Claudio Zaccone

Heavy metal concentrations in soils as determined by laser-induced breakdown spectroscopy (LIBS), with special emphasis on chromium

Soil is unanimously considered as one of the most important sink of heavy metals released by human activities. Heavy metal analysis of natural and polluted soils is generally conducted by the use of atomic absorption spectroscopy (AAS) or inductively coupled plasma optical emission spectroscopy (ICP-OES) on adequately obtained soil extracts. Although in recent years the emergent technique of laser-induced breakdown spectroscopy (LIBS) has been applied widely and with increasing success for the qualitative and quantitative analyses of a number of heavy metals in soil matrices with relevant simplification of the conventional methodologies, the technique still requires further confirmation before it can be applied fully successfully in soil analyses. The main objective of this work was to demonstrate that new developments in LIBS technique are able to provide reliable qualitative and quantitative analytical evaluation of several heavy metals in soils, with special focus on the element chromium (Cr), and with reference to the concentrations measured by conventional ICP spectroscopy. The preliminary qualitative LIBS analysis of five soil samples and one sewage sludge sample has allowed the detection of a number of elements including Al, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Si, Ti, V and Zn. Of these, a quantitative analysis was also possible for the elements Cr, Cu, Pb, V and Zn based on the obtained linearity of the calibration curves constructed for each heavy metal, i.e., the proportionality between the intensity of the LIBS emission peaks and the concentration of each heavy metal in the sample measured by ICP. In particular, a triplet of emission lines for Cr could be used for its quantitative measurement. The consistency of experiments made on various samples was supported by the same characteristics of the laser-induced plasma (LIP), i.e., the typical linear distribution confirming the existence of local thermodynamic equilibrium (LTE) condition, and similar excitation temperatures and comparable electron number density measured for all samples. An index of the anthropogenic contribution of Cr in polluted soils was calculated in comparison to a non-polluted reference soil. Thus, the intensity ratios of the emission lines of heavy metal can be used to detect in few minutes the polluted areas for which a more detailed sampling and analysis can be useful.

Airborne Petcoke Dust is a Major Source of Polycyclic Aromatic Hydrocarbons in the Athabasca Oil Sands Region

Oil sands mining has been linked to increasing atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in the Athabasca oil sands region (AOSR), but known sources cannot explain the quantity of PAHs in environmental samples. PAHs were measured in living Sphagnum moss (24 sites, n = 68), in sectioned peat cores (4 sites, n = 161), and snow (7 sites, n = 19) from ombrotrophic bogs in the AOSR. Prospective source samples were also analyzed, including petroleum coke (petcoke, from both delayed and fluid coking), fine tailings, oil sands ore, and naturally exposed bitumen. Average PAH concentrations in near-field moss (199 ng/g, n = 11) were significantly higher (p = 0.035) than in far-field moss (118 ng/g, n = 13), and increasing temporal trends were detected in three peat cores collected closest to industrial activity. A chemical mass-balance model estimated that delayed petcoke was the major source of PAHs to living moss, and among three peat core the contribution to PAHs from delayed petcoke increased over time, accounting for 45-95% of PAHs in contemporary layers. Petcoke was also estimated to be a major source of vanadium, nickel, and molybdenum. Scanning electron microscopy with energy-dispersive X-ray spectroscopy confirmed large petcoke particles (>10 μm) in snow at near-field sites. Petcoke dust has not previously been considered in environmental impact assessments of oil sands upgrading, and improved dust control from growing stockpiles may mitigate future risks.

