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1.
In this study the occurrence of diclofenac and sub‐products in effluent emerging from the University Hospital at the Federal University of Santa Maria was investigated. One metabolite was identified and, in aqueous solution, three degradation products. The quantification was conducted by means of HPLC‐DAD, and the determination of metabolite and degradation products by LC–ESI–MS/MS–QTrap. For the HPLC‐DAD method, a 70:30 mixture of methanol/sodium phosphate was used in isocratic mode. For the LC–ESI–MS/MS–QTrap determinations, a mobile phase, where phase A was an ammonium acetate solution 5 × 10?3 mol L?1, and phase B was methanol (5 × 10?3 mol L?1)/ammonium acetate (9:1, v/v), on gradient mode. The LDs for the HPLC and LC–MS/MS methods, respectively, were 2.5 and 0.02 µg L?1, the LQs, 8.3 and 0.05 µg L?1, and the linear range from 10 up to 2000 µg L?1 and 0.05 up to 10 µg L?1. As expected, the LC–ESI–MS/MS–QTrap method was more sensitive and less laborious. The metabolite 4′‐hydroxy‐diclofenac was identified. Photolysis was used for the degradation studies and three products of diclofenac were identified (m/z of 214, 286 and 303) in aqueous solution. These results notwithstanding, no degradation products of diclofenac were found in the hospital effluent.  相似文献   

2.
In this work, an analytical methodological study was carried out to determine the antimicrobials sulfamethoxazole and trimethoprim, as well as their metabolites, in hospital effluent. The determinations were conducted by liquid chromatography tandem mass spectrometry using a hybrid triple quadrupole‐linear ion trap mass spectrometer (LC‐QqLIT‐MS). The data acquisition was made in selected reaction monitoring (SRM) mode, in which two SRM transitions were monitored to ensure that the target compounds were accurately identified by the information dependent acquisition (IDA) function. The limits of detection (LOD) and quantification (LOQ) were 0.25 and 0.80 µg L?1 for sulfamethoxazole and 0.15 and 0.50 µg L?1 for trimethoprim. The linear range for the SMX was 0.8–100.0 µg L?1 and TMP was 0.5–100.0 µg L?1 on the basis of six‐point calibration curves generated by means of linear regression analysis. The coefficients of the correlation were higher than 0.999, which ensured the linearity of the method. The average concentration of sulfamethoxazole and trimethoprim found in hospital effluent was 27.8 and 6.65 µg L?1, respectively. The analytical methodology employed allowed two metabolites to be identified, N4‐acetyl‐sulfamethoxazole and α‐hydroxy‐trimethoprim. Fragmentation pathways were proposed.  相似文献   

3.
Bezafibrate (BZF), a widely used lipid regulator, is a potential threat to ecosystems and human health in water, and the recent research showed that advanced oxidation processes (AOPs) are much more effective for BZF degradation. In this study, we investigated the photochemical decomposition of BZF in surface water and effluent from waste water treatment plants (WWTP) by UV/H2O2 process. The results showed that the UV/H2O2 process was a promising method to remove BZF at low concentration, generally at µg L?1 level. When initial concentrations reach 100 µg L?1 in the deionized water, >99.8% of BZF could be removed in 16 min under UV intensity of 61.4 µm cm?2, at the H2O2 concentration of 0.1 mg L?1, and neutral pH condition. Moreover, BZF degradation was inhibited in this process when humic acid (HA) and inorganic solution anions were added to the deionized water solutions, including chloride, nitrate, bicarbonate, and sulfate, significantly. In the surface water and effluent of WWTP, however, the removal efficiency of BZF was lower than that in the deionized water because of the interference of complex constituents in the surface water and effluent. Some main intermediates at the m/z range of 100–400 were observed by high performance LC‐MS (HPLC/MS) and a simple pathway of BZF degradation by UV/H2O2 was proposed.  相似文献   

