环境介质中喹诺酮类抗生素的前处理与检测方法研究进展

由于在人类医疗保健与集约化禽畜和水产养殖中的大量使用,痕量水平的喹诺酮类抗生素在水体、土壤及沉积物中广泛出现.因此,使用灵敏度高、选择性强的分析方法来检测环境中的痕量喹诺酮类抗生素,对了解其潜在的环境风险极为重要.本文综述了水体、土壤及沉积物样品中喹诺酮类抗生素萃取、富集与检测方法的最新进展.固相萃取(solid phase extraction,SPE)和超声/微波辅助萃取联合SPE分别是萃取和富集液相和固相(土壤和沉积物)样品中喹诺酮类抗生素最成熟可靠的方法.液相色谱-荧光检测联用和液相色谱-串联质谱联用技术是使用最为广泛的常规分析方法.此外,近年发展的免疫测定、生物传感器与电化学方法有望在筛检方面替代昂贵的仪器分析,尤其在现场实时监测领域具有较好的应用前景.     

快速溶剂(ASE)提取、凝胶渗透色谱(GPC)联合固相萃取(SPE)净化,高效液相色谱法测定土壤中的多环芳烃

建立了采用快速溶剂提取(ASE),固相萃取(SPE)与凝胶渗透色谱(GPC)协同净化方法,使用高效液相色谱-紫外-荧光检测器(HPLC-UV-FLD)串联检测土壤中多环芳烃类化合物多残留的检测方法.通过对加速溶剂提取仪提取条件,凝胶渗透色谱和固相萃取净化条件的优化,确定土壤中多环芳烃类化合物多残留的前处理方法:提取溶剂...     

在线固相萃取-超高效液相色谱-三重四极杆串联质谱法检测水中痕量有机磷农药和五氯酚

建立了在线固相萃取-超高效液相色谱-三重四极杆串联质谱法测定地下水中痕量乐果、呋喃丹、敌敌畏、莠去津、甲基对硫磷、马拉硫磷、毒死蜱、滴灭威、2,4-滴、五氯酚等10种农药有机磷农药和五氯酚的方法.用0.22μm滤膜过滤后,采用直接进样,在线固相萃取-超高效液相色谱-串联质谱联用仪测定,在1—40μg·L~(-1)范围内线性良好,10种有机磷农药和五氯酚的线性相关系数R~20.995,实际水样加标回收率在80.2%—109%.     

环境样品中有机锡分析方法研究进展

有机锡具有毒性作用,其引起的环境问题日益受到人们的关注.但由于有机锡种类繁多、性质复杂,分析过程存在较大困难.本文概述了近年来国内外有机锡分析方法的研究现状,介绍了从水、沉积物、生物等环境介质中提取富集、衍生化、净化有机锡的多种方法,其中水样的富集提取以固相萃取或固相微萃取为主,沉积物样和生物样以超声波萃取或微波萃取为主.同时重点介绍了气相色谱联用技术、高效液相色谱联用技术等分析测定方法.最后,对未来有机锡分析方法的发展趋势做出了展望.     

在线固相萃取超高效液相色谱串联质谱法测定水中微囊藻毒素

建立了水中微囊藻毒素(MCs)的直接进样分析方法.在全自动在线固相萃取/超高效液相色谱/串联质谱(SPE-UPLC-MS/MS)系统上开发,具有可直接进样、重现性好、快速、高灵敏、抗污染等特点.     

在线固相萃取-超快速液相色谱-质谱联用测定水中超痕量呋喃丹和甲萘威

采用在线固相萃取技术对水体中痕量甲萘威和呋喃丹富集,并利用快速液相色谱串联质谱检测器检测.采用固相萃取小柱富集待测物,以色谱梯度泵完成样品的在线净化后,利用阀切换技术将待测物反冲至分析柱进行分离,以串联质谱定性及定量.水样无需样品浓缩富集,过滤后即可进样.方法在1.0—100μg·L~(-1)范围内线性良好,呋喃丹和甲萘威的线性相关系数R~2 0.999.呋喃丹和甲萘威的检出限(S/N=3)分别为0.3、0.15 ng·L~(-1),加标回收率在90.1%—108%.用所建立的方法测定了自来水中的痕量甲萘威与呋喃丹,结果令人满意.     

超高效液相色谱串联质谱法同时测定城市污水处理厂污泥中12种抗生素

建立了一种固相萃取-超高效液相色谱-串联质谱法同时测定污泥中4类12种抗生素的方法.采用SAX串联Oasis HLB固相萃取柱净化富集污泥样品中的抗生素,选定p H 3、洗脱体积8 m L作为最佳前处理条件.采用超高效液相色谱-串联质谱检测抗生素样品,以0.3%的甲酸和乙腈作为流动相,经梯度洗脱进行分离,在多反应检测模式下进行测定.经测定,污泥样品中磺胺类抗生素、脱水红霉素和罗红霉素平均回收率为50%—80%,其余抗生素的平均回收率为82%—119%,12种抗生素在污泥中的定量限为0.001—0.008μg·kg~(-1)dw.并用该法对天津市某污水处理厂污泥样品进行检测,证明该方法可满足实际检测要求.     

