Benzyl-penicillin (Penicillin G) transformation in aqueous solution at low temperature under controlled laboratory conditions

Antibiotics are released into the environment in a variety of ways: via wastewater effluent as a result of incomplete metabolism in the body after use in human therapy, as runoff after use in agriculture, through improper disposal by private households or hospitals or through insufficient removal by water treatment plants. Unlike in most European countries, in Arctic regions effluents are not suitably treated prior to their release into the aquatic environment. Also, many of the scattered human settlements in remote regions of the Arctic do not possess sewage treatment facilities and pharmaceutical residues therefore enter the aqueous environment untreated. Only limited data are available on the biodegradation of antibiotics under Arctic conditions. However, such information is needed to estimate the potential harm of antibiotics for the environment. Pen-G is used in this study since it is a widely prescribed antibiotic compound whose environmental properties have not yet been investigated in detail. Thus, for a very first assessment, the OECD approved biodegradation Zahn-Wellens test (ZWT, OECD 302 B) was used to study biodegradation and non-biotic elimination of the antibiotic Benzyl-penicillin (Pen-G) at different temperatures (5°C, 12.5°C and 20°C). The testing period was extended from the OECD standard of 28-42d. In addition to dissolved organic carbon (DOC), Pen-G levels and major transformation products were recorded continuously by LC-ion-trap-MS/MS. DOC monitoring revealed considerable temperature dependence for the degradation process of Pen-G. DOC loss was slowest at 5°C and considerably faster at 12.5°C and 20°C. In the initial step of degradation it was found that Pen-G was hydrolyzed. This hydrolyzed Pen-G was subsequently further degraded by decarboxylation, the result of which was 2-(5,5-dimethyl-1,3-thiazolidin-2-yl)-2-(2-phenylacetamido)acetic acid. Furthermore, direct elimination of 2-phenyl-acetaldehyde from the hydrolyzed and decarboxylated Pen-G also led to the formation of 2-[amino(carboxy)methyl]-5,5-dimethyl-1,3-thiazolidone-4-carboxylic acid. Since biodegradation slows down considerably at a low temperature, the resulting transformation products had considerably longer residence times at 5°C compared to higher temperature conditions within the 42-d experiment. The results presented here clearly demonstrate that a risk assessment for pharmaceuticals present in low ambient temperature environments (i.e. the Arctic) cannot be based on test results obtained under standard laboratory conditions (i.e. 20°C ambient temperatures).     

Degradation kinetics of tebufenozide in model aquatic systems under controlled laboratory conditions

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 (k_obsd) and half‐lives (T_1/2) 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 k_obsd (10^‐4 d^‐1) and T_1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (E_a) 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 (T_1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T_1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T_1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T_1/2 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.     

Bioconcentration of two pharmaceuticals (benzodiazepines) and two personal care products (UV filters) in marine mussels (Mytilus galloprovincialis) under controlled laboratory conditions

Bioaccumulation is essential for gaining insight into the impact of exposure to organic micropollutants in aquatic fauna. Data are currently available on the bioaccumulation of persistent organic pollutants, but there is very little documentation on the bioaccumulation of pharmaceuticals and personal care products (PPCPs). The bioconcentration of selected PPCPs was studied in marine mussels (Mytilus galloprovincialis). The selected PPCPs were two organic UV filters, i.e., 2-ethylhexyl-4-trimethoxycinnamate (EHMC) and octocrylene (OC), and two benzodiazepines (BZP), i.e., diazepam (DZP) and tetrazepam (TZP). Laboratory experiments were performed in which M. galloprovincialis was exposed to these compounds either directly from water, for the less lipophilic substances (BZP) or via spiked food for lipophilic UV filters. M. galloprovincialis uptook and eliminated BZP following first-order kinetics. The biological half-life (t (1/2)) of TZP was 1.4?days, resulting in a bioconcentration factor of 64 and 99?mL?g(-1) dry weight (dw), respectively, for 2.3 and 14.5?μg?L(-1) of exposure, while the biological half-life (t (1/2)) of DZP was 0.4?days, resulting in a bioconcentration factor of 51?mL?g(-1) dw for 13.2?μg?L(-1) of exposure. The uptake of UV filter was rapid in mussels, followed by elimination within 24?h. EHMC increased from 15 to 138?ng?g(-1) dw in 1?h and decreased to 25?ng?g(-1) after 24?h for 11.9?μg?L(-1) exposure. OC reached 839?ng?g(-1) dw after 1?h and decreased to 33?ng?g(-1) after 24?h for 11.6?μg?L(-1) exposure. However, EHMC and OC were slightly accumulated in 48?h, i.e., 38 and 60?ng?g(-1) dw, respectively.     

