Analysis of PFAAs in American alligators part 1: Concentrations in alligators harvested for consumption during South Carolina public hunts

Environmental contamination resulting from the production or release of harmful chemicals can lead to negative consequences for wildlife and human health. Perfluorinated alkyl acids (PFAAs) were historically produced as protective coatings for many household items and currently persist in the environment, wildlife, and humans. PFAAs have been linked to immune suppression, endocrine disruption, and developmental toxicity in wildlife and laboratory studies. This study examines the American alligator, Alligator mississippiensis, as an important indicator of ecosystem contamination and a potential pathway for PFAA exposure in humans. Alligator meat harvested in the 2015 South Carolina (SC) public hunt season and prepared for human consumption was collected and analyzed for PFAAs to determine meat concentrations and relationships with animal body size (total length), sex, and location of harvest. Of the 15 PFAAs analyzed, perfluorooctane sulfonate (PFOS) was found in all alligator meat samples and at the highest concentrations (median 6.73 ng/g). No relationship was found between PFAA concentrations and total length or sex. Concentrations of one or all compounds varied significantly across sampling locations, with alligators harvested in the Middle Coastal hunt unit having the highest PFOS concentrations (median 16.0 ng/g; p = 0.0001). Alligators harvested specifically from Berkley County, SC (located in the Middle Coastal hunt unit) had the highest PFOS concentrations and the greatest number of PFAAs detected (p < 0.0001). The site-specific nature of PFAA concentrations in alligator meat observed in this study suggests a source of PFAA contamination in Berkley County, SC.     

我国部分地区自来水和不同水体中的PFOS污染

采用高效液相色谱/质谱仪联机选择离子监测(LC/MS-SIM, m/z = 499)方法,测定了我国部分城市自来水、地面水、地下水和海水中的全氟辛磺酸(PFOS)含量.从全部样品中均检测到PFOS,表明我国境内水环境中普遍存在着PFOS污染.被调查部分城市自来水、海水和远离人类活动地区的水中PFOS浓度大多数低于1ng/L,容易受到生活污水和工业废水污染的水中PFOS浓度范围为1.50～44.6ng/L.     

Sorption of Perfluorooctane sulfonate（PFOS） including its isomers on hydrargillite as a function of pH,humic substances and Na2SO4

Perfluorooctane sulfonate（PFOS） is a persistent organic pollutant（POP） and emergent contaminant that are widespread in the environment. Understanding the mechanisms controlling the distribution of PFOS and its isomers between hydrargillite and the water phase is important in order to study their redistribution and mobility in the environment. This study investigated the effects of pH, humic acid, fulvic acid and Na₂SO₄ on sorption of PFOS isomers to hydrargillite. A mixture...     

Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study

Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono- and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5 mg/L Ca(ClO)₂. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (< 10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 μg/L–0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water.     

Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study

Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono-and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5 mg/L Ca(ClO)₂. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (<10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 μg/L-0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate(TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl-and PO₄^3- of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system ...     

全氟辛烷磺酸(PFOS)对斑马鱼卵黄蛋白原mRNA水平的影响

为了研究环境低剂量全氟辛烷磺酸（perfluorooctane sulfonate,PFOS）对水生生物的内分泌干扰效应和可能的作用机制,测定了PFOS对斑马鱼（Brachydanio rerio）肝脏中卵黄蛋白原（vitellogenin,VTG）mRNA水平的影响.将斑马鱼暴露于4个PFOS的环境低剂量浓度组（0.1、1、10、100μg.L-1）中进行21d毒性试验,收集肝脏样品,提取RNA,采用荧光定量PCR（qRT-PCR）分别检测VTG1和VTG3的mRNA水平.结果表明：①PFOS暴露引起雄性斑马鱼肝脏VTG1和VTG3 mRNA水平升高,VTG1 mRNA水平升高与剂量呈正相关,在100μg.L-1暴露浓度处与对照组呈现显著性差异;VTG3的mRNA水平变化与剂量呈倒U型曲线,呈现典型的毒物刺激荷尔蒙效应,在10和100μg.L-1暴露浓度处与对照组呈现显著性差异;②PFOS暴露引起雌性斑马鱼肝脏中VTG1 mRNA水平升高,在10μg.L-1暴露浓度处与对照组呈现显著性差异,但在高浓度（10和100μg.L-1）处试验结果误差较大;VTG3 mRNA水平只在10μg.L-1暴露浓度处升高,但相比于对照组均没有显著性差异.试验结果表明PFOS暴露对斑马鱼的内分泌干扰作用明显,其毒性作用机制可能是类雌激素效应,而肝脏中VTG1和VTG3mRNA水平可能作为PFOS内分泌干扰效应评价的敏感生物标志物,但VTG1和VTG3 mRNA水平的响应曲线呈现基因亚型和性别差异.     

