Ultrasonic treatment of water contaminated with ibuprofen

The application of ultrasound (US) waves for remediation of wastewater is an area of increasing interest and promising results. The aim of this paper is to evaluate the influence of several parameters of the US process on the degradation of ibuprofen (IBP), a widely used non-steroidal anti-inflammatory recalcitrant drug found in water. Applied US power, dissolved gas, pH and initial concentration of IBP were the parameters investigated under sonication (300 kHz).Ultrasound increased the degradation of IBP from 30 to 98% in 30 min. Initial rate of IBP degradation was evaluated in the range of 1.35 and 6.1 μmol L⁻¹ min⁻¹ for initial concentrations of 2 to 21 mg L⁻¹ or 9.7 μmol L⁻¹ to 101 μmol L⁻¹, respectively. Under air and oxygen the degradation rate of IBP was 4 μmol L⁻¹ min⁻¹ being higher than that when argon was used. The most favorable degradation pH was acidic media. Complete removal of IBP was achieved but some dissolved organic carbon (DOC) remained in solution showing that long-lived intermediates were recalcitrant to the US irradiation. However, chemical and biological oxygen demands (COD and BOD₅) indicated that the process oxidize the ibuprofen compound to biodegradable substances removable in a subsequent biological step.     

Occurrence of endocrine disrupting compounds, pharmaceuticals, and personal care products in the Han River (Seoul, South Korea)

The occurrence of 31 selected endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) in Korean surface waters was investigated. The area was selected since there is a lack of information in the Seoul area on the suspected contamination of rivers by micropollutants, although over 99% of drinking water is produced from surface waters in this area that has a population of approximately 15 million inhabitants. Samples were collected from upstream/downstream and effluent-dominated creeks along the Han River, Seoul (South Korea) and analyzed by liquid chromatography with tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). Most target compounds were detected in both the Han River samples (63%) and the effluent-dominated creek samples (79%). Iopromide, atenolol, TCPP, TECP, musk ketone, naproxen, DEET, carbamazepine, caffeine, and benzophenone were frequently detected in both river and creek samples, although the mean concentrations in effluent-dominated creek samples (102 ng/L-3745 ng/L) were significantly higher than those in river samples (56 ng/L-1013 ng/L). However, the steroid hormones 17β-estradiol, 17α-ethynylestradiol, progesterone, and testosterone, were not detected (< 1 ng/L) in both the river and creek samples. Numerous target compounds (15) were found to be positively correlated (over 0.8) to the conventional water quality parameters (chemical oxygen demand, biochemical oxygen demand, dissolved organic carbon, and ultraviolet absorbance). Results of this study provide increasing evidence that certain EDCs and PPCPs commonly occur in the Han River as the result of wastewater outfalls.     

Fate of hormones and pharmaceuticals during combined anaerobic treatment and nitrogen removal by partial nitritation-anammox in vacuum collected black water

Vacuum collected black (toilet) water contains hormones and pharmaceuticals in relatively high concentrations (μg/L to mg/L range) and separate specific treatment has the potential of minimizing their discharge to surface waters. In this study, the fate of estrogens (natural and synthetical hormones) and pharmaceuticals (paracetamol, metoprolol, propranolol, cetirizine, doxycycline, tetracycline, ciprofloxacin, trimethoprim, carbamazepine, ibuprofen and diclofenac) in the anaerobic treatment of vacuum collected black water followed by nitrogen removal by partial nitritation-anammox was investigated. A new analytical method was developed to detect the presence of several compounds in the complex matrix of concentrated black water. Detected concentrations in black water ranged from 1.1 μg/L for carbamazepine to >1000 μg/L for paracetamol. Anaerobic treatment was only suitable to remove the majority of paracetamol (>90%). Metoprolol was partly removed (67%) during aerobic treatment. Deconjugation could have affected the removal efficiency of ibuprofen as concentrations even increased during anaerobic treatment and only after the anammox treatment 77% of ibuprofen was removed. The presence of persistent micro-pollutants (diclofenac, carbamazepine and cetirizine), which are not susceptible for biodegradation, makes the application of advanced physical and chemical treatment unavoidable.     