4.
The aim of this study is to investigate the concentrations of U, Th, V, Mo, and Zr in natural waters taken from Turkey. Among these water species, Lake Van is the largest soda lake and the fourth largest closed basin on Earth. The water samples were collected from 51 locations between 2008 and 2009. The inductively coupled plasma‐MS was used for determinations. The obtained U and Zr concentrations are in the range of 37–110 µg L?1 and 17–78 µg L?1 in Lake Van and 0.53–0.81 µg L?1 and 0.15–0.19 µg L?1 in Lake Hazar, respectively. The concentration of uranium in other studied waters varies from the lowest 0.09 µg L?1 in Tigris (Dicle) river to the highest 4.0 µg L?1 in Mediterranean Sea water. Mean Mo and V concentrations in the studied water samples were found to be in ranges of 0.1–17 and 2.7–113 µg L?1, respectively. The obtained highest U concentration in Lake Van correlates with the highest Mo and Zr levels compared to the Lake Hazar and river waters. These results imply that there is a young occurrence of uranium minerals around Lake Van. It is concluded that there is about 50.000 ton of uranium in Lake Van water.  相似文献   

5.
The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L?1 for Fe(III) and 0.43 µg L?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.  相似文献   

6.
Laccase from the white‐rot fungus Pleurotus florida, produced under solid‐state fermentation conditions, was used for the decolorization of reactive dye Remazol Brilliant Blue R (RBBR). RBBR was decolorized up to 46% by P. florida laccase alone in 10 min. In the presence of N‐hydroxybenzotriazole (HBT), the rate of decolorization was enhanced 1.56‐fold. Central composite design of response surface methodology with four variables namely, dye, enzyme, redox mediator concentrations, and time at five levels was applied to optimize the RBBR decolorization. The predicted optimum level of variables for maximum RBBR decolorization (87%) was found to be 52.90 mg L?1 (RBBR), 1.87 U mL?1 (laccase), 0.85 mM (HBT), and 7.17 min (time), respectively. The validation results showed that the experimental value of RBBR decolorization (82%) was close to the predicted one. The disappearance of C–N and C–X groups, and a small shift in N–H groups in Fourier‐transform infra red (FTIR) spectroscopy confirms the degradation of RBBR chromophore by laccase enzyme. The phytotoxicity of RBBR was considerably reduced after the treatment with laccase. RBBR decolorization kinetics; Km and Vmax were calculated to be 145.82 mg L?1 and 24.86 mg L?1 min, respectively.  相似文献   

7.
The effects of oxygen supply rate and the presence or absence of nutrients on the kinetics of phenol degradation and oxygen consumption by a mixed microbial population were tested in a model system. The values for the maximum specific rate of phenol degradation (qSmax), the saturation constant (KS), and the inhibition concentration (SCR) were determined for unlimited growth (KLa = 340 h?1, growth medium) with 1.7 mmol g?1 h?1, 65 mg L?1, and 190 mg L?1. Under limitation conditions, alterations occur depending on the type of limitation. Nutrient limitations lead to values of 0.8 mmol g?1 h?1, 45 mg L?1, and 160 mg L?1, and oxygen limitations lead to 1.2 mmol g?1 h?1. 30 mg L?1, and 120 mg L?1, respectively. The results suggest that with excess oxygen, the rate of phenol degradation was higher and the inhibition effect of phenol was suppressed to some extent. Under the same high oxygen supply rate, the presence of nutrients in the model water significantly supported the phenol degradation rate.  相似文献   

