抗生素制药废水有机污染物分布特性研究

采用气相色谱/质谱法对β-内酰胺类抗生素制药废水中有机污染物进行了定性与定量分析,得到了废水中有机污染物的种类、相对含量及分子量分布特性.通过理论COD计算公式,计算分析了废水中有机污染物对COD指标的贡献程度.结果表明,该类废水中含有84种有机物,其中以胺类、烷烃类和烯烃类有机物的相对含量最高.有机污染物的分子量集中在100～400,分子量小于100或大于500的有机物含量相对较低,其中分子量在100～200的有机物含量最大.通过对比有机污染物的理论COD贡献度可知,胺类、烷烃类和烯烃类有机物含量对废水污染负荷影响最大.根据有机物污染源分析,提出了此类抗生素制药废水合理化处理的生产工艺建议和处理工艺方案.     

454焦磷酸测序技术分析A+OSA污泥减量工艺真核生物特征

以缺氧-好氧(AO)工艺为参照,利用454焦磷酸测序技术研究了缺氧-好氧-沉淀-厌氧(A+ OSA)污泥减量工艺真核生物分布特征.实验结果表明,A+ OSA污泥减量工艺真核生物丰富度与多样性均低于AO参照工艺,两工艺主要真核生物门为环节动物门Annelida,纤毛虫门Intramacronucleata和SAR超类群(不等鞭毛生物Stramenopiles,囊泡虫Alveolates,有孔虫Rhizaria),Annelida及SAR相对含量在减量工艺中明显减低.纲水平分类结果表明,前口纲Prostomatea在减量工艺中消失,寡膜纲Oligohymenophorea在减量工艺贮泥池中成为优势真核生物.A+OSA污泥减量工艺贮泥池中选择性富集真核生物Oligohymenophorea表明微型生物捕食作用存在该工艺中,对减量工艺的污泥减量具有贡献.     

催化氧化还原吸收法脱除工业含湿废气中NOx

基于精细化工、制药行业排出 NOx 废气氧化度低、氧气含量高的特点,提出以改性活性炭(MAC)为催化剂的催化氧化-还原吸收脱除 NOx 的方法.考察了相对湿度、氧化温度、氧化时间对 NO 催化氧化以及还原液种类对 NOx 吸收的影响.结果表明,随着相对湿度的增加 NO 转化率急剧下降,但随着氧化时间的延长有所提高;干气条件下,随着温度升高,NO 转化率下降;湿气条件下,NO 氧化反应最佳反应温度范围为 50～70℃,实验条件下的 NO 最高转化率可达 51%;还原液种类中以尿素-碱液对 NOx 和 NO 的吸收效果最好,亚硫酸铵-碱液对 NOx 的吸收效果最好.通过催化氧化-还原吸收的多级组合可实现 NOx 的有效脱除与达标排放.     

不同Cd2+浓度与硝酸盐浓度、磷酸盐浓度交互作用对杜氏盐藻生长及叶绿素荧光特性的影响

研究了不同Cd2+浓度与硝酸盐浓度、磷酸盐浓度交互作用对杜氏盐藻(Dunaliella salina)生长及叶绿素荧光特性的影响.结果表明,Cd2+浓度与硝酸盐浓度、磷酸盐浓度对杜氏盐藻的光合作用及生长均具有显著影响(P＜0.05);Cd2+胁迫24 h后,杜氏盐藻的荧光参数Fv/Fm、Fv/Fo、Yield、rETR、细胞密度和叶绿素相对含量均与Cd2+浓度表现为显著的负相关;在低硝酸盐摩尔浓度(55μmol/L)下,杜氏盐藻的荧光参数Fv/Fm、Fv/F.、Yield、rETR、细胞密度和叶绿素相对含量均明显下降;在高硝酸盐摩尔浓度(7 040 μmol/L)下,杜氏盐藻的上述荧光参数下降幅度小;在正常硝酸盐摩尔浓度(880 μmol/L)下,杜氏盐藻荧光参数Fv/Fo、NPQ和叶绿素相对含量均最高,对Cd2+的耐受性更强;在低磷酸盐摩尔浓度(2.27 μmol/L)下,杜氏盐藻的荧光参数(除NPQ外)、细胞密度和叶绿素相对含量均显著低于对照组和高磷处理组,表现为磷限制现象;在离磷酸盐摩尔浓度(290.40 μmol/L)下,杜氏盐藻的荧光参数(除NPQ外)、细胞密度和叶绿素相对含量均明显高于低磷处理组和对照组,杜氏盐藻受Cd2+胁迫程度最小.     

