Efficiency of phenol biodegradation by planktonic Pseudomonas pseudoalcaligenes (a constructed wetland isolate) vs. root and gravel biofilm

In the last two decades, constructed wetland systems gained increasing interest in wastewater treatment and as such have been intensively studied around the world. While most of the studies showed excellent removal of various pollutants, the exact contribution, in kinetic terms, of its particular components (such as: root, gravel and water) combined with bacteria is almost nonexistent.In the present study, a phenol degrader bacterium identified as Pseudomonas pseudoalcaligenes was isolated from a constructed wetland, and used in an experimental set-up containing: plants and gravel. Phenol removal rate by planktonic and biofilm bacteria (on sterile Zea mays roots and gravel surfaces) was studied. Specific phenol removal rates revealed significant advantage of planktonic cells (1.04 × 10⁻⁹ mg phenol/CFU/h) compared to root and gravel biofilms: 4.59 × 10⁻¹¹-2.04 × 10⁻¹⁰ and 8.04 × 10⁻¹¹-4.39 × 10⁻¹⁰ (mg phenol/CFU/h), respectively.In batch cultures, phenol biodegradation kinetic parameters were determined by biomass growth rates and phenol removal as a function of time. Based on Haldane equation, kinetic constants such as μ_max = 1.15/h, K_s = 35.4 mg/L and K_i = 198.6 mg/L fit well phenol removal by P. pseudoalcaligenes.Although P. pseudoalcaligenes planktonic cells showed the highest phenol removal rate, in constructed wetland systems and especially in those with sub-surface flow, it is expected that surface associated microorganisms (biofilms) will provide a much higher contribution in phenol and other organics removal, due to greater bacterial biomass.Factors affecting the performance of planktonic vs. biofilm bacteria in sub-surface flow constructed wetlands are further discussed.     

Silage supports sulfate reduction in the treatment of metals- and sulfate-containing waste waters

Silage was used as source of carbon and electrons for enrichment of silage-degrading and sulfate reducing bacteria (SRB) from boreal, acidic, metals-containing peat-bog samples and to support their use in batch and semi-batch systems in treatment of synthetic waste water. Sulfidogenic silage utilization resulted in a rapid decrease in lactate concentrations; concentrations of acetate, butyrate and propionate increased concomitantly. Synthetic waste water consisting of Mn, Mg and Fe (II) ions inhibited sulfate reduction at concentrations of 6 g/l, 8 g/l and 1 g/l respectively. During treatment, Mn and Mg ions remained in solution while Fe ions partially precipitated. Up to 87 mg sulfate was reduced per gram of silage. Sulfate reduction rates of 34, 22 and 6 mg/l/day were obtained at temperatures of 30, 20 and 9 °C respectively. In semi-batch reactors operated at low pH, the iron precipitation capacity was controlled by sulfate reduction rates and by partial loss of hydrogen sulfide to the gas phase. Passive reactor systems should, therefore, be operated at neutral pH. Metals tolerant, silage-fermenting (predominantly species belonging to genus Clostridium) and sulfate reducing bacteria (including a species similar to the psychrotolerant Desulfovibrio arcticus) were obtained from the peat bog samples. This work demonstrates that silage supports sulfate reduction and can be used as a low cost carbon and electron source for SRB in treatment of metals-containing waste water.     

Solar photo-Fenton process on the abatement of antibiotics at a pilot scale: Degradation kinetics, ecotoxicity and phytotoxicity assessment and removal of antibiotic resistant enterococci

This work investigated the application of a solar driven advanced oxidation process (solar photo-Fenton), for the degradation of antibiotics at low concentration level (μg L⁻¹) in secondary treated domestic effluents at a pilot-scale. The examined antibiotics were ofloxacin (OFX) and trimethoprim (TMP). A compound parabolic collector (CPC) pilot plant was used for the photocatalytic experiments. The process was mainly evaluated by a fast and reliable analytical method based on a UPLC-MS/MS system. Solar photo-Fenton process using low iron and hydrogen peroxide doses ([Fe²⁺]₀ = 5 mg L⁻¹; [H₂O₂]₀ = 75 mg L⁻¹) was proved to be an efficient method for the elimination of these compounds with relatively high degradation rates. The photocatalytic degradation of OFX and TMP with the solar photo-Fenton process followed apparent first-order kinetics. A modification of the first-order kinetic expression was proposed and has been successfully used to explain the degradation kinetics of the compounds during the solar photo-Fenton treatment. The results demonstrated the capacity of the applied advanced process to reduce the initial wastewater toxicity against the examined plant species (Sorghum saccharatum, Lepidium sativum, Sinapis alba) and the water flea Daphnia magna. The phytotoxicity of the treated samples, expressed as root growth inhibition, was higher compared to that observed on the inhibition of seed germination. Enterococci, including those resistant to OFX and TMP, were completely eliminated at the end of the treatment. The total cost of the full scale unit for the treatment of 150 m³ day⁻¹ of secondary wastewater effluent was found to be 0.85 € m⁻³.     