Effect of ozone exposure on the oxidation of trace organic contaminants in wastewater

Three tertiary-treated wastewater effluents were evaluated to determine the impact of wastewater quality (i.e. effluent organic matter (EfOM), nitrite, and alkalinity) on ozone (O₃) decomposition and subsequent removal of 31 organic contaminants including endocrine disrupting compounds, pharmaceuticals, and personal care products. The O₃ dose was normalized based upon total organic carbon (TOC) and nitrite to allow comparison between the different wastewaters with respect to O₃ decomposition. EfOM with higher molecular weight components underwent greater transformation, which corresponded to increased O₃ decomposition when compared on a TOC basis. Hydroxyl radical (OH) exposure, measured by parachlorobenzoic acid (pCBA), showed that limited OH was available for contaminant destruction during the initial stage of O₃ decomposition (t < 30 s) due to the effect of the scavenging by the water quality. Advanced oxidation using O₃ and hydrogen peroxide did not increase the net production of OH compared to O₃ under the conditions studied. EfOM reactivity impacted the removal of trace contaminants when evaluated based on the O₃:TOC ratio. Trace contaminants with second order reaction rate constants with O₃ (kO3) > 10⁵ M⁻¹ s⁻¹ and OH (k_OH) > 10⁹ M⁻¹ s⁻¹, including carbamazepine, diclofenac, naproxen, sulfamethoxazole, and triclosan, were >95% removed independent of water quality when the O₃ exposure () was measurable (0-0.8 mg min/L). O₃ exposure would be a conservative surrogate to assess the removal of trace contaminants that are fast-reacting with O₃. Removal of contaminants with and k_OH > 10⁹ M⁻¹ s⁻¹, including atrazine, iopromide, diazepam, and ibuprofen, varied when O₃ exposure could not be measured, and appeared to be dependent upon the compound specific k_OH. Atrazine, diazepam, ibuprofen and iopromide provided excellent linear correlation with pCBA (R² > 0.86) making them good indicators of OH availability.     

Profile storage of organic/inorganic carbon in soil: From forest to desert

Understanding the distribution of organic/inorganic carbon storage in soil profile is crucial for assessing regional, continental and global soil C stores and predicting the consequences of global change. However, little is known about the organic/inorganic carbon storages in deep soil layers at various landscapes. This study was conducted to determine the soil organic/inorganic carbon storage in soil profile of 0-3 m at 5 sites of natural landscape from forest to desert. Landscapes are temperate forest, temperate grassland, temperate shrub-grassland, temperate shrub desert, and temperate desert. Root mass density and carbon contents at the profile were determined for each site. The results showed that considerable decrease in root biomass and soil organic carbon content at the soil profile of 0-3 m when landscape varied from forest to desert along a precipitation gradient, while soil inorganic carbon content increased significantly along the precipitation gradient. Namely, for density of soil organic carbon: forest > grassland > shrub-grassland > shrub desert > desert; for density of soil inorganic carbon: forest, grassland < shrub-grassland < shrub desert < desert (P < 0.05 in all cases). In landscapes other than forest, more than 50% soil carbon storage was found in 1-3 m depth. For grassland and shrub-grassland, the contribution from 1-3 m was mainly in the form of organic carbon, while for shrub desert and desert the contribution from this depth was mainly in the form of inorganic carbon. The comparison of soil C storage between top 0-1 m and 1-3 m showed that the using top 1 m of soil profile to estimate soil carbon storages would considerably underestimate soil carbon storage. This is especially true for organic soil carbon at grassland region, and for soil inorganic carbon at desert region.     

Steroid hormones in biosolids and poultry litter: a comparison of potential environmental inputs

Steroid hormones can act as potent endocrine disruptors when released into the environment. The main sources of these chemicals are thought to be wastewater treatment plant discharges and waste from animal feeding operations. While these compounds have frequently been found in wastewater effluents, few studies have investigated biosolids or manure, which are routinely land applied, as potential sources. This study assessed the potential environmental contribution of steroid hormones from biosolids and chicken litter. Hormone concentrations in samples of limed biosolids collected at a waste treatment plant over a four year period ranged from < 2.5 to 21.7 ng/g dry weight for estrone (E1) and < 2.5 to 470 ng/g dry weight for progesterone. Chicken litter from 12 mid-Atlantic farms had averages of 41.4 ng/g dry weight E1, 63.4 ng/g dry weight progesterone, and 19.2 ng/g dry weight E1-sulfate (E1-S). Other analytes studied were 17β-estradiol (E2), estriol (E3), 17α-ethinylestradiol (EE2), testosterone, E2-3-sulfate (E2-3-S), and E2-17-sulfate (E2-17-3).     

