Hydrolysis and photolysis of oxytetracycline in aqueous solution

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 Ca^{2 +} 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 Ca^{2 +} accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca^{2 +}. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.     

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.     

Interaction between nitrogen and phosphorus cycles in mining-affected aquatic systems—experiences from field and laboratory measurements

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.     

Electrochemical Monitoring of Methylparathion Degradation in an Acid Aqueous Medium in Presence of Cu(II)

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.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

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.     

Effect of Fe (III) on acid degradation of methylparathion

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.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

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.     

Photochemical Behavior of Parathion in the Presence of Humic Acids from Different Origins

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.     

Spatial distribution and partitioning of polychlorinated biphenyl and organochlorine pesticide in water and sediment from Sarno River and Estuary,Southern Italy

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.     

Photochemical degradation of methylparathion in the presence of humic acid

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.     

Long-term copper partitioning of metal-spiked sediments used in outdoor mesocosms

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.     

Identification and quantitative detection of Legionella spp. in various aquatic environments by real-time PCR assay

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.     

Effect of fulvic acid on the photochemical degradation of methylparathion

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.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

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.     

Effects of nitrogen application rate and a nitrification inhibitor dicyandiamide on methanotroph abundance and methane uptake in a grazed pasture soil

Methane-oxidizing bacteria (methanotrophs) in the soil are a unique group of methylotrophic bacteria that utilize methane (CH₄) as their sole source of carbon and energy which limit the flux of methane to the atmosphere from soils and consume atmospheric methane. A field experiment was conducted to determine the effect of nitrogen application rates and the nitrification inhibitor dicyandiamide (DCD) on the abundance of methanotrophs and on methane flux in a grazed pasture soil. Nitrogen (N) was applied at four different rates, with urea applied at 50 and 100 kg N ha^?1 and animal urine at 300 and 600 kg N ha^?1. DCD was applied at 10 kg ha^?1. The results showed that both the DNA and selected mRNA copy numbers of the methanotroph pmoA gene were not affected by the application of urea, urine or DCD. The methanotroph DNA and mRNA pmoA gene copy numbers were low in this soil, below 7.13?×?10³ g^?1 soil and 3.75?×?10³ μg^?1 RNA, respectively. Daily CH₄ flux varied slightly among different treatments during the experimental period, ranging from ?12.89 g CH₄ ha^?1 day^?1 to ?0.83 g CH₄ ha^?1 day^?1, but no significant treatment effect was found. This study suggests that the application of urea fertilizer, animal urine returns and the use of the nitrification inhibitor DCD do not significantly affect soil methanotroph abundance or daily CH₄ fluxes in grazed grassland soils.     

Repeated batch and continuous degradation of chlorpyrifos by Pseudomonas putida

The present study was undertaken with the objective of studying repeated batch and continuous degradation of chlorpyrifos (O,O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) using Ca-alginate immobilized cells of Pseudomonas putida isolated from an agricultural soil, and to study the genes and enzymes involved in degradation. The study was carried out to reduce the toxicity of chlorpyrifos by degrading it to less toxic metabolites. Long-term stability of pesticide degradation was studied during repeated batch degradation of chlorpyrifos, which was carried out over a period of 50 days. Immobilized cells were able to show 65% degradation of chlorpyrifos at the end of the 50th cycle with a cell leakage of 112 × 10³ cfu mL^?1. During continuous treatment, 100% degradation was observed at 100 mL h^?1 flow rate with 2% chlorpyrifos, and with 10% concentration of chlorpyrifos 98% and 80% degradation was recorded at 20 mL h^?1 and 100 mL h^?1 flow rate respectively. The products of degradation detected by liquid chromatography–mass spectrometry analysis were 3,5,6-trichloro-2-pyridinol and chlorpyrifos oxon. Plasmid curing experiments with ethidium bromide indicated that genes responsible for the degradation of chlorpyrifos are present on the chromosome and not on the plasmid. The results of Polymerase chain reaction indicate that a ~890-bp product expected for mpd gene was present in Ps. putida. Enzymatic degradation studies indicated that the enzymes involved in the degradation of chlorpyrifos are membrane-bound. The study indicates that immobilized cells of Ps. putida have the potential to be used in bioremediation of water contaminated with chlorpyrifos.     

The capability of estuarine sediments to remove nitrogen: implications for drinking water resource in Yangtze Estuary

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.     

Transformation of sulfaquinoxaline by chlorine and UV light in water: kinetics and by-product identification

Sulfaquinoxaline (SQX) is an antimicrobial of the sulfonamide class, frequently detected at low levels in drinking and surface water as organic micropollutant. The main goal of the present study is the evaluation of SQX reactivity during chlorination and UV irradiations which are two processes mainly used in water treatment plants. The SQX transformation by chlorination and UV lights (254 nm) was investigated in purified water at common conditions used for water disinfection (pH =?7.2, temperature =?25 °C, [chlorine] =?3 mg L^?1). The result shows a slow degradation of SQX during photolysis compared with chlorination process. Kinetic studies that fitted a fluence-based first-order kinetic model were used to determine the kinetic constants of SQX degradation; they were equal to 0.7?×?10^?4 and 0.7?×?10^?2 s^?1corresponding to the half time lives of 162 and 1.64 min during photolysis and chlorination, respectively. In the second step, seven by-products were generated during a chlorination and photo-transformation of SQX and identified using liquid chromatography with electrospray ionization and tandem mass spectrometry (MS-MS). SO₂ extrusion and direct decomposition were the common degradation pathway during photolysis and chlorination. Hydroxylation and isomerization were observed during photodegradation only while electrophilic substitution was observed during chlorination process.     

Adsorption,desorption, soil mobility,aqueous persistence and octanol‐water partitioning coefficients of terbufos,terbufos sulfoxide and terbufos sulfone

Abstract

Terbufos, t. sulfoxide and t. sulfone (5 μg ml^‐1) were incubated in natural, sterilized natural and distilled water, with initial pH values of 8.8, 8.8 and 6.0, respectively, at 20°C. First‐order disappearance was observed for the three compounds. Rates in natural and sterilized water were similar indicating chemical degradation predominated. Terbufos disappeared rapidly (t½>=3 days) in all systems. T. sulfoxide and t. sulfone were more persistent in the natural (t½>=18–40 days) and distilled water (t½>=280–350 days). Adsorption data for the three compounds in four soil‐water systems showed the decreasing order of adsorption to be terbufos>>t. sulfoxide=t. sulfone. Desorption from soils fortified at 5 μg g^‐1 with water was examined for 4 successive 18‐hr cycles. T. sulfoxide and t. sulfone were totally desorbed; terbufos was too unstable to study. The mobility of the compound in soil eluted with water was in the order, t. sulfoxide=t. sulfone>> terbufos, in agreement with adsorption‐desorption results. The octanol‐water partitioning coefficients for terbufos, t. sulfoxide and t. sulfone, at 23°C, were 3:30 x 10 , 164, and 302, respectively.     

Remediation of alachlor and atrazine contaminated water with zero-valent iron nanoparticles

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.