High-throughput characterization of sediment organic matter by pyrolysis–gas chromatography/mass spectrometry and multivariate curve resolution: A promising analytical tool in (paleo)limnology

Molecular-level chemical information about organic matter (OM) in sediments helps to establish the sources of OM and the prevalent degradation/diagenetic processes, both essential for understanding the cycling of carbon (C) and of the elements associated with OM (toxic trace metals and nutrients) in lake ecosystems. Ideally, analytical methods for characterizing OM should allow high sample throughput, consume small amounts of sample and yield relevant chemical information, which are essential for multidisciplinary, high-temporal resolution and/or large spatial scale investigations. We have developed a high-throughput analytical method based on pyrolysis–gas chromatography/mass spectrometry and automated data processing to characterize sedimentary OM in sediments. Our method consumes 200 μg of freeze-dried and ground sediment sample. Pyrolysis was performed at 450 °C, which was found to avoid degradation of specific biomarkers (e.g., lignin compounds, fresh carbohydrates/cellulose) compared to 650 °C, which is in the range of temperatures commonly applied for environmental samples. The optimization was conducted using the top ten sediment samples of an annually resolved sediment record (containing 16–18% and 1.3–1.9% of total carbon and nitrogen, respectively). Several hundred pyrolytic compound peaks were detected of which over 200 were identified, which represent different classes of organic compounds (i.e., n-alkanes, n-alkenes, 2-ketones, carboxylic acids, carbohydrates, proteins, other N compounds, (methoxy)phenols, (poly)aromatics, chlorophyll and steroids/hopanoids). Technical reproducibility measured as relative standard deviation of the identified peaks in triplicate analyses was 5.5 ± 4.3%, with 90% of the RSD values within 10% and 98% within 15%. Finally, a multivariate calibration model was calculated between the pyrolytic degradation compounds and the sediment depth (i.e., sediment age), which is a function of degradation processes and changes in OM source type. This allowed validation of the Py–GC/MS dataset against fundamental processes involved in OM cycling in aquatic ecosystems.     

On the separation of a suspension in a tube centrifuge: critical comments on theoretical models and experimental verifications

Summary We consider the batch centrifugal separation of a suspension of heavy particles in a cylindrical tube which rotates about an axis perpendicular to the axis of the tube. The theoretical analysis by means of a kinematic approximation covers two models: (1) the one-dimensional, which assumes that the particles settle along lines parallel to the sidewalls of the tube and sediment on the outer wall, and (2) the two-dimensional, which assumes that the particles settle along the centrifugal-field lines and sediment on both sidewalls and outer wall. A comparison shows that both models produce similarly simple formulas for the motion of the interface and the volume fraction as functions of time. However, the two-dimensional model is recommended for use because its results and insights are more reliable from both mathematical and physical considerations, and provide a more acceptable interpretation to recent experimental data, [5]. The author wishes to thank Prof. W. Schneider for stimulating discussions on the subject. The research was partially supported by the the Technion Fund V.P.R Fund – New York Metropolitan Research Fund.     

Sediment records of Sb and Pb stable isotopic ratios in Lake Qinghai

A sediment core in Lake Qinghai in northwest China was collected in 2006. ¹³⁷Cs and ²¹⁰Pb activities were analyzed to investigate the chronology of the sediment core. Sb and Pb concentrations, and Pb stable isotopic ratios were analyzed to study the historical atmospheric deposition records and sources of Sb over the past 15 centuries. The Sb concentration was 4.21 ± 1.52 μg/g in the sediments, its vertical distribution of Sb shows three large peaks in the recent two centuries, 1799, 1896 and 1944, coincided with Sb contamination from large wars, respectively. The peak in 1920 responded the large earthquake that happened in northern China, which was not far away from Lake Qinghai. The Sb/Pb ratio, ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb results suggest that Sb and Pb were probably from the ores in South China and coals in North China before 1965, but obviously from uses of leaded gasoline after 1965.     

