Discovery of emerging organic pollutants in the atmosphere through an omics approach

● We review the framework of discovering emerging pollutants through an omics approach. ● High-resolution MS can digitalize atmospheric samples to full-component data. ● Chemical features and databases can help to translate untargeted data to compounds. ● Biological effect-directed untargeted analyses consider both existence and toxicity. Ambient air pollution, containing numerous known and hitherto unknown compounds, is a major risk factor for public health. The discovery of harmful components is the prerequisite for pollution control; however, this raises a great challenge on recognizing previously unknown species. Here we systematically review the analytical techniques on air pollution in the framework of an omics approach, with a brief introduction on sample preparation and analysis, and in more detail, compounds prioritization and identification. Through high-resolution mass spectrometry (HRMS, typically coupled with chromatography), the complicated environmental matrix can be digitalized into “full-component” data. A key step to discover emerging compounds is the prioritization of compounds from massive data. Chemical fingerprints, suspect lists and biological effects are the most vital untargeted strategies for comprehensively screening critical and hazardous substances. Afterward, compressed data of compounds can be identified at various confidence levels according to exact mass and the derived molecular formula, MS libraries, and authentic standards. Such an omics approach on full-component data provides a paradigm for discovering emerging air pollutants; nonetheless, new technological advancements of instruments and databases are warranted for further tracking the environmental behaviors, hence to evaluate the health risk of key pollutants.     

Post-war levels of persistent organic pollutants (POPs) in air from Serbia determined by active and passive sampling methods

For the duration of the war accident in former Yugoslavia, several industrial and military targets were burnt and damaged, resulting in a significant release of persistent organic pollutants. Locations heavily targeted in the attacks were later defined by UNEP as four “hot spots”: Kragujevac, Novi Sad, Pancevo and Bor. We analyzed concentration levels of pollutants collected in 2004 and 2005 in air samples from the city of Kragujevac, Serbia, following the war accident of 1999. Pollutants included polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), dichloro-diphenyl-dichloroethane (DDD) and polychlorinated biphenyls (PCBs). We present results obtained during air sampling campaign conducted in July 2004 by the active sampling method; and during September 2004–June 2005 by the passive sampling method. Our findings show the occurrence of residual quantities of DDT, HCH, PCBs and PAHs in air samples. High levels of PCBs are probably due to the destruction of transformers during the war accident.     

Carbon nanotubes and cyclodextrin polymers for removing organic pollutants from water

Some organic compounds are major water pollutants. They can be toxic or carcinogenic even at low concentrations. Current technologies, however, fail to remove these contaminants to parts per billion (ppb) levels. Here we report on the removal of organic pollutants from water using cross-linked nanoporous polymers that have been copolymerized with previously functionalized carbon nanotubes. These novel polymers can remove model organic species such as p-nitrophenol by as much as 99% from a 10 mg/L spiked water sample compared to granular activated carbon and native cyclodextrin polymer that removed only 47 and 58%, respectively. These polymers have also demonstrated the ability to remove trichloroethylene (10 mg/L spiked sample) to non-detectable levels (detection limit <0.01 ppb) compared to 55 and 70% for activated carbon and native cyclodextrin polymers, respectively.     

Organic pollutants in snow of urban and rural Russia and Finland

To check the effect of possible deposition of organic contaminants in northern regions of the Earth due to atmospheric transport snow samples were collected in early March in 6 places in Russia and 4 in Finland including arctic territories. GC‐MS was used as an analytical tool to identify and quantify individual organic compounds belonging to the various classes. As a result more than 250 compounds were detected. The possible presence of more than 100 other priority pollutants from the US EPA list was also screened.     

Nuclear magnetic resonance studies of interactions between organic pollutants and soil components,a review

This article presents a short overview of selected recent papers using nuclear magnetic resonance (NMR) to investigate interactions between organic pollutants and soil components such as organic matter, clays, whole soils, and sediments. First, we describe solid state cross polarisation magic angle spinning (CP-MAS) experiments as the main tools to investigate covalent bonds. Second, we report NMR approaches allowing us to assess molecule mobility and to characterise non-covalent interactions. Those approaches include correlations between K _oc values and soil organic matter functions determined by CP-MAS, ²H NMR fingerprints, relaxation time measurements, ¹⁹F and ¹H high resolution (HR)-MAS experiments.     

