餐厨垃圾水热炭对全(多)氟烷基化合物的吸附性能

以高湿餐厨垃圾为对象,通过水热碳化结合高温活化制备水热炭(AC).采用多种表征手段对水热炭的理化性质进行刻画,并对一类全球关注的新污染物——全(多)氟烷基化合物(PFAS)进行吸附实验及动力学分析,以期为“以废治污”提供新思路.结果显示,经过活化处理的水热炭具有较高的比表面积(206.97m²/g)和疏水表面特性,有利于与PFAS的吸附结合.在环境相关浓度下(～40μg/L),PFAS在AC上的吸附分配系数(log K_d)在2.3 8～6.49L/kg范围内,高于其他生物炭的报道结果,说明AC对目标PFAS具有良好的吸附性能.吸附过程较符合Langmuir等温吸附模型及Elovich动力学模型,证明PFAS在AC上的吸附从机理上近似单分子层化学吸附过程.此外,对于PFCA和PFSA,log K_d值与全氟烷基链长呈正相关,表明疏水作用在AC与PFAS的吸附过程中发挥重要作用.     

水中全/多氟化合物污染现状及控制技术研究进展

全氟/多氟烷基化合物(PFASs)是21世纪受到重点关注的新型持久性有机污染物。PFASs化合物具有疏水、疏油,化学稳定性强、表面活性高的特性,能够承受光照、高温,不易被微生物降解。因PFASs应用广泛,在环境中的化学稳定性好,近年来陆续在全球范围内的各种环境介质和生物体中被检出。大量研究表明,环境介质和生物体中检出的PFASs类物质多为全氟辛烷磺酸和全氟辛酸,PFASs具有多种高等毒性,已严重威胁到生态系统和人类健康,有必要深入研究它们的环境行为。该文总结了多种水域、沉积物和生物体中PFASs的污染现状,概述了目前各种PFASs的去除技术,重点对吸附去除PFASs的机理以及迁移规律等环境行为进行了总结,并对PFASs的未来研究方向与发展趋势提出了相应的建议,旨在为今后的研究提供参考。     

典型氟工业园周边河流沉积物中全(多)氟化合物的分布特征

采用超高效液相色谱/质谱联用(UPLC/MS-MS)分析了我国重要的氟化物工业园区周边河流——辽宁细河(阜新段)、山东小清河(淄博段)和长江(江苏常熟段)表层沉积物中全(多)氟烷基化合物(PFASs)的污染状况.细河表层沉积物中,PFASs含量范围(以干重计,下同)为15.8～2 770 ng·g^-1,全氟丁烷磺酸(PFBS)和六氟环氧丙烷二聚酸(HFPO-DA)是主要污染物;小清河表层沉积物中,PFASs含量为12.2～7 853 ng·g^-1,全氟烷基辛酸(PFOA)和HFPO-DA为主要污染物;长江表层沉积物中,PFASs含量为9.20～35.9 ng·g^-1,全氟十四酸(PFTeDA)和6∶2氟调磺酸(6∶2FTS)为主要污染物.工业园区废水排放(点源污染)是本研究中3个区域PFASs的主要来源. 3个区域PFASs含量及组成差异明显,与工业园区生产规模和产业类型有关.PFASs含量及各组分含量与TOC、沉积物粒径没有显著相关性,PFASs各组分间相关性也有差异,说明PFASs在沉积物中的富集过程与多种因素有关.     

黄河中游(渭南-郑州段)全/多氟烷基化合物的分布及通量

本研究收集黄河中游(渭南—郑州段)表层水样品,利用高效液相色谱质谱串联的方法分析了水相和颗粒相中的28种全氟和多氟烷基化合物(PFASs).结果表明,水相和颗粒相中Σ28PFASs的含量分别为18.4~56.9 ng·L~(-1)和26.8~164ng·g~(-1)(以干重计).水相和颗粒相中以全氟己酸(PFHx A)为主要污染物,分别占总含量的27%和16%,且3H-全氟-3-(3-甲氧基丙氧基)丙酸(ADONA)、氯代多氟醚基磺酸(6∶2和8∶2 Cl-PFESA)在颗粒相均有检出,表明PFASs替代品的生产和使用逐渐增多.PFASs在水相-颗粒相中的lg Kd变化范围为2.95±0.553(PFPe A)~3.85±0.237(8∶2 FTUCA),颗粒物吸附氟调聚羧酸(FTCAs)和不饱和氟调聚羧酸(FTUCAs)的能力随碳链长度的增长而增加,全氟烷基磺酸(PFSAs)较全氟烷基羧酸(PFCAs)更容易被颗粒物吸附.黄河郑州—渭南段PFASs的通量呈现先降低后增加的趋势,表明该河段接纳了来自上游及支流的污染输入.此外,结果表明水相中的PFASs通量大于颗粒相.     