Biodegradation of endocrine disrupting compounds in harbour seawater and sediments

The biodegradation of three endocrine disrupting compounds was examined using samples of seawater and sediment collected from Halifax Harbour, Nova Scotia, Canada, an urbanized harbour impacted by over two centuries of anthropogenic contamination. Flask experiments, where the samples were mixed to form a slurry were used to monitor the aerobic biodegradation of the synthetic plasticizer bisphenol A (BPA), the natural hormone 17β-estradiol (E2), and the pharmaceutical and contraceptive ethinylestradiol (EE2). Degradation rates followed the order E2 > EE2 > BPA with half-lives of up to 1, 5 and 14 days in seawater, respectively. A rapid initial degradation rate for all three compounds with no apparent lag phase indicated the ability of the microbial community to readily catabolise the chemicals. The formation of unidentified non-persistent intermediate metabolites was observed during the E2 degradation experiments. These degradation rates are more rapid and complete than reported in previous studies, indicating the adaptation of native microbial communities to these contaminants.     

Selected personal care products and endocrine disruptors in biosolids: an Australia-wide survey

Personal care products (PCPs) and endocrine disrupting compounds (EDCs) are groups of organic contaminants that have been detected in biosolids around the world. There is a shortage of data on these types on compounds in Australian biosolids, making it difficult to gain an understanding of their potential risks in the environment following land application. In this study, 14 biosolids samples were collected from 13 Australian wastewater treatment plants (WWTPs) to determine concentrations of eight compounds that are PCPs and/or EDCs: 4-t-octylphenol (4tOP), 4-nonylphenol (4NP), triclosan (TCS), bisphenol A (BPA), estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2). Concentration data were evaluated to determine if there were any differences between samples that had undergone anaerobic or aerobic treatment. The concentration data were also compared to other Australian and international data. Only 4tOP, 4NP, TCS, and BPA were detected in all samples and E1 was detected in four of the 14 samples. Their concentrations ranged from 0.05 to 3.08 mg/kg, 0.35 to 513 mg/kg, < 0.01 to 11.2 mg/kg, < 0.01 to 1.47 mg/kg and < 45 to 370 μg/kg, respectively. The samples that were obtained from WWTPs that used predominantly anaerobic treatment showed significantly higher concentrations of the compounds than those obtained from WWTPs that used aerobic treatment. Overall, 4NP, TCS and BPA concentrations in Australian biosolids were lower than global averages (by 42%, 12% and 62%, respectively) and 4tOP concentrations were higher (by 25%), however, of these differences only that for BPA was statistically significant. The European Union limit value for NP in biosolids is 50 mg/kg, which 4 of the 14 samples in this study exceeded.     

Fate of nine recycled water trace organic contaminants and metal(loid)s during managed aquifer recharge into a anaerobic aquifer: Column studies

Water quality changes associated with the passage of aerobic reverse osmosis (RO) treated recycled water through a deep anaerobic pyritic aquifer system was evaluated in sediment-filled laboratory columns as part of a managed aquifer recharge (MAR) strategy. The fate of nine recycled water trace organic compounds along with potential negative water quality changes such as the release of metal(loid)s were investigated in large-scale columns over a period of 12 months.The anaerobic geochemical conditions provided a suitable environment for denitrification, and rapid (half-life <1-25 days) degradation of the endocrine disrupting compounds (bisphenol A, 17β-estradiol, 17α-ethynylestradiol), and iodipamide. However, pharmaceuticals (carbamazepine and oxazepam), disinfection by-products (N-nitrosodimethylamine, N-nitrosomorpholine) and iohexol did not degrade rapidly (half-life > 100 days).High retardation coefficients (R) determined for many of the trace organics (R 13 to 67) would increase aquifer residence time and be beneficial for many of the slow degrading compounds. However, for the trace organics with low R values (1.1-2.6) and slow degradation rates (half-life > 100 days), such as N-nitrosodimethylamine, N-nitrosomorpholine and iohexol, substantial biodegradation during aquifer passage may not occur and additional investigations are required.Only minor transient increases in some metal(loid) concentrations were observed, as a result of either pyrite oxidation, mineral dissolution or pH induced metal desorption, followed by metal re-sorption downgradient in the oxygen depleted zone.     