活性炭浓集、原子吸收分光光度法测定水中ppb级金属含量

前言 人们在环境污染6开究初期,主要关心的是含量相对较多的污染物。随着对污染效应(无机和有机污染物恶化水体环境,毒害水生物及人体健康的影响过程及后果)认识的不断深入,人们注意力日益转向水中的微量及痕量污染物,目前所关心的含量浓度已从PPm(10~(-6))级降低到PPb(10~(-9))级以至     

湿热处理餐厨废弃物不饱和脂肪酸

为了研究湿热水解技术对餐厨废弃物中脂类物质的影响,促进餐厨废弃物的资源化处理利用,通过实验研究,分析了餐厨废弃物固相中油酸、亚油酸、α-亚麻酸和花生四烯酸4种不饱和脂肪酸在90～140℃湿热条件下处理随时间的变化规律。结果表明：实验所取餐厨废弃物经湿热处理后固相中油酸和亚油酸的含量相对较高,约为30％,花生四烯酸的含量较低,约为0．3％,随着加热时间延长,亚油酸在湿热环境下发生化学分解,其含量不断降低,而花生四烯酸的含量显著增加。当加热温度为100～120℃,加热时间为30-60min时,餐厨废弃物脂类含量比较稳定,作为适宜的湿热处理条件。值得注意的是,湿热处理后的餐厨废弃物中花生四烯酸的含量只约为0．3％,不能满足饲料标准中2％的要求。     

三垟湿地沉积物-间隙水-上覆水界面磷形态研究

沉积物与上覆水间营养物质交换,成为导致水体发生富营养化的首要化学变迁过程.分别在三垟湿地的柑橘林(S1)、景观用地(S2)和生活用地(S3)取样,研究了沉积物-间隙水-上覆水界面磷形态以及相互关系.结果表明:(1)沉积物TP增加时,间隙水PO3-4和可溶性总磷(TDP)也增加.要削减磷在上覆水中的含量,控制间隙水PO3-4或TDP是一良策.(2)随着沉积物铁磷、铝磷的增加,间隙水PO3-4也增加.在三垟湿地沉积物中,铁磷和铝磷含量都可作为间隙水PO34-含量的指示.(3)S1、S2和S3的沉积物活性磷、间隙水TDP和上覆水TDP存在明显的浓度梯度,沉积物活性磷＞间隙水TDP＞上覆水TDP.说明在三垟湿地中,沉积物活性磷是磷释放的关键因子,而沉积物-间隙水界面则是磷释放的关键界面.     

高效液相色谱法测定南昌市环境空气PM10中16种多环芳烃

建立了以二极管阵列检测器和荧光检测器串联的高效液相色谱分析方法,在标样未完全分离的情况下,采用双激发波长有效地改善了色谱分离条件.在设定的色谱条件下,各种多环芳烃(PAHs)的检出限为0.11～39.83μg/L,平均回收率为76.7%～98.3%,相对标准偏差为3.6%～12.6%.在南昌市布设4个环境空气采样点,测定PM10中PAHs含量.结果表明,八一广场、南昌市区二中老校区和罗家集区苯并(a)芘日均质量浓度最大值均超过<环境空气质量标准>(GB 3095-1996)的限值,PAHs污染状况较严重.     

