Photochemical reaction of peroxynitrite and carbon dioxide could account for up to 15 % of carbonate radicals generation in surface waters

The carbonate radical (CO ₃ ^?· ) is a photoinduced transient species occurring in surface waters. The carbonate radical can transform both natural compounds and xenobiotics. For instance, it can react with electron-rich substrates such as anilines, phenols and organic sulfur compounds. Here we used the APEX software to assess photochemical reactions, including the formation rates of transient species, based on water chemistry and depth, under summertime irradiation conditions. We found that the reaction between peroxynitrite and carbon dioxide is a potentially significant source of CO ₃ ^?· in sunlit surface waters, and could account for up to 10–15 % of the total CO ₃ ^?· formation. The peroxynitrite pathway to CO ₃ ^?· would be most significant at pH 7–8 and would be enhanced in waters with elevated nitrate and low alkalinity. Therefore, the proposed process could add to the known photochemical sources of CO ₃ ^?· in surface-water environments.     

Reactivity of sulfate radicals with natural organic matters

Advanced oxidation processes based on sulfate radicals (SO ₄ ^·? ) are capable of efficiently degrade organic pollutants from ground, surface and wastewaters. However, this degradation may be limited by aqueous natural organic matter (NOM). Here we measured the absolute rate constants of reaction of SO ₄ ^·? with four types of organic matter: two fulvic acids and two lake organic matter. We used laser flash photolysis technique to monitor the SO ₄ ^·? decay and the formation of the transients from organic matters. Reaction rate constants comprised between 1530 and 3500 s^?1 mgC^?1 L were obtained by numerical analysis of differential equations and the weighted average of the extinction coefficient of the generated organic matters radicals between 400 and 800 M^?1 cm^?1.     

Efficient oxidation of bisphenol A with oxysulfur radicals generated by iron-catalyzed autoxidation of sulfite at circumneutral pH under UV irradiation

There is actually a need for efficient methods to clean waters and wastewaters from pollutants such as the bisphenol A endocrine disrupter. Advanced oxidation processes currently use persulfate or peroxymonosulfate to generate sulfate radicals. There are, however, few reports on the use of sulfite to generate sulfate radicals, instead of persulfate or peroxymonosulfate, except for dyes. Here we studied the degradation of the bisphenol A using iron(III) as catalyst and sulfite as precursor of oxysulfur radicals, at initial pH of 6, under UV irradiation at 395 nm. The occurrence of radicals was checked by quenching with tert-butyl alcohol and ethanol. Bisphenol A degradation products were analyzed by liquid chromatography coupled with mass spectrometry (LC–MS). Results reveal that iron(III) or iron(II) have a similar oxidation efficiency. Quenching experiments show that the oxidation rate of bisphenol A is 47.7 % for SO ₄ ^·? , 37.3 % for SO ₅ ^·? and 15 % for HO^·. Bisphenol A degradation products include catechol and quinone derivatives. Overall, our findings show that the photo-iron(III)–sulfite system is efficient for the oxidation of bisphenol A at circumneutral pH.     

Buffer sensitivity of photosynthetic carbon utilisation in eight tropical seagrasses