8.
Here we characterize the nutrient content in the outflow of the Green Lake 5 rock glacier, located in the Green Lakes Valley of the Colorado Front Range. Dissolved organic carbon (DOC) was present in all samples with a mean concentration of 0·85 mg L?1 . A one‐way analysis of variance test shows no statistical difference in DOC amounts among surface waters (p = 0·42). Average nitrate concentrations were 69 µmoles L?1 in the outflow of the rock glacier, compared to 7 µmoles L?1 in snow and 25 µmoles L?1 in rain. Nitrate concentrations from the rock glacier generally increased with time, with maximum concentrations of 135 µmoles L?1 in October, among the highest nitrate concentrations reported for high‐elevation surface waters. These high nitrate concentrations appear to be characteristic of rock glacier outflow in the Rocky Mountains, as a paired‐difference t‐test shows that nitrate concentrations from the outflow of 7 additional rock glaciers were significantly greater compared to their reference streams (p = 0·003). End‐member mixing analysis suggest that snow was the dominant source of nitrate in June, ‘soil’ solution was the dominant nitrate source in July, and base flow was the dominant source in September. Fluoresence index values and PARAFAC analyses of dissolved organic matter (DOM) are also consistent with a switch from terrestrial DOM in the summer time period to an increasing aquatic‐like microbial source during the autumn months. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

9.
Pseudomonas putida MHF 7109 has been isolated and identified from cow dung microbial consortium for biodegradation of selected petroleum hydrocarbon compounds – benzene, toluene, and o‐xylene (BTX). Each compound was applied separately at concentrations of 50, 100, 250, and 500 mg L?1 in minimal salt medium to evaluate degradation activity of the identified microbial strain. The results indicated that the strain used has high potential to degrade BTX at a concentration of 50 mg L?1 within a period of 48, 96, and 168 h, respectively; whereas the concentration of 100 mg L?1 of benzene and toluene was found to be completely degraded within 120 and 168 h, respectively. Sixty‐two percent of o‐xylene were degraded within 168 h at the 100 mg L?1 concentration level. The maximum degradation rates for BTX were 1.35, 1.04, and 0.51 mg L?1 h?1, respectively. At higher concentrations (250 and 500 mg L?1) BTX inhibited the activity of microorganisms. The mass spectrometry analysis identified the intermediates as catechol, 2‐hydroxymuconic semialdehyde, 3‐methylcatechol, cis‐2‐hydroxypenta‐2,4‐dienoate, 2‐methylbenzyl alcohol, and 1,2‐dihydroxy‐6‐methylcyclohexa‐3,5‐dienecarboxylate, for BTX, respectively. P. putida MHF 7109 has been found to have high potential for biodegradation of volatile petroleum hydrocarbons.  相似文献   

10.
Biological Degradation of 2,4-Dinitrotoluene in a Continuous Bioreactor and Kinetic Studies Experimental results on the aerobic biological degradation with complete mineralization of 2,4-dinitrotoluene (2,4-DNT) are presented. A culture of Pseudomonas sp. DNT from Spain and Nishino was used. The degradation was examined with batch cultures for the determination of kinetic and stoichiometric coefficients. Further experiments were carried out with a continuous culture in a fixed-bed reactor with recirculation in order to obtain high degradation rates. The reactor was packed with ceramic Raschig rings (55 mL) and had a liquid reaction volume of 160 mL. The minimal salt media from Spanggord et al. with and without (NH4)2S)4 as nitrogen source was used as substrate. 2,4-DNT was the sole source of carbon and energy. From batch experiments a yield coefficient YB/S = (0.30 ± 0.05) g g?1 was calculated from a mass balance of the elements. This result was confirmed by calculations using literature data. Fitting the experimental data to the Monod equation, μmax = 0.1 h?1 and KS = 0.01…0.03 mmol L?1 were obtained. It was demonstrated by batch experiments that 2,4-DNT is not only used as the source of carbon and energy but also as the nitrogen source. In the fixed-bed reactor, a degradation of 92…97% was reached with a maximal 2,4-DNT load of 95 mg L?1 h?1. The rate of continuous degradation could be described by a pseudo-first-order reaction (k = 9.73 h?1). The complete mineralization of 2,4-DNT was verified by the measurement of DOC and the formed nitrite and nitrate. The formed nitrite was nitrified simultaneously. It was demonstrated by these experiments that large scale biological treatment of industrial effluent containing 2,4-DNT may be successful.  相似文献   

