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1.
Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day? 1 were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 102 to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca2 + made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day? 1, which is comparable to that of hydrolysis at 60°C. The presence of Ca2 + accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca2 +. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.  相似文献   

2.
Abstract

The hydrolysis of the insecticide tebufenozide was studied in the dark at 20 to 40°C in buffered (pH 4 to 10) distilled water, and at 20°C in unbuffered, sterilized and unsterilized stream water. Tebufenozide was very stable in acidic and neutral buffers at 20°C and the corresponding pseudo‐first‐order rate constants (kobsd) and half‐lives (T1/2) were 5.946 × 10‐4 and 13.10 × 10‐4 d‐1, and 1166 and 529 d, respectively. The hydrolytic degradation was dependent on pH and temperature. At pH 10 and at 20,30 and 40°C, the kobsd (10‐4 d‐1) and T1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (Ea) values for the hydrolysis of tebufenozide at pH 4, 7 and 10, calculated from the Arrhenius plots, were 83.50, 66.71 and 50.87 kJ/mol, respectively. Tebufenozide was stable in sterilized stream water in the dark (T1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T1/2 values at 254 and 365 nm were 9.92 and 27.6 h, respectively); nevertheless, it was still appreciable during the summer months at 46°31’ N latitude. The differences in degradation rates between the unsterilized and sterilized stream water and the degradation of the chemical in the sterile, distilled water in sunlight, suggests that microbial processes and photolysis are the two main degradative routes for tebufenozide in natural aquatic systems.  相似文献   

3.
The main objectives of this study were to (a) study the interaction between N and P cycles in mining-affected aquatic systems and (b) to quantify release rates of sedimentary soluble reactive phosphorus (SRP) that may be related to this interaction. Sediment cores and water from Lake Bruträsket (Boliden, northern Sweden) were collected and a time series of water sampling and flow measurements was conducted in the Brubäcken stream connected to the lake. Factors affecting SRP release were studied in a sediment incubation experiment and water column experiments. Field and laboratory measurements indicated that pH and dissolved oxygen are two important factors for SRP release. At the end of the low-oxygen incubation, an SRP concentration of 56 μg?L?1 resulted in a sedimentary flux of 1.1 mg SRP?m?2?day?1. This is ~10 times higher than the flux of 0.12 mg SRP?m?2?day?1 obtained from depth integration of vertical SRP profiles measured in the lake, and ~100 times higher than the external flux of 0.014 mg SRP?m?2?d?1 into the lake (based on catchment area). Field measurements indicated that oxidation of organic matter and mining-related chemicals (ammonium and thiosulphates) may result in increased internal SRP flux from the sediment. Increased P loading in the lake as a result of low-oxygen conditions could change water column total nitrogen/total phosphorus ratios from 27 to 17, consequently changing the lake from being P-limited to be co-limited by N and P. The obtained findings point to possible interaction between the cycles of nitrogen (oxygen consumption) and P (flux from sediment) that may be important for nutrient regulation in mine water recipients.  相似文献   

4.
A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 × 10? 3 h? 1 to 7.0 × 10? 3 h? 1. The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.  相似文献   

5.
Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10?3 s?1 at pH 2, 5.5 × 10?3 s?1 at pH 4 and 9.0 × 10?3 s?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.  相似文献   

6.
Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at λ = 254 nm. The photolysis of (α + β: 2 + 1) endosulfan, α-endosulfan and β-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 × 10?4 s?1; 1 × 10?4 s?1; and 2 × 10?5 s?1, respectively, and the calculated quantum yields (φ) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.  相似文献   

7.
Zero-valent iron nanoparticles (nZVI, diameter < 90 nm, specific surface area = 25 m2 g?1) have been used under anoxic conditions for the remediation of pesticides alachlor and atrazine in water. While alachlor (10, 20, 40 mg L?1) was reduced by 92–96% within 72 h, no degradation of atrazine was observed. The alachlor degradation reaction was found to obey first-order kinetics very closely. The reaction rate (35.5 × 10?3–43.0 × 10?3 h?1) increased with increasing alachlor concentration. The results are in conformity with other researchers who worked on these pesticides but mostly with micro ZVI and iron filings. This is for the first time that alachlor has been degraded under reductive environment using nZVI. The authors contend that nZVI may prove to be a simple method for on-site treatment of high concentration pesticide rinse water (100 mg L?1) and for use in flooring materials in pesticide filling and storage stations.  相似文献   