Manganese(II) catalyzed sulfur dioxide oxidation in aqueous solution at environmental concentrations

Manganese(II) catalyzed SO₂ oxidation in aqueous solution at atmospheric concentrations over the wide pH range from 3 to 8 has been studied by using a continuously flowing stirred reactor. The S(IV) oxidation rate is proportional directly to both Mn(II) and S(IV) concentration in the solution with a rate constant of k = (5.1 +- 0.5) × 10³ / mole⁻¹ s⁻¹ at 23.72C. The rate constant is constant over the range of pH from 3 to 6, while it sharply decreases below pH = 3 and above pH = 6. The activation energy is obtained to be 17.8 kcal mole⁻¹.This pH dependence is discussed in terms of the solution chemistry of both S(IV) and Mn(II) as a function of pH and in terms of the complex formation of Mn(II) with S(IV) species on the basis of the observed anion effect on the reaction rate.     

Photochemical transformation of the thyroid hormone levothyroxine in aqueous solution

Purpose  

The direct aqueous photolysis of the thyroid hormone levothyroxine (T₄) has been studied.     

Dissipation and translocation of saisenxin in tobacco and soil under conventional field and controlled laboratory conditions

Abstract

The aim of this investigation was to investigate the fate and translocation characteristics of saisenxin (SSX), a novel organic zinc fungicide, in the environment and tobacco plants under conventional field and laboratory conditions. A rapid and sensitive analytical technique based on high-performance liquid chromatography was used for determination of SSX, in soil samples and tobacco leaf, stem and root samples. The method had satisfactiry linearity (R^2?=?0.9999) and the limits of detection and of quantitation of the target compound were 0.06 and 0.20?mg kg^?1, respectively. The average recoveries were in the range of 89.74–94.24% in soil, leaf, stem and root samples, with relative standard deviations of <8%. For conventional field trials, the half-life (t_1/2) of SSX was 5.9–6.5 days in soil and 4.8–5.3 days in tobacco leaves; the corresponding values under controlled laboratory conditions were extended to 7.1 and 7.6?days. The translocation factor (TF) values were in the range of 0–2.25 and 0–0.25 for foliage and root irrigation treatments, respectively. The TFs of SSX in tobacco indicated that tobacco had a high ability to transfer SSX upward.     

Electrocatalytic oxidation of methyl tert-butyl ether (MTBE) in aqueous solution at a nickel electrode

This study utilized the electrocatalytic characteristics of nickel electrode to perform degradation of methyl tert-butyl ether (MTBE) in aqueous solution. Lab experiments were conducted in a spiltless bath type cell equipped with a nickel electrode as working electrode, a platinum wire as counter electrode, and an Ag/AgCl electrode as reference electrode. Effects of controlled potential, supporting electrolyte, and solution pH on the efficiency of MTBE removal were examined under the control of the constant-potential conditions. Experiment results showed that the optimum electrolytic condition was operated at 0.35 V in a 1M KOH electrolyte solution, and the initial 20 mgl(-1) MTBE was reduced by 73% within 180 min under the optimum control. As using 1M Na2SO4 and 1M KCl as electrolyte, the efficiency of MTBE removal dropped to 60% and 50% under the similar controls. Comparing with various pH controls, the strong basic condition is favorable for electrocatalytic oxidation of MTBE in the Ni-electrolytic system. The efficiency of MTBE removal showed a rising trend with increasing initial pH of the solution. The formation of a redox NiOOH/Ni(OH)2 layer on the anode surface, which was observed on the SEM image, can explain that nickel plays a mediator role on improving electrocatalytic oxidation of MTBE at 0.35 V in a strong basic condition. The by-products of MTBE degradation were identified as acetone and CO(2) by GC/MS, and the distributions of carbon atoms in acetone, CO2, and MTBE were found 22%, 51%, and 27% through the optimum control of electrochemical oxidation.     

