The determination of the extractability of selected elements from agricultural soil

Concentrations of Ag, Al, Ba, Cd, Co, Cr, Cu, Fe, K, Mn, Na, Ni, Pb, Sr, and Zn—isolated by sequential extraction steps from apple orchard soil—were analyzed by inductively coupled plasma-atomic emission spectroscopy and compared to the total amount of metal in soil determined by XRF. The extractable amount of each metal was calculated by the extraction yields of the four steps. The LODs of the different elements in all extracts ware below 3 μg/L except for Ba (steps 1 and 2), Cu (step 1), Fe (all steps), K (steps 1–3), Mn (step 2), Na (steps 1–3), Ni (step 1), Pb (steps 1 and 4), and Zn (steps 1 and 2). The highest LOD (>10 μg/L) was found for Fe, K, and Na (step 1). The recovery of all metals after four sequential extraction steps was 90–112%. The repeatability (<1.1%), the intermediate precision (<5.3%), the day-to-day reproducibility (<6.2%), and the overall uncertainty of measurement (approximately 4–8.5%) for all analyzed metals supports the choice of the method used.     

Application of impregnated filters to determination of smoke and ammonia

Whatman No. 1 filters impregnated with a 3% solution of oxalic acid in ethanol which are used for elimination of ammonia from the air stream before entering the absorber for collecting SO₂, were tested for a possible application (a) in the spectrophotometric determination of ammonia with Nessler's reagent and (b) in the reflectometric determination of smoke. It was shown that impregnated filters were as suitable for the determination of ammonia as absorbing solution and as applicable for smoke measurement as untreated filters. Further, the advantage of using impregnated filters for sampling ammonia lies in avoiding the interference of organic vapours which may occur, if absorbing solution is used.     

Elimination of ammonia interference in acidimetric determination of sulphur dioxide

Ammonia interference in acidimetric determination of sulphur dioxide can be eliminated by separate determination of ammonia in the same sample and by correction of results. However, with this addition the procedure is no longer simple.To avoid two separate determinations a selective absorption of ammonia from the air stream before it enters the absorbent solution for SO₂ has been considered. Several absorbents used to remove or to collect ammonia for subsequent determination were tested in the laboratory. Whatman No. 1 (or 41) filter papers impregnated with 3% oxalic acid solution in ethanol proved to be the most efficient for ammonia retention without an effect on SO₂. In a comparative testing over 52 days at a permanent sampling station no statistically significant difference was observed between two trains with impregnated filters and a third train where correction for ammonia, separately determined in the same sample, was performed.Regression analysis, however, showed that the results obtained in the third train are more dispersed due to accumulated errors in two analyses at low concentration levels further aggravated by conversion of ammonia to equivalent SO₂ concentrations. The removal of ammonia with impregnated filters gives better precision with less inconvenience and is therefore preferable.     

导数示波极谱法测定废水中微量的对硝基乙苯

研究了导数示波极谱法测定废水中微量的对硝基乙苯的方法.在0.0150mol/L乙二胺-0.0100mol/L EDTA底液中,对硝基乙苯产生一灵敏的二阶导数极谱峰,峰电位为-0.54V(Vs·SCE).对硝基乙苯浓度在1.00×10-7～7.00×10-5mol/L范围内,浓度与峰电流成线性关系.检测限为1.00×10-7mol/L.本方法可用于废水中微量对硝基乙苯的测定.     

高浓度含氨废水中氨氮的快速测定

依据铵盐与甲醛反应生成等物质量酸的原理,建立了一种快速测定高浓度含氨废水中氨氮含量的甲醛法。试验结果表明,甲醛法所测结果与国家标准分析方法比较无显著性差异。该方法的加标回收率范围为96％～103％,具有快速、简便的优点,对合成氨工业废水和生活污水中氨氮的测定结果令人满意。     

Optimization of sampling for the determination of mean radium-226 concentration in surface soil

There are thousands of properties in the United States on which the soil has been contaminated to some degree with uranium mill tailings. An effort is now underway by the United States Department of Energy to identify sites contaminated with tailings and to perform remedial action when ²²⁶Ra levels exceed current guidelines. Because of the large number of sites involved, it is imperative that sample collection be performed in a cost-effective manner. In this paper we describe the results of a study in which we compared the efficiencies of different methods of sample collection in order to determine an optimal method for estimating the mean ²²⁶Ra concentration in soil. The study involved a field experiment in which extensive sampling was performed on sites known to be contaminated with uranium tailings. The experiment was designed to identify the advantages and limitations of composite sampling, the relative merits of random and uniformly spaced sample collection, the use of field gamma measurements for supplementing and reducing soil sample collection, and practical levels of accuracy and precision that can be obtained. Conclusions regarding gamma measurements are unique to ²²⁶Ra contamination. On the other hand, conclusions concerning composite sampling and random versus uniformly spaced sampling may depend primarily on the way the contamination was spread by man and hence may not be unique to ²²⁶Ra.Research sponsored by the Department of Remedial Action Projects, Office of Terminal Waste Disposal, U. S. Department of Energy under contract DE-AC05-84OR21400 with the Martin Marietta Energy Systems, Inc.ORNL—Grand Junction Office, Grand Junction, Colorado.     

