Determination of 41 polybrominated diphenyl ethers in soil using a pressurised solvent extraction and GC-NCI-MS method

A rapid and reliable analytical method based on pressurised solvent extraction (PSE) and GC-NCI-MS was developed for the determination of 41 different PBDEs in soil. All PBDEs, including mono- to hepta-BDEs (sum of 39 congeners), one nona-BDE and deca-BDE, were efficiently extracted from soil samples using the extraction technology of PSE. The extract was then cleaned up on a florisil column. Satisfactory separation of 41 PBDE congeners was obtained on a 15-m DB-5MS capillary column, saving the use of another 30-m column specific for the separation of mono- to hepta-BDEs. PBDEs were identified and quantified by GC-MS in negative chemical ionisation (NCI) mode, and further confirmed in semi electron impact (SEI) mode when the ion source was also NCI. The method detection limits ranged from 0.01 to 0.03?ng?g^?1?dw for mono- to hepta-BDEs, 1.43?ng?g^?1?dw for the nona-BDE and 0.20?ng?g^?1?dw for deca-BDE. The applicability of the method was tested in soil samples collected from an e-waste recycling site at Guiyu. Twenty-one PBDEs (mono- to deca-) were detected, and eighteen congeners were quantified. The concentration range of PBDEs was 0.78–436?ng?g^?1?dw. BDE-47, BDE-99, BDE-153, BDE-183, BDE-206 and BDE-209 were the dominant congeners, and BDE-209 accounted for 62% of the total PBDEs. The congener profiles of PBDEs in soil samples were similar to those in three commercial PBDE products (Penta-, Octa- and Deca-BDE), and Deca-BDE product was the most important contributor.     

Simultaneous multi-residue pesticide analysis in soil samples with ultra-high-performance liquid chromatography–tandem mass spectrometry using QuEChERS and pressurised liquid extraction methods

To assess soil contamination, it is important to be able to measure different classes of pesticides simultaneously. For this reason we developed a sensitive ultra-high-performance liquid chromatography–tandem mass spectrometry method for the simultaneous analysis of 25 pesticides in soil samples. Multi-class pesticides (triazines, phenylureas, phenoxy acid pesticides etc.) were analysed using a single mass spectrometry method with a fast polarity switching option, allowing the analysis of 19 compounds in the positive ionisation mode and six compounds in the negative ionisation mode. Extraction of pesticides from soil samples was performed employing a pressurised liquid extraction (PLE) and a quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure, recently developed for the extraction of multi-residue pesticides from food matrices. The extraction efficiency, performance and recoveries of these two procedures were evaluated and compared. In addition, we studied the effect of matrix on signal suppression or enhancement. Isotope-labelled internal standards (ILIS) were used to compensate the suppression or enhancement of signal intensities in the extracted samples. The method was validated using reference soil material (EUROSOIL 7) spiked with 50 μg/kg of each pesticide. The average recovery by PLE varied between 65.1% and 122.2% with RSDs of 1.7–23.4%. QuEChERS provided better recoveries for most of the pesticides, the extraction recovery ranging from 79.4% to 113.3% with RSDs of 1.0–12.2%. Limits of quantification for all target compounds were within a range of 0.1–2.9 µg/kg.     

Determination and dynamics of kanamycin A residue in soil by HPLC with SPE and precolumn derivatization

As one of the aminoglycoside antibiotics, kanamycin has been widely used in human therapy and as an additive to promote growth and prevent disease in forage. The kanamycin residue may have potenital risks for organisms and the environment. Therefore, the monitoring of this drug may have dynamic importance. In this work, a novel method for determination and dynamic study of kanamycin A was developed through solid phase extraction and derivatization with 4-chloro-3,5-dinitrobenzotrifluoride before high-performance liquid chromatography analysis. The calculated recoveries were from 72.3 to 92.5%, with relative standard deviations from 2.99 to 6.94%. The detection limit of kanamycin A in soil was 0.006?mg?kg^?1 with a signal-to-noise ratio of 3. The dynamics in soil showed that the degradation of kanamycin A coincided with the equations C?=?1.951e^{?0.0482 t} for black soil and C?=?1.807?e^{?0.0247 t} for red soil and the half-lives were 14.38 and 28.06?d respectively. The degradation rate reached 95.19% in black soil after 63 days compared with 77.14% in red soil.     

Residue dynamics of chlorpyrifos and cypermethrin in/on pomegranate (Punica granatum L.) fruits and soil

Study on the residue dynamics of chlorpyrifos and cypermethrin in/on pomegranate (Punica granatum L.) and soil was carried out by conducting supervised field trials as per good agricultural practices. A modified QuEChERS was used to extract the insecticides in pomegranate peel and aril and soil. The limit of quantification (LOQ) of chlorpyrifos and cypermethrin were 0.01 and 0.05 mg kg^?1, respectively. Residues of the insecticides remained on the fruit surface and movement to the edible part (aril) was not observed. The residues after treatment on fruit peel were 2.46 and 3.51 mg kg^?1 and 2.84 and 4.54 mg kg^?1 for chlorpyrifos and cypermethrin, respectively, from recommended and double dose treatments. Chlorpyrifos residues degraded faster compared to cypermethrin. The pre-harvest intervals (PHIs) of chlorpyrifos were 22 and 35 days and those of cypermethrin 50 and 73 days, respectively, at recommended and double dose treatments. In the experimental field soil after the second application chlorpyrifos residues were 0.21 and 0.46 mg kg^?1 and cypermethrin residues 0.15 and 0.36 mg kg^?1. At harvest, both pesticides showed residues below the LOQ. Based on this study, application of cypermethrin towards harvest may be avoided whereas chlorpyrifos can be applied with 22 days PHI.     