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.     

Reduction of fecal indicator bacteria (FIB) in the Ballona Wetlands saltwater marsh (Los Angeles County, California, USA) with implications for restoration actions

A benefit of wetland preservation and restoration is the ecosystem service of improving water quality, typically assessed based on bacterial loading. The Ballona Wetlands, a degraded salt marsh of approximately 100 ac located on the southern border of Marina Del Rey (Los Angeles County, California, USA) are currently the focus of publicly funded restoration planning. The wetlands receive tidal water, usually contaminated with fecal indicator bacteria (FIB: total and fecal coliforms, Escherichia coli, enterococci) from the adjacent Ballona Creek and Estuary. During the summer of 2007, two 24-h studies were conducted to determine FIB tidal dynamics within the wetland. Measurements of water flow and mean FIB concentrations (n = 3) were measured every 1.5 h to determine total FIB load estimates. FIB loading rates (MPN/s) were greatest during flood tides as water entered the wetlands, and then again during spring tide conditions when sediments were resuspended during swifter spring ebb flows. During daylight hours, the wetland acted as a sink for these bacteria as loads diminished, presumably by sunlight and other processes. Conversely, during late afternoon and night, the wetlands shifted to being a source as excess FIB departed on ebb flows. Therefore, the wetlands act as both a source and sink for FIB depending on tidal conditions and exposure to sunlight. Future restoration actions would result in a tradeoff - increased tidal channels offer a greater surface area for FIB inactivation, but also would result in a greater volume of FIB-contaminated resuspended sediments carried out of the wetlands on stronger ebb flows. As levels of FIB in Ballona Creek and Estuary diminish through recently established regulatory actions, the wetlands could shift into a greater sink for FIB.     

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.     

Electrochemical disinfection of Escherichia coli in the presence and absence of primary sludge particulates

Electrochemical (EC) residual disinfection of Escherichia coli (E. coli) in the presence and absence of primary sludge particulates (PSPs) was studied. The kinetics followed a first-order rate law. When PSPs were absent, the EC residual disinfection rate coefficient (k) increased linearly with EC pretreatment energy (E_C, 0–0.63 kWh/m³). However, with 143 mg PSPs/L, k first increased linearly with E_C (0–0.28 kWh/m³) and then decreased linearly with E_C (0.28–0.42 kWh/m³). H₂O₂ was detected during EC pretreatment in PSPs-free samples and the H₂O₂ concentration (C_H) increased with E_C (0–0.83 kWh/m³) linearly. Chloride was detected in PSPs aqueous samples (143 mg PSPs/L) and its concentration (C_C) changed during EC pretreatment: initially, a decrease of C_C was observed when E_C increased from 0 to 0.28 kWh/m³, followed by an increase of C_C when E_C increased 0.28–0.42 kWh/m³. In both cases, k correlated to the initial post-EC chloride concentration (C_CI) in an inverse linear relationship. This two-stage change of C_C and k was caused by a combination of two reactions: anodic oxidation of chloride and the reaction of chloramines with excess chlorine. This paper explains the mechanisms underlying EC residual disinfection in the presence and absence of PSPs, and proposes a feasible strategy for EC disinfection when PSPs are present, an approach that could be useful in the treatment of combined sewage overflow (CSO).     

