土壤中不同老化时间的DDT对小麦根系的生物有效性

研究了水、正己烷、正己烷/丙酮ASE对土壤中不同老化时间的DDT的逐级提取量的差别及其与小麦根吸收的关系。结果表明,有机氯的水提量随老化时间增加而下降,正己烷提取量随老化时间增加而下降,正己烷/丙酮提取量随老化时间增加而上升。植物根吸收随老化时间增加而下降。根吸收与水提量没有确定关系,与正己烷提取量具正相关关系,与正己烷/丙酮提取量有负相关关系。正己烷提取量可被作为土壤有机氯DDT的有效态部分。     

Soxhlet extraction parameters’ influence on the recovery of polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) from a sediment,and artifact formation of PCDD

Soxhlet extraction of polychlorinated dibenzo‐p‐dioxins/dibenzofurans (PCDD/F) from sediment was studied using a designed experimental set‐up. Three variables were studied: three solvent combinations n‐hexane/methanol, dichloromethane/acetone and toluene/methanol; two extraction times, 8 and 16 h, and addition of bulk substances (sodium carbonate). The extraction efficiency was almost identical in all extractions, with the exception of extraction where toluene/ methanol was combined with sodium carbonate. In these samples a major effect was observed, due to formation of Hx‐, Hp‐ and OCDD isomers. Composition of formed PCDD was similar to PCDD isomers found in pentachlorophenol products.     

不同有机质含量的土壤中DDT对小麦根系的生物有效性

对不同有机质含量的土壤中，分别选用水、正己烷、正己烷／丙酮混合溶剂作为DDT的提取剂，用这3种提取剂逐级连续提取，研究了这3级提取剂所提取的DDT量的差别及其与小麦根吸收的关系。结果表明，有机氯的水提取量随土壤D0c的增加而上升，正己烷提取量随土壤TOC的增加而下降，正己烷／丙酮提取量随土壤TOC的增加而上升。根吸收与水提取量没有确定的关系，但与正己烷提取量具正相关关系，与正己烷／丙酮提取量有负相关关系。     

Analysis of a broad range of perfluoroalkyl acids in accipiter feathers: method optimization and their occurrence in Nam Co Basin,Tibetan Plateau

Perfluoroalkyl acids (PFAAs) are ubiquitous in the environment. They are prone to accumulate in organisms and have raised public attention in recent decades. Feather samples have been successfully applied as nondestructive indicators for several contaminants. However, a sophisticated analytical method for determining PFAAs in feathers is still lacking. In the present study, a series of conditions, such as the use of the solid-phase extraction cartridge type and extraction/digestion methods, were optimized for the analysis of 13 PFAAs in feathers. According to the spiked recoveries, a weak-anion exchange cartridge was chosen and the methanol was selected as the extraction solvent. In the present study, an optimized pretreatment procedure combined with high-performance liquid chromatography–electrospray ionization–tandem mass spectrometric (HPLC–ESI–MS/MS) method was established for the determination of PFAAs in feathers. The recoveries and method detection limits of the PFAAs ranged from 71 to 120% and 0.16 to 0.54 ng/g, respectively. Finally, 13 PFAAs in four accipiter feather samples from Nam Co Basin, Tibetan Plateau, were analyzed, indicating that PFOS was the predominant PFAA in accipiter feathers, with an average of 4.67 ng/g, followed by the short-chain PFAAs, PFBS and PFBA, with averages of 1.91 and 1.39 ng/g, respectively. These results partly indicated the current situation of PFAA pollution in the Nam Co Basin, especially the existence of short-chain PFAAs in this region.     

Detection of geosmin and 2-methylisoborneol by liquid-liquid extraction-gas chromatograph mass spectrum (LLE-GCMS) and solid phase extraction-gas chromatograph mass spectrum (SPE-GCMS)

Two sample preparation methods were introduced and compared in this paper to establish a simple, quick and exact analysis of geosmin and 2-methylisoborneol. LC-18 column was employed in solid phase extraction (SPE), 1.0 mL of hexane was adopted in liquid-liquid extraction (LLE), and the extracts were analyzed by gas chromatograph mass spectrum (GCMS) in selected ion mode. Mean recoveries of SPE were low for 2-methylisoborneol (2-MIB) and geosmin (GSM) with values below 50%. For LLE, the recoveries were satisfyingly above 50% for 2-MIB and 80% for GSM. Detection limits of the LLE method were as low as 1.0 ng/L for GSM and 5.0 ng/L for 2-MIB. A year-long investigation on odor chemicals of drinking water in Shanghai demonstrated that in the summer, there was a serious odor problem induced by a high concentration of 2-MIB. The highest concentration of 152.82 ng/L appeared in July in raw water, while GSM flocculation was minimal with concentrations below odor threshold.     