Activated soil filters (bio filters) for the elimination of xenobiotics (micro-pollutants) from storm- and waste waters

A technical scale (0.12 m³) activated soil filter (bio filter) has been used to eliminate diverse xenobiotics (organic micro-pollutants) such as organophosphate flame retardants, and -plasticisers, musk fragrances, DEHP, benzothiazoles and triclosan from water. Model experiments to treat combined sewer overflow, storm water and a post treatment of waste water were performed in controlled laboratory experiments. The indicator compounds were typical for waste water. Diverse chemical compound groups and a wide spectrum from the lipophilic (pK_ow = 5.9) to the hydrophilic (pK_ow = 2.6) were included. The system consisted of a layer with high organic content (with vegetation to prevent clogging), a sand filter and a gravel drainage layer. The organic layer was spiked with activated sludge to enhance biomass and biodegradation potential. Usually the elimination rates varied from 64% to 99%, with only one compound reaching as little as 17%. For a technical suitability assessment it was calculated how long these filters would be stable in eliminating organic compounds from water. The estimated operating times for such systems was found to be about 100 years for a stack height of 2 m a year in regard to most compounds in this study.     

Emission of trace gases and organic components in smoke particles from a wildfire in a mixed-evergreen forest in Portugal

On May 2009, both the gas and particulate fractions of smoke from a wildfire in Sever do Vouga, central Portugal, were sampled. Total hydrocarbons and carbon oxides (CO₂ and CO) were measured using automatic analysers with flame ionisation and non-dispersive infrared detectors, respectively. Fine (PM_2.5) and coarse (PM_2.5-10) particles from the smoke plume were analysed by a thermal-optical transmission technique to determine the elemental and organic carbon (EC and OC) content. Subsequently, the particle samples were solvent extracted and fractionated by vacuum flash chromatography into different classes of organic compounds. The detailed organic speciation was performed by gas chromatography-mass spectrometry. The CO, CO₂ and total hydrocarbon emission factors (g kg⁻¹ dry fuel) were 170 ± 83, 1485 ± 147, and 9.8 ± 0.90, respectively. It was observed that the particulate matter and OC emissions are significantly enhanced under smouldering fire conditions. The aerosol emissions were dominated by fine particles whose mass was mainly composed of organic constituents, such as degradation products from biopolymers (e.g. levoglucosan from cellulose, methoxyphenols from lignin). The compound classes also included homologous series (n-alkanes, n-alkenes, n-alkanoic acids and n-alkanols), monosaccharide derivatives from cellulose, steroid and terpenoid biomarkers, and polycyclic aromatic hydrocarbons (PAHs). The most abundant PAH was retene. Even carbon number homologs of monoglycerides were identified for the first time as biomarkers in biomass burning aerosols.     

Isotopic exchangeability as a measure of the available fraction of the human pharmaceutical carbamazepine in river sediment

Cabamazepine (CBZ), an antiepileptic pharmaceutical compound, is a pollutant of aquatic ecosystems entering via wastewater treatment plants that is considered to be persistent to degradation. An isotope exchange technique was employed using radiolabelled CBZ as a model compound, to determine the amount of isotopic exchangeability of CBZ in river sediment. The amount of isotopically exchangeable CBZ was used as an estimate of the extent of desorption hysteresis in solution from river sediment, including a treatment where the sediment was amended with black carbon. The isotopically exchangeable CBZ was measured by equilibrating ¹²C-CBZ with sediment for 0 to 28 days followed by a 24 hour equilibration with ¹⁴C-CBZ at the end of the incubation period. The isotopically exchangeable fraction of CBZ decreased over time in the sediment, particularly following amendment with black carbon. This has important implications for the fate of CBZ, which, apart from being resistant to degradation, is constantly released into aquatic ecosystems from wastewater treatment plants. This study demonstrates the availability of a relatively quick and simple alternative to batch desorption techniques for the assessment of the available fraction of organic compounds in sediments following their release into aquatic ecosystems.     