PFOS前体物质(PreFOSs)降解菌的分离鉴定及其降解特性

从氟化工厂附近土壤中分离出1株能以全氟辛烷磺酸前体物质(Pre FOSs)为唯一碳源和能源生长的降解菌PF1,经形态观察及16S r DNA基因序列分析,初步鉴定该菌为生丝微菌属(Hyphomicrobium sp.).在温度为30℃、p H为7.0~7.2条件下,菌株PF1对全氟辛基磺酰胺(PFOSA)和N-乙基全氟辛基磺酰胺(N-Et FOSA)48 h降解率分别为14.6%和8.2%,对PFOS无降解能力.对降解产物进行检测和分析,结果表明PFOSA的降解产物为PFOS;N-Et FOSA能被降解生成PFOSA和PFOS,同时也产生少量的全氟辛基磺酰胺乙酸(FOSAA).由此推断Pre FOSs降解途径,在菌株PF1的作用下,PFOSA脱去氨基直接转化成PFOS.NEt FOSA主要有2种降解途径:(1)N-Et FOSA脱乙基产生PFOSA,PFOSA再进一步脱氨基生成PFOS,此为主要途径;(2)NEt FOSA中的N-乙基被氧化成乙酸基生成FOSAA,FOSAA进一步脱去乙酸基生成PFOSA,并最终脱氨基生成PFOS.     

6:2氟调羧酸在蚯蚓体内的毒理效应及代谢转化

以赤子爱胜蚓(Eisenia fetida)为受试生物,通过活体与离体实验,研究6:2氟调羧酸(6:2FTCA)在蚯蚓体内的毒理效应和代谢转化机制.结果表明,6:2FTCA对蚯蚓体内丙二醛(MDA)含量和过氧化物酶(POD)活性无显著影响,但能够使过氧化氢酶(CAT)活性提高,使超氧化物歧化酶(SOD)和谷胱甘肽转移酶(GST)活性显著升高,说明6:2FTCA对蚯蚓产生了氧化胁迫效应.6:2FTCA在蚯蚓细胞色素P450(CYP450)和GST酶提取液中的降解动力学均符合一级动力学模型,在CYP450(0.014/h)酶液中的降解速率明显高于GST (0.006/h),其终端全氟羧酸(PFCAs)代谢产物为全氟己酸(PFHxA)、全氟戊酸(PFPeA)和全氟丁酸(PFBA),说明CYP450和GST参与了6:2FTCA在蚯蚓体内的代谢转化,且CYP450贡献大于GST.蚯蚓肠道好氧微生物对6:2FTCA具有显著的降解效果,终端PFCAs降解产物为PFHxA和PFPeA,而肠道厌氧微生物对6:2FTCA无降解作用.     

γ辐照和H2O2联合作用下五氯酚(PCP)的降解

研究了水溶液中的五氯酚(PCP)在γ辐照和过氧化氢(H2O2)联合作用下的降解.PCP的初始浓度为27.7 mg·L-1,外加H2O2的初始浓度为0、50和100 mg·L-1.结果表明,PCP在不同条件下的辐照降解符合准一级动力学方程.当外加H2O2的初始浓度在0～100 mg·L-1时,PCP的去除率、矿化率和脱氯...     

6-2氟调醇在活性污泥中的降解

为了解6-2氟调醇(6-2 FTOH)在城市污水处理厂活性污泥中的好氧降解规律,利用室内模拟实验装置,研究了6-2FTOH在未经稀释驯化的活性污泥中的降解动力学及降解产物分布.结果表明,6-2 FTOH能被活性污泥快速吸附并发生降解,降解反应符合一级动力学,半衰期为0.9d.降解产物包括6-2氟调酸(6-2 FTCA)、6-2不饱和氟调酸(6-2 FTUCA)、5-3氟调酸(5-3 FTCA)、5-2s氟调醇(5-2s FTOH)和全氟己酸(PFHxA).第28 d实验结束时,6-2 FTOH残留率为5.5％,6-2 FTCA和6-2 FTUCA的最终产率分别为0和1.2％.5-3FTCA、5-2s FTOH、PFHxA最终产率分别为23.4％、17.6％和1.3％.     