Determination of fungicides in sediments using a dispersive liquid–liquid microextraction procedure based on solidification of floating organic drop

A dispersive liquid–liquid microextraction procedure based on solidification of floating organic droplet has been investigated for the determination of fungicides (cyprodinil, difenoconazole, myclobutanil, and spiroxamine) in sediments by HPLC with diode array detection. In the overall extraction process, the extraction solvents can be separated easily from the sample solution, and the experiment time was shortened. Moreover, several parameters such as the type and volume of the extraction solvent and dispersive solvent, centrifugal speed, extraction time, and salt effect that affect the extraction efficiencies of the target fungicides were studied and optimized. Under the optimized conditions, the LOD for the target analytes were in the range of 0.1–0.5 μg/g. Satisfactory recoveries of the target analytes in the sediment samples were 81.00–99.00%, with RSDs (n = 5) that ranged from 1.8 to 6.5%. Finally, the simple, sensitive, and environmentally friendly method was successfully applied to determine the target fungicides in actual sediment samples.     

Synthesis, characterization and comparison of sediment electro-codeposited nickel-micro and nano SiC composites

Nickel-silicon carbide composites were produced using 1 μm and 50 nm size powders from a conventional Watt's bath using tetra methyl ammonium hydroxide as the surfactant. Sediment codeposition technique with horizontal electrodes was used. The effect of silicon carbide concentration and bath operating parameters on the volume percents and deposition rates of coatings obtained with the two different particles was studied. Substantial improvements in mechanical properties such as hardness, wear resistance, scratch resistance and roughness were obtained with the nanocomposite material, as compared with composites containing microsized particles.     

A simplified version of the total kjeldahl nitrogen method using an ammonia extraction ultrasound-assisted purge-and-trap system and ion chromatography for analyses of geological samples

The total Kjeldahl nitrogen (TKN) method was simplified by using a manifold connected to a purge-and-trap system immersed into an ultrasonic (US) bath for simultaneous ammonia (NH₃) extraction from many previously digested samples. Then, ammonia was collected in an acidic solution, converted to ammonium (NH₄⁺), and finally determined by ion chromatography method. Some variables were optimized, such as ultrasonic irradiation power and frequency, ultrasound-assisted NH₃ extraction time, NH₄⁺ mass and sulfuric acid concentration added to the NH₃ collector flask. Recovery tests revealed no changes in the pH values and no conversion of NH₄⁺ into other nitrogen species during the irradiation of NH₄Cl solutions with 25 or 40 kHz ultrasonic waves for up to 20 min. Sediment and oil free sandstone samples and soil certified reference materials (NCS DC 73319, NCS DC 73321 and NCS DC 73326) with different total nitrogen concentrations were analysed. The proposed method is faster, simpler and more sensitive than the classical Kjeldahl steam distillation method. The time for NH₃ extraction by the US-assisted purge-and-trap system (20 min) was half of that by the Kjeldahl steam distillation (40 min) for 10 previously digested samples. The detection limit was 9 μg g⁻¹ N, while for the Kjeldahl classical/indophenol method was 58 μg g⁻¹ N. Precision was always better than 13%. In the proposed method, carcinogenic reagents are not used, contrarily to the indophenol method. Furthermore, the proposed method can be adapted for fixed-NH₄⁺ determination.     

Antimony distribution and mobility in rivers around the world's largest antimony mine of Xikuangshan, Hunan Province, China

Mining and smelting activities of the world largest Antimony (Sb) mine which is located at Xikuangshan area of Hunan Province, China, constitute important sources of Sb pollution throughout the rivers in or around the mine. Water samples show high levels of Sb (2-6384 µg/l) relative to the average concentration of the world rivers (1 µg/l) and it occurs mainly in oxidized form. Sb has a higher affinity for the particulate phase than for the aqueous phase. Its contents in sediments decreased along with the distance from the mine (from 7316 to 57 mg/kg) and had good correlation relationships (p < 0.001) with porewaters. In addition to the major pools in the Fe-Mn oxide (22.2-66.4%) and residual fractions (5.66-53.5%), Sb was relatively abundant in strongly adsorbed fraction. Laboratory experiments of the contaminated sediments show that with increasing amounts of Sb in the sediment, an increasing amount of Sb was leached and went into solution. Although Sb(V) was the predominant form, the release of Sb(III) in oxic conditions was also observed during laboratory experiments. And the amount of Sb released into solution was higher in anaerobic conditions than in oxygenated water.     