南京典型县区饮用水源抗生素含量特征

采用固相萃取-高效液相色谱/串联质谱法分析南京3个典型县区地表饮用水源中5类(14种)抗生素含量.结果表明,14种目标抗生素的含量在ND—14.9 ng·L-1,检出率在0—78%.主要检出物为诺氟沙星、氧氟沙星、强力霉素和磺胺嘧啶,其中四环素类含量相对最高,但总体上,抗生素的含量水平低于国内外其他河流中相应污染物.抗生素含量受季节影响,呈现丰水期(8月)平水期(5月)枯水期(2月)的特点.取自湖泊的饮用水源地抗生素含量略高于取自长江.     

液相色谱-串联质谱法测定贝类组织中硝基呋喃类代谢物残留量

建立了液相色谱-串联质谱法测定贝类产品中硝基呋喃类代谢物残留量的分析方法.贝类组织中残留的硝基呋喃类蛋白结合态代谢物在酸性条件下水解,用2-硝基苯甲醛衍生化,经乙酸乙酯液-液萃取、浓缩及基质分散固相萃取和超滤净化后,采用液相色谱串联质谱仪测定,以电喷雾离子源正离子扫描模式进行质谱分析,内标法定量.硝基呋喃类代谢物在0.5—20μg·L~(-1)范围内线性关系良好,相关系数R20.999.4种硝基呋喃类代谢物添加水平为1.00,2.50、10.0μg·kg~(-1)时,平均回收率在90.1%—99.5%之间,批内和批间变异系数均15%.4种硝基呋喃类代谢物的检出限均为0.50μg·kg~(-1).本方法灵敏、高效、简单、重现性好,满足贝类产品中硝基呋喃类代谢物残留量的检测要求.     

分散固相萃取-超高效液相色谱-串联质谱法测定城市污水中2种溴代阻燃剂

建立了分散固相萃取-超高效液相色谱-串联质谱法准确测定城市污水中六溴环十二烷(HBCD)和三-(2,3-二溴丙基)异氰脲酸酯(TBC)的方法.对萃取剂用量、萃取时间、淋洗剂、洗脱剂及色谱分离和质谱测定等条件进行了优化.优化后方法为:待测水样加入同位素标记的回收率内标,用0.4 g Silica、C18和HLB(1∶1∶1)混合填料分散固相萃取,回收萃取剂后用5 m L的10%的甲醇水溶液淋洗,8 m L甲醇洗脱,氮吹浓缩,加入同位素标记的进样内标测定.方法在1—200μg·L-1范围线性关系良好,HBCD和TBC的线性相关系数R20.9986,检出限为0.6—1.2 ng·L-1.应用该方法在某大型污水处理厂各工艺段污水中检测出了α-HBCD,浓度水平为1.3—5.4 ng·L-1.该方法操作简单、灵敏度高,尤其适合城市污水复杂基质中HBCD和TBC的分析.     

普萘洛尔在太湖沉积物上的吸附特征

主要研究了pH、离子强度、腐殖酸和沉积物有机质对普萘洛尔在太湖沉积物上吸附行为的影响.结果表明,沉积物对普萘洛尔具有一定的吸附能力.在强酸环境下,由于H⁺与带正电荷的普萘洛尔之间的竞争作用使得普萘洛尔的吸附量较小,随着pH的增大,吸附量逐渐增大至基本稳定,但当pH>9时,吸附量明显下降.K⁺、Na⁺和Ca²⁺的存在会减少普萘洛尔在沉积物上的吸附.在pH 5.8—6.0的情况下,随着腐殖酸浓度的增加,普萘洛尔在沉积物上的吸附量逐渐增加,而后逐渐到达平台期.有机质对普萘洛尔在沉积物上的吸附起到一定作用,普萘洛尔在天然水体中更倾向于吸附到沉积物的无机矿物成分上.普萘洛尔在太湖沉积物上的吸附等温线符合Freundlich吸附模型,拟二级动力学方程能较好地描述普萘洛尔在太湖沉积物上的吸附过程.     

