大气中全氟与多氟有机化合物研究进展

全氟与多氟有机化合物(PFCs)作为表面活性剂被广泛应用于工业生产及生活家居领域,部分PFCs已被列为斯德哥尔摩公约受控持久性有机污染物(POPs).PFCs具有一些特殊的理化性质(如高表面活性、憎水憎油性等),使其采样、分析、环境迁移转化过程等都不同于"传统"POPs(如PCBs、PAHs等).相对于其它环境介质(水、沉积物和生物等)研究,大气中PFCs的研究相对较少.本文针对大气中PFCs的研究现状进行综述,内容涵盖了大气PFCs的样品采集、前处理、仪器分析、含量水平和迁移转化过程,其中重点概述了大气中PFCs的气-颗粒两相分配、长距离迁移、干湿沉降和大气降解,并提出了今后的重点研究方向建议.     

OASIS(R) WAX固相提取吸附剂用于水及组织中PFOS和相关化合物的UPLC(R)/MS定量分析

近年来,全氟化合物(PFCs)如全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA,其分子结构如图1所示)已经被明确为持久性有机污染物(POPs),并在环境中普遍存在[1].由于PFCs可能具有毒性和生物积聚性,因此,对食品、饮用水、组织、血浆和全血中PFCs分析方法的建立受到越来越多的关注.     

4种短链全氟化合物替代物在城市污水处理厂的污染特征研究

全氟辛烷羧酸(perfluorooctanoic acid,PFOA)和全氟辛烷磺酸(perfluorooctyl sulfonate,PFOS)等长链全氟化合物(perfluorinated compounds,PFCs)具有持久性、生物累积性和毒性,近年来发现一些短链PFCs具有相对较短的半衰期,可以成为PFOA和PFOS的替代品,这些物质包括C4和C6结构的PFCs,如全氟丁烷羧酸(perfluorobutanoic acid,PFBA)、全氟己烷羧酸(perfluorohexanoic acid,PFHx A)、全氟丁烷磺酸(perfluorobutyl sulfonate,PFBS)和全氟己烷磺酸(perfluorohexyl sulfonate,PFHx S)。为解析我国城市污水厂短链PFCs污染水平和地域分布特征,本研究调查了我国不同地区17座城市污水处理厂的进水、二沉出水和污泥中4种短链PFCs的分布和浓度水平。结果表明4种短链PFCs、PFOA和PFOS在17座污水厂进水中检出率均为100%(6种目标物单体浓度范围:0.19~274.72 ng·L-1);污泥中PFOS和PFOA检出率为100%(PFOS:2.08~72.31 ng·g-1,PFOA:1.03~24.81 ng·g-1),PFBA、PFHx A检出率为100%(0.60~3.33 ng·g-1),PFBS和PFHx S的检出率分别为42.11%和63.16%。在污水厂进水中,将PFOA和PFOS与其同类的短链PFCs浓度进行比较,发现短链PFCs分别相对于PFOA和PFOS的比例最高可达93.47%和94.57%。4种短链PFCs、PFOA和PFOS的地域分布差异明显,总浓度呈现出华东、华南地区高于西北、东北、华北地区的趋势,其中华东地区调查的污水处理厂浓度最高。污水厂4种短链替代物主要通过污水排放,不同污水厂的日排放总量(污泥和出水)为0.25~273.07 g·d-1,万吨水排放量范围为0.04~1.37 g。研究将为我国全氟化合物替代物污染和控制提供数据基础和科学依据。     

OASIS~ WAX固相提取吸附剂用于水及组织中PFOS和相关化合物的UPLC~/MS定量分析

近年来,全氟化合物(PFCs)如全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA,其分子结构如图1所示)已经被明确为持久性有机污染物(POPs),并在环境中普遍存在[1].由于PFCs可能具有毒性和生物积聚性,因此,对食品、饮用水、组织、血浆和全血中PFCs分析方法的建立受到越来越多的关注.本文将讨论     

