughterhouse wastewater in an intermittently aerated sequencing batch reactor

The performance of a 10 L sequencing batch reactor (SBR) treating slaughterhouse wastewater was examined at ambient temperature. The influent wastewater comprised 4672+/-952 mg chemical oxygen demand (COD)/L, 356+/-46 mg total nitrogen (TN)/L and 29+/-10 mg total phosphorus (TP)/L. The duration of a complete cycle was 8 h and comprised four phases: fill (7 min), react (393 min), settle (30 min) and draw/idle (50 min). During the react phase, the reactor was intermittently aerated with an air supply of 0.8L/min four times at 50-min intervals, 50 min each time. At an influent organic loading rate of 1.2g COD/(Ld), average effluent concentrations of COD, TN and TP were 150 mg/L, 15 mg/L and 0.8 mg/L, respectively. This represented COD, TN and TP removals of 96%, 96% and 99%, respectively. Phase studies show that biological phosphorus uptake occurred in the first aeration period and nitrogen removal took place in the following reaction time by means of partial nitrification and denitrification. The nitrogen balance analysis indicates that denitrification and biomass synthesis contributed to 66% and 34% of TN removed, respectively.     

Co-degradation of resorcinol and catechol in an UASB reactor

Co-degradation of resorcinol and catechol was studied in a catechol acclimated up flow anaerobic sludge blanket (UASB) reactor. Synthetic binary aqueous solution having a total concentration of 1000 mg/L with the resorcinol/catechol (R/C) ratio of 1/19, 1/9, 3/17, 1/4, 1/3, 3/7, 2/3 and then 1/3 was fed at various time intervals to the UASB reactor with a fixed organic loading rate of 5.7 kg COD/m(3) d and hydraulic retention time of 8h. The reactor was operated over a period of 145 days after its acclimation with catechol bearing synthetic wastewater at a constant feed rate of 1.2 L/h. When the resorcinol concentration was increased to have a R/C ratio of 1/4, the COD removal efficiency and the biogas production increased to the maximum levels. Pseudo steady state condition for COD removal was achieved at each of the stepped-up loading condition. An increase in the R/C ratio above 1/4 in the binary feed solution led to a decrease in the COD removal efficiency and the biogas production rate.     

Influence of organic shock loads in an ASBBR treating synthetic wastewater with different concentration levels

Safe application of the anaerobic sequencing biofilm batch reactor (ASBBR) still depends on deeper insight into its behavior when faced with common operational problems in wastewater treatments such as tolerance to abrupt variations in influent concentration, so called shock loads. To this end the current work shows the effect of organic shock loads on the performance of an ASBBR, with a useful volume of 5L, containing 0.5-cm polyurethane cubes and operating at 30 degrees C with mechanical stirring of 500 rpm. In the assays 2L of two types of synthetic wastewater were treated in 8-h cycles. Synthetic wastewater I was based on sucrose-amide-cellulose with concentration of 500 mg COD/L and synthetic wastewater II was based on volatile acids with concentration ranging from 500 to 2000 mg COD/L. Organic shock loads of 2-4 times the operation concentration were applied during one and two cycles. System efficiency was monitored before and after application of the perturbation. When operating with concentrations from 500 to 1000 mg COD/L and shock loads of 2-4 times the influent concentration during one or two cycles the system was able to regain stability after one cycle and the values of organic matter, total and intermediate volatile acids, bicarbonate alkalinity and pH were similar to those prior to the perturbations. At a concentration of 2000 mg COD/L the reactor appeared to be robust, regaining removal efficiencies similar to those prior to perturbation at shock loads twice the operation concentration lasting one cycle and stability was recovered after two cycles. However, for shock loads twice the operation concentration during two cycles and shock loads four times the operation concentration during one or two cycles filtered sample removal efficiency decreased to levels different from those prior to perturbation, on an average of 90-80%, approximately, yet the system managed to attain stability within two cycles after shock application. Therefore, this investigation envisions the potential of full scale application of this type of bioreactor which showed robustness to organic shock loads, despite discontinuous operation and the short times available for treating total wastewater volume.     

