Fast and Greener Ultrasound-Assisted Acid Extraction for the Determination of Potentially Toxic Elements in Fluorescent Lamp Waste Using ICP OES.

BACKGROUND: Understanding the chemical composition of fluorescent lamp residue, particularly potentially toxic elements, is crucial for reducing environmental impacts and human health risks after disposal. However, the challenge lies in effectively analyzing these heterogeneous solid samples. Techniques involving quantitative dissolution become imperative, playing a fundamental role in quantifying trace elements. OBJECTIVE: The aim of this work is to develop and present a new, faster, and more efficient and environmentally friendly method using ultrasound-assisted acid extraction to quantify potentially toxic elements (Cu, Mn, Ni, Sr, and Zn) present in fluorescent lamp waste using the inductively coupled plasma-optical emission spectrometry technique. METHODS: An ultrasound-assisted acid extraction method for the quantification of potentially toxic elements in fluorescent lamp waste was developed and applied as a greener alternative to conventional digestion methods. For variable optimization, a full factorial design with two levels and two variables (time and temperature) was used to determine which factors significantly affected the observed response. RESULTS: The results obtained for the developed extraction method were compared with a reference method employing a heating acid digestion (with a mixture of HCl, HClO4, and HF) using statistical tools. The best results were obtained using an extraction time of 10 min and a temperature of 25°C. Inductively coupled plasma optical emission spectrometry was applied for element quantification. CONCLUSION: The proposed extraction method showed good results for Cu, Mn, Ni, Sr, and Zn. Furthermore, the proposed method based on ultrasound radiation presents additional criteria that align with the concepts of green analytical chemistry. HIGHLIGHTS: A greener alternative method for the determination of Cu, Mn, Ni, Sr, and Zn in fluorescent lamp waste was developed. Optimal conditions for ultrasound extraction of potentially toxic elements were achieved in 10 min at a temperature of 25°C. Environmentally friendly aspects of ultrasound align with the requirements of green analytical chemistry.

Elemental composition, rare earths and minority elements in organic and conventional wines from volcanic areas: The Canary Islands (Spain).

The organic wine market is rapidly growing worldwide, both in terms of production and consumption. However, the scientific literature is not conclusive regarding differences in the elemental composition of wines according to their production method, including both major and trace elements. Minerals can be present in wine as a result of both anthropogenic and environmental factors. To date, this has not been evaluated in volcanic contexts, neither has the emergent issue of rare earths and other minority elements as potential sources of food contamination. This study using inductively coupled plasma mass spectrometry (ICP-MS) analyses organic and conventional wines produced in the Canary Islands (Spain), an archipelago of volcanic origin, to compare their content of 49 elements, including rare earths and minority elements. Our results showed that organic wines presented lower potential toxic element content on average than their conventional counterparts, but differences were not significant. Geographical origin of the wine samples (island) was the only significant variable differentiating wine samples by their composition profiles. By comparing our data with the literature, no agreement was found in terms of differences between organic and conventionally-produced wines. This confirms that other factors prevail over elemental composition when considering differences between wine production methods. Regarding the toxicological profile of the wines, five samples (three organic and two conventional) exceeded the maximum limits established by international legislation. This highlights the need for stricter analytical monitoring in the Canary Islands, with a particular focus on Cu and Ni concentration, and potentially in other volcanic areas.

Elemental Characterization of Ciders and Other Low-Percentage Alcoholic Beverages Available on the Polish Market.