8.
This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH? · pH?1. The sediments were spiked with atrazine at 7.25-36.23 mg kg?1 (6.21 × 10?7–3.09 × 10?6 mol atrazine · g?1 sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 × 10?2?7.04 × 10?2 d?1 for the atrazine-spiked sediments.  相似文献   

9.
Water in the Yangtze Estuary is fresh most of the year because of the large discharge of Yangtze River. The Qingcaosha Reservoir built on the Changxing Island in the Yangtze Estuary is an estuarine reservoir for drinking water. Denitrification rate in the top 10 cm sediment of the intertidal marshes and bare mudflat of Yangtze Estuarine islands was measured by the acetylene inhibition method. Annual denitrification rate in the top 10 cm of sediment was 23.1 μmol m?2 h?1 in marshes (ranged from 7.5 to 42.1 μmol m?2 h?1) and 15.1 μmol m?2 h?1 at the mudflat (ranged from 6.6 to 26.5 μmol m?2 h?1). Annual average denitrification rate is higher at mashes than at mudflat, but without a significant difference (p?=?0.084, paired t test.). Taking into account the vegetation and water area of the reservoir, a total 1.42?×?108 g N could be converted into nitrogen gas (N2) annually by the sediment, which is 97.7 % of the dissolved inorganic nitrogen input through precipitation. Denitrification in reservoir sediment can control the bioavailable nitrogen level of the water body. At the Yangtze estuary, denitrification primarily took place in the top 4 cm of sediment, and there was no significant spatial or temporal variation of denitrification during the year at the marshes and mudflat, which led to no single factor determining the denitrification process but the combined effects of the environmental factors, hydrologic condition, and wetland vegetation.  相似文献   

10.

This paper reports the effect of ultraviolet radiation on the degradation of pesticide ethyl parathion in the presence of humic acids. Ethyl parathion was completely degraded in 300 min using an artificial lamp of 7.41 × 10? 10 einstein/s. Humic acid from peat did not influence the photochemical rate (k = 8.92 × 10?3 min). However, in the presence of aquatic humic acid, the photochemical rate was higher (11.5 × 10?3 min). The analytical determinations show the presence of p-nitrophenol and aminophenol in the reaction medium during the photochemical experiments. The kinetic of degradation in all experiments obeyed a first-order reaction pattern.  相似文献   

11.
The Sarno River is nicknamed “the most polluted river in Europe”. The main goal of this study is to enhance our knowledge on the Sarno River water and sediment quality and on its environmental impact on the gulf of Naples (Tyrrhenian Sea, Central Mediterranean Sea) in order to become a useful assessment tool for the regional administrations. For these reasons, 32 selected polychlorinated biphenyls (PCBs) and aldrin, α-BHC, β-BHC, δ-BHC, γ-BHC (lindane), 4,4′-DDD, 4,4′-DDE, 4,4′-DDT, dieldrin, endosulfan I, endosulfan II, endosulfan sulphate, endrin, endrin aldehyde, heptachlor, heptachlor epoxide (isomer B) and methoxychlor were determined in the water dissolved phase (DP), suspended particulate matter (SPM) and sediments. Total concentrations of PCBs ranged from 1.4 to 24.9 ng L?1 in water (sum of DP and SPM) and from 1.01 to 42.54 ng g?1 in sediment samples. The concentrations of total organochlorine pesticides (OCPs) obtained in water (sum of DP and SPM) ranged from 0.54 to 7.32 ng L?1 and from 0.08 to 5.99 ng g?1 in sediment samples. Contaminant discharges of PCBs and OCPs into the sea were calculated in about 1,247 g day?1 (948 g day?1 of PCBs and 326 g day?1 of OCPs), showing that this river should account as one of the main contribution sources of PCBs and OCPs to the Tyrrhenian Sea.  相似文献   

12.
Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of humic acid between pH 2 and 7 was monitored by differential pulse polarography. Humic acid was not electro-active under the experimental conditions used in this study. Only the pesticide and its main degradation product at pH 2 exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by humic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation in the presence of humic acid was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 2 × 10?3 to 6.3 × 10?3 min?1.  相似文献   