山东省典型湿地水体和沉积物中全氟辛烷羧酸(PFOA)和全氟辛烷磺酸(PFOS)的污染特征

全氟辛烷羧酸(perfluorooctanoic acid,PFOA)和全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)广泛存在于全球范围内的各种环境介质中,是全氟化合物中最典型的持久性有机污染物.为考察山东省典型湿地中PFOA和PFOS的浓度水平与空间分布特征,采用超高效液相色谱-串联质谱与WAX固相萃取相结合的方法,检测并系统分析了南四湖流域和东部沿海地区水和沉积物体系中PFOA和PFOS含量状况.研究结果表明,PFOA和PFOS在研究区域全部水样中均被检测出,浓度范围分别为10.49—84.6 ng·L~(-1)和0.49—25.4 ng·L~(-1);其中南四湖流域表层水中污染物的含量高于东部沿海地区,并且污染物浓度从下游到上游呈上升趋势.沉积物样品中PFOA和PFOS的浓度范围(干重)分别为0.09—2.76 ng·g~(-1)和0.17—5.25 ng·g~(-1),其空间分布趋势和水样中的大致相同.与国内外其他地区水和沉积物中PFOA和PFOS含量进行对比,山东省典型湿地中两种污染物的污染水平较高且PFOA污染更为严重.与PFOA相比,水和沉积物体系中PFOS的分配系数更高,并且不同区域间的分配系数存在差异.此外,本文采用熵值法对研究区域内两种污染物进行了初步风险评估,分析结果显示PFOA和PFOS对水生生物和野生鸟类可能存在一定的生态风险,且PFOS的风险较高,考虑到全氟化合物的生物累积性和食物链放大效应,应重视PFOA和PFOS的生态风险.     

近岸海水中全氟化合物的液相色谱-离子阱质谱法测定

建立了利用高效液相色谱-电喷雾离子阱质谱(HPLC-ESI-IT-MS/MS)测定近岸海水中多种常见全氟化合物(PFCs)的分析方法.采用固相萃取法(SPE)对海水中的PFCs净化富集,用HPLC-ESI-IT-MS/MS多反应离子监测(MRM)模式对各组分(全氟己烷磺酸、全氟辛烷磺酸、全氟辛烷磺酰胺、全氟己酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟癸酸、全氟十一酸、全氟十二酸)进行测定.在最佳实验条件下,采用基质匹配标准曲线法定量,以消除海水基质的影响,8种目标化合物的检出限介于0.50—1.00 ng·L-1,9种PFCs的回收率在71.0%—130.2%之间,能满足近岸海水中多种PFCs检测的要求.青岛沿岸表层海水样品测定结果显示,全部采样站点的海水样品中均检测到≥4种PFCs,说明青岛沿岸海水中已有一定程度的PFCs污染.     

云南省会泽县农田土壤中全氟化合物污染特征研究

为探究云南省会泽县农田土壤中全氟化合物(perfluorinated compounds,PFCs)的污染特征及其潜在来源,2015年6月采集云南省会泽县农田土壤42份,利用高效液相色谱-串联质谱仪(HPLC-MS/MS)分析了11种PFCs的含量水平。结果表明,云南省会泽县农田土壤中全氟己酸(perfluorohexanoic acid,PFHx A)、全氟庚酸(perfluoroheptanoic acid,PFHp A)和全氟己烷磺酸(perfluorohexane sulfonate,PFHx S)均未检出,其余8种PFCs(ΣPFCs)的平均含量水平为0.392 ng·g-1,含量范围为0.298~0.998ng·g-1。全氟辛酸(perfluorooctanoic acid,PFOA)和全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)是最主要的PFCs,相对百分含量范围为45.93%~81.86%,其平均含量水平分别为0.116 ng·g-1和0.120 ng·g-1。与国内其他地区土壤中PFCs的含量水平相比,云南省会泽县农田土壤中PFCs含量水平低于上海,与广州、深圳、东莞、安徽、中国东部农村等地区土壤中PFCs的含量相当。主成分分析结果表明,以全氟癸酸(perfluorodecanoic acid,PFDA)、全氟辛烷磺酸(PFOS)和全氟十三酸(perfluorotridecanoic acid,PFTr DA)为主要标志物的2个主成分可以解释云南省会泽县农田土壤中73%的ΣPFCs。工业活动、大气沉降及长距离传输为云南省会泽县农田土壤中PFCs的主要来源。     

