Entrapped biomass for removal of organics and total nitrogen from anaerobic reactor effluents.

Anaerobic processes have been applied to treat low-strength domestic wastewaters with significant energy saving. However, anaerobic process effluents must be further removed of residual organics and total nitrogen before discharge. Reported here are an aerobic entrapped bio-technology (EBT) system and an EBT coupled with activated sludge (EBT + AS) system being tested as a post-anaerobic treatment. Both systems have been operated under aerobic condition to provide organics and total nitrogen removal, achieving COD removal by 74-88% and TN removal by 58-65% at hydraulic retention times of 8-24 h. ΔCOD/ΔNO3 ratios that represent the carbon usage efficiency as electron donors for denitrification were 1.82-1.93 in the EBT and 2.01-2.02 in the EBT + AS systems, with both ratios being lower (i.e. more efficient) than 6 typically required in traditional activated sludge bioreactors. Both systems demonstrate promise for polishing removal of COD and TN.

Role of Dissolved Organic Matter in Sorption of Perfluorooctanoic Acid to Metal Oxides.

Perfluorooctanoic acid (PFOA) is an important perfluorinated chemical of significant environmental concern. It has been widely found at high concentrations in the environment. We have exposed sediment constituent minerals SiO2, Fe2O3, and Al2O3 to PFOA and humic acid (HA) and studied the adsorption of PFOA by introducing the adsorbates in different orders. The results suggest concurrent sorption of PFOA and HA to the mineral surface or enhanced PFOA sorption when both are introduced to the aqueous phase. However, when PFOA is introduced to the mineral surface that has already been exposed to and extensively coated with HA, little PFOA adsorption occurs, which implies that PFOA released to rivers rich in dissolved organic matter (DOM, i.e. HA) may be immune to sorptive retention by the sediment and be transported downstream unabated. DOM thus can play a significant role in the transport and fate of PFOA in the natural water system.

Photocatalytic mineralization of codeine by UV-A/TiO2--Kinetics, intermediates, and pathways.

This study investigated the photocatalytic degradation of codeine by UV-irradiated TiO2. The degradation kinetics was determined under varied conditions including the TiO2 loading, codeine concentration, and pH. Codeine and several reaction intermediates including morphine were identified and tracked during degradation using HPLC/MS-MS technique, along with TOC and IC measurements. Specifically, removal of 100 µg/L of spike codeine was complete in 3 min by contact with a 0.1 g/L suspension of TiO2 under UV irradiation at pH 7. The degradation kinetics of codeine was first-order with respect to both the catalyst TiO2 and the reactant codeine, with enhanced reaction rates with increasing pH up to pH 9. Mineralization of codeine was possible upon prolonged contact; near complete mineralization of 10 mg/L of codeine was achieved in 90 min with 0.1 g/L TiO2 under irradiation at pH 5, during which the organic nitrogen was converted to NH3-N (74%) and NO3-N (22%). Based on the identified intermediates, two degradation pathways were proposed of which one involved ipso-substitution followed by cleavage of the aromatic ring and another involved repeated hydroxylation of the codeine molecule followed by its fragmentation.

Photocatalytic degradation of methamphetamine by UV/TiO2 - kinetics, intermediates, and products.

Methamphetamine (MAT) is a prescription drug and often a substance of abuse. It is found in WWTP influents and effluents as well as surface waters in many regions, elevating concerns about their potential impact. MAT is not effectively removed by conventional processes of domestic wastewater treatment plants (WWTPs). To contemplate advanced treatment, this study evaluates the feasibility of eliminating MAT by UV-illuminated TiO2, a potential retrofit to existing UV disinfection units. The degradation kinetics and mechanism of MAT by TiO2 under low-wattage UV illumination (9 W with maximum output at 365 nm) were investigated. Experimental parameters were varied including the TiO2 loading, MAT concentration, and pH. During treatment, MAT and its intermediates were tracked by HPLC-MS/MS, along with TOC and IC measurements to determine the mineralization extent. In contact with 0.1 g/L of TiO2 under illumination at pH 7, an entire spike amount of 100 µg/L of MAT was removed from deionized water after 3 min and 76 µg/L of MAT was removed from the secondary wastewater effluent after 30 min. The degradation of MAT followed an apparent first-order kinetics. Near complete mineralization of MAT from 10 mg/L was achieved in 180 min with 0.1 g/L of TiO2 at pH 5, by which the organic nitrogen was converted to NH4(+) and NO3(-). Based on identified intermediates, two degradation pathways were deduced that involved cleavage of the side chain as well as hydroxylation of the MAT compound. The photocatalytic UV/TiO2 process shows promise in arresting the release of MAT and its intermediate derivatives into the water environment.

Improving total nitrogen removal in aeration basin retrofitted with entrapped biomass.

