Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).     

Identification and characterization of Fe3O4/peroxodisulfate advanced oxidation products from sulfameter

Sulfonamides (SAs) are one of the most widely used antibiotics and their residuals in the environment could cause some negative environmental issues. Advanced oxidation such as Fenton-like reaction has been widely applied in the treatment of SAs polluted water. Degradation rates of 95%-99.7% were achieved in this work for the tested 8 SAs, including sulfisomidine, sulfameter (SME), phthalylsulfathiazole, sulfamethoxypyridazine, sulfamonomethoxine, sulfisoxazole, sulfachloropyridazine, and sulfadimethoxine, in the Fe₃O₄/peroxodisulfate (PDS) oxidation system after the optimization of PDS concentration and pH. Meanwhile, it was found that a lot of unknown oxidation products were formed, which brought up the uncertainty of health risks to the environment, and the identification of these unknown products was critical. Therefore, SME was selected as the model compound, from which the oxidation products were never elucidated, to identify these intermediates/products. With liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS), 10 new products were identified, in which 2-amino-5-methoxypyrimidine (AMP) was confirmed by its standard. The investigation of the oxidation process of SME indicated that most of the products were not stable and the degradation pathways were very complicated as multiple reactions, such as oxidation of the amino group, SO₂ extrusion, and potential cross-reaction occurred simultaneously. Though most of the products were not verified due to the lack of standards, our results could be helpful in the evaluation of the treatment performance of SAs containing wastewater.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

高效液相色谱法测定鸡蛋清和蛋黄中磺胺类药物残留

采用高效液相色谱法测定鸡蛋清和蛋黄中磺胺嘧啶、磺胺吡啶、磺胺二甲基嘧啶、磺胺甲氧哒嗪、磺胺甲恶唑、磺胺间甲氧嘧啶、磺胺喹恶啉等7种磺胺类药物残留,优化了色谱条件和样品预处理方法。7种磺胺类药物在0.050 mg/L~10.0 mg/L范围内线性良好,检出限和定量限分别低于0.02 mg/kg和0.04 mg/kg。在0.250 mg/kg和0.500 mg/kg两个添加水平,蛋清中的回收率为81.0%~100%,RSD为0.8%~4.8%,蛋黄中的回收率为72.2%~94.1%,RSD为1.1%~6.9%。     

Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province, China

The objective of this investigation was to obtain a broad profile of veterinary antibiotics residues in animal wastewater and surface water around large-scale livestock and poultry farms in Jiangsu Province of China. Therefore, 53 samples collected from 27 large-scale animal farms in 11 cities and counties of Jiangsu Province in 2009, were monitored for 10 selected veterinary antibiotics using solid phase extraction and high performance liquid chromatography/electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS) techniques. Ten veterinary antibiotics were found in animal wastewaters, eight antibiotics were detected in pond waters, and animal farm-effluents and river water samples were contaminated by nine antibiotics. The most frequently detected antibiotics were sulfamethazine (75%), oxytetracycline (64%), tetracycline (60%), sulfadiazine (55%) and sulfamethoxazole (51%) which were detected with a maximum concentration of 211, 72.9, 10.3, 17.0 and 63.6 μg L⁻¹, respectively. The maximum concentration of 0.55 μg L⁻¹ for cyromazine, 3.67 μg L⁻¹ for chlortetracycline, 0.63 μg L⁻¹ for sulfadoxine, 39.5 μg L⁻¹ for doxycycline and 0.64 μg L⁻¹ for sulfaquinoxaline were determined in the collected samples. In general, the maximum concentration of the selected veterinary antibiotics was detected in animal wastewaters except for chlortetracycline in animal farm-effluents. In addition, residue levels of selected veterinary antibiotics in animal wastewater and surface water around the farms were related to animal species and have a high spatial variation.     

Sulfadimethoxine and sulfaguanidine: their sorption potential on natural soils

Sulfonamides (SAs) are one of the oldest groups of veterinary chemotherapeutic agents. As these compounds are not completely metabolized in animals, a high proportion of the native form is excreted in feces and urine. They are therefore released either directly to the environment in aquacultures and by grazing animals, or indirectly during the application of manure or slurry. Once released into the environment, SAs become distributed among various environmental compartments and may be transported to surface or ground waters. The physicochemical properties of SAs, dosage and nature of the matrix are the factors mainly responsible for their distribution in the natural environment. Although these rather polar compounds have been in use for over half a century, knowledge of their fate and behavior in soil ecosystems is still limited. Therefore, in this work we have determined the sorption potential of sulfadimethoxine and sulfaguanidine on various natural soils. The influence on sorption of external factors, such as ionic strength and pH, were also determined. The sorption coefficients (K_d) obtained for the sulfonamides investigated were quite low (from 0.20 to 381.17 mL g⁻¹ for sulfadimethoxine and from 0.39 to 35.09 mL g⁻¹ for sulfaguanidine), which indicated that these substances are highly mobile and have the potential to run off into surface waters and/or infiltrate ground water. Moreover, the sorption of these pharmaceuticals was found to be influenced by OC, soil solution pH and ionic strength, with higher K_d values for soils of higher OC and lower K_d values with increasing pH and ionic strength.     

