Dithizone-functionalized C18 online solid-phase extraction-HPLC-ICP-MS for speciation of ultra-trace organic and inorganic mercury in cereals and environmental samples

A simple and efficient dithizone-functionalized solid-phase extraction (SPE) procedure, online coupled with high-performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry, was developed for the first time for enrichment and determination of ultra-trace mercury (Hg) species (inorganic divalent Hg (Hg(II)), methylmercury (CH₃Hg(II)) and ethylmercury (C₂H₅Hg(II)) in cereals and environmental samples. In the proposed method, functionalization of the commercial C₁₈ column with dithizone, enrichment, and elution of the above Hg species can be completed online with the developed SPE device. A simple solution of 2-mercaptoethanol (1% (V/V)) could be used as an eluent for both the SPE and HPLC separation of Hg species, significantly simplifying the method and instrumentation. The online SPE method was optimized by varying dithizone dose, 2-mercaptoethanol concentration, and sample volume. In addition, the effect of pH, coexisting interfering ions, and salt effect on the enrichment was also discussed. Under the optimized conditions, the detection limits of Hg species for 5 mL water sample were 0.15 ng/L for Hg(II), 0.07 ng/L for CH₃Hg(II), and 0.04 ng/L for C₂H₅Hg(II) with recoveries in the range of 85%–100%. The developed dithizone-functionalized C₁₈ SPE column can be reused after a single functionalization, which significantly simplifies the enrichment step. Moreover, the stability of Hg species enriched on the SPE column demonstrated its suitability for field sampling of Hg species for later laboratory analysis. This environment-friendly method offers a robust tool to detect ultra-trace Hg species in cereals and environmental samples.     

PM2.5 chemical composition and health risks by inhalation near a chemical complex

Particulate matter (PM_2.5) samples were collected in the vicinity of an industrial chemical pole and analysed for organic and elemental carbon (OC and EC), 47 trace elements and around 150 organic constituents. On average, OC and EC accounted for 25.2% and 11.4% of the PM_2.5 mass, respectively. Organic compounds comprised polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, anhydrosugars, phenolics, aromatic ketones, glycerol derivatives, aliphatic alcohols, sterols, and carboxyl groups, including aromatic, carboxylic and dicarboxylic acids. Enrichment factors > 100 were obtained for Pb, Cd, Zn, Cu, Sn, B, Se, Bi, Sb and Mo, showing the contribution of industrial emissions and nearby major roads. Principal component analysis revealed that vehicle, industrial and biomass burning emissions accounted for 66%, 11% and 9%, respectively, of the total PM_2.5-bound PAHs. Some of the detected organic constituents are likely associated with plasticiser ingredients and thermal stabilisers used in the manufacture of PVC and other plastics in the industrial complex. Photooxidation products of both anthropogenic (e.g., toluene) and biogenic (e.g., isoprene and pinenes) precursors were also observed. It was estimated that biomass burning accounted for 13.8% of the PM_2.5 concentrations and that secondary OC represented 37.6% of the total OC. The lifetime cancer risk from inhalation exposure to PM_2.5-bound PAHs was found to be negligible, but it exceeded the threshold of 10⁻⁶ for metal(loi)s, mainly due to Cr and As.     

Atmospheric Particle Hygroscopicity and the Influence by Oxidation State of Organic Aerosols in Urban Beijing