This study presented a method to upgrade existing aeration tanks to remove total nitrogen (TN). Bioplates carrying entrapped biomass were installed in an aeration basin to create anoxic/anaerobic zones where denitrification can proceed. In a reactor that coupled bioplates containing entrapped biomass (equivalent to as high as 7,500 mg/L of biomass) and an activated sludge suspension (at mixed liquor suspended solids of 1,300-2,400 mg/L), nitrification efficiency exceeded 95% for an influent wastewater containing 21-54 mg/L of NH3-N. In all cases amended with alkalinity and with or without added methanol as an electron source, TN removal was between 60 and 70%. The results demonstrated anoxic/oxic or anaerobic/anoxic/oxic processes could be incorporated in a conventional aeration basin, requiring no substantial modifications of the vessel and operation, and thus providing improved treatment in terms of nitrogen removal in the conventional suspended-growth process.

Enhancing total nitrogen removal from wastewater of a science and industrial park using entrapped biomass.

This study employed entrapped biomass technology to augment the conventional activated sludge process with anoxic-oxic (AO)/anaerobic-anoxic-oxic (A20) functions for the removal of total nitrogen (TN) from wastewater of a science and industrial park in Taiwan. The entrapped biomass unit was fabricated in the format of carrier plates on which microbial cells were entrapped. Due to mass transport limitations, anoxic and anaerobic conditions were created within the bioplates that enabled denitrification to occur. The treatment basin incorporated an equivalent amount of 1300-2400mg MLSS/L of activated sludge on the bioplates at packing ratios of 10-30% (volume ratio ofbioplates to basin) operating with the addition of sodium carbonate for alkalinity and methanol for the electron donor. The results showed nearly 90% of ammonia nitrogen being converted to nitrate and 63% of TN removal, in comparison with typically 10% of TN removal in traditional activated sludge process of domestic wastewater plants.

Fate of sulfonamide antibiotics in contact with activated sludge--sorption and biodegradation.

The sorption and biodegradation of three sulfonamide antibiotics, namely sulfamethoxazole (SMX), sulfadimethoxine (SDM), and sulfamonomethoxine (SMM), in an activated sludge system were investigated. Experiments were carried out by contacting 100 µg/L of each sulfonamide compound individually with 2.56 g/L of MLSS at 25±0.5 °C, pH 7.0, and dissolved oxygen of 3.0±0.1 mg/L in a batch reactor over different periods of 2 d and 14 d. All sulfonamides were removed completely over 11-13 d. Sorptive equilibrium was established well within the first few hours, followed by a lag period of 1-3 days before biodegradation was to deplete the antibiotic compounds linearly in the ensuing 10 days. Apparent zeroth-order rate constants were obtained by regression analysis of measured aqueous concentration vs. time profiles to a kinetic model accounting for sorption and biodegradation; they were 8.1, 7.9, and 7.7 µg/L/d for SDM, SMX, and SMM, respectively, at activated sludge concentration of 2.56 g/L. The measured kinetics implied that with typical hydraulic retention time (e.g. 6 h) provided by WWTP the removal of sulfonamide compounds from the wastewater during the activated sludge process would approximate 2 µg/L.

Biodegradation and bio-sorption of antibiotics and non-steroidal anti-inflammatory drugs using immobilized cell process.

In the present study, the removal mechanisms of four antibiotics (sulfamethoxazole, sulfadimethoxine, sulfamethazine, and trimethoprim) and four non-steroidal anti-inflammatory drugs (acetaminophen, ibuprofen, ketoprofen, and naproxen) in immobilized cell process were investigated using batch reactors. This work principally explores the individual or collective roles of biodegradation and bio-sorption as removal routes of the target pharmaceuticals and the results were validated by various experimental and analytical tools. Biodegradation and bio-sorption were found as dominant mechanisms for the drug removal, while volatilization and hydrolysis were negligible for all target pharmaceuticals. The target pharmaceuticals responded to the two observed removal mechanisms in different ways, typically: (1) strong biodegradability and bio-sorption by acetaminophen, (2) strong biodegradability and weak bio-sorption by sulfamethoxazole, sulfadimethoxine, ibuprofen and naproxen, (3) low biodegradability and weak bio-sorption by sulfamethazine and ketoprofen, and (4) low biodegradability and medium bio-sorption by trimethoprim. In the sorption/desorption experiment, acetaminophen, sulfamethoxazole and sulfadimethoxine were characterized by strong sorption and weak desorption. A phenomenon of moderate sorption and well desorption was observed for sulfamethazine, trimethoprim and naproxen. Both ibuprofen and ketoprofen were weakly sorbed and strongly desorbed.

Sorption and biodegradation of sulfonamide antibiotics by activated sludge: experimental assessment using batch data obtained under aerobic conditions.

