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1.
Removal of carbamazepine from urban wastewater by sulfate radical oxidation   总被引:2,自引:0,他引:2  
The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/CoII are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H2O2/FeII) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO4 ·− with carbamazepine is 1.92·109 M−1 s−1. In laboratory grade water and in real urban wastewater, SO4 ·− yielded a faster degradation of carbamazepine compared to HO· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.  相似文献   

2.
The shortfin mako shark, Isurus oxyrinchus, is a highly streamlined epipelagic predator that has several anatomical and physiological specializations hypothesized to increase aerobic swimming performance. A large swim-tunnel respirometer was used to measure oxygen consumption (MO2) in juvenile mako sharks (swimming under controlled temperature and flow conditions) to test the hypothesis that the mako shark has an elevated maintenance metabolism when compared to other sharks of similar size swimming at the same water temperature. Specimen collections were conducted off the coast of southern California, USA (32.94°N and 117.37°W) in 2001-2002 at sea-surface temperatures of 16.0–21.0°C. Swimming MO2 and tail beat frequency (TBF) were measured for nine mako sharks [77–107 cm in total length (TL) and 4.4 to 9.5 kg body mass] at speeds from 28 to 54 cm s−1 (0.27–0.65 TL s−1) and water temperatures of 16.5–19.5°C. Standard metabolic rate (SMR) was estimated from the extrapolation to 0-velocity of the linear regression through the LogMO2 and swimming speed data. The estimated LogSMR (±SE) for the pooled data was 2.0937 ± 0.058 or 124 mg O2 kg−1 h−1. The routine metabolic rate (RMR) calculated from seventeen MO2 measurements from all specimens, at all test speeds was (mean ± SE) 344 ± 22 mg O2 kg−1h−1 at 0.44 ± 0.03 TL s−1. The maximum metabolic rate (MMR) measured for any one shark in this study was 541 mg O2 kg−1h−1 at 54 cm s−1 (0.65 TL s−1). The mean (±SE) TBF for 39 observations of steady swimming at all test speeds was 1.00 ± 0.01 Hz, which agrees with field observations of 1.03 ± 0.03 Hz in four undisturbed free-swimming mako sharks observed during the same time period. These findings suggest that the estimate of SMR for juvenile makos is comparable to that recorded for other similar-sized, ram-ventilating shark species (when corrected for differences in experimental temperature). However, the mako RMR and MMR are apparently among the highest measured for any shark species.  相似文献   

3.
The anticancer drugs: adriamycin, farmorubicin and mitomycin C greatly enhance the generation of hydroxyl radicals (HO.) from H2O2 in the presence of Co(II) ions (CoCl2) at pH 7.4 and 8, as measured by the deoxyribose assay. Catalase, hydroxyl radical scavengers (mannitol, cysteine, glutathione, thiourea, lactic dehydrogenase) inhibited the degradation of deoxyribose confirming that HO‐radicals are responsible for the degradation of the carbohydrate.  相似文献   

4.
A solution of atrazine in a TiO2 suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s?1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H2O2 displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.  相似文献   

5.
The photocatalytic degradation of a sulfonylurea herbicide, cinosulfuron, has been studied in TiO2 aqueous suspensions. A first order kinetic law was found. The influence of the initial concentration of cinosulfuron and of the initial radiant flux on the kinetics were evaluated. The identification of the intermediate products was based on high performance liquid chromatography coupled with mass spectrometry analyses (HPLC-MS). The mineralization of cinosulfuron was traced using ion chromatography and total organic carbon (TOC) measurements. These results indicate that the photocatalytic degradation of cinosulfuron leads to CO2, NO3 and SO4 2− as final products, and in addition cyanuric acid (C3H3O3N3), confirming previous results on triazinic ring-containing compounds. Electronic Publication  相似文献   

6.
Degradation of diuron by the electro-Fenton process   总被引:2,自引:0,他引:2  
The degradation of the herbicide diuron has been undertaken by electrochemical advanced oxidation in aqueous solution. This process generates catalytically hydroxyl radicals that are strong oxidizing reagents for the oxidation of organic substances. Hydroxyl radicals degrade diuron in less than 10 min. Kinetic results evidence a pseudo-first-order degradation, with a rate constant of reaction between diuron and hydroxyl radicals of 4.8x109 M–1 s–1. Several degradation products were identified by chromatography-mass spectrometry (LC-MS). The mineralization degree of a 1.7x10–4 M diuron solution reached 93% at 1,000 coulombs.  相似文献   

