Application of the gas tracer method for measuring oxygen transfer rates in subsurface flow constructed wetlands

The oxygen transfer rate (OTR) has a significant impact on the design, optimal operation and modelling of constructed wetlands treating wastewater. Oxygen consumption is very fast in wetlands and the OTR cannot be determined using an oxygen mass balance. This problem is circumvented in this study by applying the gas tracer method. Experiments were conducted in an unplanted gravel bed (dimensions L × W × d 125 × 50 × 35 cm filled with a 30-cm layer of 10-11-mm gravel) and a planted horizontal subsurface flow constructed wetland (HSSFCW) (L × W × d 110 × 70 × 38 cm filled with a 30-cm layer of 3.5-mm gravel with Phragmites australis). Tap water saturated with propane as gas tracer (pure or commercial cooking gas, depending on the test) was used. The mass transfer ratio between oxygen and commercial propane gas was quite constant and averaged R = 1.03, which is slightly lower than the value of R = 1.39 that is usually reported for pure propane. The OTR ranged from 0.31 to 5.04 g O₂ m⁻² d⁻¹ in the unplanted gravel bed and from 0.3 to 3.2 g O₂ m⁻² d⁻¹ in the HSSFCW, depending on the hydraulic retention time (HRT). The results of this study suggest that the OTR in HSSFCW is very low for the oxygen demand of standard wastewater and the OTR calculations based on mass balances and theoretical stoichiometric considerations overestimate OTR values by a factor that ranges from 10 to 100. The gas tracer method is a promising tool for determining OTR in constructed wetlands, with commercial gas proving to be a viable low-cost alternative for determining OTR.     

Bacterial community dynamics in horizontal flow constructed wetlands with different plants for high salinity industrial wastewater polishing

This study is focused on the diversity of bacterial communities from two series of horizontal subsurface flow constructed wetlands (CW) polishing high salinity tannery wastewater. Each series was planted with Arundo donax or Sarcocornia sp. in a substrate composed by expanded clay and sand. Chemical and biochemical oxygen demand removal efficiencies were similar in each series, varying between 58 and 67% (inlet COD 218 ± 28 mg L⁻¹) and 60 and 77% (inlet BOD₅ 37 ± 6 mg L⁻¹), respectively. High numbers of culturable bacteria were obtained from substrate and root samples - 5.75 × 10⁶-3.95 × 10⁸ CFU g⁻¹ recovered on marine agar and 1.72 × 10⁷-8.46 × 10⁸ CFU g⁻¹ on nutrient agar. Fifty bacterial isolates were retrieved from the CW, related phylogenetically to Firmicutes, Actinobacteria, Bacteroidetes, α-, β-, and γ-Proteobacteria. Changes in the bacterial communities, from roots and substrate of each series, related to the plant species, hydraulic loading rates and along CW operation were examined using denaturating gradient gel electrophoresis (DGGE). The clustering analysis suggested that a diverse and distinct bacterial community inhabits each series, which was related to the type of plant present in each CW.     

Performance comparison of constructed wetlands with gravel- and rice husk-based media for phenol and nitrogen removal

This study aims to compare the performance of planted and unplanted constructed wetlands with gravel- and raw rice husk-based media for phenol and nitrogen removal. Four laboratory-scale horizontal subsurface-flow constructed wetland units, two of which planted with cattail (Typha latifolia) were operated outdoors. The units were operated at a nominal hydraulic retention time of 7 days and fed with domestic wastewater spiked with phenol concentration at 300 mg/L for 74 days and then at 500 mg/L for 198 days. The results show that planted wetland units performed better than the unplanted ones in the removal and mineralization of phenol. This was explained by the creation of more micro-aerobic zones in the root zone of the wetland plants which allow a faster rate of phenol biodegradation, and the phenol uptake by plants. The better performance of the rice husk-based planted wetland compared to that of the gravel-based planted wetland in phenol removal could be explained by the observation that more rhizomes were established in the rice husk-based wetland unit thus creating more micro-aerobic zones for phenol degradation. The role of rice husk as an adsorbent in phenol removal was considered not of importance.     