气相色谱／质谱测定电子垃圾拆解区土壤中四溴双酚A的方法

本研究建立气相色谱/质谱来测定电子垃圾拆解区土壤中四溴双酚 A（TBBPA）的方法。该化合物通过超声波辅助萃取,溶剂选择V（丙酮）﹕V（正己烷）=1﹕1或乙酸乙酯;净化柱选择酸化的氟罗里硅土和无水硫酸钠混合物或CleanertC18-SPE进行净化;净化液浓缩后经衍生反应,衍生试剂选用N,O-双（三甲基硅烷基）三氟乙酰胺（BSTFA）和含1%的三甲基氯硅烷（TMCS）。该方法测定电子垃圾拆解区土壤中TBBPA的检出限为（S/N=3）0.1μg·kg^-1加标回收率平均值为92.7%（n=5）,重现性RSD为2.52%（n=5）;线性范围是20～400μg·kg^-1相关系数0.999。该方法用于调查电子垃圾拆解区土壤中四溴双酚A,范围值为5.17～218.00μg·kg^-1其周围农田土壤中四溴双酚A,范围值为0.312～4.170μg·kg^-1     

Simultaneous analysis of five taste and odor compounds in surface water using solid-phase extraction and gas chromatography-mass spectrometry

In this paper, a method using solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) was developed to simultaneously analyze five taste and odor compounds in surface water, i.e., 2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-methoxy pyrazine (IPMP), 2-isobutyl-3-methoxy pyrazine (IBMP), and trans-1,10-dimethyl-trans-9-decalol (geosmin, GSM). The mass spectrometry was operated in selective ion monitoring (SIM) mode. Three kinds of SPE columns and three eluting solvents were compared, the C18 column was chosen as optimum SPE column, and methanol was chosen as the optimum eluting solvent. It was found that the method showed good linearity in the range of 1–200 ng·L^-1 and gave detection limits of 0.5–1.5 ng·L^-1 for individual compounds. Good recoveries (93.5%–108%) and relative standard deviations (1.58%–7.31%) were also obtained. Additionally, concentrations of these taste and odor compounds in Jinan’s surface and drinking water were analyzed by applying this method, and the results showed that GSM and 2-MIB were the dominant taste and odor compounds in Jinan’s raw water.     

五氟苯甲酰氯衍生色谱法分析水体中痕量羟基多溴联苯醚

以五氟苯甲酰氯(PFBCl)作为衍生化试剂,气相色谱-电子捕获检测器(Gas chromatography-electron capture detector,GC-ECD)为检测手段,建立了水体中痕量羟基多溴联苯醚(Hydroxylated polybrominated diphenyl ethers,简称OH-PBDEs)的酰基化衍生-GC/ECD检测方法.通过实验讨论了衍生化缓冲溶液、衍生化时间以及衍生后萃取溶液异辛烷的用量对检测结果的影响,确定了最佳的衍生化条件.在最佳的衍生化条件下,4-OH-BDE 42、4’-OH-BDE 49、6-OH-BDE 47、2’-OH-BDE 68和6’-OH-BDE 99的衍生化产物均获得了良好的分离度和色谱响应值.本方法的仪器检出限为0.02—0.14 pg,方法检出限为0.61—4.67 pg.L-1,标准曲线线性相关系数的范围为0.9973—0.9996,相对标准偏差均小于10%.3种采自大连市不同地区环境水样的加标回收率检测结果表明,所建立的分析方法适于水体中痕量OH-PBDEs的检测.     