Simultaneous quantification of several classes of antibiotics in water,sediments, and fish muscles by liquid chromatography–tandem mass spectrometry

Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction (SPE) by passing 1000 mL of water through hydrophilic lipophilic balanced (HLB) SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE (strong anion exchange (SAX) + HLB) clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer (80:20, v/v) solution, and cleaned by SPE. Liquid chromatography–tandem mass spectrometry (LC-MS/MS) with multiple reaction monitoring (MRM) detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%–95.8%, 48.1%–105.3%, and 59.8%–103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification (LOQ) to 713.6 ng·L^-1 (ofloxacin) in surface water and from less than LOQ to 344.8 μg·kg^-1 (sulphamethoxazole) in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfloxacin was the highest (up to 38.5 μg·kg^-1), but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.     

Fractionation of heavy metals in surface sediments of Taihu Lake, East China

The BCR (European Communities Bureau of Reference) three-step sequential extraction procedure was applied to fractionate heavy metals in the sediment of Taihu Lake. For the determination of total metal concentration of the sediments, sample digestion was achieved by using HF/H2O2/HNO3 (2/1/1) acid mixture in a microwave-irradiated closed vessel system. The concentrations of Cd, Ni, Cr, Zn, Cu and Pb in various extracts solutions were analyzed by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The results obtained from the BCR three-step sequential extraction indicated relatively high mobility of Zn, Cu, Pb and Ni in the sediments while Cd and Cr were poorly mobile. Enrichment of heavy metals was found in the sediments collected in the northern parts of Taihu Lake. In the sediments collected in the southern and western sides of the Lake, heavy metal concentrations were relatively low. The relationship between total organic carbon (TOC) and heavy metals concentrations in the sediments is discussed.     

Fractionation of Heavy Metals in Surface Sediments of Taihu Lake, East China

The BCR (European Communities Bureau of Reference) three-step sequential extraction procedure was applied to fractionate heavy metals in the sediment of Taihu Lake. For the determination of total metal concentration of the sediments, sample digestion was achieved by using HF/H₂O₂/HNO₃(2/1/1) acid mixture in a microwave-irradiated closed vessel system. The concentrations of Cd, Ni, Cr, Zn, Cu and Pb in various extracts solutions were analyzed by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The results obtained from the BCR three-step sequential extraction indicated relatively high mobility of Zn, Cu, Pb and Ni in the sediments while Cd and Cr were poorly mobile. Enrichment of heavy metals was found in the sediments collected in the northern parts of Taihu Lake. In the sediments collected in the southern and western sides of the Lake, heavy metal concentrations were relatively low. The relationship between total organic carbon (TOC) and heavy metals concentrations in the sediments is discussed.     

不同生态类型富营养化湖泊沉积物中有机质赋存形态

以藻型湖泊(太湖)、草藻型湖泊(南四湖)、草型湖泊(白洋淀)湖泊沉积物为研究对象,采集了11个表层沉积物样品,测定沉积物中总氮(TN)和总磷(TP)含量并利用物理分组方法,研究了3种不同生态型湖及同一湖泊不同区域沉积物中总有机质(OM)、轻组有机质(LFOM)和重组有机质(HFOM)的赋存特征.结果表明,南四湖沉积物中总氮、总磷和总有机质含量显著高于太湖和白洋淀;尽管太湖、南四湖和白洋淀沉积物中总有机质含量较高,但是轻组有机质(LFOM)含量较低,分别占总有机质的0.95%—1.08%、0.21%—1.37%和1.4%—1.78%;重组有机质(HFOM)含量较高,分别占总有机质的83.83%—87.4%、94%—98.98%和88.2%—98.3%,表明3种不同生态型湖泊沉积物中所含有机质绝大部分为难分解的重组有机质,轻组有机质基本矿化分解.相关性分析表明,轻组有机质(LFOM)、重组有机质(HFOM)与总有机质(OM)之间均呈现显著正相关关系.     

Organophosphate esters in sediment from Taihu Lake,China: Bridging the gap between riverine sources and lake sinks

• Eleven OPEs were detected in river sediment and lake sediment in Taihu Lake. • TnBP dominated in river sediment, while TBEP dominated in lake sediment. • A strong correlation existed between logK_oc and logK_ow of OPEs. • Vertical profiles of OPEs in sediment cores varied according to sampling location. Surface sediment samples from Taihu Lake in China and its inflow rivers, along with two lake sediment core samples, were collected and analyzed for organophosphate esters (OPEs). The concentrations of total OPEs varied from 28.60 ng/g to 158.72 ng/g (median: 54.25 ng/g) in river surface sediment and from 62.57 ng/g to 326.84 ng/g (median: 86.37 ng/g) in lake sediment. Tributyl phosphate (TnBP) was the predominant compound in river surface sediment, and tris(2-butoxyethyl) phosphate was predominant in lake sediment. High contamination occurred in the north-west region, which was related to the high level of urbanization and high usage of OPEs. The sediment–water partition coefficients of OPEs (logK_oc) were calculated, showing a significant correlation with logK_ow (p<0.05). The concentration and composition of OPEs in two sediment cores varied due to the different sampling locations, with more OPE species found in the northern region than in the southern one. Principal component analysis and positive matrix factorization indicated that sewage discharges, vehicle emissions, and atmospheric deposition were the possible sources of OPEs in Taihu Lake sediments. Tris(1-chloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, and TnBP were the main OPEs causing ecological risks.     