Nitrate removal, communities of denitrifiers and adverse effects in different carbon substrates for use in denitrification beds

Denitrification beds are containers filled with wood by-products that serve as a carbon and energy source to denitrifiers, which reduce nitrate (NO₃⁻) from point source discharges into non-reactive dinitrogen (N₂) gas. This study investigates a range of alternative carbon sources and determines rates, mechanisms and factors controlling NO₃⁻ removal, denitrifying bacterial community, and the adverse effects of these substrates. Experimental barrels (0.2 m³) filled with either maize cobs, wheat straw, green waste, sawdust, pine woodchips or eucalyptus woodchips were incubated at 16.8 °C or 27.1 °C (outlet temperature), and received NO₃⁻ enriched water (14.38 mg N L⁻¹ and 17.15 mg N L⁻¹). After 2.5 years of incubation measurements were made of NO₃⁻-N removal rates, in vitro denitrification rates (DR), factors limiting denitrification (carbon and nitrate availability, dissolved oxygen, temperature, pH, and concentrations of NO₃⁻, nitrite and ammonia), copy number of nitrite reductase (nirS and nirK) and nitrous oxide reductase (nosZ) genes, and greenhouse gas production (dissolved nitrous oxide (N₂O) and methane), and carbon (TOC) loss. Microbial denitrification was the main mechanism for NO₃⁻-N removal. Nitrate-N removal rates ranged from 1.3 (pine woodchips) to 6.2 g N m⁻³ d⁻¹ (maize cobs), and were predominantly limited by C availability and temperature (Q₁₀ = 1.2) when NO₃⁻-N outlet concentrations remained above 1 mg L⁻¹. The NO₃⁻-N removal rate did not depend directly on substrate type, but on the quantity of microbially available carbon, which differed between carbon sources. The abundance of denitrifying genes (nirS, nirK and nosZ) was similar in replicate barrels under cold incubation, but varied substantially under warm incubation, and between substrates. Warm incubation enhanced growth of nirS containing bacteria and bacteria that lacked the nosZ gene, potentially explaining the greater N₂O emission in warmer environments. Maize cob substrate had the highest NO₃⁻-N removal rate, but adverse effects include TOC release, dissolved N₂O release and substantial carbon consumption by non-denitrifiers. Woodchips removed less than half of NO₃⁻ removed by maize cobs, but provided ideal conditions for denitrifying bacteria, and adverse effects were not observed. Therefore we recommend the combination of maize cobs and woodchips to enhance NO₃⁻ removal while minimizing adverse effects in denitrification beds.     

Adsorption, sedimentation, and inactivation of E. coli within wastewater treatment wetlands

Bacteria fate and transport within constructed wetlands must be understood if engineered wetlands are to become a reliable form of wastewater treatment. This study investigated the relative importance of microbial treatment mechanisms in constructed wetlands treating both domestic and agricultural wastewater. Escherichia coli (E. coli) inactivation, adsorption, and settling rates were measured in the lab within two types of wastewater (dairy wastewater lagoon effluent and domestic septic tank effluent). In situ E. coli inactivation was also measured within a domestic wastewater treatment wetland and the adsorption of E. coli was also measured within the wetland effluent.Inactivation of E. coli appears to be the most significant contributor to E. coli removal within the wastewaters and wetland environments examined in this study. E. coli survived longer within the dairy wastewater (DW) compared to the domestic wastewater treatment wetland water (WW). First order rate constants for E. coli inactivation within the WW in the lab ranged from 0.09 day⁻¹ (d⁻¹) at 7.6 °C to 0.18 d⁻¹ at 22.8 °C. The average in situ rate constant observed within the domestic wetland ranged from 0.02 d⁻¹ to 0.03 d⁻¹ at an average water temperature of 17 °C. First order rate constants for E. coli inactivation within the DW ranged from 0.01 d⁻¹ at 7.7 °C to 0.04 d⁻¹ at 24.6 °C. Calculated distribution coefficients (K_d) were 19,000 mL g⁻¹, 324,000 mL g⁻¹, and 293 mL g⁻¹ for E. coli with domestic septic tank effluent (STE), treated wetland effluent (WLE), and DW, respectively. Approximately 50%, 20%, and 90% of E. coli were “free floating” or associated with particles <5 μm in size within the STE, WLE, and DW respectively. Although 10-50% of E. coli were found to associate with particles >5 μm within both the STE and DW, settling did not appear to contribute to E. coli removal within sedimentation experiments, indicating that the particles the bacteria were associated with had very small settling velocities.The results of this study highlight the importance of wastewater characterization when designing a treatment wetland system for bacterial removal. This study illustrated the level of variability in E. coli removal processes that can be observed within different wastewater, and wetland environments.     

