长江重庆段溶解性有机物的荧光特性分析

利用三维荧光光谱(EEMs),并结合平行因子分析(PARAFAC)及主成分分析(PCA),研究了长江重庆段溶解有机物(DOM)的荧光组分特征及其污染来源,并探讨了荧光强度同溶解性有机碳(DOC)及溶解氧(DO)的相关性.结果表明,PARAFAC模型识别出长江重庆段DOM由2类6个荧光组分组成,即类腐殖质荧光组分C1(350/422 nm)、C4(245,305/395 nm)、C5(260,340/420 nm)、C6(260/480 nm)及类蛋白荧光组分C2(275/300 nm)、C3(227,278/329 nm).在DOM来源组成中,陆源的类腐殖质含量占62.56%,类蛋白物质含量占31.31%.类腐殖质组分的荧光强度同DOC的含量存在明显的线性正相关(r=0.73),类蛋白组分的荧光强度同DO的含量呈明显的线性负相关(r=0.80).EEMs-PARAFAC不仅可以表征长江重庆段DOM的光谱特征,示踪长江重庆段的有机污染程度,还可以为三峡库区水体保护提供依据.     

丹江口水库表层沉积物有色可溶性有机物空间分布特征及其来源分析

利用三维荧光光谱(Excitation-emission matrices,EEMs)与平行因子分析模型(Parallel factor analysis,PARAFAC)技术研究丹江口水库表层沉积物有色可溶性有机物(Chromophoric dissolved organic matter,CDOM)荧光组分、空间分布特征和来源,以及不同组分荧光强度与其它沉积物指标的相关性.结果表明,丹江口水库37个采样点CDOM由3类5个荧光组分组成,即类蛋白组分C1(285/345 nm)和C2(225,270/335 nm);陆源类腐殖质组分C3(260/450 nm)和C4(360/450 nm)及自生源类腐殖质组分C5(225,310/405 nm).其中代表类蛋白组分的C1和C2占较高比例,占总荧光强度的百分比的平均值为46.37%,C3与C4和C5占总组分的比例平均值分别为34.33%和19.31%.空间分布上3种荧光峰高值都集中在汉江的入湖河口处及丹江库区居民较多的城镇处,且呈现河流大于库区的趋势.荧光指数(FI)、腐殖化指数(HIX)和生物源指数(BIX)都表明丹江口水库沉积物CDOM的来源具有陆源及生物源的双重特征,陆源主要来源于汉江干流和周边城市居民的活动,以及部分区域农业畜禽养殖;生物源主要来自微生物及藻类的降解.相关性分析说明沉积物CDOM与N、P元素的迁移和转化有密切的关系.     

夏季渭河西安段溶解性有机质(DOM)的特征、分布及来源分析

通过紫外吸收光谱,三维荧光光谱结合平行因子分析(EEMs-PARAFAC)方法及主成分分析(PCA),研究了夏季渭河西安段水体中的溶解性有机质(DOM)的组成、来源,及其与水质指标的相关性.在研究区域共检出2种类别5个不同的DOM组分,分别为类腐殖质荧光组分C1、C2、C3、C5和1个类蛋白类荧光组分C4,5个组分具有同源性.对比分析光谱斜率S、SUVA₂₅₄、α355和DOC浓度,上游(S1—S5)和下游(S13—S17)各组分分子量和腐殖化程度接近但来源有所差异,中游(S6—S12、S18—S19)分子量和腐殖化程度最低;研究区域DOM和CDOM浓度值变化基本保持一致.通过三维光谱参数和主成分分析进行DOM源解析,内源贡献率为72.36%,外源贡献率为12.45%,累计方差贡献率为84.81%;污废水排放是组分C1、C4的主要来源,C2、C3、C5则来源于城市景观水体和湿地公园中微生物和浮游动植物的活动产生,TN与外源具有较好的相关性而TP与内源相关性较高.水质指标DO、DOC、COD、TN、TP与DOM组分有较强的相关性.在此基础上建立了多元线性回归方程,一定程度上能够利用荧光组分组成和特征反映渭河夏季的水质状况.     