全氟化合物及其替代品的处理技术

全氟化合物(PFCs)及其替代品是具有污染持久性、生物毒性和累积性的氟烃类化合物,严重威胁生态系统乃至人类健康.已有PFCs及其替代品的处理技术主要包括吸附、电化学氧化等,各技术的去除效果和适用范围不尽相同.目前我国缺少针对PFCs及其替代品处理技术的系统总结和对比研究.为了选择适合且有效的技术去除PFCs及其替代品污染物,本文详细介绍了近年来处理该类污染物的常用技术,从去除效果、去除机理及适用性等方面对比不同技术的优势与不足,并展望不同技术的发展趋势,为我国PFCs及其替代品的有效治理与控制提供科学依据.     

固相萃取-高效液相色谱串联质谱技术测定污水中的全氟化合物

以全氟辛烷羧酸(PFOA)和全氟辛烷磺酸(PFOS)为代表的全氟化合物(PFCs),在日用消费品和工业生产中被广泛使用,并可通过各种途径大量进入环境.在全球各类环境介质以及生物体中已经普遍检测到了PFCs的存在.目前有关水环境中PFCs的分布及归趋研究,主要针对PFOS和PFOA及其长链同系物.随着PFOS和PFOA的禁用,一系列短链同系物作为替代物质进入生产和应用领域,并最终进入环境.目前针对短链全氟化合物的分析方法报道的还较少.     

全氟化合物对水生植物的生态效应研究Ⅰ——典型城市河道全氟化合物的暴露水平及植物富集特征

全氟化合物(perfluorinated compounds,PFCs)近年来得到国内外广泛关注,针对工业源排放区域的环境暴露、来源解析以及动物层面的生态效应有较多研究,但对于普遍存在于非工业源(生活源)的城市河道PFCs暴露及水生植物富集等研究较为缺乏。本研究选择位于北京北部东西贯通的城市河道——清河水体为对象,分析结果表明,清河水体中12种目标PFCs均有检出(总量最高为65.45 ng·L-1),并以全氟丁烷磺酸盐(perfluorobutane sulfonate,PFBS)为主(最高达45.63 ng·L-1);6种水生植物(篦齿眼子菜、黑藻、金鱼藻、芦苇、菖蒲及水葱)的富集物质均以全氟辛烷磺酸盐(perfluorooctane sulfonate,PFOS)和全氟辛酸(perfluorooctanoic acid,PFOA)为主,沉水植物中金鱼藻对于PFOS的蓄积效果优于黑藻及篦齿眼子菜,挺水植物中根部PFCs含量高于茎叶,根部PFOA及PFOS含量高于茎叶,但全氟丁酸(perfluorobutanoic acid,PFBA)含量茎叶则高于根部。整体来看,尽管芦苇、菖蒲和水葱3种挺水植物尚不能作为PFCs的超富集植物,但其根部对PFCs均有显著的吸收效果,具有一定的生态修复潜质;沉水植物中金鱼藻是北方自然河道的优势物种,且对PFOS具有显著的富集效应,因此有必要进一步探索其PFCs生物指示和生态修复功能。     

Applications of chitosan in food,pharmaceuticals, medicine,cosmetics, agriculture,textiles, pulp and paper,biotechnology, and environmental chemistry

Environmental Chemistry Letters - Chitosan is a biopolymer obtained from chitin, one of the most abundant and renewable materials on Earth. Chitin is a primary component of cell walls in fungi, the...     

