基于GC-MS测定中药材茯苓中的禁用农药残留

目的：采用气相色谱-串联质谱法（GC-MS）分析技术建立定性和定量检测中药材茯苓中25种禁用农药残留的方法。方法：以乙腈为提取溶剂,对干燥茯苓样品进行提取、净化、浓缩等预处理后,经气相色谱-三重四极杆串联质谱分析测定,并用内标法定量。结果：茯苓中25种禁用农药在1～100 ng/ml范围内具有良好的线性关系,相关系数均在0.9900以上;检出限在0.00040～0.0100 mg/kg;定量限在0.000667～0.0333 mg/kg;以上检测均符合农药残留的检测要求。加标回收实验的平均加标率为70.1%～123.3%,加标率和加标样品的重复性验证结果也均符合标准要求。18批茯苓样品均未检出25种农药残留。结论：该方法简便快速、灵敏度高、重现性好,可适用于多种中药材中禁用农药残留的检测。     

莱州湾海域水体中有机氯农药和多氯联苯的浓度水平和分布特征

以固相萃取/气相色谱法测定了莱州湾海域水体中22种有机氯农药和多氯联苯类化合物的浓度水平和分布特征。结果表明,莱州湾海域表层水体中有机氯农药浓度范围为N.D.~32.7ng/L,底层水中的浓度范围为N.D.~11.7ng/L。在该海域水体中共检出有机氯农药3种,β-666是水体中主要的有机氯农药污染物。多氯联苯类在底层水样中检出2种,总浓度范围在4.5~27.7ng/L之间。该海域有机氯农药和多氯联苯的分布特征是近岸高,离岸低,由近岸向湾外延伸方向依次递减。并对莱州湾表层水中总有机氯农药与海水盐度、氯度、溶解氧和pH间的关系作了初步探讨,得出总有机氯农药与盐度、氯度间有一定的相关关系,相关系数均为0.59。方法测定5种有机氯农药化合物的空白加标回收率为97.3%~126.0%,相对标准偏差为2.8%~8.6%;测定5种多氯联苯类化合物的空白加标回收率为88.6%~151.8%,相对标准偏差为6.7%~10.4%。     

离子色谱法同时测定嗜热厌氧菌发酵液中的有机酸与无机阴离子

建立了一种利用离子色谱法同时测定甲酸、乙酸、乳酸、丙酸、丁酸5种有机酸及PO4-3、SO4-2、NO3-、Cl-、F-5种无机阴离子的方法。样品通过过滤、预柱处理后用IonPac AS11柱分离,以自动淋洗液发生器生成的KOH为淋洗液进行梯度洗脱,建立了优化的洗脱程序。用抑制型电导检测器检测有机酸的相对标准偏差为0.73%~1.01%,加标回收率为88.1%~100.2%;无机阴离子的平均相对标准偏差为2.03%,加标回收率为92.6%~101.1%,该方法可用于嗜热厌氧菌发酵液中低分子的有机酸和无机阴离子的同时测定。     

等离子质谱(ICP-MS)对高含量元素硫样品中的微量元素分析前处理方法初探

用等离子质谱(ICP-MS)分析一些特殊样品的时候,前处理方法成为分析样品成功与否的关键,对于高基质含量的样品测量其微量元素含量更是如此。元素硫超过99%的自然硫样品中微量元素的测定一般使用燃烧的方法去除自然硫,但是一些易挥发性的元素也因此失去而测不出来。作者试图采用硫升华的方法去除硫基质,通过在原样品中加入内标,分析测定后计算内标的回收率确定出元素Be,Sn,Sc,U和稀土元素(REE)的回收率都在90%以上,可以用升华硫方法很好地测定,而元素Tl,Hf,W,Nb,Zr,Ta等的回收率则在75%以下,不适合用该种方法测定。     