Kinetics of electro-oxidation of ammonia-N, nitrites and COD from a recirculating aquaculture saline water system using BDD anodes

The viability of the electro-oxidation technology provided with boron doped diamond (BDD) electrodes for the treatment and reuse of the seawater used in a Recirculating Aquaculture System (RAS) was evaluated in this work.The influence of the applied current density (5-50 A m⁻²) in the removal of Total Ammonia Nitrogen (TAN), nitrite and chemical oxygen demand (COD) was analyzed observing that complete TAN removal together with important reductions of the other considered contaminants could be achieved, thus meeting the requirements for reuse of seawater in RAS systems.TAN removal, mainly due to an indirect oxidation mechanism was described by a second order kinetics while COD and nitrite removal followed zero-th order kinetics. The values of the kinetic constants for the anodic oxidation of each compound were obtained as a function of the applied current density (k_TAN = 7.86 × 10⁻⁵·exp(6.30 × 10⁻² J); k₂NO = 3.43 × 10⁻² J; k_COD = 1.35 × 10⁻² J). The formation of free chlorine and oxidation by-products, i.e., trihalomethanes (THMs) was followed along the electro-oxidation process. Although a maximum concentration of 1.7 mg l⁻¹ of total trihalomethanes was detected an integrated process combining electrochemical oxidation in order to eliminate TAN, nitrite and COD and adsorption onto activated carbon to remove the residual chlorine and THMs is proposed, as an efficient alternative to treat and reuse the seawater in fish culture systems. Finally, the energy consumption of the treatment has been evaluated.     

Floc-based sequential partial nitritation and anammox at full scale with contrasting N2O emissions

New Activated Sludge (NAS^®) is a hybrid, floc-based nitrogen removal process without carbon addition, based on the control of sludge retention times (SRT) and dissolved oxygen (DO) levels. The aim of this study was to examine the performance of a retrofitted four-stage NAS^® plant, including on-line measurements of greenhouse gas emissions (N₂O and CH₄). The plant treated anaerobically digested industrial wastewater, containing 264 mg N L⁻¹, 1154 mg chemical oxygen demand (COD) L⁻¹ and an inorganic carbon alkalinity of 34 meq L⁻¹. The batch-fed partial nitritation step received an overall nitrogen loading rate of 0.18-0.22 kg N m⁻³ d⁻¹, thereby oxidized nitrogen to nitrite (45-47%) and some nitrate (13-15%), but also to N₂O (5.1-6.6%). This was achieved at a SRT of 1.7 d and DO around 1.0 mg O₂ L⁻¹. Subsequently, anammox, denitrification and nitrification compartments were followed by a final settler, at an overall SRT of 46 d. None of the latter three reactors emitted N₂O. In the anammox step, 0.26 kg N m⁻³ d⁻¹ was removed, with an estimated contribution of 71% by the genus Kuenenia, which constituted 3.1% of the biomass. Overall, a nitrogen removal efficiency of 95% was obtained, yielding a dischargeable effluent. Retrofitting floc-based nitrification/denitrification with carbon addition to NAS^® allowed to save 40% of the operational wastewater treatment costs. Yet, a decrease of the N₂O emissions by about 50% is necessary in order to obtain a CO₂ neutral footprint. The impact of emitted CH₄ was 20 times lower.     

Pilot treatment of olive pomace leachate by vertical-flow constructed wetland and electrochemical oxidation: An efficient hybrid process