实验室模拟高负荷SPAC厌氧反应器运行

采用模拟废水, 对新型高负荷螺旋式自循环(Spiral automatic circulation, SPAC)厌氧反应器的运行性能进行了实验室模拟研究。结果表明: 在30oC, 水力停留时间(HRT)为12 h, 进水COD浓度从8000 mg/L升至20 000 mg/L的条件下, 反应器的COD去除率为91.1%~95.7%, 平均去除率为93.6％。在进水浓度为20 000 mg/L, HRT由5.95 h缩短至1.57 h的工况下, COD去除率从96.0%降低至78.7%, 反应器达到最高容积负荷率306 g COD/(L·d), 最大容积COD去除率240 g/(L·d), 最高容积产气率131 L/(L·d)。该反应器对基质浓度的连续提升具有良好的适应能力。进水COD浓度由8000 mg/L提升至20 000 mg/L时, 出水COD浓度一直处在较低水平(平均为852?mg/L), 容积COD去除率和容积产气率分别提高162%和119%。该反应器对HRT的连续缩短也有良好的适应能力。HRT由5.95 h缩短至1.57 h时,反应器容积COD去除率和容积产气率分别升高191%和195%。     

Start-up procedures and analysis of heavy metals inhibition on methanogenic activity in EGSB reactor

The effectiveness of operating an industrial UASB reactor, treating wastewater from the beer industry, with flows containing heavy metals was evaluated. A pilot-scale UASB reactor, already used to simulate the industrial reactor, was unsuccessfully employed. An easy start-up was obtained arranging it as an EGSB reactor. Considerations about this modification are reported. The effects of Cu(II), Ni(II) and Cr(III) ions on the anaerobic activity were analyzed by measurements of methane production rate and COD removal. The employed biomass was the sludge of the industrial UASB reactor, while a solution of ethanol and sodium acetate with COD of 3000 mg/L and a heavy metal concentration of 50 mg/L were continuously fed. Experimental results proved higher biomass sensitivity for copper and much slighter for nickel and chromium. Moreover, copper inhibition has been demonstrated to be less significant if a metal-free feed was provided to the system before copper addition.     

Organics, sulfates and ammonia removal from acrylic fiber manufacturing wastewater using a combined Fenton-UASB (2 phase)-SBR system

A combined Fenton-UASB (2 phase)-SBR system was employed to treat acrylic fiber manufacturing wastewater. The Chemical Oxygen Demand (COD) removal and effluent Biochemical Oxygen Demand (BOD) to COD were 65.5% and 0.529%, respectively, with the optimal Fenton conditions: ferrous was 300 mg/L; hydrogen peroxide was 500 mg/L; pH was 3.0; reaction time was 2.0 h. In two-phase UASB reactor, mesophilic operation (35±0.5 °C) was performed with hydraulic retention time (HRT) varied between 28 and 40 h. The results showed that with the HRT not less than 38 h, COD and sulfate removal were 65% and 75%, respectively. The greatest sizes of granule formed in the sulfate-reducing and methane-producing phases were 5 and 2 mm, respectively. Sulfate-reducing bacteria (SRB) accounted for 35% in the sulfate-reducing phase while methane-producing archaea (MPA) accounted for 72% in the methane-producing phase. During the SBR process, shortcut nitrification was achieved by temperature control of 30 °C.     

Influence of nitrate and COD on phosphorus, nitrogen and dinitrotoluene (DNT) removals under batch anaerobic and anoxic conditions

In this study, the effects of COD to NO(3)-N ratio in the feed on PO(4)-P removal was investigated. Maximum PO(4)-P uptake was obtained in the anoxic reactor when the COD to NO(3)-N ratios were between 2 and 3.75. With the influent COD of 800-1500 mg COD/L a total of the maximum removable PO(4)-P was 56 mg PO(4)-P/L through 20 days of anaerobic/anoxic incubation, indicating 98% P removal in the anoxic reactor. Similarly, for the COD to NO(3)-N ratios varying between 2 and 3.75 maximum denitrification was observed. Through anoxic operation the poly-P bacteria are capable of removing NO(3)-N using VFA, COD as carbon source and NO(3)-N as the electron acceptor after methanogenesis has been completed. High NO(3)-N concentrations stopped significantly the P uptake. A total of 97-99% dinitrotoluene removal efficiencies in the reactors containing COD to NO(3)-N ratio of 2 and 3.75 after 20 days of incubation period. For maximum NO(3)-N and PO(4)-P removals optimal COD to NO(3)-N ratios, COD and NO(3)-N concentrations were 2-3.75, 2000-4000 mg COD/L and, 800-1500 mg NO(3)-N/L, respectively.     