Potential of glucose measurement in soil and food sample using low molecular weight O-(2-hydroxyl)propyl-3-trimethylammonium chitosan chloride nanoparticle-glucose oxidase immobilised on a natural fibre membrane

Low, medium and high molecular weights O-(2-hydroxyl)propyl-3-trimethylammonium chitosan chloride nanoparticles (L-, M- and H-O-HTCC NP) have been synthesised and used to immobilise glucose oxidase on eggshell membranes for glucose biosensing. Among these O-HTCC NP-based biosensors, L-O-HTCC NP provides the highest sensitivity to glucose with a linear response of 0.012–0.60 mM and a detection limit of 12 μM (S/N = 3). The effect of L-O-HTCC NP and enzyme loading ratio, pH, temperature and phosphate buffer concentration on the sensitivity of the biosensor was studied in detail. The biosensor exhibits fast response time (40 s), good repeatability (3.0%, n = 10) and storage stability (95% of initial sensitivity after 1-year storage). Common interferents including acetic acid, DL-α-alanine, L-ascorbic acid, butyric acid, citric acid, DL-cysteine, ethanol, folic acid, glycine, lactic acid, lactose, propionic acid, sodium benzoate and sucrose do not cause significant interference on the L-O-HTCC NP biosensor. The recoveries 88.3%–102% and 102%–116% and relative standard deviations (RSDs) 3.90%–5.56% and 1.25%–3.00% are respectively, for the soil and food sample analyses. The proposed biosensor method has been applied to determine glucose in soil and food samples with good accuracy and recovery, inferring that it has potential for detection and quantification of diversified samples of different matrices. Finally, it has successfully monitored the changes of glucose contents in soil samples at various incubation times, demonstrating its potential use in environmental and geochemical analysis.     

Degradation of Isoproturon in Soil in Relation to Changes of Microbial Biomass and Activity in Small-Scale Laboratory and Outdoor Studies

Abstract

The soil degradation of isoproturon under standardized laboratory conditions was compared to that carried out in an outdoor experiment using lysimeters. After application of ¹⁴C-labelled formulated isoproturon (1.5 kg A.I./ha), radiochemical analysis, as well as microbial investigations, were performed to relate changes in soil microbial biomass to its capability of degrading isoproturon. The results showed that the microbial biomass, as well as its dehydrogenase activity, varied under field conditions due to fluctuations of temperature and soil moisture. In the laboratory experiment the microbial biomass decreased during the 100 day experimental period, this reduction being the result of the experimental conditions. Consequently, the herbicide was degraded more quickly in the outdoor experiment where leaching, formation of ¹⁴CO₂ uptake by plants, and photolysis also took place, than in the laboratory experiment. Further microbiological investigation in the laboratory experiment showed that specific populations known to be responsible for the metabolic degradation of the compound were enhanced in the isoproturon-treated soil.     

Chemical Speciation and Fractionation in Soil and Sediment Heavy Metal Analysis: A Review

Abstract

Today it is generally recognized that the particular behaviour of trace metals in the environment is determined by their specific physicochemical forms rather than by their total concentration. Several chemical speciation and fractionation methods for heavy metal analysis in soils and sediments have been and are still being developed and applied. They primarily are intended to understand the particular environmental behaviour of metals, present in a variety of forms and in a variety of matrices.

Analytical developments, modifications of existing methods, and recent new approaches are reviewed and discussed. Techniques used include chemical extractions, ion-exchange/gel chromatography, filtration, centrifugation and sieving, selective solvent extraction.

Moreover, the application of these various techniques in different research fields over the last years is explored. The value and the limitations of speciation and fractionation techniques applied in specific experimental work is outlined. It is discussed to what extent these methods have, up to now, filled in the expectations or have been satisfactory in particular applications.     

Systematic Identification of Analytical Indicators to Measure Soil Load on Plants for Safety Assessment Purposes

Abstract

Contaminants in soil can be transferred to humans and other biota when soil dust on plants is ingested as food. Measuring how much soil is on plants, in the absence of artificial tracers or contaminants, is difficult because of the very small amounts involved and the confounding effect of absorption of elements through roots. However, measurements of soil load are essential for assessment modelling. We compared the ability of several analysis strategies, involving naturally occurring elements, to predict the soil load on plants. Large samples of 12 vegetable and fruit crops were collected, along with corresponding soil samples. An independent measure of soil load on the crop samples was derived from a combination of gravimetric measurements, including loss on washing and the acid-insoluble ash content. The best agreement between the elemental-abundance and the gravimetric methods was for Sr in the plant acid-insoluble ash. Through a systematic process of elimination, we conclude that analyses of the acid-insoluble ash fraction of the plant samples for Al, Ba, Fe, Si, Sr and Ti are most reliable. If analyses are to be restricted to the full plant ash, then the choice of analytes is restricted to Al, Fe, Si and Ti. Soil loads in our study averaged 20 mg soil kg^?1 dry plant for leafy tissues and 2 mg soil kg^?1 for fruits, and washing decreased soil loads about 1.5 fold.     

土工参数随机模型中相关函数的选择

本文研究土性剖面的随机模型,给出了相关文献中使用的方差衰减函数与相关距离的数学模型,并证明了相关函数的类型在某种条件下必为指数函数,纠正了相关文献中的错误概念。