多元回归-紫外分光光度法同时测定硝基苯类化合物

对多元线性回归、多元逐步回归和岭回归三种方法应用于硝基苯类五元体系进行定量分析的结果进行了比较研究,结果表明,对于所涉及的组分光谱重叠严重的病态的混合体系,多元逐步回归和岭回归间接校正都是合适的算法,总平均相对误差分别为3.84%和3.00%.     

Simultaneous determination of parathion and p-nitrophenol in vegetable tissues by derivative spectrophotometry

A first derivative spectrophotometric method has been developedfor the determination of parathion and p-nitrophenol in vegetabletissues. Ethanol was used as solvent for extracting the compoundsfrom the tissues and subsequently the samples were evaluated against a vegetable tissue blank, directly by derivative spectrophotometry. The simultaneous determination of these compounds can be carried out using the zero-crossing approach for parathion at 253.0 nm and for p-nitrophenol at 273.1 nm. In the samples each analyte was determined in the presence of one another in the ranges between 4.9 to 3883.5 g g^-1 forparathion and 4.9 to 3285.3 g g^-1 for p-nitrophenol.The detection limits (3) were found to be 1.5 and 1.4 g g^-1 for parathion and p-nitrophenol, respectively. The relative standard deviations were in all instances less than1.8%. The proposed method was applied to the determination ofthe analytes in spiked leafs of corn. The results show a goodrecovery and they are in agreement with those obtained bypolarography.     

Evaluation of the methyl ester O-methyl acetate derivative of muramic acid for the determination of peptidoglycan in environmental samples by ion-trap GC-MS-MS

Muramic acid (MA) is a unique amino sugar that is a constituent of the peptidoglycan (PG) present in prokaryotic cell walls. MA can serve as a marker for quantifying bacterial load, e.g. in indoor environments, by using gas chromatography-tandem mass spectrometry (GC-MS-MS). We demonstrated recently that the methyl ester O-methyl acetate (MMA) derivative can be used to detect MA in house dust by ion-trap GC-MS-MS. However, since the MMA derivative is not formed from free MA quantification was not optimal. Here we report 1) significant improvements in sample preparation of the MMA derivative and 2) an evaluation of the performance of derivative, using for comparison the alditol acetate derivative, the gold standard in quantitative trace analysis of MA in complex matrices. The MMA derivative was analysed using an MS instrument with internal ionization and the alditol acetate derivative was analysed using an instrument with external ionization. 13C-labelled cyanobacteria, containing MA in their PG, were used as the internal standard. A linear relationship was found between the two methods in studies on 27 parallel samples of airborne dust from school classes collected on filters. Although the analytical sensitivity of the MMA derivatives was somewhat slightly lower than of the alditol acetate derivative, this may be due to differences in yield of derivative, sample clean-up efficiency, or different performance of the GC columns or MS instruments. However preparation of the MMA derivative is quick and compatible with preparation of methyl esters of 3-hydroxy fatty acids (used as markers of Gram negative endotoxin) allowing the levels of both markers to be determined in the same dust sample. In conclusion, the MMA procedure can be used to determine MA in environmental samples with good reproducibility provided the concentration of the 13C-labelled MA internal standard in the cyanobacteria is first determined with an alternative method.     

Addressing analytical uncertainties in the determination of trichloroacetic acid in soil

