抗生素类污染物对硝化污泥的生物抑制

抗生素类物质在生活和生产中的过度使用导致其在水环境中高度残留。做为这类污染物去除的最后屏障,传统污水处理系统不仅对这类物质的去除效果有限,而且可能会对生物处理工程产生影响。本文分别以易溶和不溶于水的四环素类抗生素和磺胺类抗生素为研究对象,研究其对污水处理中硝化过程的生物影响。结果表明,随着两类抗生素浓度的增加,硝化速率迅速降低,且水溶性更好的四环素类物质的生物毒性更大(EC5010 mg/L),较磺胺类抗生素(EC50介于100~200 mg/L)低1个数量级;随着反应时间的延长,抗生素类物质致使硝化污泥胞外聚合物的总量急剧下降,同时,胞外聚合物中DNA和色氨酸的含量明显上升,说明这类物质的存在可能削弱硝化污泥表面形成保护膜,破坏硝化污泥颗粒的完整性,导致絮体解体和细胞破裂,从而影响硝化速率。     

抗生素类污染物对活性污泥生物毒性测定方法的筛选与评价

尽管衡量化学物质生物毒性的标准方法很多,但关于环境中抗生素类污染物的生物毒性及其对污泥活性影响的科学数据较少。以磺胺和四环素两类作用机理和作用谱带不同的抗生素为研究对象,分别用发光细菌法、脱氢酶活性法、生长抑制法及呼吸速率法进行了抗生素类污染物生物毒性测定方法的筛选与评价。结果表明,发光细菌标准方法中30min的作用时间太短,延长作用时间不仅导致各种抗生素的EC50值大幅度降低,同时毒性排列顺序也发生了改变;以活性污泥为对象的脱氢酶活性和呼吸速率抑制实验的EC50值与抗生素类物质对敏感致病菌的MICs相比异常高,不适宜于作为单独方法准确评估抗生素类污染物的生物毒性。生长抑制实验中,活性污泥混合菌种增殖生长对磺胺类抗生素敏感,而假单胞杆菌对四环素类抗生素敏感。不同方法测定抗生素毒性的灵敏度顺序是发光细菌(24 h)>生长抑制(7 h)>呼吸速率(24 h)>脱氢酶活性(24 h)。用标准方法评价抗生素类污染物的生物毒性,可能导致对抗生素排放到水环境中所带来的风险估计不足。     

抗生素发酵制药工程中异味的特征与关键污染物识别

抗生素原料药在生产过程中产生异味污染引发的民众投诉增多,逐渐成为发酵制药企业亟需解决的污染治理难点。以红霉素、四环素和泰乐菌素3种抗生素原料药的发酵生产过程为例,通过采用感官评价、电子鼻、气相离子迁移谱和气相质谱等多手段分析方法,解析发酵过程中产生的异味污染特征。结果表明:3种发酵尾气的气味特征、挥发性物质组分和含量差异较大;尾气中含有的挥发性物质有相同的组分,如乙醇、丙酮、2-戊酮、辛醛和苯甲醛,也各有特异性成分。未经处理的红霉素发酵尾气具有明显的土霉味,且臭气浓度值明显大于四环素和泰乐菌素发酵尾气。气味活度值(OAV)的计算结果表明:2-MIB和土臭素2种萜烯类物质是红霉素发酵最主要的异味污染物;而四环素和泰乐菌素的发酵异味是多种醛等含氧有机物和有机硫化物混合后形成的,因而气味特征较复杂。3种废气中,红霉素发酵尾气具有气量大、异味物质嗅阈值极低的特点,易造成异味污染且影响范围广,去除治理的技术难度也相对更大。本研究通过解析识别不同品种抗生素的发酵异味污染特征,以期为抗生素发酵异味污染治理和环境管理提供参考。     

堆肥对污泥中四环素类抗生素及抗性基因的影响

近年来,抗生素及抗性基因的污染与扩散成为全球关注的热点。污泥,作为污水处理系统的副产物,是环境中抗生素抗性基因的重要存储库。污泥经堆肥后可作为肥料施用于农田,然而关于污泥堆肥过程中抗性基因丰度变化的研究却很少。对污泥堆肥过程中四环素类抗生素(四环素、土霉素和金霉素)和四环素类抗性基因(tet(A),tet(C),tet(M),tet(O)和tet(X))的动态变化进行了定量研究。结果表明,四环素、土霉素和金霉素的浓度经堆肥处理后分别减少85.6%,91.4%和85.3%。高温是导致四环素类抗生素降解的主要因素。经堆肥处理后,tet(A)和tet(X)的相对丰度增加,tet(C)、tet(M)和tet(O)的相对丰度略微下降,说明堆肥处理对污泥中四环素类抗性基因的削减效果有限。     