A hygroscopic tandem differential mobility analyser (H-TDMA) was used to observe the size-resolved hygroscopic characteristics of submicron particles in January and April 2018 in urban Beijing. The probability distribution of the hygroscopic growth factor (HGF-PDF) in winter and spring usually showed a bimodal pattern, with more hygroscopic mode (MH) being more dominant. The seasonal variation in particle hygroscopicity was related to the origin of air mass, which received polluted southerly air masses in spring and clean northwesterly air masses in winter. Particles showed stronger hygroscopic behaviour during heavy pollution episodes (HPEs) with elevated concentrations of secondary aerosols, especially higher mass fraction of nitrate, which were indicated using the PM_2.5 (particulate matter with diameter below 2.5 µm) mass concentration normalised by CO mass concentration. The hygroscopic parameter (κ) values were calculated using H-TDMA (κ_htdma) and chemical composition (κ_chem). The closure study showed that κ_chem was overestimated in winter afternoon when compared with κ_htdma, because the organic particle hygroscopic parameter (κ_org) was overestimated in the calculations. It was influenced by the presence of a high concentration of hydrocarbon-like organic aerosol (HOA) with a weak water uptake ability. A positive relationship was observed between κ_org and the ratio of oxygenated organic aerosol (OOA) and HOA, thereby indicating that the strong oxidation state enhanced the hygroscopicity of the particles. This study revealed the effect of local emission sources and secondary aerosol formation processes on particle hygroscopicity, which is of great significance for understanding the pollution formation mechanism in the North China Plain.     

Seasonal variation and sources of atmospheric polycyclic aromatic hydrocarbons in a background site on the Tibetan Plateau

The study of atmospheric polycyclic aromatic hydrocarbons (PAHs) in northeastern Tibetan Plateau with fragile ecological environment and complex atmospheric circulation system is blank. To understand the characteristics and sources of persistent organic pollutants in the atmosphere of the northeastern Tibetan Plateau, we monitored levels in the central Qilian Mountain. From 2016 to 2017, we collected 45-pair (particle + gas) samples using active air samplers to investigate the sources, transport paths, and their influencing factors. Sources of PAHs were analysed with a source diagnostic model, and atmospheric transport paths were calculated. The concentration range for ∑₁₅PAHs was 439–4666 pg/m³, and the average was 2015 pg/m³. The PAHs in central Qilian Mountain are mainly low molecular weight (LMW) PAHs. Winter concentrations of PAHs were higher than those in summer. The transport of PAHs is mainly affected by westerlies, and there are seasonal differences. Source analysis showed that PAHs mainly came from coal and biomass combustion and vehicle emissions, with seasonal differences. This study clarifies the concentration and seasonal variation of PAHs in the northern Tibetan Plateau, which is conducive to understanding the atmospheric transport process and fate of pollutants. The background site of Qilian Mountains located in the Silk Road economic belt has the value and significance of long-term observation of pollutants.     

Degradation mechanism of Direct Pink 12B treated by iron-carbon micro-electrolysis and Fenton reaction

The Direct Pink 12B dye was treated by iron-carbon micro-electrolysis (ICME) and Fenton oxidation. The degradation pathway of Direct Pink 12B dye was inferred by ultraviolet visible (UV-Vis), infrared absorption spectrum (IR) and high performance liquid chromatography-mass spectrometry (HPLC-MS). The major reason of decolorization was that the conjugate structure was disrupted in the iron-carbon micro-electrolysis (ICME) process. However, the dye was not degraded completely because benzene rings and naphthalene rings were not broken. In the Fenton oxidation process, the azo bond groups surrounded by higher electron cloud density were first attacked by hydroxyl radicals to decolorize the dye molecule. Finally benzene rings and naphthalene rings were mineralized to H₂O and CO₂ under the oxidation of hydroxyl radicals.     

Sources and health risks of PM2.5-bound polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in a North China rural area