Soil is an important compartment in the environmental cycling of trichloroacetic acid (TCA), but soil TCA concentration is a methodologically defined quantity; analytical methods either quantify TCA in an aqueous extract of the soil, or thermally decarboxylate TCA to chloroform in the whole soil sample. The former may underestimate the total soil TCA, whereas the latter may overestimate TCA if other soil components (e.g. humic material) liberate chloroform under the decarboxylation conditions. The aim of this work was to show that extraction and decarboxylation methods yield different TCA concentrations because the decarboxylation method can also determine "bound" TCA. Experiments with commercial humic acid solutions showed there was no additional chloroform formation under decarboxylation conditions, and that all TCA in a TCA-humic acid mixture could be quantitatively determined (108 +/- 13%). Anion exchange resin was used as a provider of solid-phase TCA binding; only 5 +/- 1% of a TCA solution mixed with the resin was present in the aqueous extract subsequently separated from the resin, yet the decarboxylation method yielded mass balance (123 +/- 22%) with TCA remaining in the resin. In aqueous extraction of a range of soil samples (with or without added TCA spike), the decarboxylation method was able to satisfactorily account for TCA in the extractant + residue post-extraction, compared with whole-soil TCA (+ spike) pre-extraction: e.g. mass balances for unspiked soil from Sikta spruce and larch forest were 99 +/- 8% and 93 +/- 6%, respectively, and for TCA-spiked forest and agricultural soils were 114 +/- 13% and 102 +/- 2%. In each case recovery of TCA in the extractant was substantially less than 100%(<20% for unspiked soils, <55% for spiked soils). Extraction efficiencies were generally lower in more organic soils. The results suggest that analytical methods which utilise aqueous extraction may underestimate whole-soil TCA concentrations. Application of both methodologies together may enhance insight into TCA behaviour in soil.     

Screening of brick-kiln area soil for determination of heavy metal Pb using LIBS

Rapid measurement of heavy metals in soil is an important factor in modeling the effect of industrial pollution on agricultural soil. Conventional methods of heavy metal analysis are relatively slow in terms of measurement/analysis time and sample preparation time with the requirement of skilled manpower. Our results highlight the quantitative analysis of toxic metal lead (Pb), for the first time, in an Indian agricultural soil, in the vicinity of brick-kiln area, Phaphamau, near Allahabad, India, by using a novel technique named as Laser-induced breakdown spectroscopy (LIBS). LIBS spectra of soil has been recorded in the wavelength range from ultraviolet (UV) to infrared region (200-1,100 nm). The suitability of Pb lines for drawing the calibration curve is checked and realized, for the first time, that 220.3 nm, which is observed in the UV region of LIBS spectra, is completely interference free and best suited for the quantification of trace amount of Pb in soil instead of any other Pb lines, because it has best linear regression coefficient and smallest standard deviation of the background signal. In the present work the detection limit for Pb in soil is found to be 45 ppm. Based on the present work the concentration of Pb in agricultural soil of brick-kiln area in Phaphamau is found to be congruent with 570 ppm, which is more than the regulatory standards imposed by US Environmental Protection Agency (400 ppm) for the presence of lead in soil, therefore, it is of great concern to us.     

A field-based spectrophotometric flow-injection system for automatic determination of chloride in soil water

The use of chloride as a tracer for soil water investigations is discussed. Limitations with laboratory based soil core and field based sampling are considered with respect to the poor suitability of the data for rigorous assessment of mechanistic models. Investigation of water movement in soil has been restricted by limitations in spatial and temporal sampling. Fine resolution sampling generates large numbers of samples which cause problems with post sampling laboratory analysis. This paper describes a field-based system for the analysis of chloride in soil water. There are three component parts to the system, (i) a custom sampling sub-system comprising of ceramic cup suction samplers and sample traps, (ii) a sample routing sub-system to channel sample to (iii) a sample analysis sub-system utilizing a flow injection method for sample analysis using a custom built photo-diode detector. The three sub-systems were controlled by a suitably equipped personal computer. A calibration procedure is described with a third order polynomial equation derived to convert millivolt response from the detector into chloride concentration. Field and laboratory data from a tracer experiment are presented and discussed, and it is concluded that the system is well suited to field-based applications. Finally it is noted that the photo-detector is suitable for colourimetric analysis of any tracer with suitable chemical determination.     

火焰原子吸收分光光度法测定总铬的研究

用火焰原子吸收分光光度法直接测定水和废水中的总铬.通过不同条件的实验,确定了最佳的分析条件;并通过标准样品和实际样品的分析,验证了方法的准确度和精密度.在大量实验基础上,建立空白实验、准确度质量控制图,以便定期对各种监测数据提供可行的质量保证措施.实验结果表明,该法快速方便,提高了分析效率,准确度高,精密度好,值得普及和推广.     

