Application of a LC–MS/MS method for multi-mycotoxin analysis in infant formula and milk-based products for young children commercialized in Southern Brazil

ABSTRACT

An analytical method based on liquid chromatography–tandem mass spectrometry (LC–MS/MS) was validated and applied for the analysis of aflatoxin M₁ (AFM₁), ochratoxin A (OTA) and deoxynivalenol (DON) in infant formula and milk-based products for young children commercialized in Brazil. A total of 38 samples were evaluated, including 12 infant formula, 14 follow-on formula and 12 samples of milk-based products. AFM₁ was detected in 12 (32%) samples, and seven (18%) samples contained AFM₁ levels above the method limit of quantification in a concentration range between 0.013 and 0.067 ng mL^?1 (0.026 ± 0.019). Two samples of milk-based products exceeded the maximum level (ML) fixed by the European Union for AFM₁ in baby foods, however, all samples were in agreement with the levels established by the Brazilian regulation. OTA and DON were not detected in any of the analyzed samples.     

深圳河典型内分泌干扰物分布和季节变化规律研究

2011年6月至2012年5月在深圳河沿程采集水样,采用固相萃取一氮吹一衍生化的预处理方法和气相色谱/质谱联用法,对壬基酚(NP)、辛基酚(OP)、双酚A(BPA)、雌酮(E1)、雌二醇(E2)、17α-雌二醇(17α-E2)、雌三醇(E3)、雌炔醇(EE2)等8种内分泌干扰物(EDCs)在深圳河的浓度分布和时空变化规律进行了研究.同时通过主成分分析考察了EDCs与常规水质污染物的关系.结果表明,NP、BPA、E1、E3、EE2在深圳河各河段均有检出,而OP、17α-E2、E2的检出率均低于20％,EDCs主要来源是NP和BPA;深圳河旱季和雨季EDCs的浓度变化大,其中NP浓度表现出旱季高雨季低的规律,旱季浓度是雨季的1.74～5.63倍,但BPA和3种甾醇类雌激素的浓度呈现出了雨季高旱季低的相反变化规律,这应该与污水处理厂雨季污水溢流有关;通过主成分分析发现,BPA与DO存在明显的负相关关系,生物作用可能在BPA去除和甾醇类雌激素转化中起到了重要作用,具体机制还有待进一步研究.     

Predictors of urinary bisphenol A and phthalate metabolite concentrations in Mexican children

Exposure to endocrine disrupting chemicals such as bisphenol A (BPA) and phthalates is prevalent among children and adolescents, but little is known regarding important sources of exposure at these sensitive life stages. In this study, we measured urinary concentrations of BPA and nine phthalate metabolites in 108 Mexican children aged 8–13 years. Associations of age, time of day, and questionnaire items on external environment, water use, and food container use with specific gravity-corrected urinary concentrations were assessed, as were questionnaire items concerning the use of 17 personal care products in the past 48-h. As a secondary aim, third trimester urinary concentrations were measured in 99 mothers of these children, and the relationship between specific gravity-corrected urinary concentrations at these two time points was explored. After adjusting for potential confounding by other personal care product use in the past 48-h, there were statistically significant (p < 0.05) positive associations in boys for cologne/perfume use and monoethyl phthalate (MEP), mono(3-carboxypropyl) phthalate (MCPP), mono(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP), and mono(2-ethyl-5-oxohexyl) phthalate (MEOHP), and in girls for colored cosmetics use and mono-n-butyl phthalate (MBP), mono(2-ethylhexyl) phthalate (MEHP), MEHHP, MEOHP, and mono(2-ethyl-5-carboxypentyl) phthalate (MECPP), conditioner use and MEP, deodorant use and MEP, and other hair products use and MBP. There was a statistically significant positive trend for the number of personal care products used in the past 48-h and log-MEP in girls. However, there were no statistically significant associations between the analytes and the other questionnaire items and there were no strong correlations between the analytes measured during the third trimester and at 8–13 years of age. We demonstrated that personal care product use is associated with exposure to multiple phthalates in children. Due to rapid development, children may be susceptible to impacts from exposure to endocrine disrupting chemicals; thus, reduced or delayed use of certain personal care products among children may be warranted.     