Start-up of an anaerobic hybrid (UASB/filter) reactor treating wastewater from a coffee processing plant

The ability of an anaerobic hybrid reactor, treating coffee wastewater, to achieve a quick start-up was tested at pilot scale. The unacclimatized seed sludge used showed a low specific methanogenic activity of 26.47 g CH4 as chemical oxygen demand (COD)/kg volatile suspended solids (VSS) x day. This strongly limited the reactor performance. After a few days of operation, a COD removal of 77.2% was obtained at an organic loading rate (OLR) of 1.89 kg COD/m3 x day and a hydraulic retention time (HRT) of 22 h. However, suddenly increasing OLR above 2.4 kg COD/m3 x day resulted in a deterioration in treatment efficiency. The reactor recovered from shock loads after shutdowns of 1 week. The hybrid design of the anaerobic reactor prevented the biomass from washing-out but gas clogging in the packing material was also observed. Wide variations in wastewater strength and flow rates prevented stable reactor operation in the short period of the study.     

Performance of an upflow anaerobic reactor combining a sludge blanket and a filter treating sugar waste

A new hybrid reactor, the upflow blanket filter (UBF), which combined on open volume in the bottom two-thirds of the reactor for a sludge blanket and submerged plastic rings (Flexiring, Koch Inc., 235 m(2)/m(3)) in the upper one-third of the reactor volume, was studied. This UBF reactor was operated at 27 degrees C at loading rates varying from 5 to 51 g chemical oxygen demand (COD)/L d with soluble sugar wastewater (2500 mg COD/L). Maximum removal rates of 34 g COD/L d and CH(4) production rates of 7 vol/vol d [standard temperature and pressure (STP)] were obtained. The biomass activity was about 1.2 g COD/g volatile suspended solids per day. Conversion (based on effluent soluble COD) was over 93% with loading rates up to 26 g COD/L d. At higher loading rates conversion decreased rapidly. The packing was very efficient in retaining biomass.     

Aerobic granulation with brewery wastewater in a sequencing batch reactor

Aerobic granular sludge was cultivated in a sequencing batch reactor fed with brewery wastewater. After nine-week operation, stable granules with sizes of 2-7 mm were obtained. With the granulation, the SVI value decreased from 87.5 to 32 mL/g. The granular sludge had an excellent settling ability with the settling velocity over 91 m/h. Aerobic granular sludge exhibited good performance in the organics and nitrogen removal from brewery wastewater. After granulation, high and stable removal efficiencies of 88.7% COD(t), 88.9% NH(4)(+)-N were achieved at the volumetric exchange ratio of 50% and cycle duration of 6h. The average COD(t) and COD(s) of the effluent were 212 and 134 mg/L, respectively, and the average effluent ammonium concentration was less than 14.4 mg/L. Nitrogen was removed due to nitrification and simultaneous denitrification in the inner core of granules.     

Performance of a periodic anaerobic baffled reactor fed on Chinese traditional medicine industrial wastewater

A four-compartment periodic anaerobic baffled reactor (PABR) was run in a 'clockwise sequential' switching manner continuously fed on chinese traditional medicine industrial wastewater under an alkalinity concentration between 1000 and 1500 mg CaCO(3)/L of the feed with average organic load rate (OLR) at about 1, 2, 4 and 6 kg COD/(m(3)d) for 12, 24, 24 and 6d, respectively. Hydraulic residence time was 2d, while switching period was 4d. As the average OLR increased to 6 kg COD/(m(3)d), the time of the sharp fall in pH, chemical oxygen demand (COD) removal, gas production and methane percentage of the biogas of all the compartments and the time of rapid volatile fatty acids accumulation in effluent coincided, hence the PABR became sour. Denaturing gradient gel electrophoresis (DGGE) community fingerprints and their cluster analysis revealed that community structures of each compartment tended to be more closely related if the PABR was not overloaded.     

