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.     

Chemical compositions and sources of atmospheric PM10 in heating, non-heating and sand periods at a coal-based city in northeastern China

Mass concentrations and chemical components (18 elements, 9 ions, organic carbon [OC] and elemental carbon [EC]) in atmospheric PM(10) were measured at five sites in Fushun during heating, non-heating and sand periods in 2006-2007. PM(10) mass concentrations varied from 62.0 to 226.3 μg m(-3), with 21% of the total samples' mass concentrations exceeding the Chinese national secondary standard value of 150 μg m(-3), mainly concentrated in heating and sand periods. Crustal elements, trace elements, water-soluble ions, OC and EC represented 20-47%, 2-9%, 13-34%, 15-34% and 13-25% of the particulate matter mass concentrations, respectively. OC and crustal elements exhibited the highest mass percentages, at 27-34% and 30-47% during heating and sand period. Local agricultural residuals burning may contribute to EC and ion concentrations, as shown by ion temporal variation and OC and EC correlation analysis. Heavy metals (Cr, Ni, Zn, Cu and Mn) from coal combustion and industrial processes should be paid attention to in heating and sand periods. The anion/cation ratios exhibited their highest values for the background site with the influence of stationary sources on its upper wind direction during the sand period. Secondary organic carbon were 1.6-21.7, 1.5-23.0, 0.4-17.0, 0.2-33.0 and 0.2-21.1 μg m(-3), accounting for 20-77%, 44-88%, 4-77%, 8-69% and 4-73% of OC for the five sampling sites ZQ, DZ, XH, WH and SK, respectively. From the temporal and spatial variation analysis of major species, coal combustion, agricultural residual burning and industrial emission including dust re-suspended from raw material storage piles were important sources for atmospheric PM(10) in Fushun at heating, non-heating and sand periods, respectively. It was confirmed by principal component analysis that coal combustion, vehicle emission, industrial activities, soil dust, cement and construction dust and biomass burning were the main sources for PM(10) in this coal-based city.     

废弃SCR脱硝催化剂的再生及其脱硝性能研究

对废弃脱硝催化剂处理后重新加工再生,研究了添加剂对其粉体成型和再生催化剂脱硝活性的影响,探讨了反应温度、空速、n(NH3)∶n(NO)摩尔比、氧含量、H2O和SO2对再生催化剂NH3选择性催化还原(SCR)NO的影响。结果表明:最佳再生条件是使用5%羧甲基纤维素和10%无机粘结剂辅助成型;废弃催化剂再生利用率高达90%;再生催化剂抗压强度为4.73 MPa,优于商用催化剂;空速5 000 h-1、氨氮摩尔比1、氧含量6%时,脱硝活性温度窗口为310⁴50℃,350℃时活性最高为94%;350℃时,单独通入1 000×10-6SO2或10%H2O对再生催化剂活性均有一定抑制作用,最低活性分别为70%和81%,停止通入SO2或H2O后其活性逐渐恢复;同时通入1 000×10-6SO2和10%H2O,再生催化剂活性下降至63%并于1 h内保持相对稳定,停止通入SO2和H2O 2 h后,活性逐渐恢复到73%。     

三槽氧化沟内底推位置与积泥厚度的分析研究

氧化沟工艺由于进水中含有大量的无机颗粒,无机颗粒的沉淀导致沟内积泥较厚。为了不影响正常生产,依据经验数据,依次对1号、2号氧化沟安装底推。对沟内积泥情况及影响因素进行分析比较,得出氧化沟的积泥主要由进水中密度较大的无机颗粒造成,且积泥规律与底推安装位置和运行情况相关。     

明胶厂剩余高钙污泥作为燃煤固硫剂的应用研究

明胶生产产业在废水处理工艺中产生大量剩余高钙污泥,采用该剩余污泥作为燃煤固硫剂,在高温管式电阻炉内进行燃烧实验,通过测定燃烧前和燃烧后样品中的硫含量确定该剩余污泥的固硫效果。通过单因素研究煤粉粒径、剩余污泥粒径和剩余污泥/煤样%等影响因素对固硫率的影响。在单因素试验的基础上通过正交设计法优选达到较高固硫率的实验条件。实验结果表明:影响固硫率的因素从大到小依次为燃烧温度>剩余污泥/煤样%>煤粉粒径>剩余污泥粒径。以剩余污泥作为固硫剂,固硫率最高的实验条件为:燃烧温度800℃,剩余污泥/煤样为3%,煤粉粒径60⁹0目,剩余污泥粒径9090目,剩余污泥粒径90¹20目。并且,当温度达到1150℃,煤粉粒径90120目。并且,当温度达到1150℃,煤粉粒径90¹20目,剩余污泥粒径为60120目,剩余污泥粒径为60⁹0目,污泥/煤样(质量比)为3%时,固硫率可达62.78%,说明在高温下该剩余污泥保持较高的固硫率。将明胶厂剩余污泥作为固硫剂是较为合适的再利用方法,可有效缓解当前该污泥大量堆积污染环境的状况。     