Aerosolization of an anionic surfactant (LAS) and dissolved organic carbon (DOC) under laboratory conditions.

Aerosolization of natural salt and brackish waters under laboratory conditions is responsible for the transfer of synthetic surfactants such as linear alkylbenzene sulphonate (LAS) from water to the atmosphere. Excluded the lagoon sample which stands apart, on the average ca. 45% of the LAS present at concentrations between 0.1 and 4.1 microg l(-1) in the tested coastal and offshore marine and lagoon waters was transferred to the aerosol extract. The distribution of the individual LAS homologs in the aerosol is very similar to that in water, which indicates no preferential removal from the bulk water of any LAS homolog. The fraction of dissolved organic carbon (DOC) undergoing aerosolization under the same conditions for each tested sample was on an average ca. 3.3%, corresponding to ca. 5.6 mg l(-1). On the average, the enrichment factor of the sea samples, resulting from the changing of the LAS/DOC ratio before and after aerosolization, was ca. 20.     

低电压条件下水体中诺氟沙星的去除效果及机理

研究低电压条件下诺氟沙星（NOR）的电化学降解去除效果。结果表明：在1.3 V外加电压条件下,NOR具有较好的去除效果,在初始浓度c0=0.09 mmol·L-1时,反应70 h后,NOR去除率为90%以上;NOR的去除过程符合伪一级动力学模型。溶液pH值、腐殖酸浓度、水质条件等因素均影响NOR的电化学降解效果。中性及弱碱性条件有利于NOR的电化学去除,腐殖酸及天然水体中的有机物会抑制NOR的去除效果。在低电压条件下,NOR的矿化作用不明显,NOR的电化学降解过程中伴随着大量有机中间产物生成。     

Cu(II) removal from aqueous solution usingDogantepe (Amasya) zeolites

This paper investigates the effects of zeolite particle size, zeolite/ solution ratio and stirring time on the performance of zeolites from Dogantepe in removing Cu(II) from aqueous solution to establish optimum operating conditions. The results indicated that the size of the zeolite samples, the concentration of Cu(II) and the zeolite/solution ratio affected the removal efficiencies, whilst the stirring time was found to have no significant effect on the removal efficiencies. The equivalent numbers of sodium, magnesium, calcium and potassium ions passed into the Cu(II) solution were found to be 1.196, 0.208, 0.117 and 0.009 meq/l, respectively, and the passing percentages of these ions were calculated to be 11.27, 2.45, 1.57 and 0.37%, respectively. The removal mechanism of Cu(II) with zeolite samples was mainly ion exchange with a fraction of approximately 65%. The maximum exchange capacities obtained by using Dogantepe zeolites, Yavu zeolites, and synthetic resin were found to be 9.2, 7.0 and 72.7 mg/g, respectively. However, in relatively low concentrations of Cu(II), the differences in the removal efficiencies or exchange capacities obtained for above different three materials were significantly decreased.     