11.
In this work the potential of live and active Phanerochaete chryosporium, a white rot fungi, to remove lower Cr(VI) concentration from aqueous solutions was reported for the first time. A medium pH had significant effect on the growth of the fungus and bioremoval of Cr(VI). Substrate inhibition on the growth of Phanerochaete chrysosporium was evident beyond 20 g L?1 of dextrose concentration. A maximum biomass concentration of 15.64 g L?1 was obtained for an initial dextrose concentration of 20 g L?1 in metal free medium at pH 6.0. An increase in Cr(VI) concentration beyond 10 mg L?1 inhibited the growth of the fungi, thereby, reducing the chromium bioremoval efficiency. A maximum reduction efficiency of 98.92% was reported for an initial metal concentration of 10 mg L?1. A mathematical expression for the bioreduction of Cr(VI) considering the organic compounds in the cells was proposed.  相似文献   

12.
This study examines the effect of drawdown on the timing and magnitude of suspended solids and associated phosphorus export from a 12 ha reservoir located in an urbanized watershed in southern Ontario, Canada. Water level in Columbia Lake was lowered by 1·15 m over a 2‐week period in November 2001. The total phosphorus (TP) concentrations ranged from 63 to 486 µg L?1 in Columbia Lake and 71 to 373 µg L?1 at its outflow. All samples exceeded the Provincial Water Quality Objective of 30 µg TP L?1. Outflow concentrations of suspended solids and TP increased significantly with decreasing lake level and were attributed to the resuspension of cohesive bottom sediments that occurred at a critical threshold lake level (0·65 m below summer level). Suspended solids at the outflow consisted of flocculated cohesive materials with a median diameter (D50) of c. 5 µm. Particulate organic carbon accounted for 8·5% of the suspended solids export by mass. A total mass of 18·5 t of suspended solids and 62·6 kg TP was exported from Columbia Lake, which represents a significant pulse of sediment‐associated P to downstream environments each autumn during drawdown. The downstream impacts of this release can be minimized if the water level in Columbia Lake is lowered no more than 0·5 m below summer levels. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

13.
Experiments on the degradation of acid orange 7 (AO7) using micron‐sized zero‐valent copper (ZVC) are conducted in acidic aqueous solution under ultrasonic (US) irradiation. The US/ZVC/peroxymonosulfate (PMS) process for AO7 degradation is significantly better than that of an independent system. Based on the characterization of ZVC, it is observed that the corrosion speed of ZVC increases after ultrasound, owing to which a greater amount of Cu+ (0–3.03 mg L?1) and Cu2+ are produced. Exposure to US irradiation increases the available surface area of the catalysts to generate many new reactive sites for the degradation process. The AO7 degradation rate after the addition of a new copper reagent—neocuproine hemihydrate—from 6.33% to 100% proved that Cu+ is the main activator of PMS. Results indicated that free radicals (OH? and SO4??) act as activators of PMS in the process. And higher ultrasound power, lower solution pH, and a larger ZVC dose are favorable for AO7 removal.  相似文献   

14.
A new method for determining lead (Pb) content was developed by dispersive liquid–liquid microextraction based on the solidification of floating organic droplets followed by flame atomic absorption spectrometry. Under optimum conditions, the calibration graph was linear within the Pb content range of 8.43–400 µg L?1 with a detection limit of 2.53 µg L?1. The relative standard deviation for 10 replicate measurements of 20 and 400 µg L?1 of Pb were 3.41 and 2.78%, respectively. The proposed method was assessed through the analysis of certified reference water and recovery experiments.  相似文献   