珠三角地区POPs农药的污染现状及控制对策

概述了中国及国际社会对持久性有机污染物（Persistent Organic Pollutants,POPs）的关注情况。并通过对POPs农药在珠江三角洲地区（Pearl River Delta Area,PRD）使用情况的调查，以及对珠江三角洲地区POPs农药在各环境介质中的污染现状的文献综述，结合环境污染数据以及POPs农药污染调查工作中得到的数据和信息，对该地区POPs污染的可能原因和环境中可能存在的新近污染源进行了初步探讨。同时也指出了当前珠江三角洲地区在POPs农药削减与淘汰工作中所遭遇到的缺乏完善的管理体系等困难，并针对问题提出了包括加大科研投入，加强基础研究，掌握污染物来源和去向，加强替代药物的研究，建立和实施更严格的环境法规以及标准，加强环境监测能力建设，建立POPs农药污染的信息公开机制等一系列的控制对策。     

土壤中有机污染物的气相色谱-四极杆飞行时间质谱非靶标筛查

本文基于气相色谱-四极杆飞行时间质谱(GC-QTOF/MS)对宜昌某化学工业园区内的土壤进行潜在有机污染物的非靶标筛查.根据已有高分辨数据库和保留时间信息,采用精确质量数提取筛查流程识别出样品中96种污染物,主要以多环芳烃及其代谢产物、氯苯类和农药为主.进一步通过未知物分析软件解卷积功能和质谱NIST数据库的匹配,发现...     

Heavy Metals in Terrestrial Macroinvertebrates: Species Differences Within and Between Trophic Levels

Whole animal concentrations of Pb, Zn and Cd were measured in herbivorous (1 snail species; 1 dipteran larva species), herbivorous + detritivorous (2 slug species), detritivorous (3 woodlouse species; 3 earthworm species), and carnivorous (1 carabid beetle species; 1 lithobiid centipede species) terrestrial macroinvertebrates collected at a disused Pb/Zn mine site. No evidence was found for an accretion of any metal during transference from herbivores to carnivores; the highest metal concentrations were, in fact, generally found in detritivores. The lack of metal bio-amplification during food chain transference is probably due to the sequestration of metals (notably Pb and Zn) in insoluble inorganic-rich granules within certain target organs and cells.

Earthworms and woodlice, respectively, showed major differences in metal concentrations. These differences between closely related species frequently exceeded differences between unrelated species occupying different trophic levels, and may be attributable to a combination of ill-defined ecological and physiological differences that ensure habitat and resource partitioning.     

Heavy Metals in Terrestrial Macroinvertebrates: Species Differences Within and Between Trophic Levels

Whole animal concentrations of Pb, Zn and Cd were measured in herbivorous (1 snail species; 1 dipteran larva species), herbivorous + detritivorous (2 slug species), detritivorous (3 woodlouse species; 3 earthworm species), and carnivorous (1 carabid beetle species; 1 lithobiid centipede species) terrestrial macroinvertebrates collected at a disused Pb/Zn mine site. No evidence was found for an accretion of any metal during transference from herbivores to carnivores; the highest metal concentrations were, in fact, generally found in detritivores. The lack of metal bio-amplification during food chain transference is probably due to the sequestration of metals (notably Pb and Zn) in insoluble inorganic-rich granules within certain target organs and cells.

Earthworms and woodlice, respectively, showed major differences in metal concentrations. These differences between closely related species frequently exceeded differences between unrelated species occupying different trophic levels, and may be attributable to a combination of ill-defined ecological and physiological differences that ensure habitat and resource partitioning.     

监测和净化难分解性有机污染物质的植物基因工程技术

介绍了植物基因工程技术在监测和净化难分解性有机污染物质方面的研究进展。生物中存在着能降解难分解性有机污染物质的酶及其编码基因，具有识别和除去难分解性有机污染物质的免疫系统、受体和响应元件。这方面的研究工作多以哺乳动物为材料，植物的相关研究还处于起步阶段。创造环境监测和环境污染净化为目标的新型植物将成为转基因植物研究的极其重要的研究方向之一。     

Fabrication of highly efficient Bi2WO6/CuS composite for visible-light photocatalytic removal of organic pollutants and Cr(VI) from wastewater

• A novel Bi₂WO₆/CuS composite was fabricated by a facile solvothermal method. • This composite efficiently removed organic pollutants and Cr(VI) by photocatalysis. • The DOM could promoted synchronous removal of organic pollutants and Cr(VI). • This composite could be applied at a wide pH range in photocatalytic reactions. • Possible photocatalytic mechanisms of organic pollutants and Cr(VI) were proposed. A visible-light-driven Bi₂WO₆/CuS p-n heterojunction was fabricated using an easy solvothermal method. The Bi₂WO₆/CuS exhibited high photocatalytic activity in a mixed system containing rhodamine B (RhB), tetracycline hydrochloride (TCH), and Cr (VI) under natural conditions. Approximately 98.8% of the RhB (10 mg/L), 87.6% of the TCH (10 mg/L) and 95.1% of the Cr(VI) (15 mg/L) were simultaneously removed from a mixed solution within 105 min. The removal efficiencies of TCH and Cr(VI) increased by 12.9% and 20.4%, respectively, in the mixed solution, compared with the single solutions. This is mainly ascribed to the simultaneous consumption electrons and holes, which increases the amount of excited electrons/holes and enhances the separation efficiency of photogenerated electrons and holes. Bi₂WO₆/CuS can be applied over a wide pH range (2–6) with strong photocatalytic activity for RhB, TCH and Cr(VI). Coexisiting dissolved organic matter in the solution significantly promoted the removal of TCH (from 74.7% to 87.2%) and Cr(VI) (from 75.7% to 99.9%) because it accelerated the separation of electrons and holes by consuming holes as an electron acceptor. Removal mechanisms of RhB, TCH, and Cr(VI) were proposed, Bi₂WO₆/CuS was formed into a p-n heterojunction to efficiently separate and transfer photoelectrons and holes so as to drive photocatalytic reactions. Specifically, when reducing pollutants (e.g., TCH) and oxidizing pollutants (e.g., Cr(VI)) coexist in wastewater, the p-n heterojunction in Bi₂WO₆/CuS acts as a “bridge” to shorten the electron transport and thus simultaneously increase the removal efficiencies of both types of pollutants.     