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are typical persistent organic pollutants (POPs), which have high toxicity, bioaccumulation and long-distance transfer capability. Daily variation, sources of PCBs and OCPs in PM_2.5 are rarely explored in polluted rural area. Here, the sources and health risks of the PCBs and OCPs were evaluated for 48 PM_2.5 samples collected in winter 2017 in Wangdu, a heavy polluted rural area in the North China Plain. The average diurnal and nocturnal concentrations of Σ₁₈PCBs and Σ₁₅OCPs were 1.74-24.37 and 1.77-100.49, 11.67-408.81 and 16.89-865.60 pg/m³, respectively. Hexa-CBs and penta-CBs accounted for higher proportions (29.0% and 33.6%) of clean and polluted samples, respectively. Hexachlorobenzene (HCB) was the dominant contributor to OCPs with an average concentration of 116.17 pg/m³. Hexachlorocyclohexane (ΣHCHs) and dichlorodiphenyltrichloroethane (ΣDDTs) were the other two main classes in OCPs with the average concentrations of 4.33 and 15.89 pg/m³, respectively. β-HCH and p,p’-DDE were the main degradation products of HCHs and DDTs, respectively. The principal component analysis and characteristic ratio method indicated both waste incineration and industrial activities were the main sources of PCBs, contributing 76.8% and 12.7%, respectively. The loadings of OCPs were attributed to their application characteristics and the characteristic ratio method reflected a current or past use of OCPs. Health risk assessment showed that the respiratory exposure quantity of doxin-like PCBs (DL-PCBs) and the lifetime cancer risk from airborne OCPs exposure was negligible, while the other exposure modes may pose a risk to human bodies.     

Chlorination of para-substituted phenols: Formation of α, β-unsaturated C4-dialdehydes and C4-dicarboxylic acids

Despite the widespread occurrence of phenols in anthropogenic and natural compounds, their fate in reactions with hypochlorous acid (HOCl), one of the most common water treatment disinfectants, remains incompletely understood. To close this knowledge gap, this study investigated the formation of disinfection by-products (DBPs) in the reaction of free chlorine with seven para-substituted phenols. Based on the chemical structures of the DBPs and the reaction mechanisms leading to their formation, the DBPs were categorized into four groups: chlorophenols, coupling products, substituent reaction products, and ring cleavage products. In contrast to previous studies that investigated the formation of early-stage chlorophenols, the primary focus of this study was on the elucidation of novel ring cleavage products, in particular α, β-unsaturated C₄-dialdehydes, and C₄-dicarboxylic acids, which, for the first time, were identified and quantified in this study. The molar yields of 2-butene-1,4-dial (BDA), one of the identified α, β-unsaturated C₄-dialdehydes, varied among the different phenolic compounds, reaching a maximum value of 10.4% for bisphenol S. Molar yields of 2-chloromaleic acid (Cl-MA), one of the identified C₄-dicarboxylic acids, reached a maximum value of 30.5% for 4-hydroxy-phenylacetic acid under given conditions. 2,4,6-trichlorophenol (TCP) was shown to be an important intermediate of the parent phenols and the C₄-ring cleavage products. Based on the temporal trends of α, β-unsaturated C₄-dialdehydes and C₄-dicarboxylic acids, their formation is likely attributable to two separate ring cleavage pathways. Based on the obtained results, an overall transformation pathway for the reaction of para-substituted phenols with free chlorine leading to the formation of novel C₄ ring cleavage products was proposed.     

Occurrence, partition behavior, source and ecological risk assessment of nitro-PAHs in the sediment and water of Taige Canal, China

Nitrated polycyclic aromatic hydrocarbons (NPAHs) are widespread organic pollutants that possess carcinogenic and mutagenic properties, so they may pose a risk to the environment and human health. In this study, the concentrations of 15 NPAHs and 16 polycyclic aromatic hydrocarbons (PAHs) in 30 surface water samples and 26 sediment samples were measured in 2018 from the Taige Canal, one of the main rivers flowing into Taihu Lake, China. The total NPAH concentrations in water and sediment ranged from 14.7 to 235 ng/L and 22.9 to 96.5 ng/g dw, respectively. 9-nitrophenanthrene (nd–76.3 ng/L) was the dominant compound in surface water, while 2+3-nitrofluoranthene (1.73–18.1 ng/g dw) dominated in sediment. Among PAHs, concentration ranging from 1,097 to 2,981 ng/L and 1,089 to 4,489 ng/g dw in surface water and sediment, respectively. There was a strong positive correlation between the log octanol-water partition coefficient (K_ow) and log sediment-water partition coefficient due to hydrophobic interaction. The fugacity fraction value increased with the decrease of log K_ow, and chrysene was transferred from water into sediment. The residual NPAHs in surface water and sediment of the Taige Canal have partial correlation. Diesel engine and coal combustion emissions were probably the principal sources of NPAHs in surface water and sediment. The results of ecological risk assessment showed that some NPAHs in water (e.g, 1-nitropyrene and 6-nitrochrysene) and sediment (e.g., 2-nitrobiphenyl, 5-nitroacenaphthene, 9-nitrophenanthrene and 2+3-nitrofluoranthene) had moderate ecological risks, which should be of concern.     