Assessment of chromium biostabilization in contaminated soils using standard leaching and sequential extraction techniques

The iron reducing microorganism Desulfuromonas palmitatis was evaluated as potential biostabilization agent for the remediation of chromate contaminated soils. D. palmitatis were used for the treatment of soil samples artificially contaminated with Cr(VI) at two levels, i.e. 200 and 500 mg kg^− 1. The efficiency of the treatment was evaluated by applying several standard extraction techniques on the soil samples before and after treatment, such as the EN12457 standard leaching test, the US EPA 3060A alkaline digestion method and the BCR sequential extraction procedure. The water soluble chromium as evaluated with the EN leaching test, was found to decrease after the biostabilization treatment from 13 to less than 0.5 mg kg^− 1 and from 120 to 5.6 mg kg^− 1 for the soil samples contaminated with 200 and 500 mg Cr(VI) per kg soil respectively. The BCR sequential extraction scheme, although not providing accurate estimates about the initial chromium speciation in contaminated soils, proved to be a useful tool for monitoring the relative changes in element partitioning, as a consequence of the stabilization treatment. After bioreduction, the percentage of chromium retained in the two least soluble BCR fractions, i.e. the “oxidizable” and “residual” fractions, increased from 54 and 73% to more than 96% in both soils.     

Effect of natural organic matter on toxicity and reactivity of nano-scale zero-valent iron

Nano-scale zero-valent iron (NZVI) particles are increasingly used to remediate aquifers contaminated with hazardous oxidized pollutants such as trichloroethylene (TCE). However, the high reduction potential of NZVI can result in toxicity to indigenous bacteria and hinder their participation in the cleanup process. Here, we report on the mitigation of the bactericidal activity of NZVI towards gram-negative Escherichia coli and gram-positive Bacillus subtilis in the presence of Suwannee River humic acids (SRHA), which were used as a model for natural organic matter (NOM). B. subtilis was more tolerant to NZVI (1 g/L) than E. coli in aerobic bicarbonate-buffered medium. SRHA (10 mg/L) significantly mitigated toxicity, and survival rates after 4 h exposure increased to similar levels observed for controls not exposed to NZVI. TEM images showed that the surface of NZVI and E. coli was surrounded by a visible floccus. This decreased the zeta potential of NZVI from −30 to −45 mV and apparently exerted electrosteric hindrance to minimize direct contact with bacteria, which mitigated toxicity. H₂ production during anaerobic NZVI corrosion was not significantly hindered by SRHA (p > 0.05), However, NZVI reactivity towards TCE (20 mg/L), assessed by the first-order dechlorination rate coefficient, decreased by 23%. Overall, these results suggest that the presence of NOM offers a tradeoff for NZVI-based remediation, with higher potential for concurrent or sequential bioremediation at the expense of partially inhibited abiotic reactivity with the target contaminant (TCE).     

Role of mass transfer in overall substrate removal rate in a sequential aerobic sludge blanket reactor treating a non-inhibitory substrate

A laboratory study was undertaken to explore the role of mass transfer in overall substrate removal rate and the subsequent kinetic behavior in a glucose-fed sequential aerobic sludge blanket (SASB) reactor. At the organic loading rates (OLRs) of 2-8 kg chemical oxygen demand (COD)/m³-d, the SASB reactor removed over 98% of COD from wastewater. With an increase in OLR, the average granule diameter (d_p = 1.1-1.9 mm) and the specific oxygen utilization rate increased; whereas biomass density of granules and solids retention time decreased (13-32 d). The intrinsic and apparent kinetic parameters were evaluated using break-up and intact granules, respectively. The calculated COD removal efficiencies using the kinetic model (incorporating intrinsic kinetics) and empirical model (incorporating apparent kinetics) agreed well with the experimental results, implying that both models can properly describe the overall substrate removal rate in the SASB reactor. By applying the validated kinetic model, the calculated mass transfer parameter values and the simulated substrate concentration profiles in the granule showed that the overall substrate removal rate is intra-granular diffusion controlled. By varying different d_p within a range of 0.1-3.5 mm, the simulated COD removal efficiencies disclosed that the optimal granular size could be no greater than 2.5 mm.     

Determination of low-density Escherichia coli and Helicobacter pylori suspensions in water

Determination of low-density of bacteria, especially those of pathogenic strains in water, has proven difficult and challenging. Here, we developed and evaluated a lanthanum-based concentration method coupled with quantitative real-time PCR to concentrate and detect selected bacteria (Escherichia coli and Helicobacter pylori) in water. To improve qPCR efficiency, the flocs with enmeshed bacteria after chemical flocculation need to be dissolved before PCR detection. Ethylenediaminetetraacetic acid (EDTA) salt successfully dissolved the flocs from a lanthanum-based flocculation process, but not those from the traditional processes using chemicals such as FeCl₃ or Al₂(SO₄)₃. Lanthanum-based concentration coupled with real-time PCR successfully determined E. coli at a concentration of 15 cells/mL in raw and finished water and H. pylori at a concentration of about 1 cell/mL in the finished water prior to disinfection. The H. pylori detection sensitivity could be easily increased to 60 cells/L by reducing the final volume of the DNA samples from 3 mL to 60 μL. With the elimination of membrane-clogging problem that is often encountered in direct membrane filtration, the lanthanum-based chemical flocculation coupled with qPCR is a promising method for determination of low-density of microbial suspensions in water.     

