土壤中四环素类抗生素污染研究进展

由抗生素类物质的使用引发的土壤环境污染问题已引起全球的广泛关注.中国是抗生素类物质的消费大国,其抗生素污染问题亟待解决.介绍了世界范围内使用最为广泛的四环紊类抗生索在土壤环境中的污染现状;分析了国内外有关四环素类抗生索的研究状况和进展;揭示了生物有效性研究在评价四环素类抗生索对土壤环境生态风险的重要意义;最后对四环素类...     

水中四环素类化合物在不同光源下的光降解

研究了模拟太阳光和实际室外太阳光下四环素类化合物在水溶液中的光降解。结果表明,四环素类化合物(TCs)在模拟太阳光照射下均能发生直接光降解,且其降解速率随pH不同变化很大。四环素(TC)、土霉素(OTC)、金霉素(CTC)和多西环素(DTC)的光降解速率随溶液pH升高明显加快,而米诺环素(MTC)在水中的光降解速率随溶液pH升高略有下降。天然水体pH范围内,模拟太阳光照下四环素类化合物表观光降解速率常数在0.004～0.026 min-1范围内,降解半衰期在26～136 min范围内。在室外实际太阳光照下,四环素类化合物光降解反应速率与太阳光强成正比例关系。晴朗无云天气下,四环素类化合物降解半衰期在春冬季节较长、夏季节较短;四环素在东江实际水体中表观光降解速率很快,在冬季晴天天气下,其平均半衰期仅为8.2 min。     

New insights into the characterization of the binding of tetracycline analogues with lysozyme: a biophysical study

Tetracycline (TC), chlortetracycline (CTC) and oxytetracycline (OTC) are the most common members of the widely used veterinary drug tetracyclines, the residue of which in the environment can enter human body, being potentially harmful. Lysozyme is a monomeric protein widely distributed in the nature including human beings, having many physiological and pharmaceutical functions. The aim of this study was to examine the interaction of lysozyme with the three tetracyclines (TC, CTC and OTC) through spectroscopic and molecular modeling methods. The experimental results revealed that all the three tetracyclines (TCs) can interact with lysozyme with one binding site to form TCs-lysozyme complex, mainly through electrostatic forces with the affinity order: CTC > TC > OTC. The binding of TCs can cause conformational and some microenvironmental changes of lysozyme. Furthermore, molecular docking was applied to define the specific binding sites, the results of which show that all the three TCs can bind into lysozyme cleft and interact with the key active-site residues Glu 35 or Asp 52, resulting in competitive inhibition of lysozyme activity. The accurate and full basic data in the work is beneficial to clarifying the binding mechanism of TCs with lysozyme in vivo.     

Dynamics of copper and tetracyclines during composting of water hyacinth biomass amended with peat or pig manure

Composting is one of the post-treatment methods for phytoremediation plants. Due to a high potential of water hyacinth to accumulate pollutants, the physicochemical parameters, microbial activity as well as fates of copper (Cu) and tetracyclines (TCs) were investigated for the different amended water hyacinth biomass harvested from intensive livestock and poultry wastewater, including unamended water hyacinth (W), water hyacinth amended with peat (WP), and water hyacinth amended with pig manure (WPM) during the composting process. Pig manure application accelerated the composting process as evidenced by an increase of temperature, electrical conductivity (EC), NH₄-N, as well as functional diversity of microbial communities compared to W and WP treatments. Composting process was slowed down by high Cu, but not by TCs. The addition of peat significantly increased the residual fraction of Cu, while pig manure addition increased available Cu concentration in the final compost. Cu could be effectively transformed into low available (oxidizable) and residual fractions after fermentation. In contrast, less than 0.5% of initial concentrations of TCs were determined at the end of 60-day composting for all treatments in the final composts. The dissipation of TCs was accelerated by the high Cu concentration during composting. Therefore, composting is an effective method for the post-treatment and resource utilization of phytoremediation plants containing Cu and/or TCs.     