Seventy-three samples of alcoholic beverages and juices that were purchased on the Polish market and home-made were analyzed for their elemental profiles. The levels of 23 metals were determined by ICP-MS (Ag, Ba, Bi, Cd, Co, Cr, Li, Mn, Ni, Pb, Sr and Tl), ICP-OES (Al, B, Ca, Cu, Fe, K, Mg, Na, Ti and Zn) and CVAAS (Hg) techniques in twenty-five samples of ciders widely available on the Polish market; six samples of home-made ciders; two samples of juices used in the production of these ciders; and forty samples of low-percentage, flavored alcoholic beverages based on beer. The gathered analytical data confirmed that the final elemental fingerprint of a product is affected by the elemental fingerprint of the ingredients used (apple variety) as well as the technology and equipment used by the producer, and in the case of commercial ciders, also the impact of type of the packaging used was proven. These factors are specific to each producer and the influence of the mentioned above parameters was revealed as a result of the performed analysis. Additionally, the inclusion of the home-made ciders in the data set helped us to understand the potential origin of some elements, from the raw materials to the final products. The applied statistical tests revealed (Kruskal-Wallis and ANOVA) the existence of statistically significant differences in the concentration of the following metals: Ag, Al, B, Bi, Co, Cr, Cu, Fe, K, Li, Mg, Na, Ni, Ti and Zn in terms of the type of cider origin (commercial and home-made). In turn, for different packaging (can or bottle) within one brand of commercial cider, the existence of statistically significant differences for Cu, Mn and Na was proved. The concentrations of all determined elements in the commercial cider from the Polish market and home-made cider samples can be considered as nontoxic, because the measured levels of elements indicated in the regulations were lower than the allowable limits. Moreover, the obtained results can be treated as preliminary for the potential authentication of products in order to distinguish the home-made (fake) from the authentic products, especially for premium-class alcoholic beverages.

About plant species potentially promising for phytoextraction of large amounts of toxic trace elements.

There is no information yet about plant species capable of accumulating many different metals/metalloids. The plants feasible for phytoremediation aims must grow fast, have high biomass, deep roots, and should accumulate and tolerate a range of toxicants in their aerial parts. In our research, greenhouse and field experiments have been performed to investigate accumulation and tolerance of not well-studied trace elements such as Br, Eu, Sc, Th (and also U) in couch grass and wheat. We compared bioaccumulation abilities of the plants with those of some other plant species grown under the same conditions. Additionally, we tested the effects of inoculation of seeds with Cellulomonas bacteria on phytoextraction of the trace elements from contaminated soils. For determination of elements, we used neutron activation analysis and ICP-MS. It was found that couch grass and wheat can grow in heavily contaminated soils and accumulate different toxic trace elements to levels that exceed physiological requirements typical for most plant species. Infection of seeds with bacteria resulted in a significant increase in the uptake of various trace elements and their translocation to upper plant parts. The use of couch grass and/or wheat, either alone or in combination with microorganisms, is a promising way to phytoextract metals/metalloids from contaminated soils.

Colour-assisted variation in elytral ICP-OES-based ionomics in an aposematic beetle.

Very little is known about how the elemental composition (ionome) of an insect cuticle varies as a result of different colouration. Using inductively-coupled plasma optical emission spectrometry (ICP-OES), we established ionomic profiles in microsamples of two adjacent regions of an insect cuticle with a contrasting colour pattern, namely, the black and orange regions of the elytra of the aposematic burying beetle Nicrophorus vespillo. The analysis revealed 53 elements (ranging in atomic weight from Na to Bi) occurring above the detection limit. The frequency of detectability of individual elements varied strongly, and only ten elements (Ba, Cu, Fe, K, Mg, Mn, P, Rb, Sb and Zn) were present in concentrations exceeding the detection limit in all the samples. The sum of concentrations of all elements in the orange regions of the elytra was 9% lower than in the black ones. The opposite distribution was displayed by the rare earth elements (REEs), the sum of which was 17% lower in the black elytral regions than in the orange ones. The concentrations of six elements were significantly higher in the black than in the orange regions: Al (by 97%), Cu (41%), Mn (14%), Na (46%), Se (97%) and W (47%). The concentrations of essential elements measured in both the black and orange regions exhibited very considerable variance: Ca (σ2 = 1834; 1882, respectively), K (145; 82) P (97; 76), Na (84; 53), Mg (24; 26) and Ba (9; 13). This, in part, could be attributed to individual differences, e.g. those resulting from the consumption of animal carcasses of different quality/chemical composition, but interference between elements and the consequent lowering of measurement quality are also possible. We highlight the fact that deeper insight into the basic relationship between insect colouration and variation in elemental composition requires micro-sampling of the homogeneous layers of an exoskeleton.

