Surface neutralization and H₂S oxidation at early stages of sewer corrosion: influence of temperature, relative humidity and H₂S concentration

While the involvement of a range of environmental factors in sewer corrosion is known, a comprehensive understanding of the processes involved and the exact role of individual environmental factors in sewer corrosion is still lacking. The corrosion of concrete in sewer systems is reported to be initiated through chemical reactions (involving H₂S and CO₂) that lower the surface pH to a level then conducive for biological activity. However, the specific influence of environmental variables, such as H₂S level, temperature, and relative humidity etc. remains unclear; although, they are expected to control these initial surface reactions of the concrete sewer pipe. We examined changes in the surface chemistry of concrete during the early stages of corrosion by exposing concrete coupons to thirty-six independent conditions in well-controlled laboratory chambers that simulated conditions typically found in various sewer environments across Australia. The conditions employed were combinations of six H₂S levels, three gas-phase temperatures and two relative humidity levels. Our results indicate that the role of CO₂ on initial surface pH reduction is insignificant when compared to the influence of H₂S. Within the first 12 months, a decrease in surface pH by 4.8 units was observed for coupons exposed to 30 °C and 50 ppm H₂S, while significantly lower pH reductions of 3.5 and 1.8 units were detected for coupons exposed to 25 °C and 18 °C respectively, and 50 ppm H₂S. Elemental sulphur was found to be the major oxidation product of H₂S and elevated concentrations were detected at the higher levels of H₂S, temperature and relative humidity. More significantly, the data obtained from the controlled chamber experiments correlated with those obtained from the field-exposed coupons. Hence, these findings can be extended to real sewer corrosion processes.     

Exploration of CeO₂ nanoparticles as a chemi-sensor and photo-catalyst for environmental applications

CeO₂ nanoparticles were synthesized hydrothermally and utilized as redox mediator for the fabrication of efficient ethanol chemi-sensor. The developed chemi-sensor showed an excellent performance for electrocatalytic oxidization of ethanol by exhibiting higher sensitivity (0.92 μA?cm^− 2?mM^− 1) and lower limit of detection (0.124 ± 0.010 mM) with the linear dynamic range of 0.17 mM-0.17 M. CeO₂ nanoparticles have been characterized by field emission scanning electron microscopy (FESEM), Energy dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), Raman spectrum, Fourier transform infrared spectroscopy (FTIR), and UV-visible absorption spectrum which revealed that the synthesized CeO₂ is an aggregated form of optically active spherical nanoparticles with the range of 15-36 nm (average size of ~ 25 ±10 nm) and possessing well crystalline cubic phase. Additionally, CeO₂ performed well as a photo-catalyst by degrading amido black and acridine orange.     

Effect of pH on N₂O reduction and accumulation during denitrification by methanol utilizing denitrifiers

Acidic pH has previously been found to increase nitrous oxide (N₂O) accumulation during heterotrophic denitrification in biological wastewater treatment. However, the mechanism of this phenomenon still needs to be clarified. By using an enriched methanol utilizing denitrifying culture as an example, this paper presents a comprehensive study on the effect of pH (6.0-9.0) on N₂O reduction kinetics with N₂O as the sole electron acceptor, as well as the effect of pH on N₂O accumulation with N₂O as an intermediate of nitrate reduction. The pH dependency of nitrate and nitrite reduction was also investigated. The maximum biomass-specific N₂O reduction rate is higher than the corresponding maximum nitrate and nitrite reduction rates in the entire pH range studied. However, the maximum biomass-specific N₂O reduction rate is much more sensitive to pH variation outside of the optimal range (pH 7.5 to pH 8.0) than the maximum biomass-specific nitrate and nitrite reduction rates. The half-saturation coefficient of the N₂O reductase increased from 0.10 mg N₂O-N/L to 0.92 mg N₂O-N/L as pH increased from pH 6.0 to 9.0. At pH 6.0, approximately 20% and 40% of the denitrified nitrate accumulated as N₂O in the presence and absence of methanol (as an exogenous carbon source), respectively. However, at pH 6.5, these fractions decreased to 0% and 30%, respectively. No N₂O accumulation occurred at pH 7.0 to 9.0 independent of the availability of methanol. These results suggest that the competition for electrons among different nitrogen oxides reductases likely plays a role in N₂O accumulation at low pH conditions.     

Soil management systems and short term CO₂ emissions in a clayey soil in southern Spain

The soil in general and that destined for agricultural use, more specifically, can act as a source or sink of carbon, hence its direct involvement in strategies for mitigating climate change. A large proportion of this mitigation potential is produced by the sequestration of carbon by soils and, to a lesser extent, by a reduction in emissions from the soil.The most effective practices for increasing the organic carbon in the soils are generally those linked to conservation agriculture, which includes practices of no tillage or minimum tillage and the use of cover crops. During the farming seasons of 2006/07, 2007/08, 2008/09 and 2009/10, a trial was conducted in which the carbon dioxide emissions in soil with a high percentage of clay in the Vega de Carmona (Seville) were estimated, and it was determined how climate conditions and the adoption of conservation agriculture practices vs. the use of traditional tillage influenced the flux of gas into the atmosphere.     