灭幼脲Ⅲ号杀虫剂在大白菜和土壤中持久性及残留的研究

本文报道灭幼脲Ⅲ号杀虫剂在大白菜和土壤中的残留试验结果.经在南北两地连续两年的田间试验表明,灭幼脲Ⅲ号属非持久性农药,在作物和土壤中都较快地消失,在大白菜上的半衰期为3.8—14.0d,在土壤中为8.8—27.0d.用25％灭幼脲Ⅲ号胶悬剂稀释2500倍,每亩每次按常规用药10g或加倍药量20g(有效成分)施药,喷施2或3次,距最后一次施药三周时,灭幼脲Ⅲ号杀虫剂在大白菜的最大残留量为2.67ppm,在土壤中为13.81ppm.建议该农药在大白菜上的最高允许残留量(MRL)为3ppm,安全间隔期为21d.     

奥奈达希瓦氏菌MR-1还原U(VI)的特性及影响因素

探讨了在腐殖质模式物蒽醌?2?磺酸钠(AQS)存在条件下,奥奈达希瓦氏菌MR-1的还原U(VI)特性.结果表明,在厌氧环境下奥奈达希瓦氏菌以AQS为电子穿梭载体,利用电子供体高效还原U(VI).当菌体投加量为1.2×109 个时,其还原铀的效率达95.09%; AQS的浓度低于0.5mmol/L时有利于MR-1菌厌氧还原U(VI),AQS浓度的升高U(VI)的还原明显受到抑制.当U(VI)初始浓度为30.0mg/L时,分别以甲酸盐、乙酸盐和乳酸盐为电子供体,经过7d后其还原率分别达到95.37%、92.41%和95.65%.金属离子(Cu2+、Mn2+、Ca2+)、有毒有机物等对U(VI)还原产生影响.当Ca2+的浓度为2.0mmol/L时,对U(VI)的还原有微弱的促进作用,而当Cu2+和Mn2+浓度为2.0mmol/L时,则存在较强的抑制作用.奥奈达希瓦氏菌也能利用环境中甲苯、三氯乙酸、顺丁烯二酸等有毒物质高效还原U(VI),同时使有毒物质得到降解.扫描电子显微镜(SEM)和电子能谱(EDS)分析结果表明,奥奈达希瓦氏菌菌体中沉积了铀元素.     

基于灰色理论的甲型H1N1流感传染人数预测模型研究

就我国甲型H1N1流感传染人数的预测运用灰色系统理论,建立了GM（1,1）模型和1阶残差修正模型GMε（1,1）,并分别作了精度分析。研究了GMε（1,1）的变化趋势,提出了临界值和有效域概念。用MATLAB确定了模型参数及模型预测值。     

菌株Cupriavidus sp. DT-1对液体和土壤中TCP的降解

采用液质联用（HPLC-MS）的方法检测菌株Cupriavidus sp.DT-1降解2-羟基吡啶（2-HP）的代谢产物.并用三亲结合、荧光定量PCR （q-PCR）方法评价降解菌对3,5,6-三氯-2-吡啶酚（TCP）污染土壤的修复效果.结果表明,菌株可以进一步降解2-HP,依次生成尼古丁蓝、马来酰胺酸和反丁烯二酸,直至转化成菌株DT-1生长的碳源.接种菌株DT-1对污染土壤中TCP的降解起到较大的促进作用,2组试验土壤中TCP （50mg/kg）降解率分别为94.4%和86.7%,未接种菌株的土壤中TCP降解率仅为20.4%和28.4%.带有绿色荧光蛋白基因gfp标记的菌株DT-1-gfp可在土壤中存活35d以上,并对TCP污染土壤的细菌群落丰度有显著的恢复作用.     

[HgI4-(R6G)2]n体系的共振散射光谱法测定微量汞(Ⅱ)的研究

在pH值=4.0的条件下,Hg2 ,I-与罗丹明6G(R6G)形成三元离子缔合物.由于HgI4(R6G)2分子间存在较强的分子间作用力和疏水作用力而生成[HgI4-(R6G)2]n纳米微粒.在320 nm处产生一灵敏共振散射(即共振瑞利散射)光谱峰.Hg质量浓度在0.004～0.36 mg·L-1范围内与共振散射光强度呈现出良好线性关系.实验结果表明,本法具有灵敏度较高、选择性较好等特点.用于水样中微量Hg的测定,效果良好.     