Seaweed for climate mitigation,wastewater treatment,bioenergy, bioplastic,biochar, food,pharmaceuticals, and cosmetics: a review

The development and recycling of biomass production can partly solve issues of energy, climate change, population growth, food and feed shortages, and environmental pollution. For instance, the use of seaweeds as feedstocks can reduce our reliance on fossil fuel resources, ensure the synthesis of cost-effective and eco-friendly products and biofuels, and develop sustainable biorefinery processes. Nonetheless, seaweeds use in several biorefineries is still in the infancy stage compared to terrestrial plants-based lignocellulosic biomass. Therefore, here we review seaweed biorefineries with focus on seaweed production, economical benefits, and seaweed use as feedstock for anaerobic digestion, biochar, bioplastics, crop health, food, livestock feed, pharmaceuticals and cosmetics. Globally, seaweeds could sequester between 61 and 268 megatonnes of carbon per year, with an average of 173 megatonnes. Nearly 90% of carbon is sequestered by exporting biomass to deep water, while the remaining 10% is buried in coastal sediments. 500 gigatonnes of seaweeds could replace nearly 40% of the current soy protein production. Seaweeds contain valuable bioactive molecules that could be applied as antimicrobial, antioxidant, antiviral, antifungal, anticancer, contraceptive, anti-inflammatory, anti-coagulants, and in other cosmetics and skincare products.

     

Lead,cadmium, copper,zinc, iron,and calcium in human hair as a function of gender,age, smoking,and hair dyeing

Hair samples were collected randomly from 110 subjects (55 male and 55 female) ranging in age from (<15–60) years. Each subject was asked to complete a personal questionnaire describing his/her sex, age, general health, smoking, use of hair dyes, occupational area, and living habits. Concentrations of Pb, Cd, Cu, Zn, Fe, and Ca in human hair samples were evaluated using atomic absorption spectrometry. Results indicated that concentrations of Pb, Cd, Cu, and Zn in the hair of smokers were higher than those in the hair of non-smokers, whereas, Fe and Ca concentrations in hair of smokers were lower than those in hair of non-smokers. Moreover, the concentrations of these elements are higher in dyed hair compared with undyed hair.     

Metal passivity as mechanism of metal carcinogenesis: Chromium,nickel, iron,copper, cobalt,platinum, molybdenum

For the transition metals chromium, nickel, iron, copper, cobalt, platinum, and molybdenum, mechanisms of stable bonding in biochemistry (emphasis on carcinogenic mechanisms), chemistry, industrial chemistry, as well as epidemiological, occupational, orthopedic (implant devices) effects related to carcinogenesis, were reviewed. Hypothetically, the propensity to stable bonding (inertness), which ensures the metals’ performance capacity for consumers and industrial application, relates to their carcinogenicity. For chromium, a relationship between industrial/chemical and biological reactivity was noted for the tendency of Cr(III) ions to cause hydrolysis previous to stable bonding, as occurs during anodic passivation, leather tanning, and as indicated in biochemical studies pertaining to a mechanism of DNA condensation, which was suggested as a carcinogenic mechanism. The involvement of metal hydrolysis in both anodic passivation and biochemistry was noted also for nickel, iron, and platinum; the DNA interaction of platinum (cis-platin) is known to depend on hydrolysis. For nickel, issues of potential (V) were found important in both passivation and carcinogenicity. Comparably, the passivity behavior of cobalt and copper was found atypical, and their carcinogenicity yet unclear. Molybdenum, contained in passivated metallic implants, may relate to implant-associated carcinogenesis. Occupational carcinogenic effects were indicated for chromium, nickel, iron, and cobalt as caused by both reactive and passivated metal species. Exposure to acids and chronic respiratory irritation/infection/inflammation in workers were important cofactors in metal carcinogenesis. For wood and leather workers exposed to dust, the assumed presence in dust of metal particles abraded from alloys (sawing or cutting blades) may be a carcinogenic exposure hazard.     

Concentrations of V,Cr, Mn,Fe, Ni,Co, Cu,Zn, As and Cd in mesopelagic crustaceans from the North East Atlantic Ocean

Specimens of oceanic decapods, mysids and euphausiids, collected from the North East Atlantic Ocean during July 1985, were analysed for V, Cr, Mn, Fe, Ni, Co, Cu, Zn, As and Cd. Measurement of the metals was carried out using two techniques: inductively-coupled plasma-source mass spectrometry (ICP-MS) and atomic absorption (AAS). With the exception of the iron data, good agreement was observed between the data from the two techniques. Baseline-metal data are presented for the species measured, along with any effects of animal size on metal concentration. The data presented for oceanic animals from different trophic levels are important in studies of metal fluxes and for the assessment of markers within the food web in the oceans.