The influence of capsular extracellular polymeric substances on the interaction between TiO₂ nanoparticles and planktonic bacteria

The role of capsular extracellular polymeric substances (EPS) at the surface of planktonic microorganisms was investigated for possible toxicity mitigation from titanium dioxide (TiO₂) nanoparticles, using variable EPS producing wild-type and isogenic mutant strains of Pseudomonas aeruginosa. Membrane integrity assays revealed that increased capsular EPS reduced cell membrane damage. Acting as a barrier to the cell membrane, capsular EPS permitted attachment of nanoparticles to the cell, while simultaneously delaying cellular damage caused by the production of reactive oxygen species (ROS). Modulations in ROS production were monitored in situ; while changes in the chemical composition of the microorganisms before and after exposure were examined with Fourier transform infrared spectroscopy (FTIR). The addition of methanol, a known radical scavenger, was shown to vastly reduce ROS production and membrane integrity losses, while not affecting physical interactions of nanoparticles with the microorganism. The results support that EPS provides an attachment site for nanoparticles, but more importantly act as a barrier to cell membrane oxidation from ROS. These observations provide better understanding of the overall importance of ROS in TiO₂ microbial toxicity.     

The influence of dissolved and surface-bound humic acid on the toxicity of TiO₂ nanoparticles to Chlorella sp

NOM is likely to coat TiO₂ nanoparticles (nano-TiO₂) discharged into the aquatic environment and influence the nanotoxicity to aquatic organisms, which however has not been well investigated. This study explored the influence of nanoparticle surface-bound humic acid (HA, as a model NOM) as well as dissolved HA on the toxicity of nano-TiO₂ to Chlorella sp., with a specific focus on adhesion of the nanoparticles to the algae. Results showed that nano-TiO₂ and the dissolved HA could inhibit the algal growth with an IC₅₀ of 4.9 and 8.4 mg L⁻¹, respectively, while both dissolved and nanoparticle surface-bound HA could significantly alleviate the algal toxicity of nano-TiO₂. IC₅₀ of nano-TiO₂ increased to 18 mg L⁻¹ in the presence of 5 mg L⁻¹ of the dissolved HA and to 48 mg L⁻¹ as the result of surface-saturation by HA. Co-precipitation experiment and transmission electron microscopy observation revealed that both dissolved and nanoparticle surface-bound HA prevented the adhesion of nano-TiO₂ to the algal cells due to the increased electrosteric repulsion. The generation of intracellular reactive oxygen species (ROS) was significantly limited by the dissolved and nanoparticle surface-bound HA. The prevention of adhesion and inhibition of ROS generation could account for the HA-mitigated nanotoxicity.     

An assessment of the fate, behaviour and environmental risk associated with sunscreen TiO₂ nanoparticles in UK field scenarios

The fate of Ti was examined in an activated sludge plant serving over 200,000 people. These studies revealed a decrease of 30 to 3.2 μg/L of Ti < 0.45 μm from influent to effluent and a calculated Ti presence of 305 mg/kg DW in wasted sludge. Thus, using sludge as a fertiliser would result in a predicted deposition of up to 250 mg/m² of Ti to soil surfaces using a recommended maximal agricultural application rate. Given the major use of TiO₂ in many industrial and domestic applications where loss to the sewer is possible, this measured Ti was presumed to have been largely TiO₂, a proportion of which will be nanoparticle sized. To assess the behaviour of engineered nanoparticle (ENP) TiO₂ in sewage and toxicology studies, Optisol (Oxonica Materials Ltd) and P25 (Evonik Industries AG), which are representative of forms used in sunscreen and cosmetic products, were used. These revealed a close association of TiO₂ ENPs with activated sludge. Using commercial information on consumption, and removal rates for sewage treatment, predictions were made for river water concentrations for sunscreen TiO₂ ENPs for the Anglian and Thames regions in Southern England. The highest predicted value from these exercises was 8.8 μg/L for the Thames region in which it was assumed that one in four people used the recommended application of sunscreen during a low flow (Q95) period. Ecotoxicological studies using potentially vulnerable species indicated that 1000 μg/L TiO₂ ENP did not affect the viability of a mixed community of river bacteria in the presence of UV light. Direct exposure to TiO₂ ENPs did not impair the immuno-effectiveness of earthworm coelomocyte cells at concentrations greatly above those predicted for sewage sludge.     

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.