7.
Bi2WO6 was synthesized with a hydrothermal method at different pHs and used for the degradation of tetracycline (TC) in water. The mesoporous Bi2WO6 prepared at pH 1 (BWO-1) displayed the highest adsorption and degradation capacity to TC due to its large surface area and more efficient capacity to separate photogenerated electrons and holes. 97% of TC at 20 mg·L?1 was removed by BWO-1 at 0.5 g·L?1 after 120 min irradiation under simulated solar light. Only 31% of the total organic carbon (TOC) was removed after 360 min irradiation although the TC removal reached 100%, suggesting that TC was mainly transformed to intermediate products rather than completely mineralized. The intermediates were identified by high-performance liquid chromatography-time of flight-mass spectrometry (HPLC-TOF-MS) and possible photodegradation pathways were proposed.  相似文献   

8.
We have discovered that HNO3 and related species are released from the TiO2 surface into air in the TiO2 photocatalytic oxidation of NO2 (1 ppm) under continuous UV light illumination (1 mW cm−2) by dehumidifying the outlet gas of the reaction and analyzing the recovered condensate liquid by ion chromatography. The origin of the HNO3 recovered in the dehumidifier could not be explained by a simple desorption of HNO3 overproduced on the TiO2 surface. The produced HNO3 must be activated on the TiO2 surface and causing the unidentified reaction.  相似文献   

9.
Here we show that the photolysis of FeCl2+ upon UV irradiation of Fe(III) at pH 0.5, yielding Cl and then Cl2−•, upon further reaction with Cl, induces phenol degradation. The photolysis of FeCl2+ can be highlighted and studied as the huge interference by FeOH2+ can be avoided under such conditions. Our data allowed the assessment of a photolysis quantum yield for FeCl2+ of 5.8 × 10−4 under UVA irradiation, much lower compared to the literature value of 0.5. The discrepancy can be explained if the photolysis process is efficient but photoformed Fe2+ and Cl undergo recombination inside the solvent cage.  相似文献   

10.
The concentrations and flux of CO2, 222Radon (Rn), and gaseous elemental mercury (Hg) in soil gas were investigated based on the field measurements in June 2010 at ten sites along the seismic rupture zones produced by the May 12, 2008, Wenchuan M s 8.0 earthquake in order to assess the environmental impact of degassing of CO2, Rn and Hg. Soil gas concentrations of 344 sampling points were obtained. Seventy measurements of CO2, Rn and Hg flux by the static accumulation chamber method were performed. The results of risk assessment of CO2, Rn and Hg concentration in soil gas showed that (1) the concentration of CO2 in the epicenter of Wenchuan M s 8.0 earthquake and north end of seismic ruptures had low risk of asphyxia; (2) the concentrations of Rn in the north segment of seismic ruptures had high levels of radon, Maximum was up to level 4, according to Chinese code (GB 50325-2001); (3) the average geoaccumulation index I geo of soil Hg denoted the lack of soil contamination, and maximum values classified the soil gas as moderately to strongly polluted in the epicenter. The investigation of soil gas CO2, Rn and Hg degassing rate indicated that (1) the CO2 in soil gas was characterized by a mean \(\updelta^{13}C_{CO2}\) of ?20.4 ‰ and by a mean CO2 flux of 88.1 g m?2 day?1, which were in the range of the typical values for biologic CO2 degassing. The maximum of soil CO2 flux reached values of 399 g m?2 day?1 in the epicenter; (2) the soil Rn had higher exhalation in the north segment of seismic ruptures, the maximum reached value of 1976 m Bq m?2 s?1; (3) the soil Hg flux was lower, ranging from ?2.5 to 18.7 n g m?2 h?1 and increased from south to north. The mean flux over the all profiles was 4.2 n g m?2 h?1. The total output of CO2 and Hg degassing estimated along seismic ruptures for a survey area of 18.17 km2 were approximately 0.57 Mt year?1 and 688.19 g year?1. It is recommended that land-use planners should incorporate soil gas and/or gas flux measurements in the environmental assessment of areas of possible risk. A survey of all houses along seismic ruptures is advised as structural measures to prevent the ingress of soil gases, including CO2 and Rn, were needed in some houses.  相似文献   