Monitoring of Cr, Cu, Pb, V and Zn in polluted soils by laser induced breakdown spectroscopy (LIBS)

Laser Induced Breakdown Spectroscopy (LIBS) is a fast and multi-elemental analytical technique particularly suitable for the qualitative and quantitative analysis of heavy metals in solid samples, including environmental ones. Although LIBS is often recognised in the literature as a well-established analytical technique, results about quantitative analysis of elements in chemically complex matrices such as soils are quite contrasting. In this work, soil samples of various origins have been analyzed by LIBS and data compared to those obtained by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The emission intensities of one selected line for each of the five analytes (i.e., Cr, Cu, Pb, V, and Zn) were normalized to the background signal, and plotted as a function of the concentration values previously determined by ICP-OES. Data showed a good linearity for all calibration lines drawn, and the correlation between ICP-OES and LIBS was confirmed by the satisfactory agreement obtained between the corresponding values. Consequently, LIBS method can be used at least for metal monitoring in soils. In this respect, a simple method for the estimation of the soil pollution degree by heavy metals, based on the determination of an anthropogenic index, was proposed and determined for Cr and Zn.

Soil organic carbon sequestration as affected by afforestation: the Darab Kola forest (north of Iran) case study

Following the ratification of the Kyoto Protocol, afforestation of formerly arable lands and/or degraded areas has been acknowledged as a land-use change contributing to the mitigation of increasing atmospheric CO(2) concentration in the atmosphere. In the present work, we study the soil organic carbon sequestration (SOCS) in 21 year old stands of maple (Acer velutinum Bioss.), oak (Quercus castaneifolia C.A. Mey.), and red pine (Pinus brutia Ten.) in the Darab Kola region, north of Iran. Soil samples were collected at four different depths (0-10, 10-20, 20-30, and 30-40 cm), and characterized with respect to bulk density, water content, electrical conductivity, pH, texture, lime content, total organic C, total N, and earthworm density and biomass. Data showed that afforested stands significantly affected soil characteristics, also raising SOCS phenomena, with values of 163.3, 120.6, and 102.1 Mg C ha(-1) for red pine, oak and maple stands, respectively, vs. 83.0 Mg C ha(-1) for the control region. Even if the dynamics of organic matter (OM) in soil is very complex and affected by several pedo-climatic factors, a stepwise regression method indicates that SOCS values in the studied area could be predicted using the following parameters, i.e., sand, clay, lime, and total N contents, and C/N ratio. In particular, although the chemical and physical stabilization capacity of organic C by soil is believed to be mainly governed by clay content, regression analysis showed a positive correlation between SOCS and sand (R = 0.86(**)), whereas a negative correlation with clay (R = -0.77(**)) was observed, thus suggesting that most of this organic C occurs as particulate OM instead of mineral-associated OM. Although the proposed models do not take into account possible changes due to natural and anthropogenic processes, they represent a simple way that could be used to evaluate and/or monitor the potential of each forest plantation in immobilizing organic C in soil (thus reducing atmospheric C concentration), as well as to select more appropriate species during forestation plan management at least in the north of Iran.

Comparative management of offshore posidonia residues: Composting vs. energy recovery

Residues of the marine plant posidonia (Posidonia oceanica, PO) beached in tourist zones represent a great environmental, economical, social and hygienic problem in the Mediterranean Basin, in general, and in the Apulia Region in particular, because of the great disturb to the bathers and population, and the high costs that the administrations have to bear for their removal and disposal. In the present paper, Authors determined the heating values of leaves and fibres of PO, the main offshore residues found on beaches, and, meantime, composted those residues with mowing and olive pruning wood. The final composts were characterized for pH, electrical conductivity, elemental composition, dynamic respiration index, phytotoxicity, fluorescence and infrared spectroscopic fingerprints. The aim of the paper was to investigate the composting and energy recovery of PO leaves and fibres in order to suggest alternative solutions to the landfill when offshore residues have to be removed from recreational beaches. The fibrous portion of PO residues showed heating values close to those of other biofuels, thus suggesting a possible utilization as source of energy. At the same time, compost obtained from both PO wastes showed high quality features on condition that the electrical conductivity and Na content are lowered by a correct management of wetting during the composting.

