Optical molecular fluorescence determination of ultra-trace beryllium in occupational and environmental samples using highly alkaline conditions

Exposures to beryllium (Be), even at extremely low levels, can cause severe health effects in a percentage of those exposed; consequently, occupational exposure limits (OELs) promulgated for this element are the lowest established for any element. This work describes the advantages of using highly alkaline dye solutions for determination of Be in occupational hygiene and environmental samples by means of an optical molecular fluorescence technique after sample extraction in 1–3% (w?w^?1) aqueous ammonium bifluoride (NH₄HF₂). Improved attributes include the ability to further enhance the detection limits of Be in extraction solutions of high acidity with minimal dilution, which is particularly beneficial when NH₄HF₂ solutions of higher concentration are used for extraction of Be from soil samples. Significant improvements in Be method detection limits (MDLs) are obtained at levels manyfold below those reported previously for this methodology. Notably, MDLs for Be of <0.01 ng L^?1 /0.1 ng per sample have been attained, which are superior to MDLs routinely reported for this element by means of the most widely used ultra-trace elemental measurement technique, inductively coupled plasma mass spectrometry (ICP-MS). Very low MDLs for Be are essential in consideration of reductions in OELs for this element in workplace air by health organisations and regulatory agencies in the USA and internationally. Applications of enhanced Be measurements to air filter samples, surface wipe samples, soils and newly designed occupational air sampler inserts are illustrated.     

A thermo extraction–UV/Vis spectrophotometric method for total iodine quantification in soils and sediments

Iodine in soils and sediments is a difficult element to analyze due to its volatility in acidic conditions. Traditionally it has been quantified using neutron activation analysis techniques, which, unfortunately, requires access to a nuclear reactor. We present here a simple method for solid-phase iodine analysis by thermo extraction at 1000°C and quantification by UV/Vis photometry. Samples are combusted in an oxygen stream and trapped in Milli-Q water. The extracts are then quantified by an As³⁺–Ce⁴⁺ spectrometric method whereby iodide catalyzes the oxidation of As³⁺ to As⁵⁺ and reduction of Ce⁴⁺ to Ce³⁺. Three standard reference materials were analyzed with excellent recoveries (97–113%) and RSDs (<5%). Moreover, the detection limit was less than 50 ng absolute iodine with a confidence limit of 95%. When applied to carbonate-rich samples from sediment traps deployed in Lake Constance we found very low iodine levels (0.8–2 mg kg⁻¹). Despite the low concentrations, the precision of the method was consistently better than 5% RSD. However, the method needed to be slightly modified for organic and iodine-rich sediments (20–30% organic carbon) from a lake in the Black Forest by increasing the oxygen flow rate and decreasing the combustion time. Using the modified method we were able to achieve RSDs lower than 5%.     

Development and implementation of the CCME Reference Method for the Canada-Wide Standard for Petroleum Hydrocarbons (PHC) in soil: a case study

Petroleum hydrocarbons have historically been analyzed by a wide variety of test methods. Interlaboratory studies have shown that standardization of both extraction and gas chromatographic analysis improved interlaboratory variability in hydrocarbon analysis. The Canadian Council of Ministers of the Environment has required a reference method for use with the Canada-wide standard for petroleum hydrocarbons. The process for developing and validating this method is described. This method requires the determination of 4 hydrocarbon fractions, namely, F1 (nC6 to nC10), F2 (>nC10 to nC16), F3 (>nC16 to nC34) and, F4 (nC35+), using GC-FID or gravimetry. The Tier 1 method was validated in a single laboratory study. This validated method was subjected to interlaboratory studies to determine its applicability and precision.     

Cooling/heating-assisted headspace solid-phase microextraction of polycyclic aromatic hydrocarbons from contaminated soils

A simple, low-cost, and effective cooling/heating-assisted headspace solid-phase microextraction (CHA–HS–SPME) device, capable of direct cooling the fiber to low temperatures and simultaneous heating the sample matrix to high temperatures, was fabricated and evaluated. It was able to cool down the commercial and handmade fibers for the effective tapping of volatile and semi-volatile species in the headspace of complex solid matrices, with minimal manipulation compared with conventional SPME. The CHA–HS–SPME system can create large temperature gaps (up to 200 °C) between the fiber and the sample matrix, because the cooling process is directly applied onto the fiber.     

Superposition principle for short-term solutions of Richards' equation: Application to the interaction of wetting fronts with an impervious surface

The interaction of a wetting front with an impervious layer is described by adding a reflected solution to the incoming solution for a semi-infinite medium. It is shown and checked by comparison with a numerical solution that the result is accurate during the early times of the interaction between the front and the impervious surface. This superposition principle is quite general and should prove especially useful to initiate numerical schemes by this analytical approximation as in the early times singularities are difficult to describe numerically.     