Formation of disinfection by-products after pre-oxidation with chlorine dioxide or ferrate

The effect of pre-oxidation with chlorine dioxide (ClO₂) or ferrate (Fe(VI)) on the formation of disinfection by-products (DBPs) during chlorination or chloramination was tested with natural waters from 12 sources (9 surface waters, 1 groundwater, and 2 wastewater effluents). DBPs investigated included trihalomethanes (THM), chloral hydrate (CH), haloketones (HK), haloacetonitriles (HAN) and trichloronitromethane (TCNM), chlorite and chlorate. Chlorite and chlorate were found in the ClO₂-treated waters. Application of 1 mg/L ClO₂ ahead of chlorination reduced the formation potential for THM by up to 45% and the formation of HK, HAN and TCNM in most of the samples. The CH formation results were mixed. The formation of CH and HK was enhanced with low doses of Fe(VI) (1 mg/L as Fe), but was greatly reduced at higher doses (20 mg/L Fe). Fe(VI) reduced the formation of THM, HAN and TCNM in most of the samples. Reduced potential for the formation of NDMA was observed in most of the samples after both ClO₂ and Fe(VI) pre-oxidation.     

Effect of imposed anaerobic conditions on metals release from acid-mine drainage contaminated streambed sediments

Remediation of streams influenced by mine-drainage may require removal and burial of metal-containing bed sediments. Burial of aerobic sediments into an anaerobic environment may release metals, such as through reductive dissolution of metal oxyhydroxides. Mining-impacted aerobic streambed sediments collected from North Fork Clear Creek, Colorado were held under anaerobic conditions for four months. Eh, pH, and concentrations of Cd, Cu, Fe, Mn, and Zn (filtered at 1.5 μm, 0.45 μm, and 0.2 μm), sulfate, and dissolved organic carbon (DOC) were monitored in stream water/sediment slurries. Two sediment size fractions were examined (2 mm-63 μm and <63 μm). Sequential extractions evaluated the mineral phase with which metals were associated in the aerobic sediment. Released Cu was re-sequestered within 5 weeks, while Fe and Mn still were present at 16 weeks. Mn concentration was lower than in the initial stream water at and beyond 14 weeks for the smaller sized sediment. Cd was not released from either sediment size fraction. Zn was released at early times, but concentrations never exceeded those present in the initial stream water and all was re-sequestered over time. The greatest concentrations of Cu, Fe, Mn, and Zn were associated with the Fe/Mn reducible fraction. Sulfate and Fe were strongly correlated (r = 0.90), seeming to indicate anaerobic dissolution of iron oxy-hydroxy-sulfate minerals. DOC and sulfate were strongly correlated (r = 0.81), with iron having a moderately strong correlation with DOC (r = 0.71). Overall concentrations of DOC, sulfate, Cu, Fe, and Zn and pH were significantly higher (p < 0.05) in the water overlying the small sized sediment samples, while the concentrations of Mn released from the larger sized sediment samples were greater.     

Implications of organic matter on arsenic mobilization into groundwater: Evidence from northwestern (Chapai-Nawabganj), central (Manikganj) and southeastern (Chandpur) Bangladesh