Hydroxylation of bisphenol A by hyper lignin-degrading fungus Phanerochaete sordida YK-624 under non-ligninolytic condition

Bisphenol A (BPA) is one of the representative compounds of the endocrine disrupting compounds group and the highest volume chemicals produced worldwide. As a result, BPA is often detected in many soil and water environments. In this study, we demonstrated the transformation of BPA from liquid cultures inoculated with hyper lignin-degrading fungus Phanerochaete sordida YK-624. Under non-ligninolytic condition, approximately 80% of BPA was eliminated after 7 d of incubation. High-resolution electrospray ionization mass spectra and nuclear magnetic resonance analyses of a metabolite isolated from the culture supernatant suggested that BPA was metabolized to hydroxy-BPA, 4-(2-(4-hydroxyphenyl)propan-2-yl)benzene-1,2-diol, which has a much lower estrogenic activity than BPA. In addition, we investigated the effect of the cytochrome P450 inhibitor piperonyl butoxide (PB) on the hydroxylation of BPA, markedly lower transformation activity of BPA was observed in cultures containing PB. These results suggest that cytochrome P450 plays an important role in the hydroxylation of BPA by P. sordida YK-624 under non-ligninolytic condition.     

Biodegradation of imidacloprid in liquid media by an isolated wastewater fungus Aspergillus terreus YESM3

In the present study, a new fungal strain capable of imidacloprid degradation was isolated from agricultural wastewater drain. The fungal strain of YESM3 was identified as Aspergillus terreus based on ITS1-5.8S rDNA-ITS2 gene sequence by PCR amplification of a 500 bp sequence. Screening of A. terreus YESM3 to the insecticide imidacloprid tolerance was achieved by growing fungus in Czapek Dox agar for 6 days at 28°C. High values (1.13 and 0.94 cm cm^?1) of tolerance index (TI) were recorded at 25 and 50 mg L^?1 of imidacloprid, respectively in the presence and absence of sucrose. However, at 400 mg L^?1 the fungus did not grow. Effects of the imidacloprid concentration, pH, and inoculum size on the biodegradation percentage were tested using Box–Behnken statistical design and the biodegradation was monitored by HPLC analysis at different time intervals. Box–Behnken results indicated that optimal conditions for biodegradation were at pH 4 and two fungal discs (10 mm diameter) in the presence of 61.2 mg L^?1 of imidacloprid. A. terreus YESM3 strain was capable of degrading 85% of imidacloprid 25 mg L^?1 in Czapek Dox broth medium at pH 4 and 28°C for 6 days under static conditions. In addition, after 20 days of inoculation, biodegradation recorded 96.23% of 25 mg L^?1 imidacloprid. Degradation kinetics showed that the imidacloprid followed the first order kinetics with half-life (t₅₀) of 1.532 day. Intermediate product identified as 6-chloronicotinic acid (6CNA) as one of the major metabolites during degradation of imidacloprid by using HPLC. Thus, A. terreus YESM3 showed a potential to reduce pollution by pesticides and toxicity in the effected environment. However, further studies should be conducted to understand the biodegradation mechanism of this pesticide in liquid media.     

快速高架复合道路近场交通噪声垂向分布

采用Cadna/A环境噪声模拟软件建立了高架复合道路的基本模型,根据6种基本模拟情况进行了声场模拟,并把模拟结果与实测结果进行对比分析。结果表明,高架道路结构本身对地面道路、高架道路分别形成的声场有明显的遮挡作用,但对高架复合道路所形成的声场遮挡作用不明显;对于高架复合道路垂向声场,在低层段地面道路的影响大于高架道路,而在高层段高架道路的影响起决定作用;高架复合道路较地面道路的垂向声场最大值增加2.5 dB(A),位置上移6m;在高架道路上设置声屏障有一定降噪效果,但在高架复合道路的上层设置声屏障降噪效果不理想。     

A~2/O＋硫磺填料柱组合工艺脱氮除磷的效果

以某城市污水厂进水为研究对象,采用A2/O＋硫磺填料反应柱组合工艺,考察其对COD、总氮、总磷以及溶解性磷处理效果的改善。组合工艺出水水质稳定后,连续运行55 d,并对工艺的出水进行常规指标分析。结果表明：组合工艺的脱氮除磷效果较单个A2/O工艺都得到了较大的改善,而COD去除效果变化不大。A2/O系统对COD有良好的去除效果,出水的COD平均去除率能达到94%;TN和TP去除效果相对较差,出水平均去除率分别为60%和57.4%。经硫磺填料反应柱的脱氮除磷作用,系统出水TN去除率提高到84%,TP去除率提高到69.8%,COD去除率变化不大,升高到95.3%。     