Attenuation of contaminants of emerging concern during surface-spreading aquifer recharge

The attenuation of a diverse suite of contaminants of emerging concern (CECs) and bulk water quality changes was evaluated at a surface-spreading aquifer recharge operation across a detailed subsurface profile (9 locations), representing both short- and long-travel times (10 h to 60 days). Seventeen CECs were detected in the recharge basin and the concentrations of all were reduced during soil aquifer treatment (SAT), with 11 of the target compounds attenuated by > 80% after 60 days of travel time. Select CECs (atenolol, gemfibrozil, N,N-diethly-3-methylbenzamide, meprobamate, tris(2-chloroethyl)phosphate, and primidone) and bulk water organic-carbon measurements (total organic carbon, biodegradable organic carbon, size-exclusion chromatography and fluorescence excitation-emission matrices) were identified as monitoring parameters that can be used to assess SAT performance at surface-spreading operations.     

Simultaneous colour and DON removal from sewage treatment plant effluent: Alum coagulation of melanoidin

The aim of this study was to detect and characterise melanoidin in sewage treatment plant (STP) effluent, and to study the ability of alum coagulation to remove the colour and dissolved organic nitrogen (DON) associated with melanoidin. The melanoidin is non-biodegradable due to the complex cyclic based structure and thus it directly contributes to effluent nitrogen concentrations from the sewage treatment plant (STP). Lowering of effluent total nitrogen limits and the link between colour and chlorinated disinfection by-products have therefore driven a need to understand the structure, properties and treatability of DON species found in STP effluent.The focus of this paper is the refractory coloured, organic nitrogen compound melanoidin. Wetalla STP effluent has relatively high colour (170 mg-PtCo L⁻¹) and DON (2.5 mg L⁻¹) for a biological nutrient removal STP, owing to an industrial supply of melanoidin containing molasses fermentation wastewater. Alum coagulation jar tests were performed on synthetic melanoidin solution, STP effluent containing melanoidin (Wetalla, Toowoomba, Australia) and STP effluent free of melanoidin (Merrimac, Gold Coast, Australia) to examine the treatability of melanoidin and its associated colour and DON content when present in STP effluent.The removal of melanoidin from STP effluent resulted in significant colour and DON reduction. An alum dose of 30 mg L⁻¹ as aluminium was sufficient to reach maximum removal of colour (75%), DON (42%) and dissolved organic carbon (DOC) (30%) present in melanoidin containing STP effluent. Alum was shown to preferentially remove DON with a molecular weight >10 kDa over small molecular weight DON. Fluorescence excitation-emission matrix examination of the humic compounds present in the STP effluent indicated that melanoidin type humic compounds were more readily removed by alum coagulation than other humic compounds.     

Pharmaceuticals, hormones and bisphenol A in untreated source and finished drinking water in Ontario, Canada--occurrence and treatment efficiency

The Ontario Ministry of the Environment (MOE) conducted a survey in 2006 on emerging organic contaminants (EOCs) which included pharmaceuticals, hormones and bisphenol A (BPA). The survey collected 258 samples over a 16 month period from selected source waters and 17 drinking water systems (DWSs), and analyzed them for 48 EOCs using liquid chromatography-tandem mass spectrometry (LC-MS/MS) and isotope dilution mass spectrometry (IDMS) for the highest precision and accuracy of analytical data possible. 27 of the 48 target EOCs were detected in source water, finished drinking water, or both. DWSs using river and lake source water accounted for > 90% detections. Of the 27 EOCs found, we also reported the first detection of two antibiotics roxithromycin and enrofloxacin in environmental samples. The most frequently detected compounds (≥ 10%) in finished drinking water were carbamazepine (CBZ), gemfibrozil (GFB), ibuprofen (IBU), and BPA; with their concentrations accurately determined by using IDMS and calculated to be 4 to 10 times lower than those measured in the source water. Comparison of plant specific data allowed us to determine removal efficiency (RE) of these four most frequently detected compounds in Ontario DWSs. The RE of CBZ was determined to be from 71 to 93% for DWSs using granulated activated carbon (GAC); and was 75% for DWSs using GAC followed by ultraviolet irradiation (UV). The observed RE of GFB was between 44 and 55% in DWSs using GAC and increased to 82% when GAC was followed by UV. The use of GAC or GAC followed by UV provided an RE improvement of BPA from 80 to 99%. These detected concentration levels are well below the predicted no effect concentration or total allowable concentration reported in the literature. Additional targeted, site specific comparative research is required to fully assess the effectiveness of Ontario DWSs to remove particular compounds of concern.     

