Influence of Earthworms on the Sulfur Turnover in the Soil

Abstract

The effects of earthworm activity on the concentration and isotopic composition of total sulfur in soils was investigated using batch experiments. Two ecologically different lumbricid species, the anecic Lumbricus terrestris and the endogeic Aporrectodea caliginosa, were used. The earthworms were fed birch leaves, beech leaves, cattle manure or mixed plant litter. All food sources differed isotopically (δ³⁴S) from the soil (Parabraunerde). As a reference, one experiment was carried out without additional food.

The experimental results show, that both earthworm species influence the total S-content and the δ³⁴S-values in the soil by digestion of the different food sources. The differences in the total S-content of the earthworm tissues and in the S-isotopic composition of the casts can be attributed to the ecological differences between the earthworm species.     

15N-Traceruntersuchungen zum Mechanismus der N2O-Bildung in Böden

Nitrous oxide is a potential environmental hazard responsible for the green house effect and the destruction of the ozone layer in the lower stratosphere. Biological denitrification under anaerobic conditions in soils results in the formation of both N₂O and N₂, whereby highly nitrogen-fertilized agricultural soils contribute to a considerable extent of the N₂O emission. Latest results in the literature indicate that nitrous oxide can also be formed as a byproduct of the microbial nitrification. This is of importance for soils in central Germany because of the non-existence of typical denitrification conditions in a semiaride climate.

This study was conducted to measure the path of N₂O formation in Haplic Phaeozen: using [¹⁵N] ammonium and [¹⁵N] nitrat and a GC-MS aided incubation system. The kinetic isotope method was used to evaluate the experimental data. The results are:

- Under anaerobic conditions (～ 90% of the water holding capacity = WHC) N₂O originates mainly from the nitrate pool by denitrification.

- As expected, the N₂O formation is low under aerobic conditions (～ 80% WHC) but the gas originates directly from the ammonium and not from the nitrate pool, probably as a byproduct of the nitrification process.     

Calibration Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced Breakdown Spectroscopic Analysis

The present article describes a working or combined calibration curve in laser-induced breakdown spectroscopic analysis, which is the cumulative result of the calibration curves obtained from neutral and singly ionized atomic emission spectral lines. This working calibration curve reduces the effect of change in matrix between different zone soils and certified soil samples because it includes both the species' (neutral and singly ionized) concentration of the element of interest. The limit of detection using a working calibration curve is found better as compared to its constituent calibration curves (i.e., individual calibration curves). The quantitative results obtained using the working calibration curve is in better agreement with the result of inductively coupled plasma–atomic emission spectroscopy as compared to the result obtained using its constituent calibration curves.     

Room Temperature Phosphorescence of 1-Bromo-4-(bromoacetyl)naphthalene Induced by Sodium Deoxycholate

Sodium deoxycholate (NaDOC) can induce 1-bromo-4-(bromoacetyl)naphthalene (BBAN) to undergo strong room temperature phosphorescence (RTP) without the removal of dissolved oxygen from the solution. RTP spectra, phosphorescence polarization and ¹³C NMR results, along with the molecular modeling calculations, supported the conclusion that BBAN molecule was combined in a sandwich with two NaDOC molecules by a “back-to-back” hydrophobic interaction arising from the apolar faces of the NaDOC molecules, which provided BBAN with a rigid enough microenvironment to produce RTP.     

Electron impact,electron capture negative ionization and positive chemical ionization mass spectra of organophosphorus flame retardants and plasticizers

Phosphate esters are important commercial products that have been used both as flame retardants and as plasticizers. To analyze these compounds by gas chromatographic mass spectrometry, it is important to understand the mass spectra of these compounds using various ionization modes. This paper is a systematic overview of the electron impact (EI), electron capture negative ionization (ECNI) and positive chemical ionization (PCI) mass spectra of 13 organophosphate esters. These data are useful for developing and optimizing analytical measurements. The EI spectra of these 13 compounds are dominated by ions such as H₄PO₄⁺, (M ? Cl)⁺, (M ? CH₂Cl)⁺ or (M)⁺ depending on specific chemical structures. The ECNI spectra are generally dominated by (M ? R)^?. The PCI spectra are mainly dominated by the protonated molecular ion (M + H)⁺. The branching of the alkyl substituents, the halogenation of the substituents and, for aromatic phosphate esters, ortho alkylation of the ring are all significant factors controlling the details of the fragmentation processes. EI provides the best sensitivity for the quantitative measurement of these compounds, but PCI and ECNI both have considerable qualitative selectivity. Copyright © 2013 John Wiley & Sons, Ltd.     