13.
Understanding the effects of sediment contaminants is pivotal to reducing their impact in aquatic environments. Outdoor mesocosms enable us to decipher the effects of these contaminants in environmentally realistic scenarios, providing a valuable link between laboratory and field experiments. However, because of their scale, mesocosm experiments are often complex to set up and manage. The creation of environmentally realistic conditions, particularly when using artificially contaminated sediment, is one issue. Here, we describe changes in geochemistry over 1.5 years of a sediment spiked with four different concentrations of copper, within a large freshwater mesocosm facility. The spiking procedure included proportional amendments with garden lime to counteract the decreases in pH caused by the copper additions. The majority of copper within the spiked mesocosm sediments partitioned to the particulate phase with low microgram per liter concentrations measured in the pore waters and overlying waters. The minimum partition coefficient following equilibration between pore waters and sediments was 1.5?×?104 L/kg, which is well within the range observed for field-contaminated sediments (1?×?104 to 1?×?106 L/kg). Recommendations are made for the in situ spiking of sediments with metals in large outdoor mesocosms. These include selecting an appropriate sediment type, adjusting the pH, allowing sufficient equilibration time, and regular mixing and monitoring of metal partitioning throughout the experimental period.  相似文献   

14.
The paper presents results of the studies photodegradation, photooxidation, and oxidation of phenylarsonic acid (PAA) in aquatic solution. The water solutions, which consist of 2.7 g dm?3 phenylarsonic acid, were subjected to advance oxidation process (AOP) in UV, UV/H2O2, UV/O3, H2O2, and O3 systems under two pH conditions. Kinetic rate constants and half-life of phenylarsonic acid decomposition reaction are presented. The results from the study indicate that at pH 2 and 7, PAA degradation processes takes place in accordance with the pseudo first order kinetic reaction. The highest rate constants (10.45?×?10?3 and 20.12?×?10?3) and degradation efficiencies at pH 2 and 7 were obtained at UV/O3 processes. In solution, after processes, benzene, phenol, acetophenone, o-hydroxybiphenyl, p-hydroxybiphenyl, benzoic acid, benzaldehyde, and biphenyl were identified.  相似文献   

15.
In this study, a SYBR green quantitative real-time PCR was developed to quantify and detect the Legionella spp. in various environmental water samples. The water samples were taken from watershed, water treatment plant, and thermal spring area in Taiwan. Legionella was detected in 13.6 % (24/176), and the detection rate for river water, raw drinking water, and thermal spring water was 10, 21.4, and 16.6 %, respectively. Using real-time PCR, concentration of Legionella spp. in detected samples ranged between 9.75?×?104 and 3.47?×?105?cells/L in river water, 6.92?×?104 and 4.29?×?105?cells/L in raw drinking water, and 5.71?×?104 and 2.12?×?106?cells/L for thermal spring water samples. The identified species included Legionella pneumophila (20.8 %), Legionella jordanis (4.2 %), Legionella nautarum (4.2 %), Legionella sp. (4.2 %), and uncultured Legionella sp. (66.6 %). The presence of L. pneumophila in aquatic environments suggested a potential public health threat that must be further examined.  相似文献   

16.
From April 2008 to November 2009, a field decomposition experiment was conducted to investigate the effects of sediment burial on macro (C, N) and microelement (Pb, Cr, Cu, Zn, Ni, and Mn) variations in decomposing litter of Phragmites australis in the coastal marsh of the Yellow River estuary. Three one-off sediment burial treatments [no sediment burial (0 mm year?1, S0), current sediment burial (100 mm year?1, S10), and strong sediment burial (200 mm year?1, S20)] were laid in different decomposition sites. Results showed that sediment burials showed significant influence on the decomposition rate of P. australis, in the order of S10 (0.001990 day?1)?≈?S20 (0.001710 day?1)?>?S0 (0.000768 day?1) (p?<?0.05). The macro and microelement in decomposing litters of the three burial depths exhibited different temporal variations except for Cu, Zn, and Ni. No significant differences in C, N, Pb, Cr, Zn, and Mn concentrations were observed among the three burial treatments except for Cu and Ni (p?>?0.05). With increasing burial depth, N, Cr, Cu, Ni, and Mn concentrations generally increased, while C, Pb, and Zn concentrations varied insignificantly. Sediment burial was favorable for C and N release from P. australis, and, with increasing burial depth, the C release from litter significantly increased, and the N in litter shifted from accumulation to release. With a few exceptions, Pb, Cr, Zn, and Mn stocks in P. australis in the three treatments evidenced the export of metals from litter to environment, and, with increasing burial depth, the export amounts increased greatly. Stocks of Cu and Ni in P. australis in the S10 and S20 treatments were generally positive, evidencing incorporation of the two metals in most sampling times. Except for Ni, the variations of C, N, Pb, Cr, Cu, Zn, and Mn stocks in P. australis in the S10 and S20 treatments were approximated, indicating that the strong burial episodes (S20) occurred in P. australis marsh in the future would have little influence on the stocks of these elements. With increasing burial depths, the P. australis was particularly efficient in binding Cu and Ni and releasing C, N, Pb, Cr, Zn, and Mn, implying that the potential eco-toxic risk of Pb, Cr, Zn, and Mn exposure might be very serious. This study emphasized the effects of different burials on nutrient and metal cycling and mass balance in the P. australis marsh of the Yellow River estuary.  相似文献   