养猪废水回收MAP时抗生素与重金属的残留

采用磷酸铵镁(MAP)结晶法回收养猪废水中的氮磷,考察了典型兽用抗生素(四环素类、磺胺类和氟诺喹酮类等)和重金属在回收固体中的残留情况。实验结果发现,回收固体中抗生素含量较高,其中四环素类抗生素高于300 mg/kg,磺胺类和氟喹诺酮类抗生素的含量分别为1.86~13.63 mg/kg和5.1~59.1 mg/kg;重金属中Cu、Zn含量较高,浓度分别为96.01和140.34 mg/kg。废水中的SS和腐殖酸是影响养猪废水MAP反应沉淀物中抗生素和重金属含量的主要因素。研究结果表明,养猪废水MAP回收时须考虑产物中抗生素污染的风险。     

水环境中磺胺类抗生素的污染现状与处理技术研究进展

磺胺类抗生素在医药和养殖业中广泛使用,由于难以在环境中降解,其引起的污染问题得到了广泛关注。为了解磺胺类抗生素污染及处理技术,对其使用现状、危害及其在水环境中的迁移状况进行了阐述;介绍了水环境中磺胺类抗生素的处理技术研究现状,比较了各处理技术的优劣,并对今后的研究方向提出展望。     

不同生物炭对猪粪堆肥过程中抗生素及抗生素抗性基因的削减规律研究

为探讨不同类型生物炭对猪粪堆肥过程中抗生素和抗生素抗性基因(ARGs)的削减规律,分别将玉米秸秆生物炭、竹炭和猪粪生物炭添加到猪粪中进行好氧堆肥,解析不同类型生物炭添加对猪粪堆肥过程中抗生素浓度和ARGs丰度的影响.研究发现,添加竹炭堆肥对抗生素的平均去除率最高(97％),其中对四环素类抗生素的去除率高达98％;添加玉...     

黑麦草对土壤中残留抗生素的降解及其对微生物活性的影响

为了研究抗生素污染土壤的修复方法,利用黑麦草对土壤中残留抗生素进行降解,并探讨土壤微生物生态活性及根系体表特征的响应。结果表明:黑麦草对土壤中四环素、金霉素、恩诺沙星、洛美沙星、环丙沙星、诺氟沙星的降解速率均显著大于对照(p0.05)。黑麦草对四环素类抗生素的降解率为19.1%~27.7%,其中金霉素的降解率最高,为11.4%~27.7%;而磺胺类中的磺胺二甲基嘧啶的降解率最低,仅为3.4%~8.3%;喹诺酮类的降解率为15.3%~28.8%,其中洛美沙星、恩诺沙星的降解率分别为15.3%~28.8%、14.2%~28.0%。同时,种植黑麦草缓解了抗生素对土壤微生物活性的抑制作用,在种植黑麦草的土壤中,微生物的呼吸强度和氨化强度分别是未种植黑麦草土壤的4.5和1.9倍。另外,植物根系的生长与土壤中抗生素的残留量有一定的相关性,黑麦草根系总表面积与土壤抗生素总残留量呈显著负相关关系(r=-0.948,p0.05)。     

吸附法净化低浓度废气实验研究

本文探讨了用活性炭吸附低浓度苯类废气时,空塔气速和气流在吸附层的接触时间对吸附过程的影响;研究了活性炭在已经吸附若干质量的苯类物质以后的吸附性能.据此绘制了空塔气建-吸附效率和活性炭含苯率-吸附效率等关系曲线,并进行了活性炭再生的研究.研究表明:使用活性炭可以有效地净化低浓度苯类废气.     

天然及CaCl_2改性沸石对四环素的吸附

通过静态吸附实验研究了水中四环素在天然和CaCl2改性沸石上的吸附行为及机制。实验表明,天然沸石对四环素具有吸附能力,CaCl2改性可以提高沸石对四环素的吸附能力。天然和改性沸石对四环素的吸附符合拟二级动力学模型,颗粒内扩散不是吸附过程的主要控制步骤。Freundlich和Dubinin-Radushkevich（D-R）等温吸附模型可以较好地描述实验所用2种沸石对四环素的吸附行为,D-R等温方程拟合结果显示吸附过程包含离子交换作用。通过对天然和改性沸石吸附四环素前后溶液中主要阳离子浓度变化分析证实了该吸附过程包含离子交换作用。实验研究了pH值变化对沸石吸附四环素的影响,当pH=3～5时,天然和改性沸石对四环素的吸附量均随pH值的增加而急剧下降,而pH=5～10时,天然和改性沸石对四环素的吸附量变化均不明显,推测可能是离子交换作用和化学沉淀吸附作用所致。另外,实验还初步探索了溶液离子强度对沸石吸附四环素的影响情况,随着溶液中Na＋和Ca2＋离子强度的增加,吸附量先急剧降低随后趋向平稳,进一步说明了沸石对四环素的吸附过程不是由单一机制控制的。     

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.     