11.
A pot experiment was conducted to examine the influence of potassium (K) fertilizer (K2SO4) application on the phytoavailability and speciation distribution of cadmium (Cd) and lead (Pb) in soil. Spring wheat (Triticum aestivum L.) was selected as the test plant. There were seven treatments including single and combined contamination of Cd and Pb. CdCl2·2.5 H2O and Pb(NO3)2 were added to the soil at the following dosages: Cd + Pb = 0.00 + 0.00, 5.00 + 0.00, 25.0 + 0.00, 0.00 + 500, 0.00 + 1000, 5.00 + 500 and 25.0 + 1000 mg kg−1, denoted by CK, T1, T2, T3, T4, T5 and T6, respectively. The K fertilizer had five levels: 0.00, 50.0, 100, 200 and 400 mg K2O kg−1 soil, denoted by K0, K1, K2, K3 and K4, respectively. The results showed that the K fertilizer promoted the dry weight (DW) of wheat in all treatments and alleviated the contamination by Cd and Pb. The application of K2SO4 reduced the uptake of Cd in different parts including roots, haulms and grains of wheat; the optimum dosage was the K2 level. K supply resulted in a significant (P < 0.05) decrease in the soluble plus exchangeable (SE) fraction of Cd and there was a negative correlation (not significant, P > 0.05) between the levels of K and the SE fraction of Cd in soil. The application of the K fertilizer could obviously restrain the uptake of Pb by wheat and there were significant (P < 0.05) negative correlations between the concentrations of Pb in grains and the levels of K in soil. K supply resulted in a decrease in the SE fraction of Pb (except the K1 level) from the K0 to K4 levels. At the same time, the application of the K fertilizer induced a significant (P < 0.05) decrease in the weakly specifically adsorbed (WSA) fraction of Pb and a significant (P < 0.05) increase in the bound to Fe–Mn oxides (OX) fraction of Pb. At different K levels, the concentration of Pb in the roots, haulms and grains had a positive correlation with the SE (not significant, P > 0.05) and WSA (significant, P < 0.05) fractions of Pb in the soil. All the K application levels in this experiment reduced the phytoavailability of Cd and Pb. Thus, it is feasible to apply K fertilizer (K2SO4) to alleviate contamination by Cd and/or Pb in soil. Moreover, the level of K application should be considered to obtain an optimal effect with the minimum dosage.  相似文献   

12.
Rates of routine respiration (R R, μl O2 fish−1 h−1) and total ammonia nitrogen excretion (E R, μg NH4–N + NH3–N fish−1 h−1) were measured on larval and juvenile haddock (Melanogrammus aeglefinus) to ascertain how energy losses due to metabolism were influenced by temperature (T), dry body mass (M D, mg) and specific growth rate (SGR, % per day). R R and E R increased with M D according to y =  · M D b with b-values of 0.96, 0.98, 1.14, and 0.89, 0.78, 0.74, respectively, at 10, 7, and 4°C, respectively. Multiple regressions explained 98% of the variability in the combined effects of M D and T on R R and E R in larval haddock: R R = 0.97 · M D 0.98  · e0.092 · T ; E R = 0.06 · M D 0.79  · e0.092 · T . In young juvenile (24–30 mm standard length) haddock, R R tended to decline (P = 0.06) and E R significantly declined (P = 0.02) with increasing SGR. O:N ratios significantly increased with increasing SGR suggesting that N was spared in relatively fast-growing individuals. Our results for young larval and juvenile haddock suggest: (1) nearly isometric scaling of R R with increasing body size, (2) allometric scaling of E R with increasing body size, (3) Q 10 values of 2.5 for both R R and E R, (4) metabolic differences in substrate utilization between relatively fast- and slow-growing individuals, and (5) that rates of routine energy loss and growth were not positively related. The measurements in this study will provide robust parameter estimates for individual-based models that are currently being utilized to investigate how variability in climatic forcing influences the vital rates of early life stages of haddock. Our results also stress that inter-individual differences in rates of energy loss should not be overlooked as a factor influencing growth variability among individuals.  相似文献   