环境微塑料与有机污染物的相互作用及联合毒性效应研究进展

环境微塑料可吸附有机污染物,并与有机污染物进行相互作用从而改变其毒性效应,增加微塑料的治理难度.本文就全球范围内微塑料与有机污染物的相互作用及毒性效应的研究进展进行综述,分析不同介质中微塑料与有机污染物的共存水平、吸附机理、影响因素以及联合毒性效应等.研究表明,微塑料可作为多环芳烃(PAHs)、多氯联苯(PCBs)、六...     

典型土壤持久性有机污染物空间分布特征及环境行为研究进展

持久性有机污染物(POPs)由于具有致癌性、致畸性和致突变效应的"三致性",近年来已经越来越受到人们的关注.本文综合分析了有机氯农药(OCPs)、多氯联苯(PCBs)、二英类(PCDD/Fs)、多环芳烃(PAHs)及多溴联苯醚(PBDEs)等几种典型土壤持久性有机污染物的空间分布特征.同时,对土壤POPs的挥发作用、吸附/解吸、迁移、生物降解、化学降解等环境行为进行了深入分析,并指出了这些环境行为的影响因素,包括POPs的物质属性、土壤理化性质及周围环境等共性影响因素及其它因素.此外,针对国内外研究现状中存在的问题,提出了相关建议,指出控制土壤POPs污染的根本手段在于管理措施的完善.     

Biotransfer of persistent organic pollutants from a large site in China used for the disassembly of electronic and electrical waste

Samples of groundwater, river water, river sediment, paddy soil, rice seeds, hen eggs, fish, umbilical cord blood, and newborn meconium were collected from October 2002 to October 2003 near a large site in China used for the disassembly of obsolete transformers and other electronic or electrical waste. Six indicator PCB congeners, three non-ortho dioxin-like PCB congeners, and six organochlorine pesticides were determined in the samples by GC with electron capture detector. The results demonstrated that the local environment and edible foods had been seriously polluted by toxic PCBs and organochlorine pesticides. The actual daily intakes (ADIs) of these pollutants were estimated for local residents living in the area. The intake data showed that the contents of PCBs in these local residents were substantial, as the ADI estimates greatly exceed the reference doses set by the World Health Organization and the United States Agency for Toxic Substances and Disease Registry. The presence of the indicator PCB congeners in the cord blood and the meconium samples, as well as significant correlations (r ² > 0.80, p < 0.05) between these levels, suggests a potential biotransfer of these indicators from mothers to their newborns. This preliminary study showed that obsolete transformers and other electronic or electrical waste can be an important source for the emission of persistent organic pollutants into the local environment, such as through leakage, evaporation, runoff, and leaching. Contamination from this source appears to have reached the level considered to be a serious threat to environmental and human health around the disassembly site.     

Assessment of persistent organic pollutants in soil and sediments from an urbanized flood plain area

Polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and phenolic compounds (PCs) are persistent organic compounds. Contamination of these potentially toxic organic pollutants in soils and sediments is most studied environmental compartments. In recent past, studies were carried out on PAHs, OCPs and PCs in various soils and sediments in India. But, this is the first study on these pollutants in soils and sediments from an urbanized river flood plain area in Delhi, India. During 2018, a total of fifty-four samples including twenty-seven each of soil and sediment were collected and analyzed for thirteen priority PAHs, four OCPs and six PCs. The detected concentration of ∑PAHs, ∑OCPs and ∑PCs in soils ranged between 473 and 1132, 13 and 41, and 639 and 2112 µg/kg, respectively, while their concentrations in sediments ranged between 1685 and 4010, 4.2 and 47, and 553 and 20,983 µg/kg, respectively. PAHs with 4-aromatic rings were the dominant compounds, accounting for 51 and 76% of total PAHs in soils and sediments, respectively. The contribution of seven carcinogen PAHs (7CPAHs) in soils and sediments accounted for 43% and 61%, respectively, to ∑PAHs. Among OCPs, p, p’-DDT was the dominant compound in soils, while α-HCH was found to be dominated in sediments. The concentrations of ∑CPs (chlorophenols) were dominated over ∑NPs (nitrophenols) in both the matrices. Various diagnostic tools were applied for the identification of their possible sources in soil and sediments. The observed concentrations of PAHs, OCPs and PCs were more or less comparable with the recently reports from various locations around the world including India. Soil quality guidelines and consensus-based sediment quality guidelines were applied for the assessment of ecotoxicological health effect.