分散液液微萃取-石墨炉原子吸收光谱法测定环境水样中的痕量镉

建立了分散液液微萃取分离富集一石墨炉原子吸收光谱法测定环境水样中痕量镉的新方法。以二乙基二硫代氨基甲酸钠为螯合剂、四氯化碳为萃取剂、丙酮为分散剂,详细考察YpH值、螯合剂质量分数、萃取剂体积、萃取时间等因素的影响。在优化的实验条件下,方法对水样中镉的检出限为4．2ng-L^-1,线性范围是20-300ng-L^-1,测定结果的相对标准偏差为3．5％,富集倍数达103。将建立的方法应用于三种实际环境水样中镉的检测,加标回收率在92％-108％范围内。本方法具有灵敏、准确、快速、环保的特点,是一种分析水样中痕量镉的较好方法。     

Adsorption and movement of carbaryl in soils: A verification of cosolvent theory and comparison of batch equilibrium and soil thin layer chromatography results

Batch equilibrium and soil thin layer chromatography (TLC) techniques were used to investigate the influence of different volume fractions of organic cosolvents (acetone and methanol) on the adsorption and movement of carbaryl in four different types of Indian soils. L-shaped isotherms were obtained for both the cosolvent–water mixtures at all f _s values and were in close agreement with the Freundlich equation. Higher adsorption was observed on F.R.I. soil (FSL) followed by Alampur soil (ASL), Kalai soil (KL), and Bhoran soil (BSL) at all f _s values for both the cosolvent systems as was anticipated from the K and K _D values. The K and K _D values also confirmed that carbaryl adsorption was higher in methanol–water mixture than acetone–water mixture and decreased with increasing f _s values. The frontal R _f values obtained from soil TLC studies were inversely proportional to the K and K _D values for both the cosolvent systems. The higher K and K _D values and lower R _f values in methanol–water mixtures relative to acetone–water mixtures for all the soils indicated that acetone had a greater potential for ground water contamination compared to methanol. The adsorption data were used to evaluate the cosolvent theory for describing adsorption of carbaryl in acetone–water and methanol–water mixtures. The aqueous phase partition coefficients, K _DW (mol g^?1), normalized with respect to f _oc for carbaryl was evaluated by extrapolating f _s → 0.     

Preparative and analytical extraction of pigments from brown algae with dimethyl sulfoxide

Dimethyl sulfoxide (DMSO) rapidly extracts much of the chlorophyll c and fucoxanthin from the intact thalli of brown algae. Subsequent extraction by acetone rapidly removes most of the chlorophyll a and -carotene. An analytical procedure for these pigments has been developed, based upon this extraction sequence, followed by partition of the acetone extract between hexane and aqueous acetone. Fucoxanthin and chlorophyll c can be recovered from the DMSO extract and the aqueous acetone phase by extraction into ethyl acetate and subsequent evaporation. The DMSO-acetone extraction sequence is also effective with green algae and a few red algae, although the full scope of the method has not been investigated.     

A novel extraction method for analysing available sulfamethoxazole in soil

A novel extraction method was established to determine the water-extractable (available) content of sulfamethoxazole (SMX) in soil. The SMX imprinted polymers (MIPs) were synthesised and the performance was evaluated by Fourier transform infrared spectroscopy, scanning electron microscopy and binding experiments. Results showed that the MIPs exhibited good selectivity for SMX, so the MIPs were applied as a sorbent. SMX in soil was extracted by water, sorbed from the extract to MIPs and analysed with a high performance liquid chromatography (HPLC) after its desorption from MIPs. Meanwhile, the classic organic solvent extraction was employed to measure the total SMX content in soil. Results showed that when SMX level in spiked soils varying from 1.0–500?μg?kg^?1, the observed recoveries of available SMX contents ranged from 63.27?±?3.11% to 82.11?±?2.77% (n?=?3), while the total SMX varied between 89.59?±?1.65% and 97.64?±?3.92% (n?=?3). The detection limit of the developed method for SMX in soils was 0.05?μg?kg^?1. Available SMX contents in five field soil samples ranged from 0.13 to 4.14?μg?kg^?1, which were only 0.35–25.40% of the respective total SMX contents. Results from this study manifest the importance of the extents of SMX immobilisation with different soils for assessing SMX's ecological and human health risks.     