低频超声辐照降解间苯二酚水溶液的研究

利用低频超声波对模拟间苯二酚废水进行研究，主要讨论间苯二酚本身性质以及超声操作声强对降解的影响，并通过自由基清除剂实验判定该反应的反应类型。结果表明，间苯二酚本身性质以及超声声强对间苯二酚的超声降解影响都比较大，并且该超声降解反应过程以自由基氧化反应为主，同时该反应遵循表观一级动力学反应特征。初始浓度为200mg／L的间苯二酚反应液经强度0．4W／cm^２的超声波辐照4h后，降解率为48．6％。     

低频超声辐照降解间苯二酚水溶液的研究

利用低频超声波对模拟间苯二酚废水进行研究,主要讨论间苯二酚本身性质以及超声操作声强对降解的影响,并通过自由基清除剂实验判定该反应的反应类型.结果表明,间苯二酚本身性质以及超声声强对间苯二酚的超声降解影响都比较大,并且该超声降解反应过程以自由基氧化反应为主,同时该反应遵循表观一级动力学反应特征.初始浓度为200mg/L的间苯二酚反应液经强度0.4 W/cm2的超声波辐照4 h后,降解率为48.6%.     

Mineralisation of Monuron photoinduced by Fe(III) in aqueous solution

The degradation of Monuron (3-(4-chlorophenyl)-1,1-dimethylurea) photoinduced by Fe(III) in aqueous solution has been investigated. The rate of degradation depends on the concentration of Fe(OH)2+, the most photoreactive species in terms of *OH radical formation. These *OH radicals are able to degrade Monuron until total mineralisation. The primordial role of the speciation of Fe(III)-hydroxy complex in aqueous solution, for the efficiency of the elimination of pollutant, was shown and explained in detail. The formation of Fe(II) in the irradiated solution was monitored and correlated with the total organic carbon evolution. Degradation photoproducts were identified and a mechanism of degradation is proposed.     

低温条件下摇动床生物膜反应器处理生活污水的中试研究

采用摇动床生物膜反应器,在中国北方冬春季5～10℃的低温条件下,以城市生活污水处理厂的二级处理出水为水源进行了工作体积4.8 m3的反应器深度处理的中试研究。中试过程以COD、NH4+-N和浊度的去除率为考察指标。实验结果表明:反应器对生活污水深度处理的合适的工艺参数为进水温度10℃,停留时间(HRT)4.8 h,气水比4∶1,曝气量4 m3/h,水流量1.0 m3/h,采用每间隔4 h曝气4 h的间歇式曝气方式;在低温条件下,对污水的COD和NH4+-N的去除率分别为30%和50%,而对浊度的去除率较低。中试表明,摇动床生物膜反应器可应用于中国北方冬春季低温条件下对水中COD和NH4+-N的去除。     

Photodegradation of fluoroquinolones in aqueous solution under light conditions relevant to surface waters,toxicity assessment of photoproduct mixtures

Environmental Science and Pollution Research - Photochemical degradation of fluoroquinolones ciprofloxacin, enrofloxacin and norfloxacin in aqueous solution under light conditions relevant to...     

Sonolysis of alkylphenols in aqueous solution with Fe(II) and Fe(III)

The sonolytic degradation of alkylphenols (APs), such as butylphenol, pentylphenol, octylphenol, and nonylphenol (NP), in water was investigated at a sound frequency of 200 kHz with an acoustic intensity of 6 W cm(-2) under argon, oxygen, and air atmospheres. The sonolytic degradation rate of the APs under the conditions of the present study depended upon their alkyl chain length. The decrease in the degradation rate by the radical scavenging effect was in the range of about 48-82% for APs in the presence of 3 mM 2-methyl-2-propanol. The free radicals play a significant role in the sonolytic degradation process of the APs. In the presence of Fe(II) and Fe(III), the pseudo-first-order rate constants for the sonolytic degradation of 30 microM NP as a function of the concentration of Fe(II) and Fe(III) were estimated under argon and oxygen. The maximum rate constants were observed at 50 microM Fe(II) (0.139 +/- 0.008 min(-1)) and 100 microM Fe(III) (0.103 +/- 0.001 min(-1)) under oxygen. The total organic carbon concentration (TOC) was investigated under same conditions. TOC decreased in the range of about 50-70% during the sonication in the presence of Fe(II) and Fe(III) under argon and oxygen. The sonochemical effects by the addition of Fe(II) and Fe(III) as catalyst during the sonication under the proper atmosphere result in a remarkable enhancement of degradation and mineralization.     

