Determination of mercury in soils and sediments by graphite furnace atomic absorption spectrometry with slurry sampling

A graphite furnace atomic absorption spectrometric procedure for the determination of mercury is presented, in which the samples are suspended in a solution containing hydrofluoric and nitric acids. Silver nitrate (4% m/v) and potassium permanganate (3%) are incorporated, in the order specified, and aliquots are directly introduced into the graphite furnace. A fast heating programme with no conventional pyrolysis step is used. The detection limit for mercury in a 125 mg ml⁻¹ suspension is 0.1 μg g⁻¹. Calibration is performed by using aqueous standards. The reliability of the procedure is proved by analysing certified reference materials.     

Semi-micro solvent extraction as a rapid and efficient preconcentration technique for the determination of n-alkanes in oil-contaiminated water and soil samples by capillary gas chromatography

Summary In this study, a rapid and efficient semi-micro extraction procedure is presented for the extraction of some higher n-alkanes from water and soil samples. In the case of water samples n-hexane was used as the organic phase in a phase volume ratio (volume of aqueous phase/volume of organic phase) higher than 285, while in the case of soil samples, extraction with n-hexane was carried out in the presence of an excess of 2 M NaCl solution. The extraction rate from soil samples is very high and is better than Soxhlet extraction, comparable with supercritical fluid extraction. High preconcentration factor in water samples allows the limits of detection to be in the ng.mL⁻¹ level with the use of gas chromatographic analysis. Flame ionization detector was used for monitoring the analytes. The obtained recoveries of all studied compounds from both water and soil samples are higher than 90%. This method was successfully used to determine some n-alkanes in municipal wastewater and contaminated soil.     

Composition and in vitro Antifungal Activity of Essential Oils of Erigeron canadensis and Myrtus communis from France

Essential oils of Erigeron canadensis L. and Myrtus communis L. were tested in vitro as growth inhibitors against phytopathogenic fungi Rhizoctonia solani Kuhn, Fusarium solani (Mart.) Sacc. and Colletotrichum lindemuthianum (Sacc. & Magn.) Briosi & Cav. Both showed weak fungicidal acitivity, except the essential oil of M. communis that exerted a 60% growth inhibition against R. Solani at a dose of 1600 ppm. Microscopic observation revealed that the essential oil of M. Communis caused morphological alterations of hyphae of all fungi at 1600 ppm, while, at the same dose, only the hyphal morphology of C. Lindemuthianum was affected by the essential oil of Er. Canadensis.     

Correlation Analysis of the Runoff of the Rivers and the Seisms in China

In recent hundred years the annual discharge variations of the Changjiang River (represented by the Yichang station) and the Huanghe River (represented by Shanxian and Tangnaihe, respectively) have closely related to the geographical distribution of the earthquakes coming about in China in the same year, Both the occurrence of the destructive seism or seismic swarm in the river basins and the disappearance of the shocks in the east and south of the basins are the conditions that the Changjiang and Huanghe Rivers are the high flow while that the strong earthquake of magnitude 7 or more occurred in North China is the condition for the Changjiang low flow year and that of 6 or more in the Qilian Mountains area is for the Huanghe River. In the latter part of this paper, a 2-year sample is given to explain that the conditions of the 2 rivers being high flow years are that the north-south seismic belt is active and in the meanwhile no seism occurred in South China, and those of the low flow year are that the     

Removal of humic matter interference in the determination of Cr(VI) in soil extracts by the diphenylcarbazide method

Alkaline digestion of soil samples, which is recommended for minimizing Cr(III)–Cr(VI) interconversions during the extraction of Cr(VI), may also solubilize humic matter (HM). The latter is responsible for both positive and negative interference in the analysis of Cr(VI) in the extract by the diphenylcarbazide (DPC) method. Humic compounds indeed absorb light at 540 nm as the Cr-DPC product and are also able to rapidly reduce Cr(VI) under the pH conditions of the standard DPC method. To prevent any risk of interference and make the DPC method applicable to soil extracts, a new protocol is proposed. This consists of three successive steps: (1) extraction of Cr(VI) by the U.S.EPA method 3060A in the presence of Mg²⁺; (2) batch removal of solubilised HM by the XAD-7 sorbent at pH 3.0 ± 0.1 with 3–5 min contact time; (3) analysis of Cr(VI) with the DPC method at pH 3.0 ± 0.1. The application of this new protocol to the soil product SQC-012 Lot 4 certified by R.T. Corporation (RTC, USA) gave significantly lower Cr(VI) concentrations and smaller variability compared to certified values (46.5 ± 2.3 instead of 153 ± 32.6 mg/kg). The new protocol was validated by Cr(VI) and Cr(III) spikes either to the soil/extractant suspension or to the exctract. Cr(VI) results in the wide range of acceptance limits (104–202 mg/kg) reported by RTC were only obtained when the U.S.EPA method 3060A without the addition of Mg²⁺ and DPC analysis at pH 1.0 were applied. The latter procedure appears questionable since it leads to largely variable results which reflect the complex role played by humic matter in the determination of Cr(VI) and the instability of Cr(III) during the extraction.     