加速溶剂萃取-固相萃取净化-超高效液相色谱串联质谱法测定土壤中11种全氟化合物

采用超高效液相色谱-串联质谱联用法（UPLC-ESI-MS/MS）,建立了分析土壤中11种全氟化合物（PFCs）的方法.以甲醇作为萃取剂,样品经加速溶剂萃取仪（ASE）萃取,固相萃取净化后,使用UPLC-ESI-MS/MS联用仪分析样品中11种PFCs.在6 min内就可快速稳定地将所选取的11种全氟化合物分离,且最低检测浓度为0.518—3.520 pg.g-1之间,这些化合物在土壤中的平均添加回收率在71.2%—119.2%之间.应用此方法测得宜兴市水稻土样品中所选取的PFCs含量为0.006—0.780 ng.g-1之间.     

植物类脂的提取及对菲吸附的影响

讨论了有机溶剂极性对植物类脂提取的影响,分别采用(Ⅰ)非极性正己烷和(Ⅱ)极性三氯甲烷∶甲醇(2∶1)溶液从青椒和油麦菜干样中索氏提取植物类脂,进一步研究了上述植物干样、提取类脂和去类脂组分对菲的吸附.实验结果表明,两种方法提取得到的类脂含量不同,方法(Ⅰ)从青椒和油麦菜中提取得到类脂含量为(1.9±0.1)%和(5.0±0.4)%;而方法 (Ⅱ)提取得到的相应值分别为(2.6±0.2)%和(9.5±0.5)%.两种方法得到提取类脂对菲的吸附贡献无显著性差异(P>0.05),均约占整个青椒干样对菲吸附的20%,而油麦菜的这一比例约为60%.但采用正己烷提取可避免极性物质的析出而更好地分离类脂和去类脂组分.去类脂组分在青椒和油麦菜中对菲的吸附贡献分别约为80%和40%,即去类脂组分对菲仍有较强的吸附能力,因此不能简单视为碳水化合物.     

GC-MS测定土壤中阿特拉津、六氯苯等十种农药残留

建立了气相色谱-质谱-选择离子监测(GC-MS-SIM)同时测定土壤中10种农药(三嗪类除草剂、酰胺类除草剂和有机氯农药)的多残留分析方法.样品采用正己烷/丙酮(1:1,V/V)超声提取、氟罗里硅土柱层析净化、GC-MS-SIM测定.10种农药在0.01(0.02)-1.0(2.0)mg·l~(-1)范围内线性良好,相关系数介于0.9963-0.9998之间;在10,50和250 ng·g~(-1)添加水平下,平均回收率介于81%-117%之间,相对标准偏差均小于14.4%;方法检出限达到ppb至sub-ppb级(0.1-1.3 ng·g~(-1)).将此方法应用于辽宁省不同性质土壤中70个实际土壤样品的分析,阿特拉津、乙草胺、六氯苯、丁草胺、狄氏剂和艾氏剂有检出,该法对不同性质土壤具有广泛适用性.     

水稻中氟虫双酰胺及其代谢产物的超高效液相色谱残留分析方法

采用超高效液相色谱法分析了氟虫双酰胺及其代谢产物在田水、土壤、稻秆、糙米和稻壳中的残留.水样以乙酸乙酯为萃取溶剂,液-液分配净化;土壤样品以丙酮为提取剂,液-液分配净化;水稻样品经乙腈提取,NH2-Carb柱净化.对水稻和环境中的氟虫双酰胺及其代谢产物进行不同水平的添加回收率实验,方法的回收率在78.2%—104.8%之间,相对标准偏差为1.1%—4.4%.氟虫双酰胺及其代谢产物的最小检出量在0.004—0.02 ng,其在稻田水中的最低检测浓度为0.0008—0.0009 mg.L-1,在土壤、稻秆、糙米、稻壳中的最低检测浓度为0.001—0.003 mg.kg-1.     

Effervescence assisted dispersive liquid–liquid microextraction followed by microvolume UV-Vis spectrophotometric determination of surfactants in water

The novel and simple methods for the sensitive determination of cationic and anionic surfactants in water based on effervescence assisted dispersive liquid–liquid microextraction and microvolume UV-Vis spectrophotometry have been developed. The method involves ion-pair extraction of cationic and anionic surfactants with organic dyes (methyl orange and azure A, respectively) during the dispersion of extraction solvent (CHCl₃) by CO₂ bubbles which are formed by the injection of a mixture of the extraction solvent and proton donor solvent into the sample solution which contains carbonate-ions as effervescency agent. The analytical performance of the proposed procedure was compared with the conventional dispersive liquid–liquid microextraction. Appropriate experimental conditions for both methods were investigated. The absorbances of the colored extracts at wavelengths of 440 and 625 nm obey Beer's law within the range of 0.1–5.0 mg/L for both cationic and anionic surfactants. The limit of detection (LOD) obtained using the effervescence assisted extraction method was 30 µg/L for cationic and anionic surfactants. The proposed methods were successfully applied to determination of surfactants in water samples.     

