Ari Väisänen

Ultrasound-assisted sequential extraction method for the evaluation of mobility of toxic elements in contaminated soils

A method for the fast sequential extraction of toxic elements in contaminated soil samples using an ultrasonic water bath, followed by determination with inductively coupled plasma optical emission spectrometry (ICP-OES), was developed and compared with other methods introduced in the literature. The five-step sequential extraction (Tessier scheme) was shortened using ultrasound-assisted sequential extraction (UASE). The optimization of the five-step sequential extraction was based on the analysis of SRM 2710 using Tessiers’s method as a reference. Several extracting solutions with different sonication times and temperatures were tested in the optimization procedure. Concentrations of arsenic, cadmium, copper, lead, and zinc were determined in SRM 2710, SRM 2711, and contaminated soil samples with high accuracy and precision. The certified acid-leachable concentrations of the SRM 2710 were obtained for all elements investigated by using an optimized UASE method. Tessiers’s method yielded total element concentrations that were too high. The determination of zinc in SRM 2711 yielded concentrations that were too low, whereas arsenic determination yielded concentrations that were too high by the UASE method and analysis by ICP-OES. The analysis of the SRMs showed that the UASE method is highly comparable with the other methods used for such purposes. The major advantages of the UASE method are the high treatment rate (40 samples simultaneously with a sonication time of 54 min) and a low sample and reagent usage.

Comparison of ultrasound-assisted extraction, microwave-assisted acid leaching and reflux for the determination of arsenic, cadmium and copper in contaminated soil samples by electrothermal atomic absorption spectrometry

Extraction methods for the determination of arsenic, cadmium, and copper in contaminated soil samples by Zeeman effect electrothermal atomic absorption spectrometry have been compared. The determination of cadmium and copper in ultrasound-assisted aqua regia extracts of contaminated soil SRMs by ETAAS, using a mixture of NH4H2PO4 and Mg(NO3)2, for cadmium, and a mixture of Pd and Mg(NO3)2, for copper, as a matrix modifier, was carried out with high accuracy and precision (RSD < 5.1%). The analysis of SRM 2711 failed to obtain the certified concentrations of Cd and Cu by microwave and reflux methods, respectively. The determination of arsenic was performed successfully in low chloride concentrations by using a solution of 0.2% m/v NaNO3 as a matrix modifier. With chloride concentrations higher than 0.07 M the integrated absorbance signals of arsenic decreased significantly and the repeatability observed was as low as 15% for three replicate measurements. The chloride interferences on the determination of cadmium and copper were also tested with the addition of hydrochloric acid concentrations of up to 0.5 M without registering a significant decrease in the absorbance signals of the elements. The detection limits reached by the ultrasound-assisted extraction method were as low as 5, 0.04, and 0.26 mg kg−1 for arsenic, cadmium, and copper, respectively.

The determination of trace element concentrations in fly ash samples using ultrasound-assisted digestion followed with inductively coupled plasma optical emission spectrometry

A method of ultrasound-assisted digestion followed by inductively coupled plasma optical emission spectrometry (ICP-OES) used for the determination of trace element (chromium, copper, lead, nickel, vanadium and zinc) concentrations in fly ash samples was developed. All the measurements were performed in robust plasma conditions. Ultrasound-assisted digestion procedures using digestion solutions of aqua regia and hydrofluoric acid (HF) resulted in recovery rates of over 80% for all the analyte elements. Ultrasound-assisted two-step digestion with digestion solutions of 6mL of HNO(3) (Step 1) and 3mL of HNO(3)+3mL of HF (Step 2) resulted in recovery rates of over 92% for all the analyte elements with one exception, chromium, which had a recovery of about 85%. The analysis of SRM 1633b showed that the two-step ultrasound-assisted digestion method developed resulted in chromium, copper, nickel and zinc concentrations higher than the microwave digestion method standardized by the United States Environmental Protection Agency (USEPA method 3052). This is the very first time when a digestion method using ultrasound resulted in higher efficiency than microwave (USEPA method 3052) for chromium and nickel in very hard to dissolve samples. The major advantages of the ultrasound-assisted digestion over microwave digestion is the high treatment rate (about 30 samples simultaneously with a sonication time of 18min) and the possibility to use new sample vessels without a significant increase in costs.