Utilization of W/Mg(NO3)2 modifiers for the direct determination of As and Sb in soils,sewage sludge and sediments by solid sampling electrothermal atomic absorption spectrometry

A simple method has been developed for the determination of arsenic and antimony in environmental samples by solid sampling electrothermal atomic absorption spectrometry, which was validated using certified reference materials of soils (S-VM — Soil Eutric Cambisol; S-MS — Soil Orthic Luvisols; S-SP — Soil Rendzina), sewage sludge (WT-L; WT-M) and sediments (NIES2; GBW07906). The analytical procedure combines solid sampling with utilization of a matrix modifier admixture containing 5 µg of W and 5 µg of Mg. The tungsten in the admixture serves to stabilize the solid matrix during atomisation, which results in dramatically reduced non-specific absorption compared with the conventional palladium modifier. Magnesium was efficient in reducing the accumulation of the matrix residue on the platform. An alternative resonance line of 197.2 nm for arsenic and 206.8 nm for Sb was used in order to eliminate the spectral interferences caused by aluminum compounds, and silicon and iron compounds, respectively. Under optimized experimental conditions, the effective in situ analyte/matrix separation was achieved so that the use of aqueous standards for calibration became possible. With the modifier, a 3 SD detection limit of 0.5 µg g⁻¹ As and 0.1 µg g⁻¹ Sb and 10 SD quantification limit of 1.7 µg g⁻¹As and 0.3 µg g⁻¹ Sb and a characteristic mass of 65 pg As and 53 pg Sb were obtained. For all the matrices under scrutiny, a good agreement with certified values was achieved with RSD values less than 10%.     

The use of molecularly imprinted polymers for the multicomponent determination of endocrine‐disrupting compounds in water and sediment

The method employing molecularly imprinted polymers for the extraction and clean up of endocrine‐disrupting compounds (estrogens, bisphenol A, and alkylphenols) from water and sediment is described. The identical extraction/clean‐up and LC‐MS/MS condition were used for the analysis of both types of samples. The method showed high recoveries ranging from 90 to 99% with excellent precision (intrabatch: 3.6–9.3%; interbatch: 5.6–11.4% for water; intrabatch: 4.3–8.5%; interbatch: 6.1–9.6% for sediment). The LOD was in the range of 0.7–1.9 ng/L and 0.3–0.6 ng/g for water and sediment, respectively. Overall extraction on molecularly imprinted polymers substantially enhanced sample clean‐up. The difference in efficiency of clean‐up was particularly pronounced when a large sample volume/weight was extracted and analyzed. Finally, the method was successfully applied for the analysis of 20 water and sediment samples.     

Behaviour of polycyclic aromatic hydrocarbons in dissolved,colloidal, and particulate phases in sedimentary cores

Solid-phase microextraction (SPME) has been successfully used for extracting polycyclic aromatic hydrocarbons (PAHs) from porewater samples from the Mersey Estuary, UK. The majority of the PAHs in porewater samples are associated with colloids due to the high DOC concentrations. The truly dissolved PAH concentrations varied from 66 to 1050?ng?L^?1 in core 2 and from 95 to 740?ng?L^?1 in core 3, and were dominated by naphthalene, fluoranthene, and pyrene. Although absent in the dissolved phase, the high-molecular-mass compounds were found in the colloid-associated fraction of porewater. PAHs in sediments arose from a range of compounds with 4- and 5-ring PAHs dominating. The partitioning of PAHs between sediment and porewater shows that PAHs are enriched in the sediment phase. When the soot carbon content was considered, predictions of the partition behaviour were found to agree more closely with the observed distribution. The results reiterate the importance of evaluating the speciation of organic pollutants in both porewater and sediments in order to accurately predict their environmental fate and potential toxicity.