发光细菌法检测水产品中氯霉素体系的建立

从青岛近海分离的多株发光细菌中筛选出1株对氯霉素敏感的鳆发光杆菌Photobacterium leiognathi YL,接种单菌落快速培养,制备出适宜检测的菌悬液,添加不同浓度的氯霉素溶液,研究氯霉素浓度与细菌发光强度抑制率之间的关系.通过控制菌体起始发光强度、菌液与氯霉素作用时间,建立发光细菌检测水产品中氯霉素体系.结果表明,当菌体的起始发光强度控制在(2.0～4.0)×105、菌液与氯霉素的最佳作用时间为30 min时,氯霉素浓度与细菌发光强度抑制率呈良好的线性关系.该方法的线性范围为0.1～1.0 ng/mL,相关系数R2为0.989,该体系对氯霉素的检测灵敏度可以达到0.1 ng/mL,可以作为水产品中痕量氯霉素残留的1种快速、灵敏的检测方法.在水产品的氯霉素加标回收试验中,鱼肉中添加浓度为0.1～1.0 ng/g时,回收率在40.34%～114.26%之间.     

高效液相色谱-串联质谱法同时测定海洋沉积物中27种有机磷酸酯

应用广泛且具有毒性的有机磷酸酯(organophosphate esters,OPEs)类阻燃剂,通过水、气输送等多种途径进入海洋环境,可能会导致人类和海洋生物面临潜在的健康风险。因此,建立高效可靠的分析方法对于揭示OPEs在海洋环境中的赋存状况,评估其生态风险具有重要的科学意义。文章建立了同时测定沉积物中27种OPEs的超声提取、固相萃取(SPE)净化以及高效液相色谱-串联质谱(HPLC-MS/MS)检测的分析方法。结果表明:30mL乙酸乙酯(EA)和乙腈(ACN)混合溶剂(体积比为3︰7)的提取效果明显优于单独使用甲醇(MeOH)、二氯甲烷(DCM)、EA和ACN;用5mL EA经LC-C18固相萃取小柱洗脱两次回收率最好;以MeOH和含0.0025%甲酸的水溶液作为流动相时,质谱离子丰度最高。27种OPEs的线性范围为5~500 ng/g (R²>0.99),方法检出限(MDL)范围为0.004~1.250 ng/g,定量限(LOQ)为0.01~4.17 ng/g。三个加标水平(低、中、高)基质加标样品的平均回收率在45%~130%之间,相对标准偏差(RSD)最高11.0%,表明此方法可靠,精密度和灵敏度较高。采用优化的方法分析我国长江口、杭州湾入海口以及东海和黄海交界处海域表层沉积物中OPEs的含量,共检出了21种OPEs,浓度范围为9.83~48.70 ng/g,平均浓度为28.40 ng/g。该方法检测结果高效准确,可用于海洋沉积物中27种OPEs的同时测定。     

高效液相色谱法测定海水中溶解态游离氨基酸

采用邻苯二甲醛柱前衍生-高效液相色谱-荧光检测器(OPA—HPLC-FLD)联用技术分离测定了海水中的14种主要溶解游离氨基酸(DFAA),通过邻苯二甲醛—3-巯基丙酸(OPA—3-MPA)柱前衍生后,在XDB-C18柱上分离。不同氨基酸测定的精密度(RSD)为1.62%~3.80%,检测限为11.4~69.7 ng.L-1,海水加标回收率在92%~110%之间。利用该方法测得青岛近海表层海水中氨基酸浓度为0.015~0.284μmolL-1。     

海水中丙烯酸的高效液相色谱法建立及应用

建立了一种测定海水介质中丙烯酸的高效液相色谱法。采用耐纯水相和较低pH的Agilent SB-Aq-C18柱(100 mm×4.6 mm i.d.,5 μm), 0.35%磷酸溶液(pH=2)为流动相,使用紫外检测器,检测波长为210 nm,外标法定量测定。丙烯酸的保留时间在14.2~ 14.9 min,方法的检出限为4 nmol/dm3(S/N=3),在0.01~10 μmol/dm3的范围内均有良好的线性关系,相关系数可达0.999 6,加标回收率为95.4%~98.1%,相对标准偏差为1.3%~1.6%(1.04~2.32 μmol/dm3)。采用0.2 μm滤膜重力过滤冷藏的办法来保存海水丙烯酸样品。检测出2011年5月份青岛近海海水中丙烯酸的平均浓度为(0.101±0.069) μmol/dm3;海洋微藻球形棕囊藻在整个生长周期内培养体系中丙烯酸的浓度为0.339~2.219 μmol/dm3。     