Sonophotolytic degradation of azo dye reactive black 5 in an ultrasound/UV/ferric system and the roles of different organic ligands

The sonophotolytic advance oxidation system (US/UV/Fe³⁺) could achieve synergistic degradation of reactive black 5 (RB5), as compared to UV/Fe³⁺ and US/Fe³⁺ systems. A synergy factor of 2.5 based on the pseudo-first-order degradation rate constant (k_obs) was found, along with enhancements in organic detoxification and mineralization. The presence of organic ligands could affect the US/UV/Fe³⁺ system differently. Oxalate, citrate, tartrate and succinate could enhance the RB5 degradation, while NTA and EDTA exhibited strong inhibitions. The influence of these ligands on k_obs(RB5) in the US/UV/Fe(III)-ligand systems followed the sequence of oxalate > tartrate > succinate > citrate > without ligand > NTA > EDTA, while they could be degraded simultaneously with the k_obs(ligand) order of oxalate > citrate > tartrate > succinate > NTA > EDTA. Monitoring of iron species and the generated H₂O₂ and •OH revealed that the ligands in the US/UV/Fe(III)-ligand system could play different mechanistic roles: (1) promoting H₂O₂ production, (2) accelerating Fenton reaction, and (3) competing with RB5 for reacting with •OH. Among the ligands, oxalate exhibited the most significant enhancement of RB5 oxidation in the sonophotolytic system, and the process was pH-dependent. An initial reaction lag in RB5 degradation was observed when Fe²⁺ was used in lieu of Fe³⁺ as the catalyst in the sonophotolytic system.     

Natural organic matter and sunlight accelerate the degradation of 17ß-estradiol in water

Nanomolar concentrations of steroid hormones such as 17β-estradiol can influence the reproductive development and sex ratios of invertebrate and vertebrate populations. Thus their release into surface and ground waters from wastewater facilities and agricultural applications of animal waste is of environmental concern. Many of these compounds are chromophoric and susceptible to photolytic degradation. High intensity UV-C radiation has been demonstrated to degrade some of these compounds in engineered systems. However, the degradation efficacy of natural solar radiation in shallow fresh waters is less understood. Here photolytic experiments with 17β-estradiol demonstrated modest photodegradation (~ 26%) when exposed to simulated sunlight between 290 and 720 nm. Photodegradation significantly increased (~ 40-50%) in the presence of 2.0-15.0 mg/l of dissolved organic carbon (DOC) derived from humic acids of the Suwannee River, GA. However, rates of photodegradation reached a threshold at approximately 5.0 mg/l DOC. Observed suppression of photolysis in the presence of a radical inhibitor (i.e. 2-propanol) indicated that a significant proportion of the degradation was due to radicals formed from the photolysis of DOC. Although photodegradation was greatest in full sunlight containing UV-B (290-320 nm), degradation was also detected with UV-A (320-400 nm) and visible light (400-720 nm) alone.     

Removal of Pharmaceutical and Personal Care Products (PPCPs) under nitrifying and denitrifying conditions