Dust is the dominant source of "heavy metals" to peat moss (Sphagnum fuscum) in the bogs of the Athabasca Bituminous Sands region of northern Alberta.

Sphagnum fuscum was collected from twenty-five ombrotrophic (rain-fed) peat bogs surrounding open pit mines and upgrading facilities of Athabasca Bituminous Sands (ABS) in northern Alberta (AB) in order to assess the extent of atmospheric contamination by trace elements. As a control, this moss species was also collected at a bog near Utikuma (UTK) in an undeveloped part of AB and 264km SW of the ABS region. For comparison, this moss was also collected in central AB, in the vicinity of the City of Edmonton which is approximately 500km to the south of the ABS region, from the Wagner Wetland which is 22km W of the City, from Seba Beach (ca. 90km W) and from Elk Island National Park (ca. 45km E). All of the moss samples were digested and trace elements concentrations determined using ICP-SMS at a commercial laboratory, with selected samples also analyzed using instrumental neutron activation analysis at the University of Alberta. The mosses from the ABS region yielded lower concentrations of Ag, As, Bi, Cd, Cu, Pb, Sb, Tl, and Zn compared to the moss from the Edmonton area. Concentrations of Ni and Mo in the mosses were comparable in these two regions, but V was more abundant in the ABS samples. Compared with the surface vegetation of eight peat cores collected in recent years from British Columbia, Ontario, Quebec and New Brunswick, the mean concentrations of Ag, As, Bi, Cd, Cu, Mo, Ni, Pb, Sb, Tl and Zn in the mosses from the ABS region are generally much lower. In fact, the concentrations of these trace elements in the samples from the ABS region are comparable to the corresponding values in forest moss from remote regions of central and northern Norway. Lithophile element concentrations (Ba, Be, Ga, Ge, Li, Sc, Th, Ti, Zr) explain most of the variation in trace metal concentrations in the moss samples. The mean concentrations of Th and Zr are greatest in the moss samples from the ABS region, reflecting dust inputs to the bogs from open pit mines, aggregate quarries, and gravel roads. Linear regressions of V, Ni, and Mo (elements enriched in bitumen) versus Sc (a conservative, lithophile element) show excellent correlations in the mosses from the ABS region, but this is true also of Ag, Pb, Sb and Tl: thus, most of the variation in the trace metal concentrations can be explained simply by the abundance of dust particles on the plants of this region. Unlike the moss samples from the ABS region and from UTK where Pb/Sc ratios resemble those of crustal rocks, the moss samples from the other regions studied yielded much greater Pb/Sc ratios implying significant anthropogenic Pb contributions at these other sites.

Peat bogs in northern Alberta, Canada reveal decades of declining atmospheric Pb contamination

Peat cores were collected from six bogs in northern Alberta to reconstruct changes in the atmospheric deposition of Pb, a valuable tracer of human activities. In each profile, the maximum Pb enrichment is found well below the surface. Radiometric age dating using three independent approaches (14C measurements of plant macrofossils combined with the atmospheric bomb pulse curve, plus 210Pb confirmed using the fallout radionuclides 137Cs and 241Am) showed that Pb contamination has been in decline for decades. Today, the surface layers of these bogs are comparable in composition to the “cleanest” peat samples ever found in the Northern Hemisphere, from a Swiss bog ~ 6000 to 9000 years old. The lack of contemporary Pb contamination in the Alberta bogs is testimony to successful international efforts of the past decades to reduce anthropogenic emissions of this potentially toxic metal to the atmosphere.