碱渣与生活垃圾混合填埋的实验研究

以碱渣(白泥)和生活垃圾按不同比例混合填埋,模拟真实垃圾填埋场的垃圾降解条件,进行垃圾降解实验以探索白泥存在对垃圾填埋场垃圾降解过程的影响。通过21周的室内模拟实验,垃圾填埋时填加白泥可以提高渗滤液出水的pH值和电导率DS值,降低出水的COD值。得出垃圾填埋时加入适量白泥是经济有效的固体废弃物处理处置方法的结论。     

贡嘎冰川水环境中全氟及多氟化合物的污染特征及排放通量

为掌握贡嘎冰川水环境中全氟及多氟烷基化合物(PFASs)的赋存特征,本文采用超高效液相色谱-质谱联用仪(UPLC-MS/MS)分析了贡嘎山海螺沟地区不同水样中21种PFASs的浓度水平.结果显示,11种PFASs有所检出,Σ21PFASs的浓度范围为7.09～106ng/L,平均值为30.2ng/L,主要PFASs为全氟丁酸(PFBA,131ng/L)、全氟辛酸(PFOA,37.2ng/L)和全氟辛烷磺酸(PFOS,17.1ng/L).本研究中E21PFASs浓度最高点位于海拔2735m的草海子地区,为106ng/L.贡嘎海螺沟地区无直接排放源,但在降雨中检测出较高浓度的PFASs,表明海螺沟水环境中PFASs来源于大气的干湿沉降.海螺沟地区PFASs的年排放通量为0.2197t/a,其中排放通量最高的是PFOA (0.0762t/a),占总排放量的34.71%,然后依次为PFHpA (0.0317t/a)和PFBA (0.0285t/a),分别占总排放量的14.43%和12.96%.未来应对贡嘎海螺沟地区加强PFASs的监测,更加准确掌握海螺沟冰川融水排放的PFASs通量,为科学管控...     

典型电镀厂土壤中全/多氟烷基化合物的污染特征及风险评估

采用高效液相色谱-串联质谱联用仪(HPLC-MS/MS)测定了典型电镀厂环境土壤中28种全/多氟烷基化合物(PFASs)的含量,并进行了风险评估。结果表明,PFASs在电镀厂内外环境土壤中的含量为48.18～4 655.62 ng/g dw,主要污染物为PFOS和6∶2 F-53B,占比80%以上。土壤中PFASs的存在水平随距离的增加而迅速下降,污染扩散范围非常有限。工业污染源周围环境土壤中PFASs的污染高出非工业区的环境土壤1～2个数量级。厂区内外PFOS的污染远超出土壤中的预测无效应浓度,具有一定的生态风险。     

全氟和多氟烷基化合物微生物降解与转化研究进展

全氟和多氟烷基化合物(PFASs)因其持久性、长距离迁移性、生物积累性和生物毒性而受到广泛关注.目前世界上对环境中PFASs的监测和管控主要针对全氟烷基酸(PFAAs).而大部分多氟烷基化合物在环境中能够被微生物降解为PFAAs,也被称为前体物.因此,探究前体物在环境中的微生物转化行为有助于综合评价PFASs的环境风险,以及制定相关的管控和修复措施.虽然PFAAs一直被认为是环境中的“永久化合物”,但近年来,PFAAs的厌氧微生物还原脱氟作为一项极具潜力且充满挑战的修复技术,成为研究的一个前沿热点.系统总结了前体物(氟调化合物和全氟辛烷磺胺衍生物)、 PFAAs和新型PFASs在微生物作用下的降解规律和转化路径,并讨论了PFASs微生物降解的影响因素,最后提出未来的研究方向.     