Some of the mechanisms involved in inorganic carbon (Ci) acquisition by tropical seagrasses from the western Indian Ocean were described by Björk et al. (Mar Biol 129:363–366, 1997). However, since then, it has been found that an additional, buffer-sensitive, system of Ci utilisation may operate in some temperate seagrasses (Hellblom et al. in Aquat Bot 69:55–62, 2001, Hellblom and Axelsson in Photos Res 77:173–191, 2003); this buffer sensitivity indicates a mechanism in which electrogenic H⁺ extrusion may form acidic diffusion boundary layers, in which either HCO ₃ ^? –H⁺ is co-transported into the cells, or where HCO ₃ ^? is converted to CO₂ (as catalysed by carbonic anhydrase) prior to uptake of the latter Ci form. Because a buffer was used in the 1997 study, we found it important to reinvestigate those same eight species, taking into account the direct effect of buffers on this potential mode of Ci acquisition in these plants. In doing so, it was found that all seagrass species investigated except Cymodocea serrulata were sensitive to 50 mM TRIS buffer of the same pH as the natural seawater in which they grew (pH 8.0). Especially sensitive were Halophila ovalis, Halodule wrightii and Cymodocea rotundata, which grow high up in the intertidal zone (only ca. 50–65% of the net photosynthetic activity remained after the buffer additions), followed by the submerged Enhalus acoroides and Syringodium isoetifolium (ca. 75% activity remaining), while Thalassia hemprichii and Thalassodendron ciliatum, which grow in-between the two zones, were less sensitive to buffer additions (ca. 80–85% activity remaining). In addition to buffer sensitivity, all species were also sensitive to acetazolamide (AZ, an inhibitor of extracellular carbonic anhydrase activity) such that ca. 45–80% (but 90% for H. ovalis) of the net photosynthetic activity remained after adding this inhibitor. Raising the pH to 8.8 (in the presence of AZ) drastically reduced net photosynthetic rates (0–14% remaining in all species); it is assumed that this reduction in rates was due to the decreased CO₂ concentration at the higher pH. These results indicate that part of the 1997 results for the same species were due to a buffer effect on net photosynthesis. Based on the present results, it is concluded that (1) photosynthetic Ci acquisition in six of the eight investigated species is based on carbonic anhydrase catalysed HCO ₃ ^? to CO₂ conversions within an acidified diffusion boundary layer, (2) C. serrulata appears to support its photosynthesis by extracellular carbonic anhydrase catalysed CO₂ formation from HCO ₃ ^? without the need for acidic zones, (3) H. ovalis features a system in which H⁺ extrusion may be followed by HCO ₃ ^? –H⁺ co-transport into the cells, and (4) direct, non-H⁺-mediated, uptake of HCO ₃ ^? is improbable for any of the species.     

Removal of sulfamethoxazole and trimethoprim from reclaimed water and the biodegradation mechanism

Sulfamethoxazole (SMX) and trimethoprim (TMP) are two critical sulfonamide antibiotics with enhanced persistency that are commonly found in wastewater treatment plants. Recently, more scholars have showed interests in how SMX and TMP antibiotics are biodegraded, which is seldom reported previously. Novel artificial composite soil treatment systems were designed to allow biodegradation to effectively remove adsorbed SMX and TMP from the surface of clay ceramsites. A synergy between sorption and biodegradation improves the removal of SMX and TMP. One highly efficient SMX and TMP degrading bacteria strain, Bacillus subtilis, was isolated from column reactors. In the removal process, this bacteria degrade SMX and TMP to NH ₄ ⁺ , and then further convert NH ₄ ⁺ to NO ₃ ^– in a continuous process. Microbial adaptation time was longer for SMX degradation than for TMP, and SMX was also able to be degraded in aerobic conditions. Importantly, the artificial composite soil treatment system is suitable for application in practical engineering.

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Efficient photoelectrochemical oxidation of rhodamine B on metal electrodes without photocatalyst or supporting electrolyte

We designed photoelectrochemical cells to achieve efficient oxidation of rhodamine B (RhB) without the need for photocatalyst or supporting electrolyte. RhB, the metal anode/cathode, and O₂ formed an energy-relay structure, enabling the efficient formation of O ₂ ^– species under ultraviolet illumination. In a single-compartment cell (S cell) containing a titanium (Ti) anode, Ti cathode, and 10 mg·mL^–1 RhB in water, the zero-order rate constant of the photoelectrochemical oxidation (k_PEC) of RhB was 0.049 mg·L^–1·min^–1, while those of the photochemical and electrochemical oxidations of RhB were nearly zero. k_PEC remained almost the same when 0.5 mol·L^–1 Na₂SO₄ was included in the reactive solution, regardless of the increase in the photocurrent of the S cell. The k_PEC of the illuminated anode compartment in the two-compartment cell, including a Ti anode, Ti cathode, and 10 mg·mL^–1 RhB in water, was higher than that of the S cell. These results support a simple, eco-friendly, and energysaving method to realize the efficient degradation of RhB.