环糊精对Fe(Ⅲ)引发双酚A光降解的影响

环糊精口α-CD、β-CD和γ-CD能分别与双酚A形成1:1主-客体包结物.在250W金属卤化物灯(λ≥365 nm)光照下,研究了在Fe(Ⅲ)-OH配合物体系中,不同环糊精对双酚A光降解的影响.结果表明,β-CD能较大地促进双酚A的光降解,α-CD次之,而γ-CD对双酚A的光降解存在一定的抑制;并且CDs浓度的变化对双酚A光降解的初始速率有明显的影响.双酚A光降解的初始速率随着β-CD和α-CD浓度增大而增加,当β-CD=60μmol/L时达到最大,然后随着浓度增大而降低,而BPA的光降解初始速率随γ-CD浓度的增加总的趋势是减小的.通过计算机软件Gaussian98,采用PM3方法模拟了环糊精与双酚A的包结行为,进一步说明3种环糊精与双酚A形成主-客体包结物对光降解的影响.     

模拟曝气生物滤池去除邻苯二甲酸二(2-乙基己基)酯试验研究

采用陶粒滤料曝气生物滤池(BAF)处理邻苯二甲酸二(2-乙基己基)酯(DEHP)模拟废水,考察了空床接触时间(EBCT)、温度对DEHP去除效果的影响,运用气质联用仪(GC-MS)分析了中间降解产物并推测其可能的降解途径.结果表明,当温度为25℃,空床接触时间(EBCT)为8 h时,BAF对DEHP的降解效果良好,去除率达到90.3%;BAF对DEHP的去除率随着温度的升高和EBCT的增加而增大,EBCT为去除效果的主要影响因素;BAF对DEHP的降解满足一级反应动力学方程.BAF出水中检测到邻苯二甲酸单2-乙基己基酯(MEHP)、邻苯二甲酸丁基酯2-乙基己基酯(BEHP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二甲酯(DMP)以及邻苯二甲酸(PA)等降解产物,据此推测邻苯二甲酸二(2-乙基己基)酯的生物降解途径可能为其长烷基支链先断裂为较短的直链,而后断裂一个酯键形成单酯,接着再断裂另一酯键形成邻苯二甲酸,最终分解成二氧化碳和水.     

Hepatoprotective and antioxidant effects of dietary Glycyrrhiza polysaccharide against TCDD-induced hepatic injury and RT-PCR quantification of AHR2, ARNT2, CYP1A mRNA in Jian Carp (Cyprinus carpio var. Jian)

To evaluate the protective effects of Glycyrrhiza polysaccharide (GPS) against 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-induced hepatotoxicity in Jian carp, the fish were fed diets containing GPS at doses of 0.1, 0.5 and 1.0 g/kg for 60 days before an intraperitoneal injection of 0.6 μg/kg TCDD at a volume of 0.05 mL/10 g body weight. At 72 hr post-injection, blood and liver samples were taken for biochemical analysis and the fish liver samples were used for the preparation of pathological slices. The results showed that increases in alanine aminotransferase (GPT), aspartate aminotransferase (GOT), lactate dehydrogenase (LDH), and alkaline phosphatase (AKP) in serum induced by TCDD were significantly inhibited by pre-treatment with 1.0 g/kg GPS. Following the 1.0 g/kg GPS pre-treatment, total protein (TP), albumin (Alb), catalase (CAT), glutathione peroxidase (GPx), total antioxidant capacity (T-AOC) and superoxide dismutase (SOD) activities in liver tissue increased significantly, malondialdehyde (MDA) formation (P < 0.05 or P < 0.01) was significantly inhibited, and the expression of cytochrome P4501A (CYP1A), aryl hydrocarbon receptor 2 (AHR2) and aryl hydrocarbon receptor nuclear translocator 2 (ARNT2) mRNA (P < 0.05) was significantly enhanced. Histological observations on fish liver were obtained by preparing paraffin tissue sections via HE staining, and the results showed that histological changes were obviously reduced by 0.5 and 1.0 g/kg GPS. GPS significantly reduced liver tissue damage caused by TCDD. Overall, these results proved the hepatoprotective effect of GPS in protecting against fish liver injury induced by TCDD, and supported the use of GPS (1.0 g/kg) as a hepatoprotective and antioxidant agent in fish.     

二氧化锰氧化降解乙炔基雌二醇的动力学研究

研究了化学合成的新生态δ-MnO2对乙炔基雌二醇(EE2)的氧化降解动力学,并且考察了δ-MnO2投加重、EE2初始浓度、初始pH值等因素对EE2降解动力学的影响.结果表明:EE2对新生态水合δ-MnO2的氧化作用具有较强的反应感受性,且在pH值一定和δ-MnO2充分过量的条件下,EE2氧化降解的反应动力学并不是简单的...