北京市部分地区降雪中溶解性有机物的光谱性能表征

为了解降雪中溶解性有机物(DOM)的特征,采集了北京市不同地区两场降雪,对降雪样品中的DOM进行了紫外-可见光谱、三维荧光光谱、同步荧光光谱表征.结果表明,不同区域降雪中溶解性有机碳(DOC)浓度变化规律不同,这可能与降雪所在区域的下垫面性质不同有关;降雪样品中DOM的芳香性和分子量较低,含有类色氨酸、类富里酸和类蛋白质类物质,腐殖化程度较低,受生物过程影响较大;同步荧光光谱表明,DOM为类蛋白类物质和芳香性化合物,其中存在苯环和具有共轭系统的多环芳烃,含有少量胡敏酸类物质.研究降雪中DOM光谱性质将有助于进一步研究DOM与共存污染物之间的相互作用,为有效利用降雪提供基础性数据.     

沙颍河流域水体中溶解性有机质(DOM)的荧光光谱解析

应用三维荧光光谱技术(EEMS),研究了沙颍河流域水体中溶解性有机质(DOM)的荧光光谱特征,并探讨了沿岸生态系统对水体中DOM的性质及来源的影响.结果表明,沙颍河流域水体DOM均存在类色氨酸、类酪氨酸、可见光区和紫外光区类腐殖质4种荧光峰,其中贾鲁河水样中类蛋白与类腐殖质含量均最高.相关性分析显示,沙颍河流域干流和各支流的A、C峰代表的类腐殖质组分均存在共源性.荧光参数分析显示,沿岸土地利用类型以林业为主的澧河水体的DOM陆源性更强,腐殖化程度相对较高;其余各支流受两岸农田及人为排放的影响,水体具有明显的自生源特征,且新生DOM含量较高.贾鲁河荧光特征显示了其水体受人为干扰比较大.     

基于三维荧光和二维相关光谱的城市河流溶解性有机质组成及其空间分异特征

采用三维荧光-平行因子及二维相关光谱,研究城市河流溶解性有机质(DOM)组成及变动。以沈阳市城市河流——蒲河为研究对象,采集清洁区河段、工业区河段和生活区河段上覆水,检测DOM三维荧光光谱。荧光指数、自生源指数和腐殖化指数分析结果表明,蒲河DOM以内源为主,而工业区和生活区河段同时受外源影响,腐殖化程度较弱。采用平行因子提取类富里酸(C1和C2)、类胡敏酸(C3)、类色氨酸(C4和C6)和酚类物质(C5)6个DOM荧光组分,蒲河DOM以类富里酸(37.91%～43.82%)和类色氨酸(23.64%～33.60%)为主。清洁区河段各组分含量小于生活区和工业区河段。二维相关光谱分析表明,工业区河段类色氨酸含量变化幅度比类富里酸大,生活区河段变化规律与工业区河段相同,而清洁区河段相反,这表明工业区和生活区河段有大量生活污水和工业废水汇入。基于主成分分析(PCA)结果,C1～C5为影响DOM的主要因子(55.15%),工业区河段点位得分最高,其次为生活区河段,清洁区河段最小,表明工业区和生活区河段深受人类活动影响,而清洁区河段受人类影响较弱。     

湖泊沉积物孔隙水溶解性有机质组成与光谱特性

应用紫外-可见光谱和荧光光谱分析乌梁素海沉积物孔隙水中溶解性有机质(DOM)的组成和来源信息,揭示不同来源污染物对孔隙水DOM结构及地球化学行为的影响.研究结果表明,类蛋白物质含量相对较高的区域,其污染相对较重;沉积物孔隙水DOM的生物指数BIX值都大于0.6,预示沉积物孔隙水中DOM微生物来源贡献较大;在类蛋白荧光物质较高的区域,DOM的腐殖化程度相对较低,其结构相对简单,稳定性较弱;腐殖化指数HIX254分析结果也表明,受污程度较高的区域,DOM的腐殖化程度较低;紫外吸收光谱的斜率能够反映沉积物孔隙水中类腐殖酸的变化,而光谱斜率S350—400比S275—295更能够反应沉积物孔隙水中类腐殖酸的变化,随着S350—400升高,DOM中类蛋白物质的含量呈下降趋势,类腐殖酸含量逐渐增加.     