Boreholes (50 m depth) and piezometers (50 m depth) were drilled and installed for collecting As-rich sediments and groundwater in the Ganges, Brahmaputra, and Meghna flood plains for geochemical analyses. Forty-one groundwater samples were collected from the three areas for the analyses of cations (Ca²⁺, Mg²⁺, K⁺, Na⁺), anions (Cl⁻, NO₃⁻, SO₄²⁻), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction (XRD) and X-ray fluorescence (XRF) were performed to characterize the major mineral and chemical contents of aquifer sediments. In all three study areas, results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescent intensity of humic substances in groundwater samples ranges from 30 to 102 (mean 58 ± 20, n = 20), 54-195 (mean 105 ± 48, n = 10), and 27-243 (mean 79 ± 71, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Arsenic concentration in groundwater (20-50 m of depth) ranges from 3 to 315 μg/L (mean 62.4 ± 93.1 μg/L, n = 20), 16.4-73.7 μg/L (mean 28.5 ± 22.4 μg/L, n = 10) and 4.6-215.4 μg/L (mean 30.7 ± 62.1 μg/L, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Specific ultra violet adsorption (SUVA) values (less than 3 m⁻¹ mg⁻¹ L) indicate that the groundwater in the Ganges flood plain has relatively low percentage of aromatic organic carbon compared to those in the Brahmaputra and Meghna flood plains. Arsenic content in sediments ranges from 1 to 11 mg/kg (mean 3.5 ± 2.7 mg/kg, n = 17) in the three flood plains. Total organic carbon content is 0.5-3.7 g/kg (mean 1.9 ± 1.1 g/kg) in the Ganges flood plain, 0.5-2.1 g/kg (mean: 1.1 ± 0.7 g/kg) in the Brahmaputra flood plain and 0.3-4.4 g/kg (mean 1.9 ± 1.9 g/kg) in the Meghna flood plain. Arsenic is positively correlated with TOC (R² = 0.50, 0.87, and 0.85) in sediments from the three areas. Fourier transform infrared (FT-IR) analysis of the sediments revealed that the functional groups of humic substances in three areas include amines, phenol, alkanes, and aromatic carbon. Arsenic and Fe speciation in sediments were determined using XANES and the results imply that As(V) and Fe(III) are the dominant species in most sediments. The results also imply that As (V) and Fe (III) in most of the sediment samples of the three areas are the dominant species. X-ray absorption fine structure (EXAFS) analysis shows that FeOOH is the main carrier of As in the sediments of three areas. In sediments, As is well correlated with Fe and Mn. However, there is no such correlation observed between As and Fe as well as As and Mn in groundwater, implying that mobilizations of Fe, Mn, and As are decoupled or their concentrations in groundwater have been affected by other geochemical processes following reductive dissolution of Fe or Mn-hydroxides. For example, dissolved Fe and Mn levels may be affected by precipitation of Fe- and Mn-carbonate minerals such as siderite, while liberated As remains in groundwater. The groundwaters of the Brahmaputra and Meghna flood plains contain higher humic substances in relative fluorescence intensity (or fluorescence index) and lower redox potential compared to the groundwater of Ganges flood plain. This leads to the release of arsenic and iron to groundwater of these three plains in considerable amounts, but their concentrations are distributed in spatial variations.     

Accelerated biodegradation of pyrene and benzo[a]pyrene in the Phragmites australis rhizosphere by bacteria-root exudate interactions

We investigated the biodegradation of pyrene and benzo[a]pyrene in Phragmites australis rhizosphere sediment. We collected P. australis plants, rhizosphere sediments, and unvegetated sediments from natural aquatic sites and conducted degradation experiments using sediments spiked with pyrene or benzo[a]pyrene. Accelerated removal of pyrene and benzo[a]pyrene was observed in P. australis rhizosphere sediments with plants, whereas both compounds persisted in unvegetated sediments without plants and in autoclaved rhizosphere sediments with sterilized plants, suggesting that the accelerated removal resulted largely from biodegradation by rhizosphere bacteria. Initial densities of pyrene-utilizing bacteria were substantially higher in the rhizosphere than in unvegetated sediments, but benzo[a]pyrene-utilizing bacteria were not detected in rhizosphere sediments. Mycobacterium gilvum strains isolated from rhizosphere sediments utilized pyrene aerobically as a sole carbon source and were able to degrade benzo[a]pyrene when induced with pyrene. Phragmites australis root exudates containing phenolic compounds supported growth as a carbon source for the one Mycobacterium strain tested, and induced benzo[a]pyrene-degrading activity of the strain. The stimulatory effect on benzo[a]pyrene biodegradation and the amounts of phenolic compounds in root exudates increased when P. australis was exposed to pyrene. Our results show that Mycobacterium-root exudate interactions can accelerate biodegradation of pyrene and benzo[a]pyrene in P. australis rhizosphere sediments.     