Catalytic activity of porous manganese oxides for benzene oxidation improved via citric acid solution combustion synthesis

Various manganese oxides (MnO_x) prepared via citric acid solution combustion synthesis were applied for catalytic oxidation of benzene. The results showed the ratios of citric acid/manganese nitrate in synthesizing process positively affected the physicochemical properties of MnO_x, e.g., BET (Brunauer-Emmett-Teller) surface area, porous structure, reducibility and so on, which were in close relationship with their catalytic performance. Of all the catalysts, the sample prepared at a citric acid/manganese nitrate ratio of 2:1 (C2M1) displayed the best catalytic activity with T₉₀ (the temperature when 90% of benzene was catalytically oxidized) of 212℃. Further investigation showed that C2M1 was Mn₂O₃ with abundant nano-pores, the largest surface area and the proper ratio of surface Mn⁴⁺/Mn³⁺, resulting in preferable low-temperature reducibility and abundant surface active adsorbed oxygen species. The analysis results of the in-situ Fourier transform infrared spectroscopy (in-situ FTIR) revealed that the benzene was successively oxidized to phenolate, o-benzoquinone, small molecules (such as maleates, acetates, and vinyl), and finally transformed to CO₂ and H₂O.     

Photocatalytic degradation of phenanthrene on soil surfaces in the presence of nanometer anatase TiO2 under UV-light

The effect of nanometer anatase TiO₂ was investigated on the photocatalytic degradation of phenanthrene on soil surfaces under a variety of conditions. After being spiked with phenanthrene, soil samples loaded with different amounts of TiO₂ (0 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, and 4 wt.%) were exposed to UV-light irradiation for 25 hr. The results indicated that the photocatalytic degradation of phenanthrene followed the pseudo first-order kinetics. TiO₂ significantly accelerated the degradation of phenanthrene with the half-life reduced from 45.90 to 31.36 hr for TiO₂ loading of 0 wt.% and 4 wt.%, respectively. In addition, the effects of H₂O₂, light intensity and humic acid on the degradation of phenanthrene were investigated. The degradation of phenanthrene increased with the concentration of H₂O₂, light intensity and the concentration of humic acids. It has been demonstrated that the photocatalytic method in the presence of nanometer anatase TiO₂ was a very promising technology for the treatments of soil polluted with organic substances in the future.     

土壤中总石油烃预处理方法研究

采用了索氏提取法、超声波萃取法和加速溶剂萃取对土壤中的总石油烃预处理进行了研究分析,方法在0 mg/L~500 mg/L范围内均有良好的线性.采用索氏提取法时,总石油烃的方法检出限均在0.001 mg/kg~0.016 mg/kg范围内,回收率在65%~80%之间,相对标准偏差均在6.8%~12%之间;采用超声波萃取法时,总石油烃的方法检出限均在0.002 mg/kg~0.023 mg/kg范围内,回收率在60%~88%之间,相对标准偏差均在8.6%~15%之间;采用加速溶剂萃取时,总石油烃的方法检出限均在0.001 mg/kg~0.009 mg/kg范围内,回收率在70%~95%之间,相对标准偏差均在2.5%~8.8%之间.实验表明三种方法均可以作为土壤中总石油烃的预处理分析方法,但加速溶剂萃取更加快捷方便,更适合实际样品的分析.     