渤海油气区周边海域PFASs的赋存特征与来源

为了解我国海上油田区域附近PFASs(多氟或全氟化合物)污染状况,本文针对我国渤海油田区所在海域采集了92个海水样品,并对其中19种PFASs及其新型替代品的含量进行了分析。结果表明,渤海油气区周边海水中总PFASs浓度范围为9.33~113ng/L,与中国其他海域相比,渤海油田区周边海水中总PFASs含量较高。传统PFASs中,全氟辛酸(PFOA)是大部分样品中的主要PFASs。新型替代品中,六氟环氧丙烷二聚酸(HFPO-DA)的浓度相对较高,浓度中位数为1.82ng/L,而在所有样品中6:2氯代多氟醚磺酸(6:2Cl-PFESA)均未检出。从区域分布来看,总PFASs浓度较高的油田位于渤海西部。总PFASs含量与离岸距离等影响因素相关性分析表明,渤海油气区附近海水中总PFASs含量与离岸距离显著相关,说明陆源是渤海油气区中PFASs污染的主要来源。     

植物对PFAS的富集机制研究进展

本文通过文献梳理,分析了全(多)氟烷基化合物(PFAS)对植物的暴露途径;统计了已发表文献中36种植物对19种PFAS的转运、富集特征;系统地阐释了PFAS从环境介质到植物组织内的迁移、积累机制;讨论了PFAS分子结构(如全氟碳链长度、头部官能团)、植物生理特性、环境因素对该富集过程的影响,并提出了未来有关植物富集PFAS可关注的重点和方向,以期能深入认识PFAS在环境介质-植物根际-植物组织内的赋存与迁移转化特征,更好地管控评估PFAS污染场地并制定植物修复方案,为开展生态与健康风险评价提供参考。     

Analysis of per- and polyfluoroalkyl substances in Houston Ship Channel and Galveston Bay following a large-scale industrial fire using ion-mobility-spectrometry-mass spectrometry

Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants of concern because of their ubiquitous presence in surface and ground water; analytical methods that can be used for rapid comprehensive exposure assessment and fingerprinting of PFAS are needed. Following the fires at the Intercontinental Terminals Company (ITC) in Deer Park, TX in 2019, large quantities of PFAS-containing firefighting foams were deployed. The release of these substances into the Houston Ship Channel/Galveston Bay (HSC/GB) prompted concerns over the extent and level of PFAS contamination. A targeted liquid chromatography-tandem mass spectrometry (LC-MS/MS)-based study of temporal and spatial patterns of PFAS associated with this incident revealed presence of 7 species; their levels gradually decreased over a 6-month period. Because the targeted LC-MS/MS analysis was focused on about 30 PFAS molecules, it may have missed other PFAS compounds present in firefighting foams. Therefore, we utilized untargeted LC-ion mobility spectrometry-mass spectrometry (LC-IMS-MS)-based analytical approach for a more comprehensive characterization of PFAS in these water samples. We analyzed 31 samples from 9 sites in the HSC/GB that were collected over 5 months after the incident. Our data showed that additional 19 PFAS were detected in surface water of HSC/GB, most of them decreased gradually after the incident. PFAS features detected by LC-MS/MS correlated well in abundance with LC-IMS-MS data; however, LC-IMS-MS identified a number of additional PFAS, many known to be components of firefighting foams. These findings therefore illustrate that untargeted LC-IMS-MS improved our understanding of PFAS presence in complex environmental samples.     

Diffusive gradients in thin films (DGT) probe for effectively sampling of per- and polyfluoroalkyl substances in waters and sediments

The passive sampling technique, diffusive gradients in thin films (DGT) has attracted increasing interests as an in-situ sampler for organic contaminants including per- and polyfluoroalkyl substances (PFAS). However, its effectiveness has been questioned because of the small effective sampling area (3.1 cm²). In this study, we developed a DGT probe for rapid sampling of eight PFAS in waters and applied it to a water-sediment system. It has a much larger sampling area (27 cm²) and as a result lower method quantification limits (0.15 – 0.21 ng/L for one-day deployment and 0.02 – 0.03 ng/L for one-week deployment) and much higher (by > 10 factors) sampling rate (100 mL/day) compared to the standard DGT (piston configuration). The sampler could linearly accumulate PFAS from wastewater, was sensitive enough even for a 24 hr deployment with performance comparable to grab sampling (500 mL). The DGT probe provided homogeneous sampling performance along the large exposure area. The use of the probe to investigate distributions of dissolved PFAS around the sediment-water interface was demonstrated. This work, for the first time, demonstrated that the DGT probe is a promising monitoring tool for trace levels of PFAS and a research tool for studying their distribution, migration, and fate in aquatic environments including the sediment-water interface.     