Molecular tests support the viability of rare earth elements as proxies for fossil biomolecule preservation.

The rare earth element (REE) composition of a fossil bone reflects its chemical alteration during diagenesis. Consequently, fossils presenting low REE concentrations and/or REE profiles indicative of simple diffusion, signifying minimal alteration, have been proposed as ideal candidates for paleomolecular investigation. We directly tested this prediction by conducting multiple biomolecular assays on a well-preserved fibula of the dinosaur Edmontosaurus from the Cretaceous Hell Creek Formation previously found to exhibit low REE concentrations and steeply-declining REE profiles. Gel electrophoresis identified the presence of organic material in this specimen, and subsequent immunofluorescence and enzyme-linked immunosorbant assays identified preservation of epitopes of the structural protein collagen I. Our results thereby support the utility of REE profiles as proxies for soft tissue and biomolecular preservation in fossil bones. Based on considerations of trace element taphonomy, we also draw predictions as to the biomolecular recovery potential of additional REE profile types exhibited by fossil bones.

Traces matter: Targeted optimization of monoclonal antibody N-glycosylation based on/by implementing automated high-throughput trace element screening.

The use of high-throughput systems in cell culture process optimization offers various opportunities in biopharmaceutical process development. Here we describe the potential for acceleration and enhancement of product quality optimization and de novo bioprocess design regarding monoclonal antibody N-glycosylation by using an iterative statistical Design of Experiments (DoE) strategy based on our automated microtiter plate-based system for suspension cell culture. In our example, the combination of an initial screening of trace metal building blocks with a comprehensive DoE-based screening of 13 different trace elemental ions at three concentration levels in one run revealed most effective levers for N-glycan processing and biomass formation. Obtained results served to evaluate optimal concentration ranges and the right supplementation timing of relevant trace elements at shake flask and 2 L bioreactor scale. This setup identified manganese, copper, zinc, and iron as major factors. Manganese and copper acted as inverse key players in N-glycosylation, showing a positive effect of manganese and a negative effect of copper on glycan maturation in a zinc-dependent manner. Zinc and iron similarly improved cell growth and biomass formation. These findings allowed determining optimal concentration ranges for all four trace elements to establish control on desired product quality attributes regarding premature afucosylated and mature galactosylated glycan species. Our results demonstrates the power of combining robotics with DoE screening to enhance product quality optimization and to improve process understanding, thus, enabling targeted product quality control.

Determination of trace metals in vegetables and water samples using dispersive ultrasound-assisted cloud point-dispersive µ-solid phase extraction coupled with inductively coupled plasma optical emission spectrometry.

A simple method combining ultrasound assisted cloud point extraction (UA-CPE) and dispersive µ-solid phase extraction (D-µ-SPE) was developed for preconcentration of As, Cd, Cr, Co, Sb, Pb and Tl to inductively coupled plasma optical emission spectrometric (ICP-OES). At optimum conditions, the linearity, limits of detection and limits of quantification were 0.20-1000 µg L-1, 90-150 ng L-1 and 200-500 ng L-1, respectively. The intraday (n = 20) and intraday (n = 5) precisions reported as the relative standard deviation ranged from 1.5 to 3.5% and 1.9-4.5%. The trueness of the method was investigated using CRM BCR679, NIST SRM 1573a, and SRM 1640a, as well as spiked recovery experiments. Satisfactory recoveries and relative errors ranging from 97 to 99.3% and -4.0 to 2.4% were obtained. The proposed UA-CPE-D-µ-SPE/ICP-OES method was successfully applied for various real samples such as groundwater, bottled mineral water, river water and borehole water and food samples.