消落带夏冬季土壤溶解有机质的组成特征及来源

溶解性有机质(Dissolved organic matter,DOM)普遍存在于土壤、沉积物和水体中,在环境地球化学和全球碳循环中发挥重要作用。消落带独特的"干湿交替"使土壤有不同的季节特征,但有关不同季节土壤DOM的性质、组成及来源差异还未见报道。利用紫外-可见光谱、三维荧光光谱(Excitation-emission matrices,EEMs)与平行因子分析模型(Parallel factor analysis,PARAFAC)相结合的方法,分析了丹江口库区消落带表层土壤DOM在不同季节的组成、结构,并对其来源进行解析。结果表明,不同季节消落带土壤DOM的组成特征存在一定差异。冬季土壤的有色溶解性有机物(Chromophoric dissolved organic matter,CDOM)浓度、土壤DOM的芳香性、缩合度、腐殖化程度、所含疏水性组分都高于夏季土壤,但参与光漂白的活性要低于夏季土壤。荧光指数(FI)、腐殖化指数(HIX)和生物源指数(BIX)表明该区土壤DOM的来源在不同季节都有明显的自生源特征,且腐殖化程度和生物可利用性都不高,并未表现显著差异。该区土壤DOM存在两个主要的荧光峰:紫外光区类富里酸峰、可见光区类富里酸峰和类腐殖酸峰。研究提出消落带淹水期间产生的DOM对水环境有很大影响,以内源为主的库区在水质改善的过程中需加强对内源物质的管控。这些研究结果可为消落带的水体修复和污染物的迁移转化提供科学依据。     

几种原料生物炭溶解性有机质(DOM)的光谱特征研究

溶解性有机质(DOM)在全球碳循环及污染物的迁移转化过程中起着重要作用,而光谱特征能快速识别DOM的主要来源和重要特征。研究针对几种原料(苹果枝、橘子枝、花生壳、水稻秸秆、玉米秸秆)在同一热解温度下制备的生物炭,采用紫外-可见吸收光谱、三维荧光光谱和傅里叶变换红外光谱相结合的方法对其释放的DOM光谱特征进行了研究。结果表明：秸秆类生物炭的溶解性有机碳(DOC)含量显著高于其他3种生物炭;紫外-可见光谱分析表明,5种生物炭DOM的芳香性组分含量均较少,腐殖化程度较低,亲水性组分占主导;三维荧光光谱分析表明,秸秆类生物炭DOM的荧光组分物质含量高于木质类和壳类,且各荧光组分含量占比中可溶性微生物降解产物和类胡敏酸比例最高;傅里叶变化红外光谱表明,5种生物炭DOM光谱特征相似,含有丰富的有机官能团(如羧基、酚羟基等)或半醌自由基等。     