我国淡水水体中双酚A(BPA)的生态风险评价

双酚A(BPA)对水生生物有多种毒性效应,其中雌激素作用尤为显著.本研究依据BPA对水生生物是否有雌激素效应,把数据分为两类,并通过商值法、安全阈值法、商值概率法以及联合概率曲线法评价了我国淡水水体中BPA对水生生物的风险程度.结果表明,采用4种评价方法得出的结果相近,我国淡水生物对BPA的雌激素效应较BPA对水生生物的其他毒性作用更为敏感;安全阈值法较商值法、商值概率法、联合概率风险评价法误差较小,评价结果更为可信.用安全阈值法评价结果表明,以BPA的雌激素作用为效应终点时,水生生物长期暴露于我国淡水环境中,我国64.70%的淡水水体有导致超过5%的水生生物受到雌激素作用的风险,BPA安全浓度上限为15.72 ng·L-1;而水生物种短期暴露于我国淡水环境中,我国20.43%的淡水水体有导致超过5%的我国淡水生物受BPA雌激素作用的干扰,此时BPA安全浓度上限为2.24×102ng·L-1.     

蚯蚓细胞色素P450亚酶及代谢组学对土壤亚致死剂量草甘膦除草剂的响应

以赤子爱胜蚓（Eisenia fetida）为受试生物,通过外源添加污染物的方法,研究了暴露于亚致死剂量草甘膦（添加剂量分别为5、10、20、40 mg·kg^-1）的土壤中7 d后,蚯蚓生长抑制率、细胞色素P450亚酶（CYP1A2、2C9与3A4）活力及代谢组学对土壤草甘膦的响应,旨在探讨亚致死剂量草甘膦能否对非靶标生物蚯蚓产生不良影响及其毒性作用机制,初步推断其毒性作用阈值,并筛选敏感生物标记物.结果表明：从蚯蚓生长抑制率来看,各处理组与对照组无显著差异;从蚯蚓CYP亚酶活力来看,在高剂量草甘膦（20、40 mg·kg^-1）处理下,CYP亚酶活力均受到显著抑制;基于代谢组学鉴定并筛选出14个小分子代谢物标记物,其中9个小分子代谢物（分别是1,6-二磷酸果糖、β-D-果糖6-磷酸、丙酮酸、组氨酸、赖氨酸、鸟氨酸、延胡索酸、肌酸、甜菜碱）在5~40 mg·kg^-1草甘膦暴露下显著低于对照水平,另外2个小分子代谢物（尿酸与二十-羟-二十烷四烯酸）则在草甘膦处理下显著升高.代谢组学的响应表明,草甘膦暴露（5~40 mg·kg^-1）致使蚯蚓糖酵解与三羧酸循环减弱,氨基酸代谢受损,嘌呤代谢紊乱,细胞渗透功能受损,对蚯蚓产生了明显毒副作用,其毒副作用还与细胞色素P450酶代谢相关.蚯蚓CYP亚酶活力与小分子代谢物标记物作为敏感生物标记物,可联合诊断土壤亚致死剂量草甘膦污染.     

升级A/O工艺污水处理系统中抗生素抗性基因的分布与去除研究

针对北方某采用升级A/O工艺的生活污水处理厂,使用实时荧光定量PCR技术,探究污水厂中ARGs的分布及各处理工艺段对ARGs的去除效果.结果表明：四环素抗性基因（tetA、tetC和tetM）、磺胺抗性基因（sul1和sul2）、大环内酯抗性基因（ermA和ermF）和喹诺酮抗性基因（parC和gyrA）在污水和污泥中均被检出.污水厂进水中ARGs的绝对丰度为2.65×10³~1.01×10⁶ copies·mL^-1,升级A/O工艺未能有效削减ARGs,出水中ARGs的绝对丰度为9.22×10³~1.15×10⁶ copies·mL^-1,污泥中ARGs的绝对丰度为8.07×10⁷~2.65×10¹¹ copies·g^-1.深度处理工艺对ARGs的去除效率对比结果显示,生物活性炭工艺对ARGs的削减效果优于紫外消毒.