Contenido de metales y elementos traza en aguas subterráneas de abastecimiento de la Isla de El Hierro (Islas Canarias, España) / Metal content and trace elements in groundwater supply of the island of El Hierro (Canary Islands, Spain)

OBJETIVO: Las erupciones volcánicas son una fuente natural de sustancias potencialmente peligrosas para la salud humana. La isla de El Hierro (Islas Canarias, España) sufrió una erupción volcánica marina en el año 2012, siendo necesaria la monitorización de los niveles de ciertos elementos que pueden alterar la calidad de las aguas subterráneas de abastecimiento. El objetivo de este trabajo fue determinar el contenido de metales y elementos traza de las aguas subterráneas de abastecimiento de la Isla del Hierro y comprobar si cumplían los parámetros de calidad establecidos en la legislación española. MÉTODOS: Se determinó el contenido de metales y elementos traza (aluminio, plomo, cadmio, calcio, potasio, sodio, magnesio, boro, bario, cobalto, cromo, cobre, hierro, litio, manganeso, molibdeno, níquel, estroncio, vanadio, zinc, flúor) en un total de 60 muestras de agua subterránea de abastecimiento y de agricultura procedentes de seis puntos diferentes de muestreo de la isla. La determinación fue llevada a cabo mediante espectrofotometría de emisión óptica de plasma acoplado inductivamente (ICP-OES) y mediante potenciometría de ion selectivo de fluoruro. Los datos fueron analizados estadísticamente aplicando los tests de Kolmogorov-Smirnov, estadístico de Levene, Kruskal-Wallis, U de Mann-Whitney, ANOVA y test de Tukey. Se consideraron diferencias significativas aquellas que cumplían p < 0,05. RESULTADOS: La mayor concentración media de plomo se registró en las muestras de Tigaday (0,003±0,0005 mg/L), encontrándose diferencias estadísticamente significativas (p < 0,05) en los niveles de plomo entre los puntos de muestreo. Los elementos analizados se encontraban por debajo de los valores paramétricos fijados en el Real Decreto 140/2003. CONCLUSIONES: Los resultados obtenidos reflejan que, en todas las muestras analizadas, los parámetros de calidad establecidos en la legislación española (RD 140/2003) se cumplen, siendo, por lo tanto, aguas aptas para el consumo humano

OBJECTIVE: Volcanic eruptions are a natural source of substances potentially dangerous to human health. The island of El Hierro (Canary Islands, Spain) suffered a marine volcanic eruption in 2012, making it necessary to monitor the levels of certain elements that can alter the quality of groundwater supply. The objective of this work was to determine the content of metals and trace elements in the groundwater supply of the Isla del Hierro and to check if they met the quality parameters established in Spanish legislation. METHODS: The content of metals and trace elements (aluminum, lead, cadmium, calcium, potassium, sodium, magnesium, boron, barium, cobalt, chromium, copper, iron, lithium, manganese, molybdenum, nickel, strontium, vanadium, zinc, fluorine) in a total of 60 samples of groundwater supply and agriculture from six different sampling points on the island. The determination was carried out by inductively coupled plasma optical emission spectrophotometry (ICP-OES) and by fluoride ion selective potentiometry. The data were statistically analyzed applying the Kolmogorov-Smirnov test, Levene's statistic, Kruskal-Wallis, Mann-Whitney U, ANOVA and Tukey's test. Significant differences were those that met p < 0.05. RESULTS: The highest mean concentration of lead was recorded in the Tigaday samples (0.003±0.0005 mg/L), finding statistically significant differences (p < 0.05) in the lead levels between the sampling points. The elements analyzed were below the parametric values set in Royal Decree 140/2003. CONCLUSIONS: The results obtained reflect that, in all the samples analyzed, the quality parameters established in the Spanish legislation (RD 140/2003) are met, being, therefore, waters suitable for human consumption

Characterization of the effects involved in ultrasound-assisted extraction of trace elements from artichoke leaves and soybean seeds.