Reactivation characteristics of stored aerobic granular sludge using different operational strategies

Aerobic granules after 6 months storage were employed in identical sequencing batch reactors (SBRs) using synthetic wastewater to investigate the impacts of different operational strategies on granules' reactivation process. The SBRs were operated under three operational strategies for reactivation of (a) different organic loading rate (OLR); (b) different ammonia concentration; and (c) different shear force (a superficial upflow air velocity). The results indicated that granules after long-term storage could be successfully recovered after 7 days of operation, and the excellent granule reactivation performance was closely related to the operational strategies, since inappropriate operational strategies could cause the outgrowth of filamentous bacteria and granule disintegration. Based on comprehensive comparison of reactivation performance under different operational strategies, the optimal operation strategy for granule reactivation was suggested at OLR of 0.8 kg COD/m(3)/day, ammonia concentration of 15-20 mg/L, and a superficial upflow air velocity of 2.6 cm/s. After 7 days operation under the optimal strategy, the dark brown granules (12 months storage) restored their bioactivities to previous state, in terms of COD removal efficiency (97.44%) and specific oxygen uptake rate (40.63 mg O(2)/g SS h(-1)). The results shed light on the future practical application of stored aerobic granules as bioseed for reactor fast start-up.     

Performance of upflow anaerobic sludge blanket (UASB) reactor treating wastewaters containing carbon tetrachloride

The anaerobic biodegradation of carbon tetrachloride (CT) was investigated during the granulation process by reducing the hydraulic retention time, increasing the chemical oxygen demand (COD) and CT loadings in a 2l laboratory-scale upflow anaerobic sludge blanket (UASB) reactor. Anaerobic unacclimated sludge and glucose were used as seed and primary substrate, respectively. Granules were developed 4 weeks after start-up, which grew at an accelerated rate for 8 months, and then became fully grown. The effect of operational parameters such as influent CT concentrations, COD, CT loading, food to biomass ratio and specific methanogenic activity (SMA) were also considered during granulation. The granular sludge cultivated had a maximum diameter of 2.1 mm and SMA of 1.6 g COD/g total suspended solid (TSS) day. COD and CT removal efficiencies of 92 and 88% were achieved when the reactor was firstly operating at CT and COD loading rates of 17.5 mg/l day and 12.5 g/l day, respectively. This corresponds to hydraulic retention time of 0.28 day and food to biomass ratio of 0.5 g COD/g TSS day. Kinetic coefficients of maximum specific substrate utilization rate, half velocity coefficient, growth yield coefficient and decay coefficient were determined to be 2.4 × 10^–3 mg CT/TSS day^–1, 1.37 mg CT/l, 0.69 mg TSS/mg CT and 0.046 day^–1, respectively for CT biotransformation during granulation.     

Performance of a down-flow fluidized bed reactor under sulfate reduction conditions using volatile fatty acids as electron donors

The use of a down-flow fluidized bed (DFFB) reactor for the treatment of a sulfate-rich synthetic wastewater was investigated to obtain insight into the outcome of sulfate reduction in a biofilm attached to a plastic support under a down-flow regime. Fine low-density polyethylene particles were used as support for developing a biofilm within the reactor. The reactor treated a volatile fatty acids mixture of acetate or lactate, propionate, and butyrate at different chemical oxygen demand (COD) to sulfate ratios ranging from 1.67 to 0.67 (g/g). Organic loading rate changed from 2.5 to 5 g COD/L x day and sulfate loading rate increased from 1.5 to 7.3 g SO(4) (2-)/L x day. At the beginning of continuous operation, methanogenesis was the predominant process; however, after 187 days, sulfate reduction became the main ongoing biological process. After 369 days, a COD removal of 93% and a sulfate removal of 75% were reached. Total sulfide concentrations in the reactor ranged from 105, when the reactor was mainly methanogenic, to around 1,215 mg/L at the end of the experiment. The high sulfide concentrations did not affect the performance of the reactor. Results demonstrated that the configuration of the DFFB reactor was suitable for the anaerobic treatment of sulfate-rich wastewater.     

Sequencing Batch Reactor Biodegradation of Hydrolyzed Sarin as Sole Carbon Source

The chemical nerve agent sarin (o-isopropyl methylphosphonofluoridate) was hydrolyzed at 7.18 weight percent in aqueous sodium hydroxide yielding primarily o-isopropyl methylphosphonic acid (IMPA). This hydrolysate was diluted and fed as sole carbon source to activated sludge in an aerobic sequencing batch reactor. Feed chemical oxygen demand (COD) concentrations ranged from approximately 2500 mg/L (initial) to 5000 mg/L (final). The reactor was operated essentially on a 15-day hydraulic residence time. Overall COD removal efficiency was 86.2% and the IMPA in the feed was converted to methylphosphonic acid. MICROTOX® and Daphnia magna aquatic toxicity testing showed the effluent to be of very low toxicity to aquatic test organisms. The final MPA product was effectively absorbed by Phoslock™, which is a lanthanide modified clay.