新型循环冷凝固相微萃取方法的研究

首次提出一种新型循环冷凝萃取(CC-SPME)方法,并以乙硫醚为研究对象进行了分析检测。实验优选条件得出CC-SPME法的萃取时间,溶液加热温度和解吸时间分别为25min,75℃,4min。该方法的重现性,检测限以及回收率分别为7.54%,0.010mg/L,97%。实验表明,此方法的线性很好,而且与传统的浸入萃取法和顶空萃取法相比,具有更高的灵敏度。故而CC-SPME法是一种简单且灵敏的分析检测方法,值得做进一步探讨。     

土壤二维蒸气抽排去污效果的影响研究

土壤蒸气抽排是一种经济、高效、安全并已被广泛应用的污染场址现场修复技术,它能经济高效地去除非饱和带土壤中的挥发性有机污染物。以土壤和油污染物为例,进行了土壤二维抽排模拟实验,研究了气体抽排流量对去污效果的影响,通过实验可知:在增加气体抽排流量的情况下,抽排气中挥发性较强的有机物质正戊烷(C5h12)浓度下降的很快,最终保存在较低的浓度水平。挥发性一般的正辛烷(C8h18)和挥发性较弱的正癸烷(C10h22)经过长时间的抽排后,污染物也得到了降低,但是最终保持在比较高的浓度水平。得出增加气体抽排流量可以使污染物去除速率大幅度提高,从而缩短了净化时间,获得很好的去污效果。同时对二维抽排模拟实验和一维抽排模拟实验结果做了比较。     

土壤生态系统微量元素的生物有效性研究现状

土壤中植物必需的微量营养元素的供给以及有害元素的毒性大小并不仅仅与元素的总量有关,而取决于元素的有效性。文章论述了元素生物有效性的含义,介绍了元素有效性的研究方法,即连续偏提取法和单提取法,并对一些相关问题进行了深入的分析讨论。     

Potential bioavailability of mercury in humus-coated clay minerals

It is well-known that both clay and organic matter in soils play a key role in mercury biogeochemistry, while their combined effect is less studied. In this study, kaolinite, vermiculite, and montmorillonite were coated or not with humus, and spiked with inorganic mercury (IHg) or methylmercury (MeHg). The potential bioavailability of mercury to plants or deposit-feeders was assessed by CaCl₂ or bovine serum albumin (BSA) extraction. For uncoated clay, IHg or MeHg extraction was generally lower in montmorillonite, due to its greater number of functional groups. Humus coating increased partitioning of IHg (0.5%–13.7%) and MeHg (0.8%–52.9%) in clay, because clay-sorbed humus provided more strong binding sites for mercury. Furthermore, humus coating led to a decrease in IHg (3.0%–59.8% for CaCl₂ and 2.1%–5.0% for BSA) and MeHg (8.9%–74.6% for CaCl₂ and 0.5%–8.2% for BSA) extraction, due to strong binding between mercury and clay-sorbed humus. Among various humus-coated clay particles, mercury extraction by CaCl₂ (mainly through cation exchange) was lowest in humus-coated vermiculite, explained by the strong binding between humus and vermiculite. The inhibitory effect of humus on mercury bioavailability was also evidenced by the negative relationship between mercury extraction by CaCl₂ and mercury in the organo-complexed fraction. In contrast, extraction of mercury by BSA (principally through complexation) was lowest in humus-coated montmorillonite. This was because BSA itself could be extensively sorbed onto montmorillonite. Results suggested that humus-coated clay could substantially decrease the potential bioavailability of mercury in soils, which should be considered when assessing risk in mercury-contaminated soils.     

Optimization of enrichment processes of pentachlorophenol (PCP) from water samples

The method of enriching PCP( pentachlorophenol ) from aquatic environment by solid phase extraction (SPE) was studied.Several factors affecting the recoveries of PCP, including sample pH, eluting solvent, eluting volume and flow rate of water sample, were optimized by orthogonal array design(OAD). The optimized results were sample pH 4; eluting solvent, 100% methanol; eluting solvent volume, 2 ml and flow rate of water sample, 4 ml/min. A comparison is made between SPE and liquid-liquid extraction(LLE) method. The recoveries of PCP were in the range of 87.6%-133.6% and 79%-120.3% for SPE and LLE, respectively. Important advantages of the SPE compared with the LLE include the short extraction time and reduced consumption of organic solvents. SPE can replace LLE for isolating and concentrating PCP from water samples.     