生活垃圾焚烧发电厂渗滤液全部入炉焚烧技术

生活垃圾焚烧发电厂的垃圾渗滤液含有多种有害有机物、重金属等,COD_Cr和BOD₅远高于城市污水,氨氮浓度高,并具有很强的恶臭味,必须彻底无害化处理;当前国内绝大部分垃圾发电厂的垃圾渗滤液处理方法多为生物法、物化法或其联合处理,这些方法过程复杂、成本昂贵、无害化相对不够彻底。追溯了垃圾渗滤液的来源,提出基于垃圾元素分析的燃烧计算和热力计算数据设计的垃圾焚烧发电锅炉,理论上只有将垃圾渗滤液全部入炉焚烧,才不会影响锅炉功率、效率、排烟温度等参数,提出了渗滤液全部入炉焚烧的具体工艺,即渗滤液的充分细雾,雾化渗滤液喷入口的数量及其相应位置和角度,渗滤液喷入量如何随入炉垃圾焚烧量自动跟踪相匹配等,旨在进一步完善垃圾无害化焚烧技术。     

Contribution of precursor compounds to the release of per- and polyfluoroalkyl substances (PFASs) from waste water treatment plants (WWTPs)

Per-and polyfluoroalkyl substances(PFASs) are ubiquitous in sludge and water from waste water treatment plants, as a result of their incorporation in everyday products and industrial processes. In this study, we measured several classes of persistent PFASs,precursors, transformation intermediates, and newly identified PFASs in influent and effluent sewage water and sludge from three municipal waste water treatment plants in Sweden, sampled in 2015. For sludge, samples from 2012 and 2014 were analyzed as well.Levels of precursors in sludge exceeded those of perfluoroalkyl acids and sulfonic acids(PFCAs and PFSAs), in 2015 the sum of polyfluoroalkyl phosphoric acid esters(PAPs) were 15–20 ng/g dry weight, the sum of fluorotelomer sulfonic acids(FTSAs) was 0.8–1.3 ng/g,and the sum of perfluorooctane sulfonamides and ethanols ranged from non-detected to 3.2 ng/g. Persistent PFSAs and PFCAs were detected at 1.9–3.9 ng/g and 2.4–7.3 ng/g dry weight, respectively. The influence of precursor compounds was further demonstrated by an observed substantial increase for a majority of the persistent PFCAs and PFSAs in water after waste water treatment. Perfluorohexanoic acid(PFHxA), perfluorooctanoic acid(PFOA), perfluorohexane sulfonic acid(PFHxS), and perfluorooctane sulfonic acid(PFOS)had a net mass increase in all WWTPs, with mean values of 83%, 28%, 37% and 58%,respectively. The load of precursors and intermediates in influent water and sludge combined with net mass increase support the hypothesis that degradation of precursor compounds is a significant contributor to PFAS contamination in the environment.     

我国生活垃圾焚烧发电过程中温室气体排放及影响因素 ——以上海某城市生活垃圾焚烧发电厂为例

以上海某城市生活垃圾焚烧发电厂为例,采用上游-操作-下游(UOD)表格法,分析了生活垃圾焚烧发电过程中不同环节的温室气体排放贡献,及影响其排放的主要因素.结果表明,目前我国生活垃圾焚烧发电过程是温室气体排放源,以吨垃圾净CO2排放量计,达166~212kg.生活垃圾中自含化石碳对温室气体排放的贡献最大,CO2排放量为257kg/t;因焚烧发电上网而获得的净减排量为120kg/t;垃圾收运、辅助物料消耗及焚烧灰渣处理等引起的排放量总计为27~45kg/t.生活垃圾沥出渗滤液后续处理过程的温室气体排放量为7.7kg/t.节省焚烧过程辅助物料使用和改变焚烧灰渣处置方式能够减少温室气体排放量,但是减排效果有限.我国各地区电能基准线排放因子存在差异,对焚烧过程温室气体排放的影响为0~13%.降低生活垃圾含水率、提高垃圾可发电量是我国生活垃圾焚烧发电过程温室气体排放源汇转换的关键途径.     