Ultrasonication is known to induce cavitation and can thus accelerate extraction, dissolution, digestion, and other processes, while the intense mixing caused by the propagation of ultrasound waves enhances analyte transfer to the extraction medium. Consequently, ultrasound-assisted extraction (UAE) is viewed as a simple procedure well suited for the extraction and subsequent determination of trace elements in food. Herein, we use different techniques to characterize several processes involved in probe- and bath-based UAE, apply them to the determination of trace metals (Cd, Cu, Ni, Pb, and Zn) in globe artichoke leaves and soybean seeds, and closely monitor the extraction rates of selected analytes. The developed UAE-based method is found to comply with the criteria of Green Chemistry and is concluded to be a reliable, simple, and cheap alternative to standard food analysis techniques.

Ultrasound-assisted extraction of Pb, Cd, Cr, Mn, Fe, Cu, Zn from edible oils with tetramethylammonium hydroxide and EDTA followed by determination using graphite furnace atomic absorption spectrometer.

A new method for extraction and determination of trace and ultratrace impurities from edible oils via an ultrasound-assisted extraction using tetramethylammonium hydroxide (TMAH) and ethylenediaminetetraacetic acid (EDTA) has been described. Method is simple and sensitive. Extraction variables like pH, concentrations of TMAH and EDTA, ultrasonication and centrifugation times were all optimised for analytes using engine-oil. Under optimised conditions, extraction of spiked analytes from all the edible oils into aqueous-medium were investigated and found to be quantitative (89-101%). Using this method, concentrations of impurities in edible-oils were determined by graphite furnace atomic absorption spectrometer (GFAAS) using standard-addition calibration method and validated with microwave-digestion method. The method was successfully applied to edible oils extracted from various seeds such as mustard oil, sun flower oil, sesame oil, ground nut oil, coconut oil, rice bran oil and corn oil containing ultratrace impurities. Accuracy of developed method for edible-oils was checked with corresponding results obtained by microwave digestion method.

Validation of a simple sample preparation method for multielement analysis of bovine serum.

Here we propose a single acid digestion (SAD) sample preparation method for ICP-MS analysis of animal serum samples to determine trace element contents. The method was evaluated in comparison with a commonly used procedure involving dilution of samples in an alkaline solution (AKD). In the SAD procedure, aliquots (1 mL) of bovine serum samples were treated at low temperature with a mixture of concentrated nitric acid and hydrogen peroxide. Trace elements (As, B, Ba, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Sr, U, and Zn) were directly determined by ICP-MS analysis of diluted solutions of samples. Both methods were sufficiently sensitive to enable quantification of most trace elements, with the exception of the AKD method for Cd, Hg and Pb. The quality of the data was verified by using certified reference material. Good results were obtained for the SAD procedure and all elements, but recoveries were unacceptable with the AKD procedure for Se (recovery: 57%), Cd (154%) and Fe (139%). Strong associations (R2>0.90, P = 0.000) between the data obtained by both methods were demonstrated for the elements considered. The proposed SAD sample preparation method produced satisfactory results for determining most toxic and essential trace elements targeted in monitoring studies.

A new anion exchange purification method for Cu stable isotopes in blood samples.

The isotopic composition of iron, zinc, copper, and cadmium (δ56Fe, δ66Zn, δ65Cu, and δ114Cd) are novel and promising tools to study the metabolism and homeostasis of trace metals in the human body. Serum δ65Cu has been proposed as a potential tool for diagnosis of cancer in liquid biopsy, and other metals may have similar utility. However, accurate analysis of trace metal isotopes is challenging because of the difficulties in purifying the metals from biological samples. Here we developed a simple and rapid method for sequential purification of Cu, Fe, Zn, and Cd from a single blood plasma sample. By using a combination of 11 M acetic acid and 4 M HCl in the first steps of column chemistry on AG-MP1 resin, we dramatically improve the separation of Cu from matrix elements compared to previous methods which use concentrated HCl alone. Our new method achieves full recovery of Cu, Fe, Zn, and Cd to prevent column-induced isotope fractionation effects, and effectively separates analytes from the matrix in order to reduce polyatomic interferences during isotope analysis. Our methods were verified by the analysis of isotope standards, a whole blood reference material, and a preliminary sample set including five plasma samples from healthy individuals and five plasma samples from cancer patients. This new method simplifies preparation of blood samples for metal isotope analysis, accelerating multi-isotope approaches to medical studies and contributing to our understanding of the cycling of Fe, Zn, Cu, and Cd in the human body. Graphical abstract ᅟ.