Formation of THMs and HANs during bromination of Microcystis aeruginosa

Bromine-contained disinfectants and biocides are widely used in swimming pools, recreational waters and cooling towers. The objective of this study was to evaluate the formation of thrihalomethanes (THMs) and haloacetonitriles (HANs) and their cytotoxicity in algae solutions during free bromine disinfection. Disinfection by-products formation potential experiments were conducted using model solutions containing 7 mg/L (as total organic carbon) Microcystis aeruginosa cells. Effects of free bromine dosage, pH and ammonia were investigated. The results showed that brominated disinfection by-products were the major products when free bromine was applied. The total THMs formed during bromination was much as that formed during chlorination, whereas HANs were elevated by using bromination instead of chlorination. Dibromoacetonitrice (C2H2NBr2 ) and bromoform (CHBr3 ) were the only detected species during free bromine disinfection. The production of C2H2NBr2 and CHBr 3 increased with disinfectant dosage but decreased with dosing ammonia. CHBr3 increased with the pH changing from 5 to 9. However, C2H2NBr2 achieved the highest production at neutral pH, which was due to a joint effect of variation in hydrolysis rate and free bromine reactivity. The hydrolysis of C2H2NBr2 was base-catalytic and nearly unaffected by disinfectant. Finally, estimation of cytotoxicity of the disinfected algae solutions showed that HANs formation was responsible for the majority of toxicity. Considering its highest toxicity among the measured disinfection by-products, the elevated C2H2NBr2 should be considered when using bromine-related algaecide.     

锦州市近十年降水现状调查分析

根据锦州市环境监测中心站的大气资料,通过对其3个采样点,从2001年到2010年共10年的监测数据进行综合分析,结果表明锦州地区酸雨多出现在5、6、7月,以SO42-、NO3-和NH4+、Ca2+为主要污染离子,体现了大气降水煤烟型污染的特点。通过对数据的综合分析,研究锦州市降水现状及发展变化趋势,分析了酸雨的成因并提出了酸雨控制的对策。     

哈尔滨大气中PAHs的污染源解析

通过将比值法、主成分分析和正定矩阵分析法相结合对大气中PAHs的污染源进行了解析,结果表明,煤的燃烧和汽车尾气的排放是PAHs的主要污染源,冬季,煤的燃烧是主要污染源,其贡献率为60.6%,其次为汽车尾气排放(34.4%),其他季节,汽车尾气的排放和燃煤污染是主要的污染源,其贡献率分别为59.3%和17.1%。通过等效毒性当量因子计算得到,哈尔滨大气中BaP当量浓度冬季为7.751 9 ng/m3,其他季节为0.688 6 ng/m3,均符合中国规定的10 ng/m3。     

Antioxidant responses to benzo[a]pyrene, tributyltin and their mixture in the spleen of Sebasticus marmoratus

It has been reported that there is an interaction between Benzo[a]pyrene （BaP）, a widespread carcinogenic polycyclic aromatic hydrocarbon, and tributyltin （TBT）, an organometal used as an antifouling biocide. This study was therefore designed to examine the potential in vivo influence of BaP, TBT and their mixture on splenic antioxidant defense systems of Sebastiscus marmoratus. The fish were exposed to water containing environmentally relevant concentrations of BaP, TBT and their mixture. Spleens were collected for biochemical analysis after exposure for 7, 25, 50 d and after recovery for 7, 20 d. Cotreatment with BaP and TBT for 7 d potentiated the induction of glutathione peroxidase （GPx） activity by BaP or TBT alone. The cotreatment for 25 and 50 d resulted in inhibition of GPx activity, which was similar to the effect of TBT. Splenic glutathione S-transferase （GST） activities were significantly elevated in S. marmoratus exposed to BaP starting from 7 d and remained high up to 25 d. However, no further activity change was found with prolonged exposure. Cotreatment of BaP and TBT primarily inhibited the GST activity, which was similar to the effect of TBT. Cotreatment with BaP and TBT for 25 or 50 d potentiated the depletion of GSH （glutathione） by BaP or TBT alone. MDA （malondialdehyde） contents in spleen of S. marmoratus were not significantly altered compared with the control during the test period. Spleen, as an immune organ, is sensitive to exposure of BaP or TBT. It should have an effective mechanism to counteract oxidative damage. Antioxidative defense systems in spleen of S. marmoratus should be considered as potential biomarkers. Short-term exposure of BaP or TBT could result in induction of antioxidant defense system. A significant decrease of these indices, such as GSH, GST, GPx might indicate more severe contamination.     

Effect of nutrient conditions on the toxicity of naphthalene to Chlorella pyrenoidosa

The toxicity of naphthalene to a freshwater microalga, Chlorella pyrenoidosa, and the subsequent recovery of algae from the damage were investigated under two nutrient conditions, either enriched with nitrogen (N) and phosphorus (P), or starved of N and P. Results showed that C. pyrenoidosa was more sensitive to naphthalene under N,P-enriched condition, and the inhibitory rate generally increased at first and then decreased gradually with the evaporation of naphthalene under both nutrient conditions. Enriched N, P reduced the inhibitory rate at initial naphthalene concentration of 5 and 10 mg/L, but enhanced it at 100 mg/L, at which more severe ultrastructure damages were found than those under N,P-starved condition. Observed damages included partly or totally disappearance of nucleolus, nuclear, and plasma membranes. According to the chlorophyll content and cell density measurements, C. pyrenoidosa could recover from naphthalene damage with initial concentrations 6 50 mg/L in 7 days under both nutrient conditions, while they could not recover if the initial concentration of naphthalene was at 100 mg/L. Under the N,P-starved condition, the inability of C. pyrenoidosa to recover from the naphthalene damage was consistent with the results of high inhibitory rate, low value of specific growth rate (SGR, 0.05 day??1), and the severe destruction of cell structure. However, under the N,P-enriched conditions, the observed lower inhibitory rate, higher value of SGR (0.55 day??1), and the intact cell structure of most cells suggested that algae could potentially recover from the naphthalene damage.