悬浮液直接进样塞曼石墨炉平台原子吸收法测定土壤中痕量铅

研究了悬浮液直接进样 ,石墨炉平台原子吸收法测定土壤中痕量铅 ,方法简便快速 ,检出限 (3σ)为 4.4× 1 0 - 1 2 g,相对标准偏差 (n=6)小于 3 .0 % ,回收率在 91 %～ 1 0 7%之间     

Field intercomparison of diffusive samplers for measuring ammonia

Agricultural production systems are recognised as a major source of atmospheric ammonia. Deposition of ammonia and ammonium may contribute to undesired changes in oligotrophic ecosystems. The continuous measurement of atmospheric ammonia requires expensive and sophisticated techniques and is performed only in a very restrict number of ambient air stations in Europe. Therefore, the application of passive samplers, which have the advantage of being easy to handle and cost-efficient, is useful. In the past the comparability of different passive samplers must be considered as rather scarce. In a joint European project under the leadership of the GSF-Forschungszentrum für Umwelt und Gesundheit, Neuherberg, in 1997 a comparison of different passive ammonia monitoring methods was carried out in a prealpine rural site near Garmisch-Partenkirchen. It was considered valuable to include not only well established systems but also methods still being developed. For the comparative test ten working groups with different methods took part. A wet annular denuder system, which has been developed by the Netherlands Energy Research Foundation for on-line measurement of atmospheric ammonia, served as reference of passive methods. The experiment, which started in June and finished in December, showed that most of the passive samplers fulfil the requirements and can be recommended for further measurements. Additional measurements of meteorological parameters were performed to check the influences of different weather conditions on passive sampling.     

石墨炉原子吸收光谱法测定土壤中的微量砷

土壤样品经ＨＮＯ３－ＨＣＩＯ４消解处理后,采用Ｎｉ作为基体改进剂,偏振塞曼效应扣去背景,实现了砷的石墨炉原子吸收法的直接测定。该方法操作简单,干扰少,灵敏度高,砷的检测下限为０．７ｎｇ／ｍｌ,样品分析回收率９４％－１０８％,相对标准偏差５．１％。     

Transient modeling of trickling filters for biological ammonia removal

A dynamic model for nitrifying trickling filters is developed, based on material balances in the biofilm and the bulk liquid. The model predicts the profile of ammonia as a function of the operating parameters (volumetric flow rate and feed ammonia concentration) and the biofilm thickness as a function of filter depth and time. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sensitive determination of cadmium using solidified floating organic drop microextraction-slotted quartz tube-flame atomic absorption spectroscopy

In this study, solidified floating organic drop microextraction (SFODME) by 1-undecanol was combined with slotted quartz tube flame atomic absorption spectrometry (SQT-FAAS) for the determination of cadmium at trace levels. Formation of a complex with 4,4′-dimethyl-2,2′-bipyridine facilitated the extraction of cadmium from aqueous solutions. Several chemical variables were optimized in order to obtain high extraction outputs. Parameters such as concentration of the ligand, pH, and amount of buffer solution were optimized to enhance the formation of cadmium complex. The SFODME method was assisted by dispersion of extractor solvent into aqueous solutions using 2-propanol. Under the optimum extraction and instrumental conditions, the limit of detection and limit of quantitation values obtained for cadmium using the combined methods (SFODME-SQT-FAAS) were found to be 0.4 and 1.3 μg L^?1, respectively. Matrix effects on the method were also examined for tap water and wastewater, and spiked recovery results were found to be very satisfactory.

Open image in new window

Graphical Abstract SFODME-SQT-FAAS system for sensitive determination of cadmium

     

On-filter determination of collected wood dust by diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS)

A new analytical technique based on DRIFTS spectroscopy has been developed for the specific and sensitive determination of size-fractionated wood dust from 37 mm glass fiber filter samples collected with the Respicon sampler. A translational diffuse reflectance apparatus was modified to accept filter samples by incorporating a special filter holder in the sample stage and a clockwork motor to drive the translational stage during infrared scanning, thus providing an average analysis across the filter face. Filter samples were pre-treated with ethyl acetate to uniformly redeposit dust onto the filter and extract potential chemical interferences. Two absorbance maxima (1251 and 1291 cm(-1)), corresponding to the cellulose content of the wood, were suitable for quantitation of wood dust. Analysis of seven species of wood at 1291 cm(-1) showed an equivalent quantitative response for all species except maple. The response at 1251 cm(-1) was more variable across species but more sensitive for the softwoods. There was a statistically significant effect of particle size on the analytical response, so that analytical standards should be matched to the samples in terms of particle size distribution. Analytical limit of detection was approximately 0.08 mg of wood dust per sample with overall precision of about 6%. Comparison of DRIFTS and gravimetric analyses of 51 pure wood dust samples ranging from about 0.2 to 2 mg yielded a slope of 1.08 and r2 equal to 0.9. Other particulate contaminants common in the industrial wood processing industry showed little or no interference with the determination of wood dust by this method.     

微波萃取-气相色谱/质谱法测定土壤中的有机氯农药

通过微波萃取提取土壤中的有机氯农药,萃取溶液经浓硫酸脱色、佛罗里硅土柱净化,最后用气相色谱/质谱法分析.以石英砂为基体进行加标回收测定,有机氯农药的回收率在75.5%～103%之间,检出限为0.01μg/kg.