超声波萃取-高效液相色谱法在海洋沉积物样品多环芳烃分析中的运用

建立用超声波萃取-高效液相色谱法同时检测海洋沉积物中16种优先监控的多环芳烃(PAH s)的方法。本方法采用丙酮作为萃取溶剂,在超声波作用下萃取出泥样中的PAH s,萃取液经浓缩后直接进行高效液相色谱分析。经对色谱条件和萃取条件进行优化后,各PAH组分的线性范围为1~500 ng之间,相关系数0.9921~0.999,检出限0.1~4.6 ng,达到海洋沉积物PAH s的检测要求。运用本法对粤东大规模增养殖区柘林湾表层沉积物PAH s进行检测,各PAH组分加标回收率为69.2%~108%,总平均达89.2%,相对标准偏差为0.5%~10.3%。本方法只需要萃取、浓缩和定容三个步骤,具有简便、迅速、高效、分析成本低的特点。     

液相色谱-四极杆/线性离子阱复合质谱测定双壳贝类中麻痹性贝类毒素

采用液相色谱-四极杆/线性离子阱复合质谱,建立了双壳贝类中13种麻痹性贝类毒素的定性确证和定量分析方法。样品经乙酸水溶液提取,石墨化碳黑固相萃取净化,亲水性液相色谱柱(hydrophilic interaction liquid chromatography,HILIC)分离;质谱采集使用独有的多反应监测-信息依赖性采集-增强子离子扫描模式。13种目标物线性范围相关系数不低于0.99,检出限为62.0μg STX eq/kg,其中石房蛤毒素(Saxitoxin,STX)、新石房蛤毒素(Neosaxitoxin,NEO)、脱氨甲酰基石房蛤毒素(Decarbamoylsaxitoxin,dc STX)、脱氨甲酰基新石房蛤毒素(Decarbaoylneosaxitoxin,dc NEO)以及N-磺酰氨甲酰基类毒素5(Gonyautoxin-5,GTX5)为10.0μg/kg,膝沟藻毒素12(Gonyautxins-1-2,GTX12)为12.0μg/kg,膝沟藻毒素34(Gonyautxins-3-4,GTX34)、N-磺酰氨甲酰基类毒素2(N-Sulfocarbamoylgonyautoxin-2,C2)和脱氨甲酰基膝沟藻毒素3(Decarbamoylgonyautoxins-3,dc GTX3)为4μg/kg,N-磺酰氨甲酰基类毒素1(N-Sulfocarbamoylgonyautoxin~(-1),C1)和脱氨甲酰基膝沟藻毒2(Decarbamoylgonyautoxins-2,dc GTX2)为13μg/kg。基质加标平均回收率为(79.6±10.4)%—(98.8±6.54)%。该方法能够有效降低贝类基质抑制效应,简化前处理过程并通过减少样品稀释倍数来显著提高方法灵敏度,使同分异构体达到基线分离,适用于双壳贝类中麻痹性贝类毒素的监控分析。     

渔用高强度聚乙烯和普通聚乙烯绞捻网片的拉伸力学性能比较研究

为给深水网箱设计与渔用材料的合理选配提供依据,应用ISO1806等对渔用高强度聚乙烯绞捻网片(以下简称HSPE绞捻网片)和普通聚乙烯绞捻网片(以下简称PE绞捻网片)的拉伸力学性能进行了比较研究。结果表明,(1)在同等条件下,36股HSPE绞捻网片的网目连接点断裂强力和网片单线断裂强力分别比52股PE绞捻网片增加了3.1%,3.7%;而前者的目脚直径和网片阻力可较后者减少19.6%。(2)对网片强力进行了再现性研究,36股HSPE和52股PE绞捻网片网目连接点断裂强力的标准偏差分别为35.93N,25.61N,再现性标准偏差分别为31.07N,36.93N;网片单线断裂强力的标准偏差分别为19.91N,13.49N,再现性标准偏差分别为20.48N,15.49N;网片强力测试数据的变异系数均小于4%;表示测试结果的分散性较小。(3)36股HSPE绞捻网片成本可较52股PE绞捻网片减少38.9%,其在渔业生产中进行推广应用具有可行性。(4)GB/T4925作为一个标准,对绞捻网片来说,存在不足,建议对GB/T4925进行修订。     