15.
Cadmium (Cd) has become an important heavy metal contaminant in the sediment and seawater along the Bohai Sea and been of great ecological risk due to its toxic effects to marine organisms. In this work, the toxicological effects caused by environmentally relevant concentrations (10 and 40 µg L?1) of Cd were studied in the gill tissues of Manila clam Ruditapes philippinarum after exposure for 24, 48, and 96 h. Both low (10 µg L?1) and high (40 µg L?1) doses of Cd caused the disturbances in energy metabolism and osmotic regulation and neurotoxicity based on the metabolic biomarkers such as succinate, alanine, branched chain amino acids, betaine, hypotaurine, and glutamate in clam gills after 24 h of exposure. However, the recovery of toxicological effects of Cd after exposure for 96 h was obviously observed in clam to Cd exposures. Overall, these results indicated that NMR‐based metabolomics was applicable to elucidate the toxicological effects of heavy metal contaminants in the marine bioindicator.  相似文献   

16.
The rigin and fate of six phthalate esters (dimethyl phthalate (DMP), diethyl phthalate (DEP), di‐n‐butyl phthalate (DnBP), butyl benzyl phthalate (BBP), di (2‐ethylhexyl) phthalate (DEHP) and di‐n‐octyl phthalate (DnOP)), were investigated during 2005 and 2006 in the densely populated Seine river estuary. Four compounds, DMP, DEP, DnBP and DEHP were detected at all the stations with DEHP (160–314 ng L?1), followed by DEP (71–181 ng L?1) and next DnBP (67–319 ng L?1), except at la Bouille, where DnBP was the second most important compound. BBP and DnOP concentrations remained low and were not found at all the stations. Considering all six phthalates, Caudebec‐en‐Caux (beginning of the salinity gradient) was the least polluted station (464 ng L?1), whereas Honfleur (771 ng L?1) and La Bouille (716 ng L?1) displayed the highest contamination levels, probably related to important industrial plants. From Caudebec‐en‐Caux to Honfleur (maximum turbidity), variation of DEHP concentration was related to that of suspended matter. In addition, the salinity rise in that area might have facilitated DEHP sorption upon particles. A significant correlation between flow magnitude and DEHP concentration was found (P < 0·01, n = 12), supporting the influence of the hydrological cycle upon contamination. Runoff contribution (56·9 kg d?1) to river contamination was confirmed by the annual evolution of phthalate concentrations in the Seine river at Poses. Concentrations of DEHP in the tributaries were in the same range as those of the Seine River (100–350 ng L?1), except for two in densely populated and industrialized areas: Robec (800 ng L?1) and Cailly (970 ng L?1). The treatment plant discharge fluxes were in the same range as those of tributaries (30·4–250 g d?1). During high flow periods, the influence of tributaries and of treatment plants seemed to play a minor part in the contamination level of the Seine river estuary. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

17.
An on‐line solid phase extraction method for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry has been described. The procedure is based on the retention of Cu(II) ions at pH 6.0 on a minicolumn packed with Amberlite XAD‐1180 resin impregnated with chrome azurol S. After preconcentration, Cu(II) ions adsorbed on the impregnated resin were eluted by 1 mol L?1 HNO3 solution. Several parameters, such as pH, type of eluent, flow rates of sample and eluent solutions, amount of resin were evaluated. At optimized conditions, for 3.5 min of preconcentration time, the system achieved a detection limit of 1.0 µg L?1, and a relative standard deviation of 1.2% at 0.2 µg mL?1 copper. An enrichment factor of 56‐fold was obtained with respect to the copper determination. The proposed method was successfully validated by the analysis of standard reference material (TMDA 54.4 lake water) and recovery studies. The method was applied to the preconcentration of Cu(II) in natural water samples.  相似文献   