17.
Photochemical degradation of methylparathion (O,O,–dimethyl O-4 nitrophenylphosphorothioate) in the presence of fulvic acid (FA) between pH 2 and 7 was studied by differential pulse polarography (DPP). Fulvic acid and its photoproducts were not electro-active under the experimental conditions used in this study, and only the pesticide exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by fulvic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 3.3 × 10?3 to 8.8 × 10?3min?1.  相似文献   

18.
We assessed the association between arsenic intake through water and diet, and arsenic levels in first morning-void urine under variable conditions of water contamination. This was done in a 2-year consecutive study in an endemic population. Exposure of arsenic through water and diet was assessed for participants using arsenic-contaminated water (≥50 μg L?1) in a first year (group I) and for participants using water lower in arsenic (<50 μg L?1) in the next year (group II). Participants with and without arsenical skin lesions were considered in the statistical analysis. Median dose of arsenic intake through drinking water in groups I and II males was 7.44 and 0.85 μg kg body wt.?1 day?1 (p <0.0001). In females, it was 5.3 and 0.63 μg kg body wt.?1 day?1 (p <0.0001) for groups I and II, respectively. Arsenic dose through diet was 3.3 and 2.6 μg kg body wt.?1 day?1 (p?=?0.088) in males and 2.6 and 1.9 μg kg body wt.?1 day?1 (p?=?0.0081) in females. Median arsenic levels in urine of groups I and II males were 124 and 61 μg L?1 (p?=?0.052) and in females 130 and 52 μg L?1 (p?=?0.0001), respectively. When arsenic levels in the water were reduced to below 50 μg L?1 (Indian permissible limit), total arsenic intake and arsenic intake through the water significantly decreased, but arsenic uptake through the diet was found to be not significantly affected. Moreover, it was found that drinking water mainly contributed to variations in urine arsenic concentrations. However, differences between male and female participants also indicate that not only arsenic uptake, but also many physiological factors affect arsenic behavior in the body and its excretion. As total median arsenic exposure still often exceeded 3.0 μg kg body wt.?1 day?1 (the permissible lower limit established by the Joint Expert Committee on Food Additives) after installation of the drinking water filters, it can be concluded that supplying the filtered water only may not be sufficient to minimize arsenic availability for an already endemic population.  相似文献   

19.
This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO2) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO2 nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO2 by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO2-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO2?+?monodisperse TiO2 (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO2-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO2-P25. Using NF-TiO2 layer-by-layer with monodisperse TiO2 (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10?3?min?1 for caffeine, 12.5 and 9.0?×?10?3?min?1 for carbamazepine, and 10.9 and 5.8?×?10?3?min?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO2-based films compared to the direct addition of nanoparticles into the sol.  相似文献   

20.
In this study, photocatalytic (photo-Fenton and H2O2/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H2O2). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H2O2]0 = 400 mg L?1. The photo-Fenton process mineralized 70% of the ETU with [H2O2]0 = 800 mg L?1 and [Fe2+] = 400 mg L?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H2O2 from 800 mg L?1 to 1200 mg L?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H2O2 and photo-Fenton processes were determined to be 6.2 × 10?4 mg L?1 min?1 and 7.7 × 10?4 mg L?1 min?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.  相似文献   

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