Occurrence and distribution of heavy metals and tetracyclines in agricultural soils after typical land use change in east China

Land use in east China tends to change from paddy rice to vegetables or other high-value cash crops, resulting in high input rates of organic manures and increased risk of contamination with both heavy metals (HMs) and antibiotics. This investigation was conducted to determine the accumulation, distribution and risks of HMs and tetracyclines (TCs) in surface soils and profiles receiving different amounts of farmyard manure. Soil samples collected from suburbs of Hangzhou city, Zhejiang province were introduced to represent three types of land use change from paddy rice to asparagus production, vineyards and field mustard cultivation, and divided into two portions, one of which was air-dried and sieved through 2-, 0.3- and 0.149-mm nylon mesh for determination of pH and heavy metals. The other portion was frozen at ?20 °C, freeze-dried and sieved through a 0.3-mm nylon mesh for tetracyline determination. HM and TC concentrations in surface soils of 14-year-old mustard fields were the highest with total Cu, Zn, Cd and ∑TCs of 50.5, 196, 1.03 mg?kg^?1 and 22.9 μg?kg^?1, respectively, on average. The total Cu sequence was field mustard?>?vineyards?>?asparagus when duration of land use change was considered; oxytetracycline (OTC) and doxycycline were dominant in soils used for asparagus production; OTC was dominant in vineyards and chlortetracycline (CTC) was dominant in mustard soils. There were positive pollution relationships among Cu, Zn and ∑TCs, especially between Cu and Zn or Cu and ∑TCs. Repeated and excessive application of manures from intensive farming systems may produce combined contamination with HMs and TCs which were found in the top 20 cm of the arable soil profiles and also extended to 20–40 cm depth. Increasing manure application rate and cultivation time led to continuing increases in residue concentrations and movement down the soil profile.     

Occurrence and distribution of veterinary antibiotics and tetracycline resistance genes in farmland soils around swine feedlots in Fujian Province, China

Six antibiotics, tetracyclines (TCs), and quinolones (QNs) in farmland soils from four coastal cities in Fujian Province of China were investigated. Oxytetracycline was most frequently detected, followed by enrofloxacin, ciprofloxacin, chlorotetracycline, ofloxacin, and tetracycline, with maximum concentrations of 613.2, 637.3, 237.3, 2668.9, 205.7, and 189.8 μg kg^?1, respectively. Samples from Putian City contained the highest maximum concentration of ∑TCs (3,064.2 μg kg^?1), whereas those from Fuzhou City contained the highest maximum concentration of ∑QNs (897.8 μg kg^?1). It is noteworthy that the ∑TCs and ∑QNs in 46.4 and 28.6 % of samples exceeded the ecotoxic effect trigger value (100 μg kg^?1), respectively. The concentrations of these antibiotics and five tetracycline resistance genes in four soil plots at depth profiles were quantified thereafter. In most cases, both antibiotics and resistance genes decreased with the increase of depth. Some antibiotics can be detected at a depth of 60–80 cm where the abundance of tetO, tetM, and tetX reached up to 10⁷ copies g^?1. Additionally, the sum of all tet genes (normalized to 16S rRNA genes) correlated with ∑TCs significantly (r?=?0.676). Our results suggest that resistance determinants can migrate to deeper soil layers and would probably contaminate groundwater by vertical transport.     

Occurrence and sources of antibiotics and their metabolites in river water, WWTPs, and swine wastewater in Jiulongjiang River basin, south China

In this study, the occurrence and sources of five cataloged antibiotics and metabolites were studied in Jiulongjiang River basin, south China. Nineteen antibiotics and 13 metabolites were detected in water samples from 16 river sampling sites, wastewater from 5 swine-raising facilities, and effluent from 5 wastewater treatment plants (WWTPs). The results showed that 12 antibiotics and 6 metabolites were detected in river water samples. Sulfonamides (SAs) and their metabolites were detected at high concentrations (8.59–158.94 ng/L). Tetracyclines (TCs) and their metabolites were frequently detected in swine wastewater, and the maximum concentration was up to the level in milligram per liter. Macrolides (MLs) and β-lactams (β-Ls) were found in all WWTP effluent samples and some river samples, while they were never found in any of the swine wastewater samples. SAs and quinolones (QNs) were detected in all samples. Hierarchical cluster analysis of 16 surface water samples was applied to achieve the spatial distribution characteristics of antibiotics in the Jiulongjiang River. As a result, two categories were obviously obtained. Principal component analysis and redundancy analysis showed that TCs and SAs as well as their metabolites were the major antibiotics in Jiulongjiang River, and they mainly originated from swine wastewater, while the QNs, MLs, and β-Ls in the Jiulongjiang River came from WWTP effluent.     