Occupational exposure to metals and other elements in the tractor production.

BACKGROUND: Exposure to metals via air sampling in workplace has been extensively studied; however, the magnitude of individual exposure in various occupational groups may vary dramatically. The aim of this cross-sectional study was to ascertain exposure to selected metals from metal fumes in a series of typical workplaces of contemporary tractor production. METHODS: Ninety-eight (median age 41 (interquartile range (IQR) 23) years, all men) workers from Minsk Tractor Plant were categorized into four groups, including assembly shop workers (group 1); thermal shop staff (group 2); steelmakers (group 3) and welders (group 4). Hair samples (0.25 g) of each worker were tested for Ca, Mg, P, Cu, Fe, Zn, Al, Mn, Cr, Ni, Pb and Cd using atomic emission spectrophotometry. We then tested between-group differences of log-transformed element concentrations using analysis of variance, followed by logistic regression to determine the odds ratio (OR) with its 95% confidence interval (CI) of high exposure for four selected groups. RESULTS: The median work duration in workers was 6 (IQR 15) years, more in group 1 (10 (IQR 23)). Eight out of 12 included elements yielded significant between-group differences, including Mg, P, Fe, Zn, Mn, Cr, Ni and Cd. Steelmakers had higher Mn hair concentrations (F-ratio 10.41, p<0.001); whereas Fe (F-ratio 12.48, p<0.001), P (F-ratio 12.68, p<0.001), Zn (F-ratio 6.07, p<0.001) and Cr (F-ratio 20.54, p<0.001) were higher in welders. OR of high exposure to Mg in group 3 was 10.00 (95% CI 1.14-87.52), whereas the OR of high exposure to P in group 4 was 18.64 (95% CI 2.22-156.85) compared to group 1. CONCLUSIONS: In the modern full-cycle tractor production, welders may have higher exposure to Fe, P, Zn and Cr, as opposed to steelmakers with higher Mn hair concentrations.

Short Communication- Estimation of trace elements and in vitro biological activities of lichens extracts.

Infectious diseases caused by etiological agents are still a major threat to public health. Their impact is particularly large in developing countries due to relative unavailability of medicine and the emergence of widespread drug resistance. In the current research, trace metals were detected in lichens species through inductively coupled plasma atomic emission spectroscopy. The antimicrobial potency of Pseudevernia furfruracea, Physcia species, Dermatocarpon vellerum and Parmellia species (lichens) extracts have been investigated against three local clinical bacterial isolates i.e. Escherichia coli, Pseudomonas aeruginosa and Staphylococcus epidermidis through various agar disc and well diffusion methods. The antioxidant potential effect was also evaluated by DPPH and ABTS.+ free radical scavenging methods. Phytochemical constituents were screened through thin layer chromatography (TLC) and qualitative methods. Methanolic extract of P. furfruracea, Physcia spp, and D. vellerum showed a significant inhibition of S. epidermidis (14.3±1.7mm, 12.3±2.0mm, and 11.3±0.9mm) by pouring method of disc diffusion. Moderate zone of inhibition (8.0±1.4 mm) against S. epidermidis was observed by methanolic extract of Parmellia spp, through spreading method. All the results were evaluated by ANOVA and LSD tests at p<0.05. The diethyl ether extracts showed considerable antioxidant potential activity with 80%, 81%, 79% and 66%. Thin layer chromatography profiling gave us the idea about the presence of phytochemical constituents such as tannins, phenols, saponins, and terpenoids. Various Rf values on silica gel plates provided the valuable clues about polarity and the selection of solvents for separation of phytochemicals. Significant inhibition of E. coli was also observed through TLC-Bioautography. The findings revealed the considerable inhibitory and antioxidant effect of lichens may be due to the presence of bioactive compounds. Therefore, lichens could be a potential source of new antimicrobial and antioxidant agents.