ADVANCES IN TRUE TRIAXIAL TEST OF UNSATURATED SOILS

研究非饱和土的强度是非饱和土理论及其工程应用的首要问题,但因复杂应力状态下基质吸力的控制技术、量测技术和吸力平衡时间等原因,非饱和土真三轴试验研究的进展迟缓. 在介绍非饱和土刚性真三轴仪、柔性真三轴仪和刚柔复合型真三轴仪的基础上,重点分析已有非饱和土刚性和柔性真三轴试验结果,总结现有非饱和土真三轴仪及其试验研究的不足,同时指出Mohr-Coulomb 强度准则和外接圆Drucker-Prager准则对非饱和土真三轴试验结果的不适用性. 应开展更多不同种类非饱和土的完整真三轴试验研究,特别是非饱和黏性土;应结合非饱和土的应力状态变量和强度特性,建立符合工程实际受力状况的非饱和土真三轴强度准则,完善非饱和土的理论基础.     

Buchbesprechungen

Es wird eine radiometrische Förderbandwaage nach dem Prinzip der Gammastrahlungsschwächung beschrieben. Sie arbeitet netzunabhängig und ist für den nichtstationären Einsatz geeignet. Als Strahlungsquelle wird Cäsium-137 eingesetzt, der Strahlungsnachweis erfolgt mit einer speziellen Anordnung von Halogenzählröhren und einfachen Zāhlgeräten.

Erste Erprobungen unter Feldbedingungen erfolgten zum Zwecke der Bestimmung der Überlaufmasse (Kartoffeln und Erdreich) zur Feststellung der Absiebleistung bei Forschungsvarianten an Kartoffelkombines. Der maximal mögliche Durchsatz liegt bei 180th^?1. Kartoffeln und Erdreich in der Gröβenordnung von 2 t sind mit dieser Wägeeinrichtung mit einem relativen Fehler von ±3,5% bestimmbar.     

Field Measurements of Radon Exhalation and Ra-226 Content in Soil using the Can-Technique

CR-39 and LR-115 plastic nuclear track detectors in the can-technique have been employed in the field measurements of radon exhalation, Ra-226 and U-238 content in dry-soil air at numerous regions in Sudan (the Blue and White Nile and Mogran regions). Measurements gave an average radon exhalation from the soil to the atmosphere and Ra-226 content of (23.4 ± 2.60) kBq · m^?2 and (123 ± 13.65) Bq · kg^?1 respectively. A polyethylene permeable membrane cover was used to eliminate the contribution of thoron activity inside the can. Assuming a radioactive equilibrium between the U-series, the average U-238 content in the soil was found to be (9.92 ± 1.01) ppm. This survey may be used for uranium prospection in soil.     

Investigation of distribution of soil antimony using sequential extraction and antimony complexed to soil-derived humic acids molar mass fractions extracted from various depths in a shooting range soil

Trace metal contamination from bullet fragments in shooting ranges is a major environmental concern. In particular, trace metals such as lead, antimony, and copper are toxic and have the potential to enter groundwater supplies and to be absorbed by plants. Soil humic acids can play a critical role in mobilizing some of these released metals through complexation. The purpose of this study is to investigate the antimony complexed to soil-derived humic molar mass fractions extracted from various depths in a shooting range soil and to examine the distribution of antimony in various fractions of shooting range soils using sequential chemical extraction approach. The surface soil and soil core samples from a local shooting range were collected. Soil-derived humic acids were extracted from different depths of the top soil layer and characterized by various spectroscopic methods. Results of sequential chemical extraction demonstrated that Sb was found in shooting range in the upper 30 cm depth of the soil core. Highly elevated Sb is present in the exchangeable and ammonium acetate extracted fractions. Antimony is also present in the residual fraction in both surface and core soil samples, but is most likely present in a lithic phase which may not be readily bio-available. Leached antimony complexed to soil humic acid molar mass fractions was determined by size exclusion chromatography coupled to inductively coupled plasma-mass spectrometry (SEC-ICP-MS). The results demonstrate that Sb is ‘tightly’ bound to humic acid mass molar mass fractions and confined in the top 10 cm of soil-derived humic acids.     

An Improved Method for the Determination of Molybdenum in Plants,Soils, and Rocks

Abstract

Improvements to the thiocyanate colorimetric procedure for analysis of ppm levels of molybdenum have been made. The complete procedure was studied and revisions made to the solvent extraction system to increase sensitivity. The solvent itself was stabilized by elution through an adsorption column. Revisions to the fusion procedure were made to eliminate hand fusion of samples. The use of desiceants for solvent drying was replaced by filtration before absorbance readings to eliminate turbidity. Total solution of rock samples requires a special digestion procedure with atomic absorption finish.