Adsorption of sulfonamides on lake sediments

Sulfonamides (SAs) are one class of the most widely used antibiotics around the world. Their fate and transport in the aquatic environment is of great concern. In this study, adsorption of four SAs—sulfadiazine (SD), sulfamethoxazole (SMZ), sulfadimethoxine (SDM) and sulfamethazine (SM2)—in single-solute and multi-solute systems on sediments of Dianchi (DC) Lake and Taihu (TH) Lake, China was investigated with batch experiments. In the single-solute adsorption system, the Langmuir model and the dual-mode model described the adsorption process better than the Freundlich model. Model fitness was better on DC sediment than on TH sediment. The order of adsorption capacity approximately followed a decreasing order of SDM>SD>SM2>SMZ on both sediments, which was likely attributed to the distinctly different water solubility of the four SAs. In the multi-solute system, the order of adsorption capacity was SM2>SDM>SD>SMZ, which was probably related to the compound speciation caused by the pH values of the experimental solution. In the multi-solute system, both competitive and cooperative adsorption played important roles in the adsorption of sulfonamides on sediments.     

Mercury distribution,speciation and potential ecological risk assessment in sediments from Lake Taihu,China

Abstract

Twenty-one surface sediments collected from seven surroundings areas of Lake Taihu in two different years were analyzed for total mercury (THg) concentrations, physicochemical characteristics and speciation using a sequential extraction method to assess spatial distribution, sources, and potential ecological risk. Surface sediments from Lake Taihu contained elevated levels of Hg in two sampling years with THg levels ranging from 77 to 346?ng/g (mean 145?ng/g) in October 2010 and ranging from 122 to 573?ng/g (mean 266?ng/g) in November 2012, respectively. The mean THg concentrations in all studied surface sediments exhibited an increasing trend over time. The oxidizable fraction (F3) and residual fraction (F4) were the predominant Hg species in sediments, while more mobile Hg phases of acid-soluble fraction (F1) and reducible fraction (F2) made up less than 0.5% THg. Significant relationships were found between total organic carbon (TOC) and THg and geochemical speciation indicating an important role for organic matter in affecting distribution, mobility, and bioavailability of Hg in sediments. As evidenced by Hakanson’s potential risk index the total ecological risk of Hg was low in the entire Lake Taihu in 2010 but considered moderate in Zhushan Bay, West Coast, and Meiliang Bay in 2012. These findings provide conservation managers with information needed to more effectively regulate the environment of Lake Taihu.     

Phosphorus speciation and effects of environmental factors on release of phosphorus from sediments obtained from Taihu Lake,Tien Lake,and East Lake

Phosphorus is considered the primary nutrient limiting eutrophication. The release of phosphorus from sediments not only provides hydrophytes with essential nutrients, but can also produce entrophication in lakes. In this study, the sediment characteristics, phosphorus speciation, and environmental factors affecting phosphorus release from sediments from Taihu Lake, Tien Lake, and East Lake were investigated. The results indicated that phosphorus levels of sediments ranged from 647 ± 67 to 2343 ± 122 mg/kg. Inorganic phosphorus comprised the majority of total phosphorus. The main phosphorus speciation of sediments obtained from Taihu Lake and Tien Lake was Residual-P, and the main phosphorus speciation of sediment obtained from East Lake was NaOH-P. Phosphorus release occurred in acidic and alkaline conditions but more frequently under alkaline conditions. The amount of phosphorus released from the sediments increased as the disturbing intensity rose. In addition, less phosphorus was released in natural than anaerobic conditions. The amount of phosphorus released was elevated as temperature increased.     

分散固相萃取-超高效液相色谱-串联质谱联用快速检测大豆及土壤中氟磺胺草醚残留

采用分散固相萃取(QuEChERS)样品前处理方法,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测大豆和土壤中氟磺胺草醚的残留分析方法.大豆和土壤样品采用乙腈(含0.5%甲酸)提取,N-丙基乙二胺(PSA)或石墨化碳黑(GCB)净化,UPLC-MS/MS外标法检测定量.在0.005—0.5 mg.kg-1添加范围内,氟磺胺草醚在土壤、大豆和大豆植株中的平均回收率在79.4%—109.0%之间,变异系数在3.6%—10.1%之间.在山东、河南、吉林进行了氟磺胺草醚在大豆植株和土壤中的降解动态研究,结果表明,试验点中氟磺胺草醚在土壤中的降解半衰期为8.5—23.7 d;在大豆植株中的降解半衰期为2.7—9.8 d.