A hybrid process comprising biological degradation in a vertical-flow constructed wetland (CW) and electrochemical oxidation over boron-doped diamond electrodes to decolorize, mineralize and detoxify a leachate from olive pomace processing (OPL) was investigated. Two alternative treatment schemes were compared: According to the first treatment scheme, OPL was treated by electrochemical oxidation followed by treatment in a constructed wetland pilot unit (CW-A). The second scheme comprised of treatment in a constructed wetland followed by electrochemical treatment (CW-B). The constructed wetlands units were planted with Phragmites australis (reeds) and were fed intermittently at organic loadings between 5 and 15 g COD m⁻² d⁻¹ and a residence time of 3 d. Electrochemical oxidation (EO) was performed for 360 min at 20 A.Treatment of OPL in the wetland at 15 g COD m⁻² d⁻¹ led to mean COD and color reduction of 86% and 77%, respectively; the wetland effluent with a COD of about 800 mg L⁻¹ was polished electrochemically for 360 min after which the overall COD and color removal of the combined process (i.e. CW-B/EO) was around 95%, while the final effluent was not toxic against the marine bacteria Vibrio fischeri.Electrochemical oxidation of the original OPL at COD values between 6250 and 14 100 mg L⁻¹ led to moderate COD and color reduction (i.e. less than 40%) through zero order kinetics. When this was coupled to constructed wetland post-treatment (i.e. EO/CW-A), the overall COD and color removal was 81% and 58%, respectively. The decreased efficiency may be assigned to the increased toxicity of the electrochemically treated effluent which was only partially removed in the natural treatment system.     

Optimization of phenol removal from wastewater by activation of persulfate and ultrasonic waves in the presence of biochar catalyst modified by lanthanum chloride

In this paper, the effects of phenol concentration, pH, catalyst dose, persulfate concentration, temperature and contact time on the phenol removal from wastewater by activation of persulfate (S₂O₈^?2) in the presence of biochar modified by lanthanum chloride and ultrasonic waves (US) are optimized. Experimental design and optimization were carried out by response surface methodology. The optimum conditions for the maximum phenol removal were obtained pH of 4, phenol concentration of 86 mg/L, catalyst dose of 43 mg/L, persulfate concentration of 86 mg/L, temperature of 41 °C and contact time of 63 min. The optimum phenol removal from synthetic wastewater was attained 97.68%. Phenol removal by the mentioned system was fitted with the first‐order kinetic model. The combination of the ingredients of ‘S₂O₈^?2/US/Biochar‐LaCl₃’ system had a synergistic effect on the phenol removal.     

Bio-reaction of nitrobenzene with Microcystis aeruginosa: characteristics, kinetics and application

The bio-reaction of nitrobenzene (NB) with Microcystis aeruginosa was investigated at different initial algal densities and NB concentrations by performing static experiments. The results showed that the elimination of NB was enhanced by the bio-reaction, and the reaction rate varied as a function of the reaction time. Moreover, the reaction rate was significantly affected by the algal density and NB concentration. A kinetic analysis showed that the elimination of NB in a solution without algae appeared to be pseudo-first-order with respect to the NB concentration, whereas a first-order model was too oversimplified to describe the elimination of NB in a solution with algae. Assuming that different algal cells have the same effect on the bio-reaction under the same conditions, the bio-reaction can be described as dC_NB = −k₀C_A^mA_NBⁿdt (where k₀ is the reaction rate constant, C_A is the algae density and C_NB is the concentration of NB). When the growth of algae was not considered, the value of k₀, m and n were 8.170 × 10⁻⁴, 0.5887 and 1.692, respectively. Alternatively, when algae were in the exponential growth phase, the value of k₀, m and n were 1.6871 × 10⁻⁵, 0.7248 and 2.5407, respectively, according to a nonlinear fitting analysis. The kinetic model was also used to elucidate the effect of nutritional limitation on the bio-reaction.     

A photoelectrocatalytic process that disinfects water contaminated with Mycobacterium kansasii and Mycobacterium avium

Nontuberculous mycobacteria are resistant to conventional water treatment; indeed, they have been recovered from a wide variety of environmental sources. Here, we applied the photoelectrocatalytic technique using a Ti/TiO₂–Ag photoanode to inactivate mycobacteria. For a mycobacteria population of 5 × 10⁸ CFU mL⁻¹, we achieved 99.9 and 99.8% inactivation of Mycobacterium kansasii and Mycobacterium avium with rate constant of 6.2 × 10⁻³ and 4.2 × 10⁻³ min⁻¹, respectively, after 240 min. We compared the proposed method with the photolytic and photocatalytic methods. Using a mycobacteria population of 7.5 × 10⁴ CFU mL⁻¹, the proposed Ti/TiO₂–Ag photoanode elicited total mycobacteria inactivation within 3 min of treatment; the presence of Ag nanoparticles in the electrode provided 1.5 larger degradation rate constant as compared with the Ti/TiO₂ anode (1.75 × 10⁻² for M. kansassi and 1.98 × 10⁻² for M. avium). We monitored the degradation of the metabolites released during cellular lysis by TOC removal, sugar release, chromatography, and mass spectrometry measurements; photoelectrocatalysis and Ti/TiO₂–Ag photoanodes furnished the best results.     