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.     

Pollution characteristics and environmental risk assessment of typical veterinary antibiotics in livestock farms in Southeastern China

Scientific interest in pollution from antibiotics in animal husbandry has increased during recent years. However, there have been few studies on the vertical exposure characteristics of typical veterinary antibiotics in different exposure matrices from different livestock farms. This study explores the distribution and migration of antibiotics from feed to manure, from manure to soil, and from soil to vegetables, by investigating the exposure level of typical antibiotics in feed, manure, soil, vegetables, water, fish, and pork in livestock farms. A screening environmental risk assessment was conducted to identify the hazardous potential of veterinary antibiotics from livestock farms in southeast China. The results show that adding antibiotics to drinking water as well as the excessive use of antibiotic feed additives may become the major source of antibiotics pollution in livestock farms. Physical and chemical properties significantly affect the distribution and migration of various antibiotics from manure to soil and from soil to plant. Simple migration models can predict the accumulation of antibiotics in soil and plants. The environmental risk assessment results show that more attention should be paid to the terrestrial eco-risk of sulfadiazine, sulfamethazine, sulfamethoxazole, tetracycline, oxytetracycline, chlorotetracycline, ciprofloxacin, and enrofloxacin, and to the aquatic eco-risk of chlorotetracycline, ciprofloxacin, and enrofloxacin. This is the first systematic analysis of the vertical pollution characteristics of typical veterinary antibiotics in livestock farms in southeast China. It also identifies the ecological and human health risk of veterinary antibiotics.     

Doped graphitic carbon nitride (g-C3N4) catalysts for efficient photodegradation of tetracycline antibiotics in aquatic environments

Environmental Science and Pollution Research - Tetracyclines (TCs) antibiotics are very common and often used in both human and veterinary medicines. More than 75% of TCs are excreted in an active...     

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.     

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.     

Adsorption behaviours and transfer simulation of levofloxacin in silty clay

Fluoroquinolone antibiotics in soil can cause serious antibiotic pollution. Adsorption is the main factor that influences their destination and transport of antibiotics. Therefore, research on the behaviour of antibiotics once they reach the soil environment is meaningful to design appropriate measures to reduce their potential risks. This research took levofloxacin (LVFX) as the research object and used a static adsorption experiment to study the adsorption behaviour of the vadose zone of silty clay on the North China Plain. The results showed that LVFX had high retention in silty clay, with an average adsorption ratio of more than 90%. Adsorption of LVFX on silty clay reached equilibrium in 24 h with an adsorption amount of 93.5 mg/kg at an initial LVFX concentration of 10 mg/L. Acidity, cations and soil organic matter could affect the adsorption of LVFX, with adsorption variation ratio of 3.3%, 3.4% and 0.6%, respectively. In addition, numerical simulation with Hydrus-1D was utilized, and the results show that LVFX may infiltrate into underground water through silty clay after 28 days and completely penetrate in 100 days.

     

Column studies to investigate the fate of veterinary antibiotics in clay soils following slurry application to agricultural land

The environment may be exposed to veterinary medicines administered to livestock due to the application of organic fertilisers to land. For other groups of substances that are applied to agricultural land (e.g. pesticides), preferential flow in underdrained clay soils has been identified as an extremely important pathway by which pollution of surface waters can occur. Three soil column leaching experiments have therefore been carried out using a clay soil to investigate the fate of a range of antibiotics from the sulphonamide, tetracycline and macrolide groups. These column studies complemented a range of other experiments at the field and semi-field scales, as well as modelling studies which are being reported in separate papers. Each column study had a different objective. The first examined the effect of pig slurry on the mobility of antibiotics in clay loam soil. The second experiment investigated changes in soil water pH due to the application of slurry. The final experiment quantified the extent to which soil tillage prior to slurry application can reduce the leaching of antibiotic residues found in slurry. It was found that slurry had no impact on the leaching of oxytetracycline although soil water pH was affected significantly by slurry application. It was also shown that pre-tillage can substantially reduce the leaching of antibiotic residues through macroporous clay soils.     

Earthworm biomass as additional information for risk assessment of heavy metal biomagnification: a case study for dredged sediment-derived soils and polluted floodplain soils

The important role of earthworms in the biomagnification of heavy metals in terrestrial ecosystems is widely recognised. Differences in earthworm biomass between sites is mostly not accounted for in ecological risk assessment. These differences may be large depending on soil properties and pollution status. A survey of earthworm biomass and colonisation rate was carried out on dredged sediment-derived soils (DSDS). Results were compared with observations for the surrounding alluvial plains. Mainly grain size distribution and time since disposal determined earthworm biomass on DSDS, while soil pollution status of the DSDS was of lesser importance. Highest earthworm biomass was observed on sandy loam DSDS disposed at least 40 years ago.