超声辅助提取/离子色谱法测定铬污染土壤中的六价铬

建立了超声辅助提取/离子色谱法测定铬污染场地中铬（Ⅵ）的方法。选用0.3 mol/L的KCl溶液作提取剂,对12组土壤样品中的铬（Ⅵ）进行超声辅助提取20 min。采用Metrosep A Supp 4-250（250 mm×4.0mm）型阴离子分离柱,以4 mmol/L Na₂CO₃-1 mmol/L NaHCO₃混合溶液为淋洗液对样品进行分离分析。铬（Ⅵ）在0.01²0 mg/L浓度范围有较好的线性关系,相关系数（r²）为0.999 8;该方法的检出限为0.003 mg/L,加标回收率为96.4%¹06.8%,相对标准偏差（RSD,n=3）为0.56%。该方法具有简便、快速、准确等优点,适用于铬污染场地的监测与调查。     

A New Organophosphorus Insecticides Removal Process Using Fly ASH

Abstract

Fly ash and soil mixtures with a range of fly ash content from 1 to 100% were used to study adsorption and desorption of four organophosphorus insecticides, ethyl parathion, methyl parathion, fenitrothion and fenthion, in batch experiments. The object of the study was to develop a treatment process using fly ash as sorbent material to isolate/immobilize organic contaminants from aqueous solutions. The adsorption isotherms fit the Freundlich equation x/m=K_dC^1/n. The K_d values increase with the increase of the fly ash content. The isotherms seem to fit the S type, in mixtures of soil with a fly ash content from 0 to 10%, which implies that adsorption becomes easier as the concentration in the liquid phase increases. In mixtures of soil with a fly ash content from 25 to 50% the isotherms become L type and correspond to a decrease of site availability as the solution concentration increases. Finally in mixtures of soil with a fly ash content over 50%, C type adsorption was observed which correspond to a constant partition of the insecticides between the bulk solution and the adsorbent. Mass balance estimations show that the mean percent amounts of insecticides for a range of concentration 0.5–15 mg/l, removed by adsorption in the soil sample are 81.56 % for ethyl parathion, 48.97 % for methyl parathion, 67.06 % for fenitrothion and 86.65 % for fenthion. The adsorption increases as the fly ash content increased and reach the 100% in the “pure” fly ash. The adsorbed amounts of insecticides in mixtures of soils with >50% fly ash content, are up to 99%. In contrast, the amounts of desorption in water decrease as the fly ash content increase.

The results of this research demonstrate that the fly ash shows a significant capacity for adsorption of organophosphorus compounds from aqueous solution and can be used for pesticide removal process.     

Investigation of the solubilization of car-emitted Pt,Pd and Rh in street dust and spiked soil samples

A sequential extraction procedure (three-step), proposed by the Standards, Measurements and Testing Programme (formerly BCR) of the European Union, was applied to street dust and spiked soil samples for the determination of PGEs. Analyses were carried out using inductively coupled plasma-mass spectrometry (ICP-MS). The results indicate that up to 5% from Pt, 70% from Pd and 14% from Rh are in mobile forms in street dust. The results for the soil samples spiked with crushed catalytic converter are significantly lower indicating that PGEs are oxidised more efficiently in natural conditions. Additionally Pt and Pd bound to humic acids were investigated.     

Assessment of mobility of heavy metals in two soil types by use of column leaching experiments and chemometric evaluation of elution curves

The objectives of this study were to evaluate the mobility of heavy metals (HMs) in two types of soils (acidic forest soil and neutral agricultural soil) by leaching with calcium chloride solution in column experiments. The screening properties of neutral agricultural soil towards pollution by heavy metals (Ni, Cu, Zn and Cd) are approximately 10 times higher than those of acid forest soil. The neutral agricultural soil, polluted artificially by one pore volume (PV) of an HMs solution of concentration 200 mg L^?1, can screen the leaching of these metals over several hundreds of years. The higher apparent desorption rate and per cent desorption of HMs (especially Cd) in acid forest soil indicated a higher potential of intensive migration of the metals across the profile and indicated potential risk of Cd pollution for this type of soil. The latest approach of artificial neural networks to describe transport of HMs in soil has been also evaluated. Using a simple three-layer perceptron topology with three hidden neurons, the experimental data could be simulated. The results suggested that the pH of soil is a major factor controlling the retention of the heavy metals in the soils.     

Handling of Environmental and Biological Samples via Pre-Column Technologies

Abstract

Sample handling is still a weak point in chromatography and in analytical chemisty in general. One consideration is the automation potential of new procedures. Solid-liquid extraction techniques in combination with pre-column technology are particularly promising in this regards. The construction and geometry of pre-columns both for conventional and narrow-bore HPLC are of major importance, since band broadening should be kept at a minimum for an optimal functioning of the analytical system. The various operations that can be carried out with such a pre-column are trace-enrichment, clean-up of the sample which depends on the type of adsorbents used in the precolumn, i.e., polar or apolar materials, ion exchangers or metal covered surfaces, etc., protection of the analytical column, field sampling and storage of samples and as a substrate for on-column chemical derivatizations. These various operations are demonstrated with practical examples from the fields of environmental and biological analysis. The selectivity can be further enhanced by coupling precolumn technology with selective detection modes such as diode array UV, electrochemical or fluorescence detection. This enables the construction of optimal and integrated analysis sytems which are fully automated and microprocessor controlled. They can also be made compatible with miniaturized LC-technology.