Investigating dissolved air flotation performance with cyanobacterial cells and filaments

Dissolved air flotation (DAF) performance with two different naturally occurring cyanobacterial morphologies was investigated with respect to the biomass removal efficiency, the toxin release to water and the coagulant demand by different water background natural organic matter (NOM). Coagulation (C)/Flocculation (F)/DAF bench-scale experiments (2 min coagulation at 380 s⁻¹ with polyaluminium chloride (0.5-4 mg/L Al₂O₃, the dose depending on the water NOM content); 8 min flocculation at 70 s⁻¹; 8 min DAF with 5 bar relative pressure and 8% pressurised recycle) were performed with single cells of Microcystis aeruginosa and Planktothrix rubescens filaments spiked in synthetic waters with different NOM contents (hydrophobic vs. hydrophilic NOM; moderate (2-3 mgC/L) vs. moderate-high concentration (ca. 6 mgC/L)). For both morphologies, the results show no apparent cyanobacterial damage (since the water quality did not degrade in dissolved microcystins and the removal of intracellular microcystins matched the removal of chlorophyll a) and high biomass removal efficiencies (93-99% for cells and 92-98% for filaments) provided optimal coagulant dose for chlorophyll a removal was ensured. Charge neutralisation by the polyaluminium chloride was the main coagulation mechanism of the M. aeruginosa cells and most likely also of the P. rubescens filaments. The specific coagulant demand was severely affected by NOM hydrophobicity, hydrophobic NOM (with a specific UV_254nm absorbance, SUVA, above 4 L/(m mgC)) requiring ca. the triple of hydrophilic NOM (SUVA below 3 L/(m mgC)), i.e. 0.7 vs. 0.2-0.3 mg Al₂O₃/mg DOC.     

Synergistic effect of nickel ions on the coupled dechlorination of trichloroethylene and 2,4-dichlorophenol by Fe/TiO₂ nanocomposites in the presence of UV light under anoxic conditions

The coupled removal of priority pollutants by nanocomposite materials has recently been receiving much attention. In this study, trichloroethylene (TCE) and 2,4-dichlorophenol (DCP) in aqueous solutions were simultaneously removed by Fe/TiO₂ nanocomposites under anoxic conditions in the presence of nickel ions and UV light at 365 nm. Both TCE and DCP were effectively dechlorinated by Fe/TiO₂ nanocomposites, and the pseudo-first-order rate constants (k_obs) for TCE and DCP dechlorination were (1.39 ± 0.05)×10⁻² and (1.08 ± 0.05)×10⁻² h⁻¹, respectively, which were higher than that by nanoscale zerovalent iron alone. In addition, the k_obs for DCP dechlorination was enhanced by a factor of 77 when Fe/TiO₂ was illuminated with UV light for 2 h. Hydrodechlorination was found to be the major reaction pathway for TCE dechlorination, while DCP could undergo reductive dechlorination or react with hydroxyl radicals to produce 1,4-benzoquinone and phenol. TCE was a stronger electron acceptor than DCP, which could inhibit the dechlorination efficiency and rate of DCP during simultaneous removal processes. The addition of nickel ions significantly enhanced the simultaneous photodechlorination efficiency of TCE and DCP under the illumination of UV light. The k_obs values for DCP and TCE photodechlorination by Fe/TiO₂ in the presence of 20-100 μM Ni(II) were 30.4-136 and 13.2-192 times greater, respectively, when compared with those in the dark. Electron spin resonance analysis showed that the photo-generated electron-hole pairs could be effectively separated through Ni ions cycling, leading to the improvement of electron transfer efficiency of TCE and DCP by Fe/TiO₂.     