添加造纸污泥对土壤-白萝卜系统中镉迁移的影响

采用盆栽实验方法研究了红壤、紫色土母质发育的水稻土(红壤、紫色土)添加不同量的造纸污泥对土壤-白萝卜系统Cd迁移的影响。结果表明:添加造纸污泥能提高土壤的pH、有机质、N、CEC,降低紫色土有效态Cd含量;添加造纸污泥显著降低了白萝卜叶、地下茎中Cd含量,显著降低土壤-白萝卜系统中Cd的转运系数及富集系数;Cd的转运系数和富集系数与土壤pH、有机质存在显著负相关关系;红壤和紫色土中造纸污泥最适添加量分别为5%、10%时,白萝卜根茎中Cd含量以及Cd的转运系数和富集系数可达到相对最低值。造纸污泥农用能够在一定程度上降低重金属有效性,阻止其在土壤-作物系统中的迁移,可以为造纸污泥资源化和安全利用提供新途径。     

矿化垃圾和绿色植物废弃物对盐碱土的改良效果

利用矿化垃圾和绿色植物废弃物在上海临港新城进行盐碱土现场改良试验,并监测不同处理土壤溶液中重金属元素浓度.结果表明:(1)在盐碱土中分别加入矿化垃圾、绿色植物废弃物或2者混合加入能明显降低盐碱土的盐分,提高土壤的肥力,达到改良盐碱土的目的.(2)各处理土壤溶液中重金属变化趋势基本一致:Cu浓度低于<地下水质量标准>(GB/T 14848-93)中Ⅲ类标准,Cr浓度均在GB/T 14848-93中Ⅳ类标准内,不存在Cu和Cr污染可能;个别点土壤溶液中偶尔出现Zn和Pb浓度超过GB/T 14848-93中Ⅴ类标准,大部分基本在GB/T 14848-93中Ⅳ类标准内;Cd、Fe和Mn浓度相对较高,是造成地下水潜在污染的原因,要注意合理控制.(3)不同处理会影响矿化垃圾中重金属的溢出,会使一部分重金属向下迁移,但总体对地下水质影响不大,且100 cm处各种重金属元素的平均浓度均没有超过GB/T 14848-93中Ⅳ类标准.(4)矿化垃圾中加入绿色植物废弃物处理的污染综合指数较小,主要是由于绿色植物废弃物重金属元素浓度相对较低、有机质含量高,和矿化垃圾混合使用能降低矿化垃圾潜在污染的风险.     

Vapour pressures, aqueous solubilities, Henry's law constants, partition coefficients between gas/water (Kgw), n-octanol/water (Kow) and gas/n-octanol (Kgo) of 106 polychlorinated diphenyl ethers (PCDE)

Modelling the environmental fate of persistent organic pollutants like polychlorinated diphenyl ethers (PCDE) requires the knowledge of a number of fundamental physico-chemical properties of these compounds. We report here the physico-chemical properties of 106 PCDEs, which are over 50% of all possible congeners. Vapour pressures P(OL), water solubilities S(H2O), and n-octanol/water partition coefficients K(OW) were determined with chromatographic methods. With these experimental data the Henry's law constants H, gas/water K(GW) and gas/n-octanol K(GO) partition coefficients were calculated. Vapour pressures and water solubilities and n-octanol/water partition coefficients of the PCDEs are close to those of similar groups of organochlorine compounds like polychlorinated biphenyls (PCBs) and dibenzofurans (PCDFs). A similar environmental fate can be predicted and was partially already been observed.     

Dibenzothiophene oxidation by horseradish peroxidase in organic media: effect of the DBT:H2O2 molar ratio and H2O2 addition mode

Its is well known that in the biodesulfurization (BDS) process the low water solubility of sulfur compounds hinders its transference from the oil phase to the cells being the rate-limiting step in the metabolism of dibenzothiophenes (DBT). Thus sulfur compounds derivatives with high water solubility could be more easily transported increasing the BDS efficiency. The present work performed a stepwise evaluation of the enzymatic oxidation of DBT by horseradish peroxidase (HRP). Reactions were carried out in monophasic organic media containing 25% (v/v) acetonitrile. The following parameters were evaluated: DBT:H2O2 molar ratio (1:1-1:20); H2O2 addition mode (single or stepwise); pH (6.0-8.0) and temperature (37-50 degrees C). Best results were observed in a reaction medium at pH 8.0 presenting HRP 0.06IUml(-1), DBT 0.267mM, DBT:H2O2 molar ratio of 1:20 (stepwise hydrogen peroxide addition) and incubated at 45 degrees C for 60min. Under these conditions 60% of DBT was converted into dibenzothiophene sulfoxide (12%) and dibenzothiophene sulfone (46%). The DBT oxidation rate observed in this work, of 5mmolmin(-1)g(-1) of HRP, was 250-fold higher than the BDS rate, 20mumolmin(-1)g(-1) of catalyst. As such a combined enzyme-microbial desulfurization process could be envisaged. Products were determined by HPLC RP C-18.     