Solvent effects on quantitative analysis of brominated flame retardants with Soxhlet extraction

Reliable quantifications of brominated flame retardants (BFRs) not only ensure compliance with laws and regulations on the use of BFRs in commercial products, but also is key for accurate risk assessments of BFRs. Acetone is a common solvent widely used in the analytical procedure of BFRs, but our recent study found that acetone can react with some BFRs. It is highly likely that such reactions can negatively affect the quantifications of BFRs in environmental samples. In this study, the effects of acetone on the extraction yields of three representative BFRs [i.e., decabrominated diphenyl ether (decaBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA)] were evaluated in the Soxhlet extraction (SE) system. The results showed that acetone-based SE procedure had no measureable effect for the recovery efficiencies of decaBDE but could substantially lower the extraction yields for both TBBPA and HBCD. After 24 h of extraction, the recovery efficiencies of TBBPA and HBCD by SE were 93 and 78% with acetone, 47 and 70% with 3:1 acetone:n-hexane, and 82 and 94% with 1:1 acetone:n-hexane, respectively. After 72 h of extraction, the extraction efficiencies of TBBPA and HBCD decreased to 68 and 55% with acetone, 0 and 5% with 3:1 acetone/n-hexane mixtures, and 0 and 13% with 1:1 acetone/n-hexane mixtures, respectively. The study suggested that the use of acetone alone or acetone-based mixtures should be restricted in the quantitative analysis of HBCD and TBBPA. We further evaluated nine alternative solvents for the extraction of the three BFRs. The result showed that diethyl ether might be reactive with HBCD and may not be considered as the alternative to acetone used solvents for the extraction of HBCD.     

Trace analysis of off-flavor/odor compounds in water using liquid-liquid microextraction coupled with gas chromatography—positive chemical ionization-tandem mass spectrometry

A rapid, inexpensive and laboratory friendly method was developed for analysis of off-flavor/odor compounds in fresh and salt water using gas chromatography with chemical ionization-tandem mass spectrometry. Off-flavor/odor compounds included geosmin, 2- methylisoborneol (MIB), 2-isobutyl-3-methyoxypyrazine (IBMP), and 2-isopropyl-3-methoxypyrazine (IPMP). Using this method, a single sample can be extracted within minutes using only 1 mL of organic solvent. The ion transitions for IPMP, IBMP, MIB, and geosmin were 153>121, 167>125, 152>95, and 165>109, respectively. The linearity of this method for analyzing MIB ranged from 4 to 200 ng·L^–1, and from 0.8 to 200 ng·L^–1 for the other analytes. Method recoveries ranged from 97% to 111% and percent relative standard deviations ranged from 3% to 9%, indicating that the method is accurate, precise, and reliable.     

Supercritical fluid extraction of biofuels from biomass

A sustainable source of energy production can be provided using renewable resources. For instance, biomass is transformed into biofuels using several techniques such as supercritical fluid extraction, an effective thermochemical process. Here we review results on biofuels obtained from lignocellulosic and algal biomass using supercritical fluids. Biofuel yield and composition are controlled by operating conditions such as extraction temperature, pressure, biomass and solvent type, and the presence of catalysts. The extraction temperature is the major factor controlling biofuel yield. Biofuel yields can also be improved with the use of catalysts. Major compounds in biofuels from lignocellulosic biomass are phenols, catechols, guaiacols, syringols, syringaldehydes, syringyl acetone, acids, and esters. Most of these compounds are produced by lignin decomposition in lignocellulose. Furfural and derivatives are produced by the decomposition of cellulose and hemicellulose. Fatty acid alkyl esters are formed from lignin fragmentation by condensation of compounds bearing C–O or C=O. Prominent compounds in biofuels from algal biomass are saturated or unsaturated fatty acid alkyl esters.