Halophyte filter beds for treatment of saline wastewater from aquaculture

The expansion of aquaculture and the recent development of more intensive land-based marine farms require efficient and cost-effective systems for treatment of highly nutrient-rich saline wastewater. Constructed wetlands with halophytic plants offer the potential for waste-stream treatment combined with production of valuable secondary plant crops. Pilot wetland filter beds, constructed in triplicate and planted with the saltmarsh plant Salicornia europaea, were evaluated over 88 days under commercial operating conditions on a marine fish and shrimp farm. Nitrogen waste was primarily in the form of dissolved inorganic nitrogen (TDIN) and was removed by 98.2 ± 2.2% under ambient loadings of 109-383 μmol l⁻¹. There was a linear relationship between TDIN uptake and loading over the range of inputs tested. At peak loadings of up to 8185 ± 590 μmol l⁻¹ (equivalent to 600 mmol N m⁻² d⁻¹), the filter beds removed between 30 and 58% (250 mmol N m⁻² d⁻¹) of influent TDIN. Influent dissolved inorganic phosphorus levels ranged from 34 to 90 μmol l⁻¹, with 36-89% reduction under routine operations. Dissolved organic nitrogen (DON) loadings were lower (11-144 μmol l⁻¹), and between 23 and 69% of influent DON was removed during routine operation, with no significant removal of DON under high TDIN loading. Over the 88-day study, cumulative nitrogen removal was 1.28 mol m⁻², of which 1.09 mol m⁻² was retained in plant tissue, with plant uptake ranging from 2.4 to 27.0 mmol N g⁻¹ dry weight d⁻¹. The results demonstrate the effectiveness of N and P removal from wastewater from land-based intensive marine aquaculture farms by constructed wetlands planted with S. europaea.     

Aerobic degradation of acid orange 7 in a vertical-flow constructed wetland

Biological, aerobic degradation of an azo dye and of the resultant, recalcitrant, aromatic amines in a constructed wetland (CW) was demonstrated for the first time. A vertical-flow CW, planted with Phragmites sp. was fed with 127 mg l⁻¹ of acid orange 7 (AO7) at hydraulic loads of 28, 40, 53 and 108 l m⁻²day⁻¹. Color removal efficiencies of up to 99% clearly demonstrate cleavage of the azo bond, also confirmed by the similar AO7 removal and SO₄²⁻ release rates revealing that adsorption onto the matrix was constant. The positive redox potential at the outlet demonstrates that aerobic conditions were present. Chemical oxygen demand and total organic carbon removal efficiencies of up to 93% were also indicative of AO7 mineralization. The degradation of sulfanilic acid was confirmed by the presence of NO₃⁻, SO₄²⁻ and secondary metabolites, which suggest at least two degradation pathways leading to a common compound, 3-oxoadipate.     

Determination of sorption of seventy-five pharmaceuticals in sewage sludge

Sorption of 75 active pharmaceutical ingredients (APIs) to three different types of sludge (primary sludge, secondary sludge with short and long sludge age respectively) were investigated. To obtain the sorption isotherms batch studies with the APIs mixture were performed in four nominal concentrations to water containing 1 g of sludge. The range of APIs concentrations was between ng L⁻¹ to μg L⁻¹ which are found in the wastewater effluents. Isotherms were obtained for approximately 45 of the APIs, providing distribution coefficients for linear (K_d), Freundlich (K_f) and Langmuir (K_L) isotherms. K_d, K_f and K_L ranging between 7.1 × 10⁴ and 3.8 × 10⁷, 1.1 × 10⁻² and 6.1 × 10⁴ and 9.2 × 10⁻³ and 1.1 L kg⁻¹, respectively. The obtained coefficients were applied to estimate the fraction of APIs in the water phase (see Abstract Graphic). For 37 of the 75 APIs, the predicted presence in the liquid phase was estimated to >80%. 24 APIs were estimated to be present in the liquid phase between 20 and 80%, and 14 APIs were found to have <20% presence in the liquid phase, i.e. high affinity towards sludge. Furthermore, the effect of pH at values 6, 7 and 8 was evaluated using one way ANOVA-test. A significant difference in K_ds due to pH changes were found for 6 of the APIs (variation 10-20%).     