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Accelerated degradation of orange G over a wide pH range in the presence of FeVO<Subscript>4</Subscript>

In this study, FeVO₄ was prepared and used as Fenton-like catalyst to degrade orange G (OG) dye. The removal of OG in an aqueous solution containing 0.5 g·L^–1 FeVO₄ and 15 mmol·L^–1 hydrogen peroxide at pH 7.0 reached 93.2%. Similar rates were achieved at pH 5.7 (k = 0.0471 min^–1), pH 7.0 (k = 0.0438 min^–1), and pH 7.7 (k = 0.0434 min^–1). The FeVO₄ catalyst successfully overcomes the problem faced in the heterogeneous Fenton process, i.e., the narrow working pH range. The data for the removal of OG in FeVO₄ systems containing H₂O₂ conform to the Langmuir–Hinshelwood model (R² = 0.9988), indicating that adsorption and surface reaction are the two basic mechanisms for OG removal in the FeVO₄–H₂O₂ system. Furthermore, the irradiation of FeVO₄ by visible light significantly increases the degradation rate of OG, which is attributed to the enhanced rates of the iron cycles and vanadium cycles.

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Enhanced biohydrogen generation from organic wastewater containing NH 4 + by phototrophic bacteria Rhodobacter sphaeroides AR-3

NH ₄ ⁺ is typically an inhibitor to hydrogen production from organic wastewater by photo-bacteria. In this experiment, biohydrogen generation with wild-type anoxygenic phototrophic bacterium Rhodobacter sphaeroideswas found to be sensitive to NH ₄ ⁺ due to the significant inhibition of NH ₄ ⁺ to its nitrogenase. In order to avoid the inhibition of NH ₄ ⁺ to biohydrogen generation by R. sphaeroides, a glutamine auxotrophic mutant R. sphaeroides AR-3 was obtained by mutagenizing with ethyl methane sulfonate. The AR-3 mutant could generate biohydrogen efficiently in the hydrogen production medium with a higher NH ₄ ⁺ concentration, because the inhibition of NH ₄ ⁺ to nitrogenase of AR-3 was released. Under suitable conditions, AR-3 effectively produced biohydrogen from tofu wastewater, which normally contains 50–60 mg/L NH ₄ ⁺ , with an average generation rate of 14.2 mL/L·h. This generation rate was increased by more than 100% compared with that from wild-type R. sphaeroides.     

Impact of dissolved oxygen on the production of nitrous oxide in biological aerated filters

Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and microelectrode technology were employed to evaluate the Nitrous oxide (N₂O) production in biological aerated filters (BAFs) under varied dissolved oxygen (DO) concentrations during treating wastewater under laboratory scale. The average yield of gasous N₂O showed more than 4-fold increase when the DO levels were reduced from 6.0 to 2.0 mg?L^–1, indicating that low DO may drive N₂O generation. PCR-DGGE results revealed that Nitratifractor salsuginis were dominant and may be responsible for N₂O emission from the BAFs system. While at a low DO concentration (2.0 mg?L^–1), Flavobacterium urocaniciphilum might play a role. When DO concentration was the limiting factor (reduced from 6.0 to 2.0 mg?L^–1) for nitrification, it reduced NO ₂ ^- -N oxidation as well as the total nitrification. The data from this study contribute to explain how N₂O production changes in response to DO concentration, and may be helpful for reduction of N₂O through regulation of DO levels.