The German Bight (North Sea) is a nursery area for both locally and externally produced sprat juveniles

To better understand the role of the German Bight (GB) as a nursery area for juvenile North Sea sprat Sprattus sprattus we sought to determine whether the area may receive only locally or also externally produced offspring. We sampled juveniles during 3 trawl surveys in the GB in August, September, and October 2004 and applied otolith microstructure analysis in order to reconstruct their distributions of the day-of-first-increment-formation (dif). These were contrasted with spatial and seasonal patterns of sprat egg abundance in the GB and its adjacent areas, observed during 6 monthly plankton surveys. It was found that the majority of juveniles originated mainly from April/May 2004, coinciding with high spawning activity west of the GB, whereas spawning and larval production inside the GB peaked notably later, in May/June. This indicated that a large proportion of juveniles was produced outside the GB and transported subsequently into it through passive and/or active migration. Shifts to later mean difs from one survey to the next and length distributions indicative of the simultaneous presence of multiple cohorts, supported the notion that the GB is a complex retention and nursery area for sprat offspring from different North Sea spawning grounds and times. Later born juveniles had significantly faster initial growth rates than earlier born conspecifics, which was likely temperature-mediated, given the strong correlation between back-calculated growth histories and sea surface temperature as a proxy for thermal histories of juveniles (r² = 0.52).     

Southwestward intrusion of korea strait bottom cold water observed in 2003 and 2004

Hydrographic surveys were carried out four times in the western channel of the Korea Strait in March and August 2003 and in June and November 2004. The bottom cold water, which was lower than 10°C, appeared in the channel trough except in March 2003. It flowed southwestward along the shelf of Korean coasts in August 2003 and in November 2004. The width and the maximum speed of the intrusion current were about 20 km and approximately 25 cm s^-1, respectively, off Ulsan, Korea. The volume transport of the bottom cold water was estimated 0.019 Sv (Sv≡10⁶ m³ s^-1) in August 2003 and 0.026 Sv in November 2004.     

基于SERS技术的果蔬表皮农药残留快速检测方法研究

果蔬表皮农药残留关乎食品安全问题。本文以苹果为研究对象,应用表面增强拉曼光谱(SERS)技术,结合高灵敏度、便携的纳米检测棒,检测果蔬中常用农药倍硫磷和多菌灵,研究农药残留衰减规律,并对比研究不同方法对农药残留的去除效果。研究表明,基于GMA-EDMA多孔材料和金纳米颗粒制备的纳米检测棒,对苹果表皮残留的倍硫磷和多菌灵的最低检测浓度分别达0.10和0.05 mg/L,在低浓度范围内特征峰强度与浓度成良好的线性关系。苹果表皮两种农药残留量随时间成e指数衰减,衰减为e-1的时间常数分别约为1~2 d和4~5 d。不同清洗剂(清水、盐水、小苏打水、果蔬洗涤剂)对农药残留的清洗效果不同,淡盐水可提高农药残留清洗效率,清水清洗需要延长清洗时间才能达到相同效果。研究结果表明,纳米检测棒能有效提高果蔬农药残留的检测灵敏度和检测效率,结合便携式拉曼系统,可实现果蔬农药与淡盐水残留的快速、现场检测。     

气相色谱测定沉积物中多氯联苯的样品处理方法研究

通过比较密闭微波萃取、超声波萃取、索氏提取3种方法对沉积物中多氯联苯(PCBs)提取效率,对比浓硫酸和Florisil小柱两种净化方式的净化效果,在实验基础上建立了密闭微波萃取-Florisil小柱净化-气相色谱(ECD)测定沉积物中多氯联苯的分析方法,加标质量比为0.2ng/g时,其相对标准偏差(RSD)为2.19%～8.71%,回收率为77.3%～94.6%,检出限为0.027～0.064ng/g。采用该方法对威海湾养殖区沉积物中PCBs进行了监测,结果表明本方法适用于海洋沉积物样品中PCBs的测定。     