Levels, distributions, and sources of legacy and novel per- and perfluoroalkyl substances (PFAS) in the topsoil of Tianjin, China

Soil is a major sink for per- and perfluoroalkyl substances (PFAS), wherein PFAS may be transferred through the food chain to predators at upper trophic levels, which poses a threat to human health. Herein, the concentrations and distributions of legacy and novel PFAS in topsoil samples from different functional areas in Tianjin were comprehensively investigated. Seventeen PFAS congeners were identified, with concentrations ranging from 0.21 ng/g to 5.35 ng/g, with a mean concentration of 1.25 ng/g. The main PFAS in the topsoil was perfluorooctanoic acid (PFOA). 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA; <MDL–1.95 ng/g, mean 0.11 ng/g), as an emerging substitute for perfluorooctane sulfonate (PFOS), was also detected in the topsoil. It showed slightly higher concentrations than PFOS (<MDL–1.62 ng/g, mean 0.10 ng/g), indicating it has gradually replaced legacy PFOS in this area. Based on the positive-definite matrix factor (PMF) receptor model, the major PFAS sources was dominated by textile treatment, metal electroplating plants, and some potential precursors of PFAS with longer chains (>C8) were the major sources (43.4%), followed by food packaging as well as coating materials (25.5%). In addition, Spearman correlation analysis and the structural equation model showed that population density significantly impacted the PFAS distribution in the topsoil of Tianjin.     

EGSB处理垃圾焚烧渗沥液及其微生物群落变化

研究了处理垃圾焚烧渗沥液的膨胀颗粒污泥床(EGSB)反应器在超负荷运行前后厌氧颗粒污泥的微生物群落结构变化.在实验室启动并运行了处理垃圾焚烧渗沥液的EGSB反应器,逐渐提高反应器的有机负荷(OLR),当OLR为23.1kgCOD/(m3×d)时,COD去除率保持在93%以上.当OLR继续升至24.5kgCOD/(m3×d)时,COD去除率迅速下降至73.9%,且出水挥发酸大量增高,反应器进入超负荷运行状态.对反应器中厌氧颗粒污泥进行克隆文库分析,发现经过11d的超负荷运行,污泥中的微生物群落结构发生了明显的变化,古菌的优势菌从产甲烷髦毛菌(含量为68.4%)变为产甲烷微菌(含量为51.9%);细菌的优势菌一直是低GC革兰氏阳性菌(含量约56%),且大多数属于具有形成芽孢特性的Clostridiales目.EGSB反应器超负荷运行导致乙酸营养型古菌大量死亡,小分子有机酸大量积累,处理效率急剧下降.     

The occurrence of per- and polyfluoroalkyl substances (PFASs) in fluoropolymer raw materials and products made in China

Perfluorooctanoic acid (PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019. In this study, the occurrence of residues of PFOA and other per- and polyfluoroalkyl substances (PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time. The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10⁶ ng/g, and <MDL (method detection limit) to 5.3 × 10³ ng/g, respectively. Generally, the levels of PFOA in raw materials were higher than in products, implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps. By tracking a company's polytetrafluoroethylene (PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10⁶ to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued. High concentrations of HFPO-TrA (2.7 × 10⁵ to 8.2 × 10⁵ ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.     

垃圾填埋场渗滤液中药物和个人护理品的存在与去除

采用固相萃取–高效液相色谱/串联质谱法,分析上海市某生活垃圾填埋场渗滤液中7种典型药物和个人护理品（PPCPs）的浓度水平,并考察该填埋场的渗滤液处理工艺对目标PPCPs的处理效果.结果表明,所建立的分析方法具备较好的回收率（89%~173%）、相对标准偏差（<20%）和方法检出限（0.025~1.0μg/L）,能满足实际环境样品的分析需要.应用该方法检测到渗滤液中目标PPCPs的含量在低于检出限（90%,总去除率可达到97%以上,出水PPCPs浓度范围为