Redox-stat bioreactors for elucidating mobilisation mechanisms of trace elements: an example of As-contaminated mining soils.

The environmental fate of major (e.g. C, N, S, Fe and Mn) and trace (e.g. As, Cr, Sb, Se and U) elements is governed by microbially catalysed reduction-oxidation (redox) reactions. Mesocosms are routinely used to elucidate trace metal fate on the basis of correlations between biogeochemical proxies such as dissolved element concentrations, trace element speciation and dissolved organic matter. However, several redox processes may proceed simultaneously in natural soils and sediments (particularly, reductive Mn and Fe dissolution and metal/metalloid reduction), having a contrasting effect on element mobility. Here, a novel redox-stat (Rcont) bioreactor allowed precise control of the redox potential (159 ± 11 mV, ~ 2 months), suppressing redox reactions thermodynamically favoured at lower redox potential (i.e. reductive mobilisation of Fe and As). For a historically contaminated mining soil, As release could be attributed to desorption of arsenite [As(III)] and Mn reductive dissolution. By contrast, the control bioreactor (Rnat, with naturally developing redox potential) showed almost double As release (337 vs. 181 µg g-1) due to reductive dissolution of Fe (1363 µg g-1 Fe2+ released; no Fe2+ detected in Rcont) and microbial arsenate [As(V)] reduction (189 µg g-1 released vs. 46 µg g-1 As(III) in Rcont). A redox-stat bioreactor thus represents a versatile tool to study processes underlying mobilisation and sequestration of other trace elements as well.

The importance of substrate compaction and chemical composition in the phytoextraction of elements by Pinus sylvestris L.

Trees of Scots pine (Pinus sylvestris L.) are known for their effective phytoextraction capabilities. The results obtained in this study point to the significant role of substrate composition and chemical characteristics in the phytoextraction potential of this species. A multi-elemental (53 elements) analysis of pines from unpolluted (soil) and polluted (post-flotation tailings) sites was performed using inductively coupled plasma optical emission spectrometry. The analyzed flotation tailings were characterized by alkaline pH (7.19 ± 0.06) and significantly higher conductivity (277.7 ± 2.9 µS cm-1) than the soil (pH = 5.11 ± 0.09; 81.3 ± 4.9 µS cm-1). The two substrates also differed with respect to the contribution of the clay fraction (0% in the unpolluted and 8% in the polluted substrate). The specimens of P. sylvestris growing on flotation tailings had significantly smaller height (381 ± 58 cm) and total aboveground biomass (4.78 ± 0.66 kg) than the trees growing in soil (699 ± 80 cm and 10.24 ± 2.10 kg). The biomass of the trunk, twigs and branches, and needles of the trees from polluted sites was between 40.0% and 48.7% of the biomass of the same organs of the control trees. Generally, the organs (trunk, twigs and branches, needles) of the P. sylvestris specimens from polluted sites had significantly higher concentrations of Au, Al, Ba, Cd, Co, La, Lu, Ni, Pd, Sc, Zn, and lower concentrations of B, Bi, Ca, Ce, Er, In, K, Mg, Na, Nd, P, Pr, Re, Se, Sr, Te than in the control plants, these metals being accumulated effectively in the whole of the aboveground biomass (BCF>1). Although the concentration of the majority of elements was significantly higher in the flotation tailings, significantly higher concentrations of these elements were observed in the tree organs from unpolluted sites, which points to the important role of substrate characteristics in the phytoextraction efficiency of P. sylvestris.