The statistical merits of various methods of calculating transfer coefficients between environmental media--development of the ideal formula for data-sets with a log-normal distribution

The statistical treatment of data-sets from environmental pollutant studies in which different measurements are combined to produce averages or comparative factors (e.g., transfer coefficients (TCs), input-output balance values) are considered here, with particular reference to the analysis of data from input-output balance studies of pollutants such as PCBs in animals and humans. Many methods of statistical analysis ignore the fact that all measurements are subject to error, and generally assume that the normal distribution applies to all data-sets, which is commonly inappropriate for environmental (and particularly biological system) data. Considerably different estimations can be obtained by applying different, commonly used, statistical methods, as shown in a simulation study presented here and when applied to data from an input-output balance study of PCBs in humans. Alternative average and combined factor estimators for the treatment of data from these types of studies that give considerable advantages in terms of bias and the ease of assessment of accuracy are proposed.     

Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO₂ at mild conditions (pH 4-9 and 22 °C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg²⁺ or Ca²⁺. Experimental results of TTC indicate that MnO₂ promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO₂ generate little iso-OTC, but occur mainly at the A ring’s dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO₂, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines.     

The profile of antibiotics resistance and integrons of extended-spectrum beta-lactamase producing thermotolerant coliforms isolated from the Yangtze River basin in Chongqing

The spreading of extended-spectrum β-lactamases (ESBL)-producing thermotolerant coliforms (TC) in the water environment is a threat to human health but little is known about ESBL-producing TCs in the Yangtze River. We received 319 ESBL-producing stains obtained from the Chongqing basin and we investigated antibiotic susceptibility, bla gene types and the presence of integrons and gene cassettes. 16.8% of TC isolates were ESBL-producing bacteria and bla_TEM+CTx-M was the predominant ESBL type. 65.2% of isolates contained class 1 integrons, but only 3 carried intI 2. Gene cassettes were amplified and sequenced. aadA, drfA, cmlA, sat1, aar3 and two ORF cassettes were found. In conclusion, Yangtze River is heavily polluted by ESBL-producing TC bacteria and the combined bla gene type could enhance antibiotic resistance. Class 1 integrons were widespread in ESBL-producing isolates and play an important role in multi-drug resistance. Characterization of gene cassettes could reveal the dissemination of antibiotic resistance genes.     

超声波降解四环素类抗生素废水

采用超声波降解模拟废水中四环素类抗生素(TCs):土霉素(OTC)、四环素(TC)和金霉素(CTC),考查废水初始浓度、初始pH、超声波输入功率密度、曝气量和自由基清除剂(正丁醇)对降解效率的影响。结果表明,超声波可以快速高效地降解废水中的TCs,CTC最易被降解,TC和OTC次之;在OTC、TC和CTC初始浓度0.25 mg/L,初始pH=8.2,声功率密度1.2 W/mL,气水体积比30∶1的条件下,超声波辐照20 min后去除率分别达到76.8%、84.0%和94.4%。在实验研究条件下,TCs去除率均随初始浓度(0.25~2.00 mg/L)的增大而降低,但总去除浓度升高;碱性条件有利于TCs降解,去除率随初始pH(6~11)升高而升高;功率密度(0.24~1.96 W/mL)越高,TCs去除率也越高;曝气后TCs的去除率明显升高,随着气水比(10∶1~60∶1)的增大,去除率逐渐上升;正丁醇有效抑制TCs超声波降解,可推断TCs主要降解途径为自由基氧化。TCs超声波降解过程符合伪一级动力学反应特征。     

Responses of sensitive and tolerant bush beans (Phaseolus vulgaris L.) to ozone in open-top chambers are influenced by phenotypic differences, morphological characteristics, and the chamber environment

Responses of bush bean (Phaseolus vulgaris L.) lines 'S156' (O(3)-sensitive) and 'R123' (O(3)-tolerant), and cultivars 'BBL 290' (O(3)-sensitive) and 'BBL 274' (O(3)-tolerant) to ambient ozone (O(3)) were investigated during the 2001 and 2002 growing seasons. Seedlings were grown in pots inside open-top chambers (OTCs), with charcoal filtered (CF) and non-filtered (NF) ambient air, and in non-chambered ambient air (AA) plots. Growth parameters from individual plants were evaluated after harvests at the end of vegetative (V(4)) and reproductive (R(10)) growth phases. Results at V(4) indicated that CF did not provide additional benefits over NF in 'S156' in 2001 and 2002. In contrast, exposure to CF significantly impaired the growth of 'R123'. At the end of R(10), 'S156' produced more pods, most of which remained immature, and contained fewer seeds or were more frequently aborted, whereas pods produced in 'R123' reached pod maturation and senescence more consistently. Despite increased seed weights inside the OTCs, as observed in 'S156', differences between the two lines were insignificant when grown outside OTCs. Results from the 'BBL 290'/'BBL 274' pair, especially at V(4) phase, remained inconclusive. Plant morphological characteristics, variabilities in environmental conditions, and 'chamber effects' inside OTCs were influential in determining plant response to ambient O(3).     