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Particle size distributions, PM2.5 concentrations and water-soluble inorganic ions in different public indoor environments: a case study in Jinan, China

In this study, we collected particles with aerodynamic diameter ?2.5 μm (PM_2.5) from three different public indoor places (a supermarket, a commercial office, and a university dining hall) in Jinan, a medium-sized city located in northern China. Water-soluble inorganic ions of PM_2.5 and particle size distributions were also measured. Both indoor and outdoor PM_2.5 levels (102.3–143.8 μg·m^?3 and 160.2–301.3 μg·m^?3, respectively) were substantially higher than the value recommended by the World Health Organization (25 μg·m^?3), and outdoor sources were found to be the major contributors to indoor pollutants. Diurnal particle number size distributions were different, while the maximum volume concentrations all appeared to be approximately 300 nm in the three indoor locations. Concentrations of indoor and outdoor PM_2.5 were shown to exhibit the same variation trends for the supermarket and dining hall. For the office, PM_2.5 concentrations during nighttime were observed to decrease sharply. Among others, SO ₄ ^2? , NH ₄ ⁺ and NO ₃ ^? were found to be the dominant water-soluble ions of both indoor and outdoor particles. Concentrations of NO ₃ ^? in the supermarket and office during the daytime were observed to decrease sharply, which might be attributed to the fact that the indoor temperature was much higher than the outdoor temperature. In addition, domestic activities such as cleaning, water usage, cooking, and smoking also played roles in degraded indoor air quality. However, the results obtained here might be negatively impacted by the small number of samples and short sampling durations.     

Impact of solids on biphasic biodegradation of phenanthrene in the presence of hydroxypropyl-<Emphasis Type="Italic">β</Emphasis>-cyclodextrin (HPCD)

The consequence of polycyclic aromatic hydrocarbons (PAHs) in the environment is of great concern. The hydrophobic properties of PAHs significantly impact phase distribution causing limited bioavailability. Enhanced biodegradation has been extensively carried out by surfactants and the redeployment effect was recognized. However, the quantitative relationship concerning the impact of solids was rarely reported. A batch of biphasic tests were carried out by introducing Mycobacterium vanbaalenii PYR-1 and hydroxypropyl-β-cyclodextrin (HPCD) into a mixture of phenanthrene solution and various glass beads (GB37-63, GB105-125, and GB350-500). The comparative results demonstrated that HPCD had little effect on microbial growth and was not degradable by bacterium. A model was proposed to describe the biodegradation process. The regression results indicated that the partition coefficient k _d (1.234, 0.726 and 0.448 L·g^?1) and the degradation rate k (0 mmol·L^?1: 0.055, 0.094, and 0.112; 20 mmol·L^?1: 0.126, 0.141, and 0.156; 40 mmol·L^?1: 0.141, 0.156 and 0.184 d^?1) were positively and negatively correlated with the calculated total surface area (TSA) of solids, respectively. Degradation enhanced in the presence of HPCD, and the enhancing factor f was calculated (20 mmol·L^?1: 15.16, 40.01, and 145.5; 40 mmol·L^?1: 13.29, 37.97, and 138.4), indicating that the impact of solids was significant for the enhancement of biodegradation.     

Efficient metoprolol degradation by heterogeneous copper ferrite/sulfite reaction

Metal/sulfite systems are currently used for SO ₄ ^?? generation and oxidative removal of organic contaminants. However, homogeneous metal/sulfite systems are limited because their working pHs must be acidic and metal ions cannot be separated from the bulk reaction solution. As a consequence, these drawbacks have severely limited the application of metal/sulfite systems in real conditions. To address these issues, we tested the use of copper ferrite (CuFe₂O₄), a ferromagnetic nanoparticle, to catalyze sulfite oxidation for the degradation of the metoprolol drug. The reaction mechanism was investigated by electron spin resonance, X-ray photoelectron spectroscopy, and radical quenching assay. The effects of pH, CuFe₂O₄, and sulfite dosages were also assessed. Results show that SO ₄ ^?? was the primary radical responsible for metoprolol degradation. Higher pHs induced more metoprolol degradation using CuFe₂O₄/sulfite. Moreover, CuFe₂O₄ remained morphologically intact and catalytically active after four batches of recycling. Overall, our findings show that CuFe₂O₄/sulfite can effectively degrade water contaminants in alkali pH and withhold catalyst activity after multiple reuses, therefore addressing the issues associated with homogeneous metal/sulfite systems.     