巢湖湖滨带沉积物间隙水溶解性有机质的光谱特征与时空差异

利用三维荧光光谱(3DEEM)和平行因子分析法(PARAFAC)研究巢湖湖滨带沉积物间隙水中溶解性有机质(DOM)含量组成、剖面分布特征及主要来源。结果表明,间隙水中DOM含有3种荧光组分,包括类腐殖质组分C1(275 nm, 365 nm/467 nm)、类腐殖质组分C2(330 nm/407 nm)和类酪氨酸组分C3(275 nm/319 nm)。在空间分布上,远岸带DOM总荧光强度均值为(0.432±0.306) RU,低于近岸带DOM总荧光强度均值[(0.583±0.478) RU],同时近岸带荧光强度均值大于湖心点,各点位垂直剖面上荧光强度随沉积物深度呈现下降趋势;在时间分布上,沉积物间隙水夏季DOM总荧光强度均值为(0.390±0.301) RU,小于冬季[(0.584±0.453) RU];此外,近岸带DOC浓度高于远岸带,远岸带DOC浓度高于湖心点,冬季各断面DOC浓度高于夏季;随着沉积物深度的增加,DOC浓度首先呈现升高趋势后迅速随深度增加而降低,在底泥界面10 cm以下保持稳定状态;冬季腐殖化指数(HIX)高于夏季,荧光指数(FI)和生物源指数(BIX)表明沉积物间隙水DOM受到内源中生物源与外源污染中陆源的共同影响,受到内源中生物源影响更大。该研究可为巢湖湖滨带水环境管理与面源污染控制提供一定参考。     

Effects of oxidizing environment on digestate humification and identification of substances governing the dissolved organic matter (DOM) transformation process

• Liquid digestate humification was investigated under different oxidizing environment. • Tryptophan-like substances dominated the transformation of the liquid digestate DOM. • The humification sequence of the liquid digestate DOM was identified. • UV₃₂₅ was first identified as a pre-humus intermediate during humification reaction. The formation of humic-like acids (HLAs) is an essential process for converting liquid digestate into organic soil amendments to enhance agricultural sustainability. The aim of this study was to investigate the impact of oxygen and/or MnO₂ on the production of HLAs. Herein, abiotic humification performance of the digestate dissolved organic matter (DOM) is investigated with fluxes of air and N₂ in the absence and presence of MnO₂. Our results demonstrated that the fate of digestate DOM greatly depends on the oxidizing environment, the MnO₂ enhanced nitrogen involved in the formation of HLAs. The synergistic effects of MnO₂ and oxygen effectively improved the production of HLAs, and the corresponding component evolution was analyzed using spectroscopic evidence. The two-dimensional correlation spectroscopy results demonstrated that the reaction sequence of digestate DOM followed the order of protein-like substances, substances with an absorbance at 325 nm, substances with UV absorbance at 254 nm and HLAs. Additionally, excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) showed that tryptophan-like C3 was more prone to transformation than tyrosine-like C2 and was responsible for the humification process. The substance with an absorbance at 325 nm was a reaction intermediate in the transformation process of protein-like substances to HLAs. The above findings can be used to promote the production of liquid fertilizer associated with carbon sequestration as well as the sustainable development of biogas production.     

Photosensitivity sources of dissolved organic matter from wastewater treatment plants and their mediation effect on 17α-ethinylestradiol photodegradation

● EE2 photodegradation behavior in the presence of four WWTPs’ DOM was explored. ● The ³DOM* played a major role in the EE2 photodegradation mediated by WWTPs’ DOM. ● The A²/O process DOM contained more aromatic and oxygen-containing substances. ● Possible photosensitivity sources of DOM in the A²/O process were proposed. Dissolved organic matter (DOM) from each treatment process of wastewater treatment plants (WWTPs) contains abundant photosensitive substances, which could significantly affect the photodegradation of 17α-ethinylestradiol (EE2). Nevertheless, information about EE2 photodegradation behavior mediated by DOM from diverse WWTPs and the photosensitivity sources of such DOM are inadequate. This study explored the photodegradation behavior of EE2 mediated by four typical WWTPs’ DOM solutions and investigated the photosensitivity sources of DOM in the anaerobic-anoxic-oxic (A²/O) process. The parallel factor analysis identified three varying fluorescing components of these DOM, tryptophan-like substances or protein-like substances, microbial humus-like substances, and humic-like components. The photodegradation rate constants of EE2 were positively associated with the humification degree of DOM (P < 0.05). The triplet state substances were responsible for the degradation of EE2. DOM extracted from the A²/O process, especially in the secondary treatment process had the fastest EE2 photodegradation rate compared to that of the other three processes. Four types of components (water-soluble organic matter (WSOM), extracellular polymeric substance, humic acid, and fulvic acid) were separated from the A²/O process DOM. WSOM had the highest promotion effect on EE2 photodegradation. Fulvic acid-like components and humic acid-like organic compounds in WSOM were speculated to be important photosensitivity substances that can generate triplet state substances. This research explored the physicochemical properties and photosensitive sources of DOM in WWTPs, and explained the fate of estrogens photodegradation in natural waters.     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.     

Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions

This work investigated the effect of granular activated carbon adsorption (GACA) on fluorescence characteristics of dissolved organic matter (DOM) in secondary effluent, by means of excitation–emission matrix (EEM) spectra, the fluorescence regional integration (FRI) method, synchronous spectra, the fluorescence index defined as the ratio of fluorescence emission intensity at wavelength 450 nm to that at 500 nm at excitation (λ_ex)=370 nm, and the wavelength that corresponds to the position of the normalized emission band at its half intensity (λ_0.5). DOM in the secondary effluent from the North Wastewater Treatment Plant (Shenyang, China) was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO–A), hydrophobic neutral (HPO–N), transphilic acid (TPI–A), transphilic neutral (TPI–N) and hydrophilic fraction (HPI). Results showed that fluorescent materials in HPO–N and TPI–N were less readily removed than those in the other fractions by GACA. The relative content of fluorescent materials in HPO–A, TPI–A and HPI decreased whereas that in HPO–N and TPI–N increased as a consequence of GACA. Polycyclic aromatics in all DOM fractions were preferentially absorbed by GACA, in comparison with bulk DOM expressed as DOC. On the other hand, the adsorption of aromatic amino acids and humic acid-like fluorophores exhibiting fluorescence peaks in synchronous spectra by GACA seemed to be dependent on the acid/neutral properties of DOM fractions. All five fractions had decreased fluorescence indices as a result of GACA. GACA led to a decreased λ_0.5 value for HPO–A, increased λ_0.5 values for HPO–N, TPI–A and HPI, and a consistent λ_0.5 value for TPI–N.     

Identification of sources,characteristics and photochemical transformations of dissolved organic matter with EEM-PARAFAC in the Wei River of China

• The source of DOM in surface water and sediment is inconsistent. • The DOC content changes differently in surface water and sediment. • The content of DOC in the surface water is lower than that in the sediment. • The DOM in the surface water had higher photodegradation potentials than sediment. Dissolved organic matter (DOM) in rivers is a critical regulator of the cycling and toxicity of pollutants and the behavior of DOM is a key indicator for the health of the environment. We investigated the sources and characteristics of DOM in surface water and sediment samples of the Wei River, China. Dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm (UV₂₅₄) increased in the surface water and were decreased in the sediment downstream, indicating that the source of DOM in the water differed from the sediment. Parallel factor (PARAFAC) analysis of the excitation-emission matrices (EEM) revealed the presence of terrestrial humus-like, microbial humus-like and tryptophan-like proteins in the surface water, whereas the sediment contained UVA humic-like, UVC humic-like and fulvic-like in the sediment. The DOM in the surface water and sediment were mainly derived from microbial metabolic activity and the surrounding soil. Surface water DOM displayed greater photodegradation potential than sediment DOM. PARAFAC analysis indicated that the terrestrial humic-like substance in the water and the fulvic-like component in the sediment decomposed more rapidly. These data describe the characteristics of DOM in the Wei River and are crucial to understanding the fluctuations in environmental patterns.     