Degradation of diclofenac by TiO2 photocatalysis: UV absorbance kinetics and process evaluation through a set of toxicity bioassays

In the present study the degradation kinetics and mineralization of diclofenac (DCF) by the TiO₂ photocatalysis were investigated in terms of UV absorbance and COD measurements for a wide range of initial DCF concentrations (5-80 mg L⁻¹) and photocatalyst loadings (0.2-1.6 g TiO₂ L⁻¹) in a batch reactor system. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Artemia salina) was performed to evaluate the potential detoxification of DCF. A pseudo-first-order kinetic model was found to fit well most of the experimental data, while at high initial DCF concentrations (40 and 80 mg L⁻¹) and at 1.6 g TiO₂ L⁻¹ photocatalyst loading a second-order kinetic model was found to fit the data better. The toxicity of the treated DCF samples on D. magna and P. subcapitata varied during the oxidation, probably due to the formation of some intermediate products more toxic than DCF. Unicellular freshwater algae was found to be very sensitive to the treated samples as well as the results from D. magna test were consistent to those of algae tests. A. salina was not found to be sensitive under the investigated conditions. Finally, UV absorbance analysis were found to be an useful tool for a fast and easy to perform measurement to get preliminary information on the organic intermediates that are formed during oxidation and also on their disappearance rate.     

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.     

Comparison of chlorine and chloramine in the release of mercury from dental amalgam

The purpose of this project was to compare the ability of chlorine (HOCl/OCl⁻) and monochloramine (NH₂Cl) to mobilize mercury from dental amalgam. Two types of amalgam were used in this investigation: laboratory-prepared amalgam and samples obtained from dental-unit wastewater. For disinfectant exposure simulations, 0.5 g of either the laboratory-generated or clinically obtained amalgam waste was added to 250 mL amber bottles. The amalgam samples were agitated by end-over-end rotation at 30 rpm in the presence of 1 mg/L chlorine, 10 mg/L chlorine, 1 mg/L monochloramine, 10 mg/L monochloramine, or deionized water for intervals of 0 h, 2 h, 4 h, 8 h, and 24 h for the clinically obtained amalgam waste samples and 4 h and 24 h for the laboratory-prepared samples. Chlorine and monochloramine concentrations were measured with a spectrophotometer. Samples were filtered through a 0.45 µm membrane filter and analyzed for mercury with USEPA standard method 245.7. When the two sample types were combined, the mean mercury level in the 1 mg/L chlorine group was 0.020 mg/L (n = 25, SD = 0.008). The 10 mg/L chlorine group had a mean mercury concentration of 0.59 mg/L (n = 25, SD = 1.06). The 1 mg/L chloramine group had a mean mercury level of 0.023 mg/L (n = 25, SD = 0.010). The 10 mg/L chloramine group had a mean mercury level of 0.024 mg/L (n = 25, SD = 0.011). Independent samples t-tests showed that there was a significant difference between the natural log mercury measurements of 10 mg/L chlorine compared to those of 1 mg/L and 10 mg/L chloramine. Changing from chlorine to chloramine disinfection at water treatment plants would not be expected to produce substantial increases in dissolved mercury levels in dental-unit wastewater.     

The role of Al-Goethites on arsenate mobility

The geochemical fates of Fe and As are so closely correlated that methods of As removal from contaminated water are in general based on the high affinity of this metalloid for Fe (hydr)oxides. Dissimilatory Fe reducing bacteria, however, play a fundamental role in catalysing the redox transformations that ultimately control the mobility of As in anoxic environments. The potential of Al-goethites in adsorbing As(V) compared with hematite, goethite, ferrihydrite, and gibbsite, and the stability of As retained by the Fe compounds under anoxic conditions were investigated in this study. The (hydr)oxides were synthesised, and adsorption isotherms and As(V) adsorption maxima at different pH were measured. Arsenic loaded samples were anaerobically incubated in the presence of Shewanella putrefaciens, and periodically sampled to evaluate the contents of soluble As and Fe. The As(V) adsorption maxima decreased in the following order: Fh > AlGt₁₃ > AlGt₂₀ > AlGt₂₃ > Gb > Hm > Gt. In terms of surface area, Gb, Gt, and Hm showed higher As(V) loading capacity than Fh, suggesting available reactive sites not fully occupied by arsenate on Fh. The same hypothesis can be considered for Al-goethites, as they showed even lower arsenate loading capacity per surface area. The presence of structural Al in the goethites enhanced considerably the As uptake capacity and stability under reducing conditions. Therefore, the Al-goethites showed good potential as adsorbents to remove As from water. S. putrefaciens cells were able to utilise both noncrystalline and crystalline Fe (hydr)oxides as electron acceptors, releasing As into solution. Al-goethites showed a decrease in Fe and As mobilisation as structural Al increased.