Residues of pharmaceutical products in recycled organic manure produced from sewage sludge and solid waste from livestock and relationship to their fermentation level

In recent years, sludge generated in sewage treatment plants (STPs) and solid waste from livestock being utilized is useful for circulation of nourishment in farmlands as recycled organic manure (ROM). In this study, we determined the residue levels and patterns of 12 pharmaceutical products generated by human activity in the ROMs produced from human waste sludge (HWS), sewage sludge (SS), cattle manure (CM), poultry manure (PM), swine manure (SM) and horse manure (HM).The kind and number of pharmaceutical products detected in ROMs were different. Fluoroquinolones (FQs) were detected at high levels in HWS and SS samples. In addition, the detection frequency and concentration levels of sulfonamides (SAs) in PM and SM were high. Moreover, high concentrations of chlortetracycline (CTC) were found in only SM. These differences reflect specific adherence adsorption of the pharmaceutical products to different livestock and humans. Moreover, it was found that the concentrations of pharmaceutical products and fermentation levels of ROMs had significant positive correlation (r = 0.41, p = 0.024).When the fermentation test of ROM was conducted in a rotary fermentor in a lab scale test, the residue levels of pharmaceutical products decreased effectively except carbamazepine (CBZ). The rates of decrease were in the case of tetracyclines (TCs): 85-92%, FQs: 81-100%, erythromycine: 67%, SAs: 79-95%, trimethoprim: 86% and CBZ: 37% by 30 d. Pharmaceutical products that can be decomposed by fermentation process at the lowest impact of residual antibiotic activities may therefore be considered as environmentally friendly medicines.     

Pollution characteristics of 23 veterinary antibiotics in livestock manure and manure-amended soils in Jiangsu province,China

The aim of this study was to investigate the pollution characteristics of typical veterinary antibiotics in manure and soil of livestock farms in Jiangsu province. This investigation employed solid-phase extraction (SPE) coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). A total of 53 manure and 50 amended soil samples from 16 livestock farms in Jiangsu province were collected for analysis. In the manure samples, the highest detected frequencies and concentrations were those of tetracyclines (TCs, 54.1 ± 5775.6 μgkg^?1), followed by fluoroquinolones (FQs, 8.4 ± 435.6 μgkg^?1), sulphonamides (SAs, 3.2 ± 5.2 μgkg^?1) and macrolides (MACs, 0.4 ± 110.5 μgkg^?1). Statistical analysis was used to illuminate the pollution characteristics of 23 veterinary antibiotics for various animal types and different regions in Jiangsu province. The results showed that the pollution level in cow manure was relatively lower compared with pig and chicken manure due to the relative restriction of medication. Furthermore, contamination was serious in amended soil from chicken farms. The pollution level in manure among different regions was higher to the south and north compared with the centre of the region. The same outcome was found for soil. Antibiotic residues in organic fertilizer were also investigated in this study. We found that although the detected concentration was lower in organic fertilizer than in fresh manure, detection frequencies (10–90%) were high, especially for roxithromycin (90%) in MACs (30–90%). This finding suggests attention should be paid to the pollution levels in organic fertilizer. This study is the first extensive investigation of the occurrence and distribution of many kinds of typical veterinary antibiotics in manure and soil from livestock farms of Jiangsu province. This investigation systematically assesses veterinary antibiotics usage and related emissions in southeast China.     