Simultaneous extraction of organotin, organolead and organomercury species from soils and litter

Extracting organotin compounds (OTC) from soils is difficult due to the high cation exchange and complexation capacity of soils, and little information about OTC in soils is available. In this study, a new extraction method, combining 1 M CaCl₂, 0.1% tropolone, and glacial acetic acid was developed. Recoveries of mono-substituted OTC from spiked plant litter, and soil samples were improved substantially to 40% compared to classical glacial acetic acid extraction commonly used in sedimentology, yielding <10% recovery in C-rich soil samples. Simultaneously, the recovery of other OTC, trimethyllead and monomethylmercury was satisfactory. The recoveries of most species from the spiked litter, upland and wetland soils exceeded 70%. The new method extracted much more organometallics from unspiked organic soils and litter than microwave- and ultrasound-assisted extraction and accelerated solvent extraction, most likely due to exchange of organometallics from the solid phase by Ca²⁺. The method is simple, highly efficient and with low contamination. Together with GC-ICP-mass spectrometry, the method allows the detection of these organometallics in the pg g⁻¹ range and it is particularly suitable for soil and plant materials with low organometallics contents.     

Catalytic Kinetic Spectrophotometric Method for Determination of Phosphate Ion

The kinetic method for the determination of phosphate microamounts was described. The developed method is based on catalytic effect of phosphate on sodium pyrogallol-5-sulphonate （PS） by dissolved oxygen. The reaction was followed spectrophotometrically by measuring the rate of change in the values of the absorbance of the oxidation product at 437 nm. The optimum reaction conditions are PS （0.44×10^-3 mol·L^-1） and HClO4 （3.6×10^-6 mol·L^-1） at 25 ℃. Following this procedure, phosphate can be determined with a linear calibration graph up to 0.23 μg·mL^-1. The interference effect of several species was also investigated and it was found that the most common cations and anions did not interfere with the determination. The developed procedure was successfully applied to the determination of phosphate in natural waters and soil.     

Development of a systems analysis approach for resolving the structure of biodegrading soil systems

An experimental and mathematical method is developed for the microbial systems analysis of polyaromatic hydrocarbon (PAH)-degrading mixed cultures in PAH-contaminated “town gas” soil systems. Frequency response is the primary experimental and data analysis tool used to probe the structure of these complicated systems. The objective is to provide a fundamental protocol for evaluating the performance of specific mixed microbial cultures on specific soil systems by elucidating the salient system variables and their interactions. Two well-described reactor systems, a constant volume stirred tank reactor (CSTR) and a plug flow differential volume reactor, are used in order to remove performance effects that are related to reactor type as opposed to system structure. These two reactor systems are well-defined systems that can be described mathematically and represent the two extremes of one potentially important system variable, macroscopic mass transfer. The experimental and mathematical structure of the protocol is described, experimental data is presented, and data analysis is demonstrated for the stripping, sorption, and biodegradation of napththalene.     

Mechanism and potential applications of bio-ligninolytic systems in a CELSS

A large amount of inedible plant material, generated as a result of plant growth in a Controlled Ecological Life Support System (CELSS), should be pretreated and converted into forms that can be recycled on earth as well as in space. The main portion of the inedible biomass is lignocellulosic material. Enzymatic hydrolysis of this cellulose would provide sugars for many other uses by recycling carbon, hydrogen, oxygen, and nitrogen through formation of carbon dioxide, heat, and sugars, which are potential foodstuffs. To obtain monosaccharides from cellulose, the protective effect of lignin should be removed. White-rot fungi degrade lignin more extensively and rapidly than other microorganisms.Pleurotus ostreatus degrades lignin effectively, and produces edible and flavorful mushrooms that increase the quality and nutritional value of the diet. This mushroom is also capable of metabolizing hemicellulose, thereby providing a food use of this pentose containing polysaccharide. This study presents the current knowledge of physiology and biochemistry of primary and secondary metabolisms of basidiomycetes, and degradation mechanism of lignin. A better understanding of the ligninolytic activity of white-rot fungi will impact the CELSS Program by providing insights on how edible fungi might be used to recycle the inedible portions of the crops.     

A comparative study of solvent extraction of total petroleum hydrocarbons in soil

Three non-specific methods for the extraction of total petroleum hydrocarbons (TPH) from soil into organic solvent were compared. The techniques used for sample preparation were Soxhlet extraction, closed-vessel microwave-assisted extraction, and CEN shake extraction. The total concentrations of extracted compounds in the boiling point range of C10–C40 were determined by gas chromatography with flame ionization detection. The best recovery (99%) and repeatability (±3%) from standard oil mixtures were obtained with microwave-assisted extraction. However, the different extraction methods exhibited different behaviour when spiked soil samples were extracted. The best repeatability was obtained with CEN shake extraction (±6%) but the repeatability values for Soxhlet and microwave-assisted methods were quite high (>20%). However, the larger uncertainties of the latter extraction methods does not necessarily limit the applicability of these methods to the determination of petroleum hydrocarbons in soil, as in the assessment of soil contamination the expanded uncertainty of the result is usually not limited by analytical uncertainty, but rather by the uncertainty of the primary sampling stage. However, distinctive variation found in the chromatographic profiles illustrates that discretion should be obeyed when chromatograms obtained after application of different extraction methods on petroleum contaminated samples are to be used in the fingerprinting or age dating studies. Otherwise, misleading conclusions concerning the age of spillage could be drawn.