The determination of antimony and arsenic concentrations in fly ash by hydride generation inductively coupled plasma optical emission spectrometry

Hydride generation inductively coupled plasma optical emission spectrometry (HG-ICP-OES) was used in the determination of As and Sb concentrations in fly ash samples. The effect of sample pre-treatment reagents and measurement parameters used for hydride generation was evaluated. Due to memory effects observed, the appropriate read delay time was adjusted to 60s resulting in RSDs 0.6% and 2.3% for As and Sb, respectively. The most suitable volumes of pre-reduction reagents for 10 mL of sample were 4 mL of KI/ascorbic acid (5%) and 6 mL of HCl (conc.). The determination of Sb was significantly interfered by HF, but the interference could be eliminated by adding 2 mL of saturated boric acid and heating the samples to 60°C at least 45 min. The accuracy of the method was studied by analyses of SRM 1633b and two fly ash samples with the recovery test of added As and Sb. As high a recovery as 96% for SRM 1633b was reached for As using 193.696 nm with two-step ultrasound-assisted digestion. A recovery rate of 103% was obtained for Sb using 217.582 nm and the pre-reduction method with the addition of 2 mL of saturated boric acid and heating. The quantification limits for the determination of As and Sb in the fly ash samples using two-step ultrasound-assisted digestion followed with HG-ICP-OES were 0.89 and 1.37 mg kg(-1), respectively.

Determination of mineral and trace element concentrations in pine needles by ICP-OES: evaluation of different sample pre-treatment methods

In the present study, the determination of mineral and trace elements (Al, B, Ca, Cu, Fe, K, Mg, Mn, Na, P and Zn) from pine needles using three sample pre-treatment methods followed by inductively coupled plasma optical emission spectrometry, was examined. Sample pre-treatment methods tested were microwave digestion, ultrasound-assisted digestion and dry ashing. The new ultrasound-assisted digestion method was optimised by the analysis of the standard reference material (SRM) 1575a (pine needles) sample. The speed of dry ashing method was significantly increased by ultrasound dissolution after ashing. All the ICP-OES measurements were performed in robust plasma conditions which were tested by measuring the Mg II 280.270 nm/Mg I 285.213 nm line intensity ratios. The microwave digestion resulted generally in slightly higher element concentrations than ultrasound-assisted digestion. B, Cu and Na resulted in such low concentrations that they could not be accurately determined by using the microwave digestion method. The t-tests found no significant differences between the certified and the determined element concentrations of the SRM 1575a using the dry ashing method followed with ultrasound dissolution.

Weathering of gasification and grate bottom ash in anaerobic conditions.

The effect of anaerobic conditions on weathering of gasification and grate bottom ash were studied in laboratory lysimeters. The two parallel lysimeters containing the same ash were run in anaerobic conditions for 322 days, after which one was aerated for 132 days. The lysimeters were watered throughout the study and the quality of leachates and changes in the binding of elements into ash were observed. The results show that organic carbon content and initial moisture of ashes are the key parameters affecting the weathering of ashes. In the grate ash the biodegradation of organic carbon produced enough CO(2) to regulate pH. In contrast the dry gasification ash, containing little organic carbon, was not carbonated under anaerobic conditions and the pH decreased only after aeration was started. During the aeration the CO(2) absorption capacity was not reached, indicating that intense aeration would be needed to fully carbonate gasification ash. The results indicate that in common weathering practice the main emissions-reducing processes are leaching and carbonation due to CO(2) from biodegradation. The results of the aeration study suggest that the role of atmospheric CO(2) in the weathering process was insignificant.

Ecological Risks of an Old Wood Impregnation Mill: Application of the Triad Approach

Abstract Although many studies deal with the distribution and mobility of chromated copper arsenate (CCA) metals in soil, the ecotoxicity of CCA-contaminated soils is rarely studied. The Triad approach was applied to determine the ecological risks posed by a CCA mixture at a decommissioned wood impregnation mill in southern Finland. A combination of (1) chemical analyses; (2) toxicity tests with plants (aquatic: Lemna minor; terrestrial: Lactuca sativa), earthworms (Lumbricus rubellus), and enchytraeids (Enchytraeus albidus) conducted on contaminated soils, their aqueous extracts, and well water collected from the site; and (3) determination of the abundance of enchytraeids and nematodes and the bioaccumulation of metals in plants (horsetail) collected from the field were used to assess the actual risk. Although metal concentrations were low, L. minor growth appeared to be reduced by As contamination of the well water. In soil, metals were heterogeneously distributed with total concentrations of 14.8 to 4360 mg As/kg, 15.2 to 1740 mg Cr/kg, and 4.83 to 790 mg Cu/kg. In several samples, concentrations were above Finnish regulatory guideline values and exceeded the half maximal effective concentration (EC50) or 50% lethal concentration (LC50) values for the toxicity of the individual metals to earthworms and enchytraeids, indicating hazards to the ecosystem. (Bio)availability of metals was high, as indicated by weak electrolyte extractions and body residues in L. rubellus and E. albidus exposed in bioassays. Earthworm survival correlated significantly with body metal concentrations, but not with soil total metal concentrations. Enchytraeid responses in the soil bioassays were less sensitive to CCA metal exposure. Plant growth was affected by CCA pollution, with L. sativa root elongation correlating significantly with total and available As concentrations and L. minor development being significantly reduced in H2O extracts of the most contaminated soil sample. Abundance of enchytraeids and nematodes in the field was much lower than in nonpolluted Finnish soils but did not significantly correlate with CCA contamination. Arsenic accumulation in horsetail did not correlate with As concentrations in soil. Overall, the results of the 3 lines of evidence of the Triad approach indicate possible increased risks to the ecosystem at the most contaminated sites of the CCA treatment area.