水环境数学模型的研究进展

在作者多年研究工作和查阅大量文献资料的基础上,本文综述了环境数学模型国内外的研究现状、发展历史及未来趋势。重点介绍了这方面研究的最新进展。该文还介绍了本领域所涉及的理论和实际应用问题,提出了今后值得进行研究的若干前沿课题,给出了60余篇关于水环境数学模型研究的主要参考文献目录。     

Stepwise superposition approach for the analytical solutions of multi-dimensional contaminant transport in finite- and semi-infinite aquifers

Analytical solutions of contaminant transport in multi-dimensional media are significant for theoretical and practical purposes. However, due to the problems for which the solutions are sought which are complex in most of the cases, most available analytical solutions in multi-dimensional media are not given in their closed forms. Integrals are often included in the solution expressions, which may limit the practitioners to use the solutions. In addition, available multi-dimensional solutions for the third-type sources in bounded media are fairly limited. In this paper, a stepwise superposition approach for obtaining approximate multi-dimensional transport solutions is developed. The approach is based on the condition that the one-dimensional solution along the flow direction is known. The solutions are expressed in their closed forms without integrals. The transport media to the solutions are flexible and can be finite, semi-infinite, or infinite in the transverse directions. The solutions subject to the first- and third-type boundary conditions at the inlet with a distributed source over the domain are obtained. The integrals in some known solutions can also be evaluated by the approach if they can be derived to include known longitudinal integrals with respect to time. The accuracy and efficiency of the solutions proposed in this paper are verified through test problems and calculation examples.     

Generation estimation and material flow analysis of retired mobile phones in China

The generation estimation of retired mobile phones is launched with the sales and new method using the revised sales data and amount of the subscribers. Several assumptions have been made due to the insufficient sources of the data. The sales data of legal mobile phones are calculated with the authoritative and continuous official data. The sales data of smuggled and counterfeit mobile phones in China are also estimated based on the behavior data collected from the questionnaires. The results of generation estimation show that there are 636.52 million mobile phones retired in 2020, compared with 14.44 million in 1999 and several negative values in 2000, 2001, and 2008. The annual total mass of retired mobile phones in China escalated with the contributions of both the increasing generation amount and constant mass of the single unit. There are 50,921.60 ton of mobile phones retired in 2020 compared with 1155.20 ton in 1999, while the peak is 58,131.20 ton in 2019. There are 26,066.80 ton of retired mobile phones are stockpiled in 2020, while 16,152.40 ton and 8702.40 ton of retired mobile phones are reused as a whole unit and recycled, respectively. In the retired mobile phones that are recycled, 4600.50 ton material is recovered and 1216.50 ton components are reused, while 2885.40 ton residues need final disposal. The amount and dynamic characteristics of metals in the retired mobile phones are also calculated. Based on the results, several policy implications are made to improve sustainable management system of retired mobile phones in China.

     

Bootstrap estimates of factor model variability

Receptor models for air pollutants in an airshed are constructed from a set of measured concentrations and used for apportioning sources in a quantitative way. Such a dataset even if large is but a sample from the population of pollutants occurring over time in the airshed. Thus the ensuing receptor model and its parameters constitute but one realization of a range of possible experiments. The problem studied in this paper is how large the inherent ranges of variation of the model parameters are, i.e. how reliable the model is. Factor analysis models, where data are autoscaled prior to analysis, were selected for study.Pseudo-repetitions of the experiment are carried out by bootstrapping of the original data and statistics on the model parameters are compiled and reported. The validity of the results of such numerical experiments are based on the assumption that the original data are really representative since by bootstrapping, new artificial data are generated from this set. A number of screening tests for acceptance of data and models are applied to avoid bias and errors in the results. Means and standard deviations of communalities and factor loadings are computed and compared to the original parameters. Regression analysis is used in a search for functional relationships between standard deviations and model parameters.The general conclusion is that well modelled variables carry little model uncertainty and that the largest standard deviations amounting to about 10% are found for loadings in the mid-range.     

空气中多环芳烃的研究现状

本文比较系统地讨论了空气中多环芳烃（ＰＡＨｓ）的研究现状。重点介绍了空气颗粒物及气相中多环芳烃的采样分析新办法，城市大气及居民室内外空气中多环芳烃的污染状况及其来源，简单介绍了人体接触多环芳烃的水平，指标及空气中多环芳烃的健康风险评价的研究概况。共引文献１２９篇。     

水产养殖自身污染及其生物修复技术

介绍了生物修复的概念、水产养殖存在的自身污染问题及其主要生物修复技术。营养物污染、药物污染和底泥富集污染是水产养殖存在的主要自身污染问题；微生物修复、水生植物修复和水生动物修复是污染养殖水域生物修复的3种主要形式；微生物的有效性、生物入侵、二次污染、修复生物的季节性和非水生植物的利用等方面是实施生物修复应注意的主要方面。最后指出，推行清洁生产、实行生态养殖是水产养殖业可持续发展的出路。