Occurrence of antibiotics in water, sediments, aquatic plants, and animals from Baiyangdian Lake in North China

This study investigated the presence and distribution of 22 antibiotics, including eight quinolones, nine sulfonamides and five macrolides, in the water, sediments, and biota samples from Baiyangdian Lake, China. A total of 132 samples were collected in 2008 and 2010, and laboratory analyses revealed that antibiotics were widely distributed in the lake. Sulfonamides were the dominant antibiotics in the water (0.86-1563 ng L⁻¹), while quinolones were prominent in sediments (65.5-1166 μg kg⁻¹) and aquatic plants (8.37-6532 μg kg⁻¹). Quinolones (17.8-167 μg kg⁻¹) and macrolides [from below detection limit (BDL) to 182 μg kg⁻¹] were often found in aquatic animals and birds. Salvinia natans exhibited the highest bioaccumulation capability for quinolones among three species of aquatic plants. Geographical differences of antibiotic concentrations were greatly due to anthropogenic activities. Sewage discharged from Baoding City was likely the main source of antibiotics in the lake. Risk assessment of antibiotics on aquatic organisms suggested that algae and aquatic plants might be at risk in surface water, while animals were likely not at risk.     

Evaluation of the interaction between soil and antibiotics

The aim of this study was to investigate the occurrence of tetracycline and sulfonamide antibiotics in 13 different soil samples collected from agricultural fields. As well as the antibiotic analysis 18 different physicochemical properties of the soil samples were determined in order to establish a relationship between the recovery rates of antibiotics from the samples and the characteristics of the samples that provide critical information for the reliability of an applied antibiotic analysis method. While the concentrations of tetracyclines were 0.025–0.105 mg kg^?1 sulfonamide antibiotics were not detected in any investigated soil samples. The mean recovery rates of tetracyclines and sulfonamides were 84.57 ± 14.92% and 65.88 ± 8.56%, respectively. Although, the organic carbon contents and cation exchange capacities of the soil samples exhibited a great variation the results of multivariate statistical analysis indicated that the metal content of soils was the major factor significantly influenced the recovery rates of the antibiotics. The sulfonamide recovery rates were positively influenced by the calcium and magnesium amounts in the soil samples, whereas tetracycline recovery rates were markedly diminished by increasing the amount of these polyvalent metals.     

Photoinduced degradation of sulfonamides,kinetic, and structural characterization of transformation products and assessment of environmental toxicity

This study focuses on the degradation of the sulfonamide antibiotics, sulfadiazine, sulfamethazine, sulfamethoxazole, and sulfathiazole, using ultraviolet irradiation in various conditions. Different pHs were investigated in combination with the addition of hydrogen peroxide and further oxygen removal. High-performance liquid chromatography electrospray ionization ion-trap mass spectrometry was used to identify and elucidate degradation products and to establish concentration–time curves. Previously unknown degradation products could be characterized. Reaction rate constants of all compounds and transformation products were determined. The parent sulfonamides decayed according to first-order kinetics, while the concentrations of the transformation products varied with time according to a subsequent reaction of an intermediate product. Quantum efficiencies were analyzed for mechanistic purposes. As example, sulfamethoxazole was added to effluents from a wastewater treatment plant and irradiated. Phototoxicity and environmental hazard were assessed through quantitative structure-activity relationship computations. In addition, the minimal inhibition concentrations were determined for Pseudomonas fluorescens and Bacillus subtilis. Conclusions for UV-C irradiation as a fourth purification wastewater treatment stage were derived.     

Influence of hydraulic retention time on behavior of antibiotics and antibiotic resistance genes in aerobic granular reactor treating biogas slurry

Longer HRT can enhance degradation rate of sulfamethoxazole in granular reactor. Longer HRT can reduce accumulated concentrations of TCs and QNs in sludge. Longer HRT may have increased relative abundances of ARGs in aerobic granules. The behavior of antibiotics and the corresponding resistance genes in aerobic granular reactors for treating biogas slurry under different hydraulic retention times (10.7 h, R1; 8 h, R2) was investigated in this study. The results indicated that the hydraulic retention time could affect the effluent concentrations and removal efficiencies of sulfonamides. The average removal rates of tetracyclines, fluoroquinolones, and sulfonamides were 63%, 46%, and 90% in R1, and 62%, 46%, and 86% in R2, respectively. Although the removal efficiencies of tetracyclines and fluoroquinolones were similar in both reactors, the respective accumulated concentrations of tetracyclines and fluoroquinolones in R1 were 7.00 and 11.15 µg/g SS, which were lower than those in R2 (8.92 and 13.37 µg/g SS, respectively). The difference in the relative abundance of target antibiotic resistance genes between both reactors was not significant, yet the average relative abundances of all target resistance genes in R1 were higher than those in R2 after 45 days of operation. The results of this study suggested that a longer hydraulic retention time could enhance the antibiotic removal ability of aerobic granular sludge, yet it may also increase the risk of surplus sludge utilization from a resistance genes point of view.