The contribution of volatilization, sorption and transformation to the removal of 16 Pharmaceutical and Personal Care Products (PPCPs) in two lab-scale conventional activated sludge reactors, working under nitrifying (aerobic) and denitrifying (anoxic) conditions for more than 1.5 years, have been assessed. Pseudo-first order biological degradation rate constants (k_biol) were calculated for the selected compounds in both reactors. Faster degradation kinetics were measured in the nitrifying reactor compared to the denitrifying system for the majority of PPCPs. Compounds could be classified according to their k_biol into very highly (k_biol > 5 L g_SS⁻¹ d⁻¹), highly (1 < k_biol < 5 L g_SS⁻¹ d⁻¹), moderately (0.5 < k_biol < 1 L g_SS⁻¹ d⁻¹) and hardly (k_biol < 0.5 L g_SS⁻¹ d⁻¹) biodegradable.Results indicated that fluoxetine (FLX), natural estrogens (E1 + E2) and musk fragrances (HHCB, AHTN and ADBI) were transformed to a large extent under aerobic (>75%) and anoxic (>65%) conditions, whereas naproxen (NPX), ethinylestradiol (EE2), roxithromycin (ROX) and erythromycin (ERY) were only significantly transformed in the aerobic reactor (>80%). The anti-depressant citalopram (CTL) was moderately biotransformed under both, aerobic and anoxic conditions (>60% and >40%, respectively). Some compounds, as carbamazepine (CBZ), diazepam (DZP), sulfamethoxazole (SMX) and trimethoprim (TMP), manifested high resistance to biological transformation.Solids Retention Time (SRT_aerobic >50 d and <50 d; SRT_anoxic >20 d and <20 d) had a slightly positive effect on the removal of FLX, NPX, CTL, EE2 and natural estrogens (increase in removal efficiencies <10%). Removal of diclofenac (DCF) in the aerobic reactor was positively affected by the development of nitrifying biomass and increased from 0% up to 74%. Similarly, efficient anoxic transformation of ibuprofen (75%) was observed after an adaptation period of 340 d. Temperature (16-26 °C) only had a slight effect on the removal of CTL which increased in 4%.     

Oxidative degradation of pyrene in contaminated soils by δ-MnO2 with or without sunlight irradiation

The enhanced oxidative degradation of pyrene in quartz sand and alluvial and red soils by micro-nano size birnessite (δ-MnO₂) in the presence and absence of sunlight was investigated. The degradation of pyrene by δ-MnO₂ in quartz sand showed very little synergistic effect of sunlight irradiation on δ-MnO₂ oxidizing power. However, pyrene degradation by δ-MnO₂ in alluvial and red soils was greater under solar irradiation than the combination of photooxidation of pyrene and oxidation of pyrene by δ-MnO₂. The oxidative degradation percentages of pyrene by δ-MnO₂ under sunlight irradiation are 94.8, 97.7, and 100% for alluvial soil, red soil, and quartz sand, respectively. Oxidative degradation percentages of pyrene by δ-MnO₂ in alluvial and red soils with irradiation of sunlight almost attained a maximum at 1 h with a 5% (w/w) dose of the amended oxidant. Due to their different total organic carbon (TOC) contents, the sequence of enhanced oxidative degradation of pyrene by δ-MnO₂ in quartz sand and alluvial and red soils was quartz sand > red soil > alluvial soil. Further, this study revealed that δ-MnO₂-enhanced oxidative degradation of pyrene is very pronounced in contaminated soils in situ even at deep soil layers where irradiation by sunlight is very limited.     

Solar photolysis kinetics of disinfection byproducts

Disinfection byproducts (DBPs) discharged from wastewater treatment plants may impair aquatic ecosystems and downstream drinking-water quality. Sunlight photolysis, as one process by which DBPs may dissipate in the receiving surface water, was investigated. Outdoor natural sunlight experiments were conducted in water for a series of carbonaceous DBPs (trihalomethanes, haloacetic acids, halopropanones, and haloacetaldehydes) and nitrogenous DBPs (nitrosamines, halonitromethanes, and haloacetonitriles). Their pseudo-first-order rate constants for photolytic degradation were then used to calibrate quantitative structure-activity relationship (QSAR) parameters, which, in return, predicted the photolysis potentials of other DBPs or related compounds. Nitrogenous DBPs were found to be more susceptible to solar irradiation than carbonaceous DBPs, with general rankings for the functional groups as follows: N-nitroso (N-NO) > nitro (NO₂) > nitrile (CN) > carbonyl (CO) > carboxyl (COOH). Compounds containing a high degree of halogenation (e.g., three halogens) were usually less stable than less halogenated species (e.g., those with two halogens). Bromine- or iodine-substituted species were more photosensitive than chlorinated analogs. While most bromine- and chlorine-containing trihalomethanes and haloacetic acids persisted over the 6-h test, nearly complete removal (>99%) of nitrosamines occurred within 1 h of sunlight exposure. Indoor laboratory experiments using simulated sunlight demonstrated that the degradation of nitrosamines was ∼50% slower when organic matter was present, and ∼11% slower in non-filtered water than in filtered water.