大连地区唐氏筛查孕中期妇女羊水中甲状腺激素水平与PBDEs内暴露关系初探

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是一类常用的溴代阻燃剂,由于使用广泛,已成为普遍存在的环境污染物。研究表明,PBDEs具有内分泌干扰作用,影响甲状腺功能,对胚胎发育、婴幼儿及儿童的健康存在潜在的危害。本研究采集了100例具羊水穿刺指征的孕妇的孕中期羊水样本,采用罗氏全自动电化学发光免疫分析仪测定羊水中促甲状腺激素(TSH)、三碘甲状腺原氨酸(TT3)、游离三碘甲状腺原氨酸(FT3)、甲状腺素(TT4)、游离甲状腺素(FT4)、抗甲状腺过氧化酶抗体(TPOA)和抗甲状腺球蛋白抗体(TGA)的含量,用气相色谱-负化学源-质谱法测定羊水样品中16种PBDEs同系物含量。结果显示,羊水中TSH、TT3、FT3、TT4、FT4中位数分别为0.342μIU·m L-1、0.949 nmol·L-1、1.52 pmol·L-1、11.02 nmol·L-1和3.91pmol·L-1,95%参考区间值分别为0.174~0.872μIU·m L-1、0.835~1.01 nmol·L-1、1.26~2.72 pmol·L-1、9.42~20.68 nmol·L-1和2.16~6.35 pmol·L-1。具有唐氏筛查高风险和甲状腺激素水平低下的羊水样品中共检出6种BDEs(BDE-47、BDE-71、BDE-138、BDE-183、BDE-190、BDE-209),其中BDE-71、183和190在被检羊水样品中均被检出,并且,TSH水平低下的羊水中BDE-190和209负荷水平显著高于正常组。这些结果提示,大连地区孕中期妇女羊水存在PBEDs内暴露,并且PBDEs内暴露可能与羊水的甲状腺激素水平低下、尤其TSH水平升高有关,提示PBDEs暴露可能与胎儿中枢神经系统损伤产生的下丘脑-垂体-甲状腺(HPT)轴功能失调有关。因此,羊水PBDEs内暴露对新生儿出生结局的影响值得进一步关注。     

微波萃取-气相色谱/质谱测定底泥中多溴联苯醚

文章建立微波萃取,复合硅胶氧化铝层析柱净化,气相色谱-负化学离子源质谱(GC-NCI-MS)检测对环境底泥样品中七种多溴联苯醚(PBDEs)单体定量分析的方法。底泥样品经25 mL正己烷:丙酮(1:1)萃取剂微波萃取10 min,过复合层析柱净化,70 mL正己烷:二氯甲烷(1:1)洗脱和浓缩后,加入内标物PCB-103后进行内标定量分析,7种PBDEs单体的平均基质加标回收率均值为88.6%~96.7%,相对标准偏差为1.9%~9.3%,方法检出限均小于0.06 ng/g,方法具有良好的重现性,较好的回收率和较高的灵敏度。所建立的分析方法体系已用于长江口近岸沉积物中7种PBDEs残留量的检测,四个实际样品中添加回收率指示物PCB-209,其回收率范围为79.5%~109.6%,相对标准偏差为5.2%~16.5%。     

气相色谱负离子化学电离质谱测定环境中土壤与水中硫丹及其代谢物

建立一种气相色谱负离子化学电离质谱(GC-NCI-MS)测定环境中土壤和水中硫丹及其代谢物残留的检测方法,环境中土壤样用丙酮/水浸渍,乙酸乙酯提取,固相萃取小柱净化,水样经乙酸乙酯提取,采用GC-NCI-MS选择离子监测方式进行定性和定量分析,以外标法定量,方法中每种化合物的检出限土壤为0.05 μg/kg,水为0.005 μg/L,在方法的检测限与50 μg/kg(5 μg/L)范围内,线性相关系数大于0.999 5,在所添加三个浓度水平下,方法的回收率70%~95%,相对标准偏差(RSD)1.2%~11.8%。结果表明,该方法简便、快速、灵敏、精密度好,适合对环境中土壤和水样中硫丹及其代谢物进行有效监测。     

Determination of C(5)-C(12) perfluoroalkyl carboxylic acids in river water samples in the Czech Republic by GC-MS after SPE preconcentration

A method employing solid phase extraction followed by gas chromatography-mass spectrometry with negative chemical ionization has been developed for determination of ultratrace concentrations of perfluoroalkyl carboxylic acids in river water. The effects of the experimental parameters, such as the pH, additions of NaCl and an ion-pairing agent (tetraethylammonium bromide) and the kind of the elution agent, on the efficiency of the test acid extraction have been studied. The analyte extraction recoveries and the limits of detection and determination have been found. The method developed has been tested on determinations of perfluoroalkyl carboxylic acids in the waters of the two largest Czech rivers, Vltava and Labe (Elbe). The best extraction results have been attained without any alteration of the sample pH, with an addition of tetrabutylammonium bromide (a concentration of 50 μg mL⁻¹ in the sample) and using methanol as the elution agent. Under these conditions, the recoveries of the test acids in the spiked real samples are within ranges from 60% to 104% and 53% to 111% for analyte concentration levels of 1.40 ng mL⁻¹ and 0.14 ng mL⁻¹, respectively, depending on the lengths of the perfluorinated chains of the acids. In general, the recovery decreases with increasing length of this chain. The method developed exhibits very low limits of detection and determination and the results are fully comparable with those obtained when using more expensive HPLC-MS/MS instrumentation. Typical values amount to tenths to tens of pg mL⁻¹ and units to one hundred pg mL⁻¹ for the limits of detection and determination, respectively; the measuring sensitivity increases with increasing length of the analyte chain. The analyzes of real samples from the Vltava and Elbe rivers have demonstrated that the results obtained are similar to the values published for contamination of the Elbe and other rivers in western and central Europe. The concentrations determined are of the order of units to tens of pg mL⁻¹ and the C₈-C₁₀ acids occur most often.