溶剂萃取分离地下强化抽出处理液中的污染物和表面活性剂

以正己烷为萃取剂,SDS和Tween 80为表面活性剂,苯和硝基苯为污染物,通过批次实验研究了萃取时间、油水比、表面活性剂及污染物性质对二者分离效果的影响.结果表明,萃取时间为2h、油水比为0.1是萃取的最佳条件参数;正己烷对Tween 80和苯的分离效果较SDS好,且Tween 80浓度对分离效果影响不大;随着SDS浓度的升高,其与苯的分离效果先增大后减小,在1.375CMC时达到最佳分离效果;正己烷对苯与SDS的分离效果较硝基苯好,且分离效果随着污染物浓度的升高而增大;苯和硝基苯共存时,其与SDS的分离存在竞争作用.     

漆酶的逆胶束萃取条件优化的研究

研究了生物表面活性剂逆胶束体系萃取纯化漆酶的后萃的过程.在此逆胶束体系中,表面活性剂采用一种阴离子生物表面活性剂鼠李糖脂(rhamnolipid, RL),溶剂采用异辛烷.分别考察了4种不同离子种类(NaCl, NaBr, KCl和KBr)与不同浓度、4种不同助溶剂种类(正丁醇,正己醇,正庚醇及正辛醇)与不同比例、乙醇的含量以及温度对漆酶的后萃过程的影响.结果表明,0.25mol/L KCl或0.20mol/L KBr能够得到较好的萃取效果;在四种助溶剂中,正己醇(比例为0.5)和正庚醇(比例为0.5)效果比较好;乙醇加入量为9%效果最优;最适宜温度为35℃.在上述条件下,漆酶的酶活回收率和纯化倍数分别高达90%,4.7倍.电泳分析结果进一步证实了漆酶的纯化效果较好.研究证明鼠李糖脂逆胶束萃取酶类具有广阔的应用前景.     

危险废物浸出毒性的理论基础研究

浸出毒性是危险废物毒性特性鉴别的重要指标.美国危险废物毒性特性鉴别标准是针对工业固体废物与生活垃圾共处置产生的污染特性而制定的,其主要保护目标是地下水;日本针对产业废物投海和进入管理型填埋场处置,分别制定了危险废物浸出毒性鉴别标准,其保护目标分别是海洋和普通填埋场地下水.目前中国的浸出毒性标准缺乏完整的理论基础,没有明确阐明固体废物鉴别目的,浸出项目不全.针对美国和日本等的废物浸出毒性鉴别理论基础和方法进行了比较研究,分析了中国危险废物污染特性、污染途径和环境效应,通过模拟工业废物进行不规范处置且受酸雨影响条件下毒性物质浸出向地下水渗滤迁移的过程,以此作为模型确定浸出毒性的浸取方法.     

提取时间对提取原煤中多环芳烃的影响

以淮北煤田气肥煤和夹矸样品为研究对象,以CH₂Cl₂为溶剂,采用超声提取法(提取时间为10,20和30 min)和索氏提取法(提取时间为24,48和72 h)提取其中可抽提有机物,并利用气相色谱-质谱联用仪(GC-MS)测定提取液中美国环境保护局(USEPA)优控多环芳烃(PAHs)含量,来对比不同抽提时间对提取原煤中PAHs含量和分布特征的影响,为优化原煤中PAHs的提取条件提供理论依据.研究表明:淮北煤田样品中可抽提USEPA优控PAHs以菲为主,其含量占16种PAHs总量的40.0%～65.5%;夹矸样品中可抽提PAHs含量并不因其有机质含量低而明显低于原煤样品,夹矸中PAHs的迁移特征需引起关注.在实验条件下,提取原煤中PAHs,超声提取时间应选取30 min,索氏提取时间法应选取24 h.