Physicochemical properties of selected polybrominated diphenyl ethers and extension of the UNIFAC model to brominated aromatic compounds

The aqueous solubilities (S(w)) at various temperatures from 283 K to 308 K and 1-octanol/water partition coefficients (K(ow)) for four polybrominated diphenyl ethers (PBDEs: 4,4'-dibromodiphenyl ether (BDE-15), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153)) were measured by the generator column method. The S(w) and K(ow) data revealed the effect of bromine substitution and basic structure on S(w) and K(ow). To estimate the infinite dilution activity coefficients (gamma(i)(w,infinity)) of the PBDEs in water from the S(w) data, enthalpies of fusion and melting points for those compounds were measured with a differential scanning calorimeter. Henry's Law constants (H(w)) of the PBDEs were derived from the determined gamma(i)(w,infinity) and literature vapor pressure data. Some physicochemical characteristics of PBDEs were also suggested by comparing the present property data with that of polychlorinated dibenzo-p-dioxins, brominated phenols and brominated benzenes in past studies. Furthermore, in order to represent different phase equilibria including solubility and partition equilibrium for other brominated aromatic compounds using the UNIFAC model, a pair of UNIFAC group interaction parameters between the bromine and water group were determined from the S(w) and K(ow) data of PBDEs and brominated benzenes. The ability of the determined parameters to represent both properties of brominated aromatics was evaluated.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'(W)) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb(T)) in pure water. Experimental breakthrough volumes (Vb(E)) were first determined using purified and deionized water as the matrix for selected compounds having Vb(T) < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4-5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb(E) curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5-6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb(E) in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

Formation of PFOA from 8:2 FTOH in closed-bottle experiments with brackish water

The formation of perfluorooctanoate (PFOA) from 1H,1H,2H,2H-perfluorodecanol (8:2 FTOH) was studied for the first time in laboratory experiments with brackish water. The water samples were collected from the Baltic Sea, which is one of the largest brackish water areas in the world and is polluted with PFOA and other perfluorinated compounds. The formation of PFOA was studied in closed-bottle experiments at different water temperatures. As a reference experiment, a modified OECD 310 test was conducted with sludge from a wastewater treatment plant and with brackish water. The PFOA and 8:2 FTOH were concentrated from water samples by solid-phase extraction (SPE) and were analysed using liquid chromatography–mass spectrometry. The effect of oxygen concentration on the formation of PFOA was studied using surface water samples with high and low oxygen contents. Other experiments were performed with oxygen-rich surface water and oxygen-deficient bottom water. The formation of PFOA was observed in all experiments; it was higher in the trial performed with brackish water than in the reference test carried out with sludge. Clear temperature dependence was observed in the formation of PFOA in brackish water tests; after a 30-day test period, a sixfold increase was observed in the amount of PFOA in surface water between the temperatures of 15 and 20 °C. Microbes were suggested as the major cause of the formation of PFOA, but other environmental characteristics, such as oxygen, could also affect the formation potential of PFOA.     

Biological assessment of bisphenol A degradation in water following direct photolysis and UV advanced oxidation