Urea as a nitrogen source for the phytoplankton in the Oslofjord

Ambient concentrations of urea in the inner Oslofjord, Norway, showed a pronounced yearly cycle in 1980, with values in the range 0.1 to 10.0 μg-at N l^-1; this cycle resemble that of ammonia although urea concentrations were usually lower. The uptake of urea by phytoplankton was investigated using ¹⁵N. Urea was usually a less important N source than NH ₄ ⁺ , and accounted for 0 to 53% (mean 19%) of summed NH ₄ ⁺ +NO ₃ ^- + urea uptake rates from April to October. Absolute as well as relative (specific) uptake rates of urea were higher in the summer (June–August) than at other times. Uptake of urea was inhibited by NH ₄ ⁺ concentrations higher than 1 to 2 μg-at N l^-1. The summed NH ₄ ⁺ +NO ₃ ^- + urea uptake rate was exponentially related to temperature.     

An electrochemical process that uses an Fe<Superscript>0</Superscript>/TiO<Subscript>2</Subscript> cathode to degrade typical dyes and antibiotics and a bio-anode that produces electricity

In this study, a new water treatment system that couples (photo-) electrochemical catalysis (PEC or EC) in a microbial fuel cell (MFC) was configured using a stainless-steel (SS) cathode coated with Fe⁰/TiO₂. We examined the destruction of methylene blue (MB) and tetracycline. Fe⁰/TiO₂ was prepared using a chemical reduction-deposition method and coated onto an SS wire mesh (500 mesh) using a sol technique. The anode generates electricity using microbes (bio-anode). Connected via wire and ohmic resistance, the system requires a short reaction time and operates at a low cost by effectively removing 94% MB (initial concentration 20 mg?L^–1) and 83% TOC/TOC₀ under visible light illumination (50 W; 1.99 mW?cm^–2 for 120 min, MFC-PEC). The removal was similar even without light irradiation (MFC-EC). The E _Eo of the MFC-PEC system was approximately 0.675 kWh?m^–3?order^–1, whereas that of the MFC-EC system was zero. The system was able to remove 70% COD in tetracycline solution (initial tetracycline concentration 100 mg?L^–1) after 120 min of visible light illumination; without light, the removal was 15% lower. The destruction of MB and tetracycline in both traditional photocatalysis and photoelectrocatalysis systems was notably low. The electron spinresonance spectroscopy (ESR) study demonstrated that ?OH was formed under visible light, and ?O ₂ ^– was formed without light. The bio-electricity-activated O₂ and ROS (reactive oxidizing species) generation by Fe⁰/TiO₂ effectively degraded the pollutants. This cathodic degradation improved the electricity generation by accepting and consuming more electrons from the bio-anode.

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Development and characterization of an anaerobic microcosm for reductive dechlorination of PCBs

The toxic and recalcitrant polychlorinated biphenyls (PCBs) adversely affect human and biota by bioaccumulation and biomagnification through food chain. In this study, an anaerobic microcosm was developed to extensively dechlorinate hexa- and hepta-CBs in Aroclor 1260. After 4 months of incubation in defined mineral salts medium amended PCBs (70 mmol·L^–1) and lactate (10 mmol·L^–1), the culture dechlorinated hexa-CBs from 40.2% to 8.7% and hepta-CBs 33.6% to 11.6%, with dechlorination efficiencies of 78.3% and 65.5%, respectively (all in moL ratio). This dechlorination process led to tetra-CBs (46.4%) as the predominant dechlorination products, followed by penta-(22.1%) and tri-CBs (5.4%). The number of meta chlorines per biphenyl decreased from 2.50 to 1.41. Results of quantitative real-time PCR show that Dehalococcoides cells increased from 2.39 ×10⁵±0.5 × 10⁵ to 4.99 × 10⁷±0.32 × 10⁷ copies mL^–1 after 120 days of incubation, suggesting that Dehalococcoides play a major role in reductive dechlorination of PCBs. This study could prove the feasibility of anaerobic reductive culture enrichment for the dehalogenation of highly chlorinated PCBs, which is prior to be applied for in situ bioremediation of notorious halogenated compounds.