Behaviour of DDT under laboratory and outdoor conditions in Germany

Abstract

Experiments were conducted on adsorption, volatilization and UV‐degradation of p,p'‐DDT on soil surface, and leaching and degradation in sand columns. p,p'‐DDT was shown to adsorb stronger to soils with higher organic content. UV irradiation at 290 nm for 10 hours mineralized less than 0.1% of DDT in soil.

Results show that only 0.1% of DDT volatilized in a sun‐exposed semi‐closed quartz system. Polar compounds accounted from 1.4% after 55 days. The rate of volatilization and degradation in an open system was much higher; only 15% DDT and 7% DDE were recovered after 6 weeks in the organic extract. p,p'‐DDT was adsorbed to a great extent on the top layers of sand columns; 86% in the top 8 cm.     

Impact of pyrolysis temperature and activation on oily sludge-derived char for Pb(II) and Cd(II) removal from aqueous solution

Environmental Science and Pollution Research - This study investigated the Pb(II) and Cd(II) sorption from aqueous solution by oily sludge-derived char (OSDC) prepared at different pyrolysis...     

Uptake and depuration of anatoxin-a by the mussel Mytilus galloprovincialis (Lamarck, 1819) under laboratory conditions

Cyanobacterial blooms tend to be more common in warm and nutrient-enriched waters and are increasing in many aquatic water bodies due to eutrophication. The aim of this work is to study the accumulation and depuration of anatoxin-a by Mytilus galloprovincialis a widespread distributed mussel living in estuarine and coastal waters and recognized worldwide as a bioindicator (e.g. Mussel Watch programs). Research on the distribution and biological effects of anatoxin-a in M. galloprovincialis is important. Nevertheless, the risk of human intoxication due to the consumption of contaminated bivalves should also be considered. A toxic bloom was simulated in an aquarium with 5 x 10(5) cell ml(-1) of Anabaena sp. (ANA 37), an anatoxin-a producing strain. Mussels were exposed to Anabaena for 15 days and then 15 days of depuration followed. Three or more animals were sampled every 24h for total toxin quantification and distribution in soft tissues (edible parts). Water samples were also taken every 24h in order to calculate total dissolved and particulate anatoxin-a concentrations. Anatoxin-a was quantified by HPLC with fluorescence detection. No deaths occurred during accumulation and depuration periods. One day after the beginning of depuration, the toxin could not be detected in the animals. Anatoxin-a is distributed in the digestive tract, muscles and foot and is probably actively detoxified.     

高岭土负载纳米铁镍双金属去除水中偶氮染料直接耐晒黑G

采用液相还原法制备焙烧高岭土负载纳米铁镍双金属（CK-Fe/Ni）。考察了在不同条件下,如pH、投加量、初始浓度、温度等,对负载型纳米铁镍双金属降解水中偶氮染料直接耐晒黑G的影响及动力学研究。结果表明：在pH=9.49、温度为30℃、负载型纳米铁镍双金属的投加量为1.05 g/L、搅拌速度为60 r/min,经过20 min反应后,负载型纳米铁镍双金属降解水中偶氮染料直接耐晒黑G的去除率达到了99.98%。吸附和电镜表征结果表明,作为载体的焙烧高岭土起着吸附直接耐晒黑G和分散纳米铁镍双金属颗粒的作用导致反应活性提高。降解动力学数据表明,负载型纳米铁镍双金属对直接耐晒黑G的降解过程符合伪一级反应动力学规律,速率常数k随负载型纳米铁镍双金属的投加量的增加而提高,表观活化能为19.72 kJ/mol。最后,利用高岭土负载纳米铁镍双金属对废水处理,结果表明,负载型纳米铁镍双金属在实际废水中对直接耐晒黑G的去除率达到了99.98%。