13.
The photocatalytic oxidation of humic substances in aqueous solutions and natural waters with TiO2 attached to buoyant, hollow glass micro-spheres was studied. A maximum oxidation efficiency of 3.6 mg W–1 h–1 was achieved in neutral or alkaline media at a plane surface concentration of the catalyst attached to the micro-spheres of 25 g m–2. Proceeding by different mechanisms in acidic and alkaline media, the photocatalytic oxidation efficiency did not benefit from an excessive presence of hydroxyl radical promoters, hydrogen peroxide and alkali.  相似文献   

14.
Aqueous solutions of organophosphorus pesticides were completely mineralized via in-situ generated hydroxyl radicals (HO·) by the Electro-Fenton process. Formation of Fenton's reagent (H2O2, Fe2+) was carried out by simultaneous reduction of O2 and Fe3+ on carbon cathode in acidic medium. The electrochemistry combined with Fenton's reagent provides an excellent way to continuously produce the hydroxyl radical, a powerful oxidant. We demonstrate the efficiency of the Electro-Fenton process to degrade three organophosphorus insecticides: malathion, parathion ethyl and tetra-ethyl-pyrophosphate (TEPP). Degradation kinetics and removals of chemical oxygen demand (COD) have been investigated. Here we show that the mineralization efficiency was over 80% for three organophosphorus pesticides.  相似文献   

15.
The kinetics of ammonium assimilation was investigated in Ulva pertusa (Chlorophyceae, Ulvales) from northeastern New Zealand. Ammonium assimilation exhibited Michaelis–Menten kinetics with a maximum rate of assimilation (V max) of 54 ± 5 μmol g−1 dry weight h−1 and half-saturation constant (K m) of 23 ± 8 μM. In contrast, values for ammonium uptake were considerably higher with a V max of 316 ± 59 μmol g−1 dry weight h−1 and K m of 135 ± 46 μM. At environmentally relevant ammonium concentrations (5 μM), assimilation accounted for most (70%) of the ammonium taken up. Darkness decreased the maximum rate of ammonium assimilation by 83%. We investigated the hypothesis that rates of biosynthetic processes are greater in the early part of the day in Ulva. Consistent with this hypothesis, the maximum rate of ammonium assimilation in U. pertusa peaked in the morning and coincided with low levels of the photosynthetic product sucrose, which peaked in the afternoon. There was a diurnal cycle in the rate of ammonium uptake and assimilation in light and dark, but the amplitude was much greater for assimilation than uptake. Moreover, our data suggest that net ammonium assimilation only occurs during the day in U. pertusa. We suggest that two major roles for diurnal cycles are minimisation of interspecific competition for resources and metabolic costs.  相似文献   

16.
While qualitative observations of jellyfish intraguild predation abound in the literature, there are only few rate measurements of these interactions. We quantified predation rates among two common jellyfish in northern boreal waters, Cyanea capillata and its prey Aurelia aurita, both of which also feed on crustacean zooplankton and fish larvae. A series of incubation experiments using a wide range of prey concentrations (0.38–3.8 m−3) in large containers (2.6 m3) was carried out. By replenishing the prey continuously as they were captured we maintained a nearly constant prey concentrations. Ingestion rates increased linearly up to prey concentrations of 1.92 m−3, yielding maximum clearance rates of ∼2.37 ± 0.39 m3 predator−1 h−1 for C. capillata predators 16 ± 2.3 cm in diameter. Mean ingestion rate at saturated prey concentrations (1.92–3.85 m−3) was 4.01 ± 0.78 prey predator−1 h−1. Behavioral observations suggested that predators did not alter their swimming behavior during meals, and thus that feeding rates were generally handling limited rather than encounter limited. Predators captured more prey than needed, and semi-digested prey was often discarded when fresh prey was encountered.  相似文献   