Using the critical body residue approach to determine the acute toxicity of cadmium at varying levels of water hardness and dissolved organic carbon concentrations

The linkage between acute adverse effects of cadmium and internal cadmium levels were investigated for the oligochaete worm Lumbriculus variegatus in water at varying degrees of hardness and two different dissolved organic carbon (DOC) concentrations. The LC₅₀s for the effect of cadmium on the survival of the worms greatly differed depending on water hardness and DOC. We found less variability in internal metal toxicity metrics (lethal residue; LR₅₀s) than in external toxicity metrics (lethal concentration; LC₅₀s): LC₅₀s varied from 2.4 to 66.1 μmol/L, while LR₅₀s varied only from 226 to 413 μmol/kg wet weight. The cadmium body burden appeared to be independent of exposure conditions. From our experimental data, a critical cadmium body residue (324 ± 78 μmol/kg wet weight) associated with 50% lethality was derived. The protective role of DOC and water hardness against cadmium toxicity was evident.

Control of matrix interferences by the multiple linear regression model in the determination of arsenic, antimony and tin in lead pellets by inductively coupled plasma atomic emission spectrometry

A multiple linear regression technique was used to evaluate the matrix interferences in the determination of hydride-forming elements in lead shotgun pellets by inductively coupled plasma atomic emission spectrometry. The determination of arsenic, antimony, and tin in SRM C2416 (Bullet Lead) by ICP-AES failed to obtain the certified concentrations at the 95% level of confidence using the t-test. However, it proved possible, by using the multiple linear regression technique, to correct the concentrations of all three elements to a statistically acceptable level. This method of correction is based on the multiple regression line obtained from the analysis of 19 synthetic mixtures of matrix elements (arsenic, antimony, bismuth, copper, silver, and tin) in five levels of concentrations. The direct determination of bismuth, copper and silver in SRM C2416 was performed with high accuracy and precision (RSD < 2.2%) as was the determination of arsenic, antimony, and tin after the correction. Total element recovery varied from 95.6% to 101.8% in the SRM sample analyzed.

Partitioning of nanoparticle‐originated dissolved silver in natural and artificial sediments

Sediments are believed to be a major sink for silver nanoparticles (AgNPs) in the aquatic environment, but there is a lack of knowledge about the environmental effects and behavior of AgNPs in sediments. The release of highly toxic Ag+ through dissolution of AgNPs is one mechanism leading to toxic effects in sediments. We applied an ultrasound-assisted sequential extraction method to evaluate the dissolution of AgNPs and to study the partitioning of dissolved Ag in sediments. Silver was spiked into artificial and 2 natural sediments (Lake Höytiäinen sediment and Lake Kuorinka sediment) as silver nitrate (AgNO3 ), uncoated AgNPs, or polyvinylpyrrolidone-coated AgNPs (PVP-AgNPs). In addition, the total body burdens of Ag in the sediment-dwelling oligochaete Lumbriculus variegatus were assessed over a 28-d exposure period. The dissolution rate was found to be similar between the uncoated AgNP and PVP-AgNP groups. In all sediments, dissolved Ag was mainly bound to the residual fraction of the sediment, followed by iron and manganese oxides or natural organic matter. In Lake Kuorinka sediment, dissolved Ag that originated from PVP-AgNPs was relatively more bioaccessible, also resulting in higher total body burden in L. variegatus than that from uncoated AgNPs or AgNO3 . In artificial sediment and Lake Höytiäinen sediment, AgNO3 was significantly more bioaccessible than AgNPs. Our results highlight the importance of sediment properties and AgNP surface chemistry when evaluating the environmental exposure of AgNPs. Environ Toxicol Chem 2017;36:2593-2601.