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Excellent performance of Cu-Mn/Ti-sepiolite catalysts for low-temperature CO oxidation

The Ti-modified sepiolite (Ti-Sep)-supported Mn-Cu mixed oxide (yMn5Cu/Ti-Sep) catalysts were synthesized using the co-precipitation method. The materials were characterized by the X-ray diffraction scanning electron microscope, N₂ adsorption-desorption, H₂-TPR, O₂-TPD, and XPS techniques, and their catalytic activities for CO oxidation were evaluated. It was found that the catalytic activities of yMn5Cu/Ti-Sep were higher than those of 5Cu/Ti-Sep and 30Mn/Ti-Sep, and the Mn/Cu molar ratio had a distinct influence on catalytic activity of the sample. Among the yMn5Cu/Ti- Sep samples, the 30Mn5Cu/Ti-Sep catalyst showed the best activity (which also outperformed the 30Mn5Cu/Sep catalyst), giving the highest reaction rate of 0.875 × 10^–3 mmol·g^–1·s^–1 and the lowest T _50% and T _100% of 56°C and 86°C, respectively. Moreover, the 30Mn5Cu/Ti-Sep possessed the best low-temperature reducibility, the lowest O₂ desorption temperature, and the highest surface Mn³⁺/Mn⁴⁺ atomic ratio. It is concluded that factors, such as the strong interaction between the copper or manganese oxides and the Ti-Sep support, good low-temperature reducibility, and good mobility of chemisorbed oxygen species, were responsible for the excellent catalytic activity of 30Mn5Cu/Ti-Sep.

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Effects of carrier-attached biofilm on oxygen transfer efficiency in a moving bed biofilm reactor

Three laboratory-scale moving bed biofilm reactors (MBBR) with different carrier filling ratios ranging from 40% to 60% were used to study the effects of carrier-attached biofilm on oxygen transfer efficiency. In this study, we evaluated the performance of three MBBRs in degrading chemical oxygen demand and ammonia. The three reactors removed more than 95% of NH ₄ ⁺ -N at an air flow-rate of 60 L·h^–1. The standard oxygen transfer efficiency (αSOTE) of the three reactors was also investigated at air flow-rates ranging from 60 to 100 L·h^–1. These results were compared to αSOTE of wastewater with a clean carrier (no biofilm attached). Results showed that under these process conditions, αSOTE decreased by approximately 70% as compared to αSOTE of wastewater at a different carrier-filling ratio. This indicated that the biofilm attached to the carrier had a negative effect on αSOTE. Mechanism analysis showed that the main inhibiting effects were related to biofilm flocculants and soluble microbial product (SMP). Biofilm flocs could decrease αSOTE by about 20%, and SMP could decrease αSOTE by 30%–50%.     

Comparison of chemical compositions in air particulate matter during summer and winter in Beijing,China

The development of industry in Beijing, the capital of China, particularly in last decades, has caused severe environmental pollution including particulate matter (PM), dust–haze, and photochemical smog, which has already caused considerable harm to local ecological environment. Thus, in this study, air particle samples were continuously collected in August and December, 2014. And elements (Si, Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Mo, Cd, Ba, Pb and Ti) and ions (\({\text{NO}}_{3}^{-}\), \({\text{SO}}_{4}^{2-}\), F^?, Cl^?, Na⁺, K⁺, Mg²⁺, Ca²⁺ and \({\text{NH}}_{4}^{+}\)) were analyzed by inductively coupled plasma mass spectrometer and ion chromatography. According to seasonal changes, discuss the various pollution situations in order to find possible particulate matter sources and then propose appropriate control strategies to local government. The results indicated serious PM and metallic pollution in some sampling days, especially in December. Chemical Mass Balance model revealed central heating activities, road dust and vehicles contribute as main sources, account for 5.84–32.05 % differently to the summer and winter air pollution in 2014.