18.
Cryoturbated Upper Chalk is a dichotomous porous medium wherein the intra‐fragment porosity provides water storage and the inter‐fragment porosity provides potential pathways for relatively rapid flow near saturation. Chloride tracer movement through 43 cm long and 45 cm diameter undisturbed chalk columns was studied at water application rates of 0·3, 1·0, and 1·5 cm h?1. Microscale heterogeneity in effluent was recorded using a grid collection system consisting of 98 funnel‐shaped cells each 3·5 cm in diameter. The total porosity of the columns was 0·47 ± 0·02 m3 m?3, approximately 13% of pores were ≥ 15 µm diameter, and the saturated hydraulic conductivity was 12·66 ± 1·31 m day?1. Although the column remained unsaturated during the leaching even at all application rates, proportionate flow through macropores increased as the application rate decreased. The number of dry cells (with 0 ml of effluent) increased as application rate decreased. Half of the leachate was collected from 15, 19 and 22 cells at 0·3, 1·0, 1·5 cm h?1 application rates respectively. Similar breakthrough curves (BTCs) were obtained at all three application rates when plotted as a function of cumulative drainage, but they were distinctly different when plotted as a function of time. The BTCs indicate that the columns have similar drainage requirement irrespective of application rates, as the rise to the maxima (C/Co) is almost similar. However, the time required to achieve that leaching requirement varies with application rates, and residence time was less in the case of a higher application rate. A two‐region convection–dispersion model was used to describe the BTCs and fitted well (r2 = 0·97–0·99). There was a linear relationship between dispersion coefficient and pore water velocity (correlation coefficient r = 0·95). The results demonstrate the microscale heterogeneity of hydrodynamic properties in the Upper Chalk. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

19.
Simple, rapid, and sensitive spectrophotometric methods have been proposed for the determination of cationic surfactants (CS) as cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium (DTAB), and cetylpyridinium bromide (CPB). The methods are based on the effects of CSs on the complexes of Al3+ and Be2+ with Chrome Azurol S (CAS). The optimum reaction conditions such as CAS concentration, metal ion concentration, and pH have been studied and found to be 2.0 × 10?4 mol L?1 CAS, 0.5 mg L?1 Al3+ or 0.4 mg L?1 Be2+ and pH 5.4. The analytical characteristics of the methods such as limit of detections, limit of quantifications, and linear ranges have been obtained. CTAB, CPB, and DTAB could be determined by the Al–CAS complex in the ranges of 0.50–40.00, 0.20–10.00, and 0.40–10.00 µmol L?1, and for the Be–CAS complex in the ranges of 0.08–5.00, 0.08–3.00, and 0.20–6.00 µmol L?1, respectively. The limit of the detections of the method for the determination of CTAB, CPB, and DTAB for the Be–CAS complex has been found as 0.025, 0.024, and 0.061 µmol L?1, respectively. The interfering effect of some anions and cations was also tested. The method was applied to the determination of CS CTAB in conditioner shampoo and water samples.  相似文献   

20.
Dispersive liquid–liquid microextraction based on solidification of floating organic droplet (DLLME‐SFO) technique was successfully applied for simultaneous assay of eight polychlorinated biphenyls, two organochlorine, and four pyrethroid pesticides multi‐residue in aqueous samples by using GC‐electron capture detection. The effects of various parameters such as kind of extractant and dispersant and volume of them, extraction time, effect of salt addition, and pH were optimized. As a result, 5.0 µL 1‐dodecanol was chosen as extraction solvent, 600 µL methanol were used as dispersive solvent without salt addition, pH was adjusted to 7. Under the optimized conditions, the limits of detection (LOD) were ranged from 1.4 to 8.3 ng L?1. Satisfactory linear range was observed from 5.0 to 2000 ng L?1 with correlation coefficient better than 0.9909. Good precisions were also acquired with RSD better than 13.6% for all target analytes. The enrichment factors of the method were ranged from 786 to 1427. The method can be successfully applied to simultaneous separation and determination of three class residues in real water samples and good recoveries were obtained ranging from 76 to 130, 73 to 129, and 78 to 130% for tap water, lake water, and industrial waste water, respectively.  相似文献   

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