热浸镀用锌及锌铝合金的恒电流电化学性能

在海水腐蚀过程中，热浸镀层金属(或合金)对钢铁基体的阴极保护作用是很重要的因素，只有驱动电位大且稳定、电流效率高、表面腐蚀均匀的镀层才能保证钢材在海水中使用长久。作按照国标GB／T171848-1999的要求对几种典型的热浸镀用锌及锌铝合金测试了开路电位、工作电位，计算了电流效率，观察了腐蚀产物脱落情况及腐蚀均匀性，评价了各种典型镀层金属(合金)的电化学保护性能。研究表明，Zn的电化学性能最好，Zn-55A1-1．6Si合金的电化学性能最差，Zn-5Al-0．2RE、Zn-5Al-0．1Mg、Zn-6Al-3Mg、Zn-11AL-3Mg-0．2Si、Zn-25AL-0．2Mg-0．2Si和Zn-25Al-0．2RE-0．2Si合金介于二之间。     

土壤渗滤处理技术在海岛生活污水处理中的应用

土壤渗滤处理系统设备简单、投资少、操作管理方便、能耗低,净化效果良好,在处理海岛生活污水领域具有广阔的发展前景.根据鼓浪屿目前污水水质、水量的特点,采用土壤渗滤高度水处理技术对污水进行处理,污染物经过土壤的物理、化学和生物作用,出水达到《城市污水再生利用城市杂用水水质》(GB/T18920-2002),具有不产生污泥,运行简单,氮磷去除效率高,无二次污染等特点.     

Environmental monitoring using acetylcholinesterase inhibition in vitro. A case study in two Mexican lagoons.

Cholinesterase inhibition is considered a specific biomarker of exposure and effect for organophosphorous pesticides. Its use for monitoring has been hindered, particularly in tropical countries where organophosphates are widely used for malaria and dengue control, because of the frequent lack of suitable controls. An in vitro technique is proposed as a biochemical method for monitoring pollutant mixtures in sediment toxicity tests. Brain homogenate from the fish Oreochromis niloticus is used as the enzyme source. Optimum incubation time, extraction solvent and effect of crude oil on acetylcholinesterase (AChE) are reported. The method described was used in sediments from two Mexican lagoons, located in an oil extraction area where pesticides are used in agriculture and vector control campaigns. AChE inhibitions from 3 to 21% were found in these lagoons, even in the presence of high concentrations of petroleum.     

Biogeochemical responses to the removal of maricultural structures from an eutrophic lagoon (Tapong Bay) in Taiwan

The biogeochemistry of Tapong Bay, one of the major lagoons in southern Taiwan, was studied from 1999 to 2004, encompassing a period in 2003 in which aquaculture activities were terminated and the associated structures removed. Removal of the maricultural structures resulted in the reduction of the mean time for water exchange time in Tapong Bay from about 10+/-2d to 6+/-2d. The annual mean concentration of measured nutrients (DIN, DIP and DSi) also decreased significantly, likely due to improved water exchange, ceased feeding and increased biological utilization. An overall high primary production was maintained and likely to be constrained by temperature, light availability and turbidity rather than by abundant nutrients throughout the study period. The change in stoichiometric ratios among inorganic and organic nutrients (C/N, Si/N, N/P) may be attributed to the shift of plankton community between the two periods. The annual mean of Delta POC/Delta PON was 8.1, a little bit larger than that (7.3) before removal, also possibly resulting from the shift of planktonic community (from diatom-dominated to flagellate-dominated and increase of total phytoplankton and zooplankton) and removal of periphyton and oysters. The Tapong Bay shows a 37% increase (from 5.6 to 7.7 mol C m(-2)yr(-1)) in net ecosystem production (NEP) after structure removal, although the increase was not statistically significant. The change in environmental conditions has therefore influenced profoundly the carbon and nutrient biogeochemical processes and budgets in the semi-enclosed ecosystem.