Kinetics of nitrate and perchlorate removal and biofilm stratification in an ion exchange membrane bioreactor

The biological degradation of nitrate and perchlorate was investigated in an ion exchange membrane bioreactor (IEMB) using a mixed anoxic microbial culture and ethanol as the carbon source. In this process, a membrane-supported biofilm reduces nitrate and perchlorate delivered through an anion exchange membrane from a polluted water stream, containing 60 mg/L of NO₃⁻ and 100 μg/L of ClO₄⁻. Under ammonia limiting conditions, the perchlorate reduction rate decreased by 10%, whereas the nitrate reduction rate was unaffected. Though nitrate and perchlorate accumulated in the bioreactor, their concentrations in the treated water (2.8 ± 0.5 mg/L of NO₃⁻ and 7.0 ± 0.8 μg/L of ClO₄⁻, respectively) were always below the drinking water regulatory levels, due to Donnan dialysis control of the ionic transport in the system.Kinetic parameters determined for the mixed microbial culture in suspension showed that the nitrate reduction rate was 35 times higher than the maximum perchlorate reduction rate. It was found that perchlorate reduction was inhibited by nitrate, since after nitrate depletion perchlorate reduction rate increased by 77%. The biofilm developed in the IEMB was cryosectioned and the microbial population was analyzed by fluorescence in situ hybridization (FISH). The results obtained seem to indicate that the kinetic advantage of nitrate reduction favored accumulation of denitrifiers near the membrane, whereas per(chlorate) reducing bacteria were mainly positioned at the biofilm outer surface, contacting the biomedium. As a consequence of the biofilm stratification, the reduction of perchlorate and nitrate occur sequentially in space allowing for the removal of both ions in the IEMB.     

Algal-derived organic matter as precursors of disinfection by-products and mutagens upon chlorination

Algal-derived organic materials (including algal cells, hydrophilic and hydrophobic proteins) from Chlamydomonas sp. (a common green alga in local reservoirs), were chlorinated in the laboratory (20 °C, pH 7, Cl₂/DOC ratio of 20 mg Cl₂ mg⁻¹). Levels of disinfection by-products and mutagenicity (via Salmonella T100 mutation assay, -S9) over 2 h of chlorination time were determined. The hydrophilic proteins were more effective precursors of chloroform (35.9 μmol L⁻¹ at 120 min), 35 times greater than that from the hydrophobic proteins; whereas the hydrophobic proteins were more potent precursors of direct-acting mutagens (maximum level of 50.1 rev μL⁻¹ at 30 s) than the hydrophilic proteins (maximum level of 3.38 rev μL⁻¹ at 60 min). The mutagenicity of the chlorinated solutions generally reached a peak level shortly after chlorination and then declined afterwards, a pattern different from that of chloroform generation. The results indicate that algal hydrophilic proteins, containing low aromaticity and difficult to be removed via coagulation/flocculation, are important chloroform precursors. It is also suggested that hydrophobic organic intermediates with low molecular weight formed during chlorination may serve as the direct-acting mutagens.     

Operation of a horizontal subsurface flow constructed wetland – Microbial fuel cell treating wastewater under different organic loading rates

The aim of the present work is to determine whether a horizontal subsurface flow constructed wetland treating wastewater could act simultaneously as a microbial fuel cell (MFC). Specifically, and as the main variable under study, different organic loading rates were used, and the response of the system was monitored. The installation consisted of a synthetic domestic wastewater-feeding system and a pilot-scale constructed wetland for wastewater treatment, which also included coupled devices necessary to function as an MFC. The wetland worked under continuous operation for 180 d, treating three types of synthetic wastewater with increasing organic loading rates: 13.9 g COD m⁻² d⁻¹, 31.1 g COD m⁻² d⁻¹, and 61.1 g COD m⁻² d⁻¹. The COD removal efficiencies and the cell voltage generation were continuously monitored. The wetland worked simultaneously as an MFC generating electric power. Under low organic loading rates, the wastewater organic matter was completely oxidised in the lower anaerobic compartment, and there were slight aerobic conditions in the upper cathodic compartment, thus causing an electrical current. Under high organic loading rates, the organic matter could not be completely oxidised in the anodic compartment and flowed to the cathodic one, which entered into anaerobic conditions and caused the MFC to stop working. The system developed in this work offered similar cell voltage, power density, and current density values compared with the ones obtained in previous studies using photosynthetic MFCs, sediment-type MFCs, and plant-type MFCs. The light/darkness changes caused voltage fluctuations due to the photosynthetic activity of the macrophytes used (Phragmites australis), which affected the conditions in the cathodic compartment.