Endocrine disrupting compounds (EDCs) are exogenous environmental chemicals that can interfere with normal hormone function and present a potential threat to both environmental and human health. The fate, distribution and degradation of EDCs is a subject of considerable investigation. To date, several studies have demonstrated that conventional water treatment processes are ineffective for removal of most EDCs and in some instances produce multiple unknown transformation products. In this study we have investigated the use of direct photolysis with low-pressure (LP) Hg UV lamps and UV+hydrogen peroxide (H(2)O(2)) advanced oxidation process (AOP) for the degradation of a prototypic endocrine disrupter, bisphenol A (BPA), in laboratory water. Removal rates of BPA and formation of degradation products were determined by high performance liquid chromatography (HPLC) analysis. Changes in estrogenic activity were evaluated using both in vitro yeast estrogen screen (YES) and in vivo vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). Our results demonstrate that UV alone did not effectively degrade BPA. However, UV in combination with H(2)O(2) significantly removed BPA parent compound and aqueous estrogenic activity in vitro and in vivo. Removal rates of in vivo estrogenic activity were significantly lower than those observed in vitro, demonstrating differential sensitivities of these bioassays and that certain UV/AOP metabolites may retain estrogenic activity. Furthermore, the UV/H(2)O(2) AOP was effective for reducing larval lethality in treated BPA solutions, suggesting BPA degradation occurred and that the degradation process did not result in the production of acutely toxic intermediates.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'_W) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb_T) in pure water. Experimental breakthrough volumes (Vb_E) were first determined using purified and deionized water as the matrix for selected compounds having Vb_T < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4–5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb_E curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5–6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb_E in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

A review of Henry's law coefficients for chlorine-containing C1 and C2 hydrocarbons

Experimentally determined Henry's law coefficients of 18 chlorinated C(1) and C(2) hydrocarbons reported in the literature as a function of temperature and at the single temperatures 20 and 25 degrees C were compiled and converted to common units of concentration and pressure: K(H) (moldm(-3)atm(-1)). The individual values are plotted in the ln(K(H)) versus reciprocal absolute temperature coordinate frame, data not in harmony with others were deleted, and the resulting data sets treated by linear regression analysis to derive averaged parameters in the general equation ln(K(H))=A+B/T. The quality of the evaluation was further checked by comparison of values calculated from the resulting parameter values with averages obtained from the direct measurements at 20 degrees C. Good agreement was observed for 15 compounds, larger discrepancies arise only for chloroethane, 1,2-dichloroethane and hexachloroethane. In all three cases the data base is poor and needs to be improved. The results are used to derive heats of solution for the C(1) and C(2) chlorinated hydrocarbons in water, Gibbs energies of solution and standard Henry's law coefficients at 298.15K. Henry's law coefficients calculated from the ratio of solubility of the compound in water and the saturation vapor pressure of the pure compound reported by Sangster [Sangster, J.M., 2003. Henry's law constants for compounds stable in water. In: Fogg, P.G.T., Sangster, J.M. (Eds.), Chemicals in the Atmosphere - Solubility, Sources and Reactivity. Wiley, Chichester, West Sussex, England, pp. 255-397] provide good agreement with the experimental data in eight out of eleven cases treated.     

Occurrence of psychoactive compounds and their metabolites in groundwater downgradient of a decommissioned sewage farm in Berlin (Germany)

Purpose

Psychoactive compounds??meprobamate, pyrithyldione, primidone, and its metabolites, phenobarbital, and phenylethylmalonamide??were detected in groundwater within the catchment area of a drinking water treatment plant located downgradient of a former sewage farm in Berlin, Germany. The aim of this study was to investigate the distribution of the psychoactive compounds in anoxic groundwater and to assess the risk of drinking water contamination. Groundwater age was determined to achieve a better understanding of present hydrogeological conditions.

Methods

A large number of observation and production wells were sampled. Samples were analyzed using solid-phase extraction and ultrahigh-performance liquid chromatography?Ctandem mass spectrometry. Groundwater age was estimated using the helium?Ctritium (³He?C³H) dating method.

Results

Concentrations of psychoactive compounds up to 1???g/L were encountered in the contamination plume. Generally, concentrations of phenobarbital and meprobamate were the highest. Elevated concentrations of the analytes were also detected in raw water from abstraction wells located approximately 2.5?km downgradient of the former sewage farm. Concentrations in the final drinking water were below the limit of quantification owing to dilution. The age of shallow groundwater samples ranged from years to a decade, whereas groundwater was up to four decades old at 40?m below ground. Concentrations of the compounds increased with groundwater age.

Conclusions

Elevated concentrations of psychoactive drugs indicate a strong persistence of these compounds in the environment under anoxic aquifer conditions. Results suggest that the heritage of sewage irrigation will affect raw water quality in the area for decades. Therefore, further monitoring of raw and final drinking water is recommended to ensure that contaminant concentrations remain below the health-based precautionary value.