Three-dimensional fluorescence spectral characterization of soil dissolved organic matters in the fluctuating water-level zone of Kai County, Three Gorges Reservoir

Three-dimensional fluorescence spectroscopy was used to investigate the fluorescent properties of soil dissolved organic matter (DOM) in the water-level-fluctuation zone (WLFZ) of Kai County, Three Gorges Reservoir (TGR). Most of the soil DOM analyzed in this study was found to contain four fluorescence peaks. Peaks A and C represent humic-like fluorescence, whereas peaks B and D represent tryptophan-like fluorescence. Peaks E and F, which represent tyrosine-like fluorescence, only appeared in certain soils. Soil humus was the main source of DOM in soil, and higher concentration of soil DOM was found in the exposed soil than submerged soil. Compared to the peaks A and B, the fluorescence intensities of peaks C and D were strongly influenced by the fluctuating water level. Analysis of fluorescence intensities of different peaks in soil DOM showed that WLFZ soil was not contaminated significantly. Soil DOM contained at least two types of humic-like fluorescence groups and two types of protein-like fluorescence groups. The proportion of the content of peak A in soil organic matter was quite stable. The soil DOM in exposed soil had relatively high humification and aromaticity, and periodic submerging and exposure of soil had an impact on the humification of soil DOM.     

Characterization of the dissolved organic matter in sewage effluent of sequence batch reactor: the impact of carbon source

Dissolved organic matter (DOM) transformation in sequence batch reactor (SBR) fed with carbon sources of different biodegradability was investigated. During the biologic degradation process, the low molecular weight (MW) fraction (< 1 kDa) gradually decreased, while the refractory compounds with higher aromaticity were aggregated. Size exclusion chromatography (SEC) and fluorescence of excitation emission matrices (EEM) demonstrated that more biopolymers (polysaccharides or proteins) and humic-like substances were presented in the extracellular polymeric substance (EPS) extracted from the SBR fed with sodium acetate or glucose, while the EPS from SBR fed with slowly biodegradable dissolved organic carbon (DOC) substratestarch had relatively less biopolymers. Comparing the EfOM in sewage effluent of three SBRs, the effluent from SBR fed with starch is more aromatic. Organic carbon with MW>1 kDa as well as the hydrophobic fraction in DOM gradually increased with the carbon sources changing from sodium acetate to glucose and starch. The DOC fractionation and the EEM all demonstrated that EfOM from the effluent of the SBR fed with starch contained more fulvic acid-like substances comparing with the SBR fed with sodium acetate and glucose.     

Perfluoroalkane acids in human milk under the global monitoring plan of the Stockholm Convention on Persistent Organic Pollutants (2008–2019)

● Perfluorooctanesulfonic acid and perfluorooctanoic acid highest in human milk. ● All other perfluoroalkane substances had median values of zero (101 samples). ● Branched PFOS recommended to be analyzed separately from linear isomer. ● PFOS and PFOA showed differentiated regional and income distribution. ● Human health risk assessment values not yet available at global level. Within the global monitoring plan (GMP) established by article 16 of the Stockholm Convention on Persistent Organic Pollutants, perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) are recommended for analysis in core matrices to assess occurrence and changes geographically and with time. In 101 samples consisting of 86 national pools and 15 pools from States in Brazil obtained between 2008 and 2019, PFHxS was detected in 17% of the national pools and none in Brazil. PFOA and PFOS had a detection frequency of 100% and 92%, respectively. Other perfluoroalkane substances (PFAS) had either low detection frequencies and median values of zero (carboxylic acids C₄–C₁₁; except PFOA) or could not be quantified in any sample (sulfonic acids, C₄–C₁₀, and long-chain carboxylic acids, C₁₂–C₁₄). Correlation between PFOA and PFOS was moderately (r = 0.58). Whereas median values were almost identical (18.9 pg/g f.w. for PFOS; 18.6 pg/g f.w. for PFOA), PFOS showed larger ranges (< 6.2 pg/g f.w.–212 pg/g f.w.) than PFOA (< 6.2 pg/g f.w.–63.4 pg/g f.w.). It was shown that wealthier countries had higher PFOA concentrations than poorer countries. No difference in concentrations was found for samples collected in countries having or not having ratified the Stockholm Convention amendments to list PFOS or PFOA. The goal to achieve 50% decrease in concentrations within ten years was met by Antigua and Barbuda, Kenya, and Nigeria for PFOS and by Antigua and Barbuda for PFOA. In a few cases, increases were observed; one country for PFOS, four countries for PFOA.