Preconcentration and Determination of Trace Nickel and Cobalt in Milk-Based Samples by Ultrasound-Assisted Cloud Point Extraction Coupled with Flame Atomic Absorption Spectrometry.

In this study, ultrasound-assisted cloud point extraction (UA-CPE) method was developed for the determination of Ni(II) and Co(II) in milk-based products. After extraction and preconcentration, the Ni(II) and Co(II) contents of samples were determined by flame atomic absorption spectrometry (FAAS). After their complexation with hydroxy naphthol blue (HNB) in the presence of cationic surfactant, CTAB at pH 4.0, the Ni(II) and Co(II) were taken within the micellar phase of nonionic surfactant, TX-114. The micellar phase containing the analytes were diluted to a volume of 0.7 mL with 1.0-mol/L HNO3 in ethanol to reduce its viscosity and to facilitate sample treatment and then was analyzed by FAAS. The various analytical parameters affecting UA-CPE efficiency were investigated. The analytical features obtained after optimization are as follows: limits of detection are 0.56 and 0.78 µg/L; sensitivity enhancement factors are 48.6 and 53.9; the calibration curves were linear 3-180 and 2-160 µg/L for Co(II) and Ni(II), respectively, after preconcentration of 50-fold. The precision (as RSD%) between 1.8-3.6% and 2.2-3.8% (25 and 100 µg/L, n = 5) for Ni(II) and Co(II), respectively. The accuracy was statistically verified by analysis of two certified reference material samples (CRMs), including recovery studies after spiking. The method was applied to the analysis of milk-based samples with satisfied results.

Characterization of trace metal removal products in vertical flow bioreactor substrates at the Mayer Ranch Passive Treatment System in the Tar Creek Superfund Site.

A passive treatment system (PTS), including two parallel vertical flow bioreactors (VFBR), was constructed in 2008 for the treatment of unabated net-alkaline ferruginous mine drainage in the Tar Creek Superfund Site in northeastern Oklahoma. Water quality data collected since the PTS began operation indicate significant removal of trace metals in the VFBR. Results of a sequential extraction procedure (SEP) performed on substrate samples showed that the majority of Cd, Co, Fe, Ni, Pb, and Zn were retained in the refractory organic/sulfide fraction. Subsequent acid volatile sulfide/simultaneously extracted metals (AVS/SEM) analyses confirmed the retention of Cd, Fe, Pb, and Zn as sulfides, but Co and Ni results were less certain. The majority of trace metals were retained as insoluble products in the VFBR, while up to 20% of most of the trace metals were retained in soluble, bioavailable fractions. Nearly 70% of Mn was retained in the soluble and bioavailable exchangeable, carbonate, and labile organic fractions.

Chemical extraction of trace elements from hazardous fine fraction at an old glasswork dump.

Old glassworks sites have been always associated with contamination by different trace elements like Pb, Cd, As, Zn and others. The mixture of soil and waste glass of particle sizes <2 mm at one of the oldest Swedish glassworks (the Pukeberg) was studied by analyzing the trace elements content, organic content (3.6%) and pH (7.4). The results showed hazardous concentrations of Pb (1525 mg/kg), Ba (1312 mg/kg), Sb (128 mg/kg), Cd (36 mg/kg), As (118 mg/kg), Zn (1154 mg/kg) and Co (263 mg/kg) exceeded the Swedish guidelines of contaminated soil. Batch chemical extraction by the chelating agents EDTA, DTPA and the biodegradable NTA were performed to study the effect of chelating agent concentration and mixing time on the extraction efficiencies by following a Box-Wilson design of experiments. The results displayed good extraction efficiencies (less than 41%) of Pb, Cd, As and Zn by the EDTA, DTPA and NTA, which seemed depends on the type of chelator. In addition, high correlation between the extraction efficiencies, the chelators concentration and mixing time was found based on the statistical and experimental results.