17.
In this study, we tested the hypothesis that the importance of water flow for skeletal growth (rate) becomes higher with increasing irradiance levels (i.e. a synergistic effect) and that such effect is mediated by a water flow modulated effect on net photosynthesis. Four series of nine nubbins of G. fascicularis were grown at either high (600 μE m−2 s−1) or intermediate (300 μE m−2 s−1) irradiance in combination with either high (15–25 cm s−1) or low (5–10 cm s−1) flow. Growth was measured as buoyant weight and surface area. Photosynthetic rates were measured at each coral’s specific experimental irradiance and flow speed. Additionally, the instantaneous effect of water flow on net photosynthetic rate was determined in short-term incubations in a respirometric flowcell. A significant interaction was found between irradiance and water flow for the increase in buoyant weight, the increase in surface area, and specific skeletal growth rate, indicating that flow velocity becomes more important for coral growth with increasing irradiance levels. Enhancement of coral growth with increasing water flow can be explained by increased net photosynthetic rates. Additionally, the need for costly photo-protective mechanisms at low flow regimes could explain the differences in growth with flow.  相似文献   

18.
Diel swimming behaviors of juvenile anchovies (Anchoa spp.) were observed using stationary hydroacoustics and synoptic physicochemical and zooplankton profiles during four unique water quality scenarios in the Neuse River Estuary, NC, USA. Vertical distribution of fish was restricted to waters with DO greater than 2.5 mg O2 l−1, except when greater than 70% of the water column was hypoxic and a subset of fish were occupying water with 1 mg O2 l−1. We made the prediction that an individual fish would select a swim speed that would maximize net energy gain given the abundance and availability of prey in the normoxic waters. During the day, fish adopted swim speeds between 7 and 8.8 bl s−1 that were near the theoretical optimum speeds between 7.0 and 8.0 bl s−1. An exception was found during severe hypoxia, when fish were swimming at 60% above the optimum speed (observed speed = 10.6 bl s−1, expected = 6.4 bl s−1). The anchovy is a visual planktivore; therefore, we expected a diel activity pattern characteristic of a diurnal species, with quiescence at night to minimize energetic costs. Under stratified and hypoxic conditions with high fish density coupled with limited prey availability, anchovies sustained high swimming speeds at night. The sustained nighttime activity resulted in estimated daily energy expenditure over 20% greater than fish that adopted a diurnal activity pattern. We provide evidence that the sustained nighttime activity patterns are a result of foraging at night due to a lower ration achieved during the day. During severe hypoxic events, we also observed individual fish making brief forays into the hypoxic hypolimnion. These bottom waters generally contained higher prey (copepod) concentrations than the surface waters. The bay anchovy, a facultative particle forager, adopts a range of behaviors to compensate for the effects of increased conspecific density and reduced prey availability in the presence of stratification-induced hypoxia.  相似文献   

19.
A sampling campaign including summer, autumn and winter of 2014 and spring of 2015 was accomplished to obtain the characteristic of chemical components in PM2.5 at three sites of Kunming, a plateau city in South-west China. Nine kinds of water-soluble inorganic ions (WSI), organic and element carbon (OC and EC) in PM2.5 were analyzed by ion chromatography and thermal optical reflectance method, respectively. Results showed that the average concentrations of total WSI, OC and EC were 22.85±10.95 µg·m-3, 17.83±9.57 µg·m-3 and 5.11±4.29 µg·m-3, respectively. They totally accounted for 53.0% of PM2.5. Secondary organic and inorganic aerosols (SOA and SIA) were also assessed by the minimum ratio of OC/EC, nitrogen and sulfur oxidation ratios. The annual average concentrations of SOA and SIA totally accounted for 28.3% of the PM2.5 concentration. The low proportion suggested the primary emission was the main source of PM2.5 in Kunming. However, secondary pollution in the plateau city should also not be ignorable, due to the appropriate temperature and strong solar radiation, which can promote the atmospheric photochemical reactions.
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20.
Oxidation of aldehydes to carboxylic acids is a major reaction. Conventionally, this reaction is carried out with oxidants and metal catalysts, thus producing unwanted metal waste. Recently, aqueous media have been used as an alternative for toxic organic solvents. Here, we tested the clathrate-structured, neutral hydrogen peroxide adduct 4Na2SO4·2H2O2·NaCl for the oxidation of aldehydes to acids in aqueous solution. We found that various aromatic, heteroaromatic and aliphatic aldehydes were selectively oxidized to corresponding acids in 70–98% yields. This simple acid–base treatment allows to separate easily the acid product in high purity without any organic solvent. Moreover, the adduct is produced using 25% H2O2, with inexpensive sodium sulphate, Na2SO4, and sodium chloride, NaCl. The adduct is a non-toxic white crystalline solid, readily soluble in water, and easy to handle.  相似文献   

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