Interpreting the ash trend within ombrotrophic bog profiles: atmospheric dust depositions vs. mineralization processes. The Etang de la Gruère case study

IntroductionAsh peaks along ombrotrophic bog profiles may arise from several different processes. In a recent paper, Leifeld and co-authors (Plant Soil 341:349–361, 2011) argued that ash peaks along the Etang de la Gruère (EGr) peat bog profiles are signs of previous periods of higher peat decomposition rather that an indication of periods of elevated dust inputs.Aims and methodsHere we question the approach and scrutinize results using published data on several peat cores from EGr, demonstrating that peaks in ash content at EGr are very reproducible when cores are carefully collected (e.g., using the Wardenaar corer), and age dated (using 210Pb and 14C).ResultsData clearly show that variations in ash content along bog profiles cannot be attributed simply, or exclusively, to differences in organic matter mineralization rate, and that averaging the ash contents and normalizing to a single ash peak leads to losses in valuable information and defeats the purpose of detailed paleoenvironmental reconstructions.ConclusionsComparing results obtained using sensitive spectroscopic and isotopic tools with the ash content profiles at EGr shows clearly that the distribution of ash and/or acid-insoluble ash cannot be used as a surrogate for the intensity of processes including organic matter mineralization, decomposition and/or humification.

Variability in As, Ca, Cr, K, Mn, Sr, and Ti concentrations among humic acids isolated from peat using NaOH, Na4P2O7 and NaOH+Na4P2O7 solutions

Sphagnum peat has been found to efficiently remove heavy metals, oil, detergents, dyes, pesticides and nutrients from contaminated waters since its major constituents, i.e., unesterified polyuronic acids, cellulose, and fulvic and humic acids (HA), show functional groups (e.g., alcohols, aldehydes, carboxylic acids, ketones and phenolic hydroxides) which may adsorb pollutant species. The influence of the extractant on the analytical characteristics of HA is an old but still open topic that should be studied in relation to the nature of the matrix from which they originate. While a number of works have been published on the effects of different reagents on the extraction yields and structural properties of HA from soils, relatively little attention has been devoted to peat HA. In this work, the contents of some major and trace elements (As, Ca, Cr, K, Mn, Sr, and Ti) in five Sphagnum-peat samples and in their corresponding HA fractions isolated using three common extractant solutions, i.e., 0.5M NaOH, 0.1M Na(4)P(2)O(7), and 0.5M NaOH+0.1M Na(4)P(2)O(7), where investigated by X-ray fluorescence spectroscopy. In general, Cr, Mn, and Ti concentrations of bulk peat samples were higher than those of the corresponding HA fractions regardless of the extractant used. Arsenic, Ca, K, and Sr concentrations in the HA fractions were affected by the extraction procedure, although at different extents depending on the extractant utilized. In particular, compared to both NaOH and NaOH+Na(4)P(2)O(7), the Na(4)P(2)O(7) extractant yielded HA generally richer in As, Ca, K, and Sr, and poorer in Ti. These results may be related to both the nature of each HA fraction and the physical and chemical form of each element supplied to the studied bog via atmospheric deposition.

Peat Bogs Document Decades of Declining Atmospheric Contamination by Trace Metals in the Athabasca Bituminous Sands Region

Peat cores were collected from five bogs in the vicinity of open pit mines and upgraders of the Athabasca Bituminous Sands, the largest reservoir of bitumen in the world. Frozen cores were sectioned into 1 cm slices, and trace metals determined in the ultraclean SWAMP lab using ICP-QMS. The uppermost sections of the cores were age-dated with 210Pb using ultralow background gamma spectrometry, and selected plant macrofossils dated using 14C. At each site, trace metal concentrations as well as enrichment factors (calculated relative to the corresponding element/Th ratio of the Upper Continental Crust) reveal maximum values 10 to 40 cm below the surface which shows that the zenith of atmospheric contamination occurred in the past. The age-depth relationships show that atmospheric contamination by trace metals (Ag, Cd, Sb, Tl, but also V, Ni, and Mo which are enriched in bitumen) has been declining in northern Alberta for decades. In fact, the greatest contemporary enrichments of Ag, Cd, Sb, and Tl (in the top layers of the peat cores) are found at the control site (Utikuma) which is 264 km SW, suggesting that long-range atmospheric transport from other sources must be duly considered in any source assessment.