This study investigated the adsorption, desorption, and biodegradation characteristics of sulfonamide antibiotics in the presence of activated sludge with and without being subjected to NaN(3) biocide. Batch experiments were conducted and the relative contributions of adsorption and biodegradation to the observed removal of sulfonamide antibiotics were determined. Three sulfonamide antibiotics including sulfamethoxazole (SMX), sulfadimethoxine (SDM), and sulfamonomethoxine (SMM), which had been detected in the influent and the activated sludge of wastewater treatment plants (WWTP) in Taiwan, were selected for this study. Experimental results showed that the antibiotic compounds were removed via sorption and biodegradation by the activated sludge, though biodegradation was inhibited in the first 12 h possibly due to competitive inhibition of xenobiotic oxidation by readily biodegradable substances. The affinity of sulfonamides to sterilized sludge was in the order of SDM > SMM > SMX. The sulfonamides existed predominantly as anions at the study pH of 6.8, which resulted in a low level of adsorption to the activated sludge. The adsorption/desorption isotherms were of a linear form, as well described by the Freundlich isotherm with the n value approximating unity. The linear distribution coefficients (K(d)) were determined from batch equilibrium experiments with values of 28.6 ± 1.9, 55.7 ± 2.2, and 110.0 ± 4.6 mL/g for SMX, SMM, and SDM, respectively. SMX, SMM, and SDM desorb reversibly from the activated sludge leaving behind on the solids 0.9%, 1.6%, and 5.2% of the original sorption dose of 100 µg/L. The sorbed antibiotics can be introduced into the environment if no further treatments were employed to remove them from the biomass.

Effects of water washing on removing organic residues in bottom ashes of municipal solid waste incinerators.

Due to their potential toxicity and odourous nature, the residual organics in municipal solid waste incinerators are recently gaining attention as an important issue of resources recovery apart from their complex mixture of organic counterpart. Studies of the organic fractions in municipal solid waste incinerator residues have been limited. In this study, extended solid-phase extraction of the water-washed bottom ash and liquid-phase extraction of the washing water were carried out with regard to bottom ash samples from three mass-burning incinerators in Taipei County (Taiwan) during four consecutive seasons of year 2008-2009. Supercritical fluid extraction and Soxtec extraction techniques along with GC-MS were successfully used to characterize the residual organics in weathered and washed bottom ashes. Supercritical fluid extraction provided the quantification of aliphatics and aromatic compounds such as hexanoic acid and benzaldehyde, respectively. Soxtec extraction was useful for qualitative analysis of aromatic and aliphatic groups in the ashes and many of which were odourous and toxic compounds. By mixing one unit weight (g) bottom ash with two unit volume (mL) water for 15 min, total organic carbon in the bottom ash was greatly reduced (e.g., from 4.1 to 1.8 wt.%). Among the removed were foul odour-causing compounds such as pyridine and quinoline derivatives, while some aromatic compounds such as 4-hydroxybenzaldehyde and low-molecular-weight aliphatics such as hexanoic acid remained. The results here suggest that washing with water can be an effective pre-treatment step for removing odour-causing and environmental concerned organics.

Characteristics of residual organics in municipal solid waste incinerator bottom ash.

Although heavy metals in bottom ash have been a primary issue in resource recovery of municipal solid waste incinerator residues in past decades, less studied are potentially toxic and odorous organic fractions that exist as they have not been completely oxidized during the mass burn process. Using supercritical fluid extraction (SFE) and soxtec extraction (SE) techniques, this study investigated the characteristics of un-oxidized organic residues contained in bottom ash from three municipal solid waste incinerators in Taiwan during 2008-2009. All together 99 organics were identified in bottom ash samples using gas chromatography-mass spectrometry (GC-MS). Among the identified organics, aromatic compounds were most frequently detected. No polycyclic aromatic hydrocarbons were extracted by SFE or SE. Several phthalates (e.g., phthalic acid isobutyl tridec-2-yn-1-yl ester, dibutyl phthalate and 2-butoxyethyl butyl benzene-1,2-dicarboxylate), organic phosphates (e.g., octicizer and phosphoric acid isodecyl diphenyl ester), and aromatics and amines including pyridine, quinoline derivatives, chloro- and cyano-organics were successfully extracted. Aromatic amines (e.g., 1-nitro-9,10-dioxo-9,10-dihydro-anthracene-2-carboxylic acid diethylamide and 3-bromo-N-(4-bromo-2-chlorophenyl)-propanamide) and aromatic compounds (other than amines) (e.g., 7-chloro-4-methoxy-3-methylquinoline and 2,3-dihydro-N-hydroxy-4-methoxy-3,3-dimethyl indole-2-one) are probably the major odorous compounds in bottom ash. This work identifies organic pollutants in incinerated bottom ash that have received far less attention than their heavy metals counterpart.