Co-disposal of lignite fly ash and coal mine waste rock for neutralisation of AMD.

Waste rocks (WRs) from a lignite-producing coalfield and fly ash (FA) produced from the same lignite have been investigated in this study with a primary objective to determine the potential for co-disposal of WRs and FA to reduce the environmental contamination. Mixing WRs with FA and covering WRs with FA have been investigated. Particle size effect caused ≤2 mm particles to produce low pH (~2) and metal-laden leachates, indicating higher sulphide minerals' reactivity compared to larger particles (≤10 mm, pH ~ 4). Co-disposal of FA as mixture showed an instantaneous effect, resulting in higher pH (~3-6) and better leachate quality. However, acidity produced by secondary mineralisation caused stabilisation of pH at around 4.5-5. In contrast, the pH of the leachates from the cover method gradually increased from strongly acidic (pH ~ 2) to mildly acidic (pH ~ 4-5) and circumneutral (pH ~ 7) along with a decrease in EC and elemental leaching. Gradually increasing pH can be attributed to the cover effect, which reduces the oxygen diffusion, thus sulphide oxidation. FA cover achieved the pH necessary for secondary mineralisation during the leaching experiment. The co-disposal of FA as cover and/or mixture possesses the potential for neutralisation and/or slowing down AMD and improving leachate quality.

Effects of the co-disposal of lignite fly ash and coal mine waste rocks on AMD and leachate quality.

Lignite fly ash (FA) and waste rocks (WRs) were mixed in three different ratios (1:1, 1:3 and 1:5) and studied to compare the effects of adding FA on acid mine drainage generation from coal mining WRs, leachability of elements and the potential occurrence of the secondary minerals. FA mixed with WRs showed significant differences in pH levels compared to previous research. The 1:1 mixture performed best of all the three mixtures in terms of pH and leachability of elements, mainly due to the higher proportion of FA in the mixture. The pH in the 1:1 mixtures varied between 3.3 and 5.1 compared to other mixtures (2.3-3.5). Iron and SO42- leached considerably less from the 1:1 mixture compared to the others, indicating that the oxidation of sulphides was weaker in this mixture. Aluminium leached to a high degree from all mixtures, with concentrations varying from mg L-1 to g L-1. The reason behind this increase is probably the addition of FA which, due to acidic conditions and the composition of the FA, increases the availability of Al. For the same reason, high concentrations of Mn and Zn were also measured. Geochemical modelling indicates that the 1:1 mixture performs better in terms of precipitation of Al3+ minerals, whereas Fe3+ minerals precipitated more in mixtures containing less FA. These results suggest that, with time, the pores could possibly be filled with these secondary minerals and sulphate salts (followed by a decrease in sulphide oxidation), improving the pore water pH and decreasing the leachability of elements. Since grain size plays a crucial role in the reactivity of sulphides, there is a risk that the results from the leaching tests may have been influenced by crushing and milling of the WR samples.

Elemental mobility in sulfidic mine tailings reclaimed with paper mill by-products as sealing materials.

Sealing layers made of two alkaline paper mill by-products, fly ash and green liquor dregs, were placed on top of 50-year-old sulfide-containing tailings as a full-scale remediation approach. The performance and effectiveness of the sealing layers with high water content for an oxygen barrier and low hydraulic conductivity for a sealing layer in preventing the formation of acid rock drainage were evaluated 5 years after the remediation. The leaching behavior of the covered tailings was studied using batch leaching tests (L/S ratio 10 L/kg). The leaching results revealed that, in general, the dregs- and ash-covered tailings released relatively lower concentrations of many elements contained in acid rock drainage compared to those from the uncovered tailings. A change in the chemical composition and mineralogical state of the tailings was observed for the tailings beneath the covers. The increase in pH caused by the alkaline materials promoted metal precipitation. Geochemical modeling using PHREEQC confirmed most of the geochemical changes of the covered tailings. Both the ash and dregs showed potential to function as sealing materials in terms of their geochemical properties. However, mobilization of Zn and Ni from the lower part of the dregs-covered tailings was observed. The same phenomenon was observed for the lower part of the ash-covered tailings. Ash showed advantages over dregs as a cover material; based on geochemical studies, the ash immobilized more elements than the dregs did. Lysimeters were installed below the sealing layers, and infiltrating water chemistry and hydrology were studied to monitor the amount and quality of the leachate percolating through.

Potential of fly ash for neutralisation of acid mine drainage.

Lignite (PK), bituminous (FI) and biomass (SE) fly ashes (FAs) were mineralogically and geochemically characterised, and their element leachability was studied with batch leaching tests. The potential for acid neutralisation (ANP) was quantified by their buffering capacity, reflecting their potential for neutralisation of acid mine drainage. Quartz was the common mineral in FAs detected by XRD with iron oxide, anhydrite, and magnesioferrite in PK, mullite and lime in FI, and calcite and anorthite in SE. All the FAs had high contents of major elements such as Fe, Si, Al and Ca. The Ca content in SE was six and eight times higher compared to PK and FI, respectively. Sulphur content in PK and SE was one magnitude higher than FI. Iron concentrations were higher in PK. The trace element concentrations varied between the FAs. SE had the highest ANP (corresponding to 275 kg CaCO3 tonne(-1)) which was 15 and 10 times higher than PK and FI, respectively. The concentrations of Ca(2+), SO4 (2-), Na(+) and Cl(-) in the leachates were much higher compared to other elements from all FA samples. Iron, Cu and Hg were not detected in any of the FA leachates because of their mild to strong alkaline nature with pH ranging from 9 to 13. Potassium leached in much higher quantity from SE than from the other ashes. Arsenic, Mn and Ni leached from PK only, while Co and Pb from SE only. The concentrations of Zn were higher in the leachates from SE. The FAs used in this study have strong potential for the neutralisation of AMD due to their alkaline nature. However, on the other hand, FAs must be further investigated, with scaled-up experiments before full-scale application, because they might leach pronounced concentrations of elements of concern with decreasing pH while neutralising AMD.

Mobility of as, Cu, Cr, and Zn from tailings covered with sealing materials using alkaline industrial residues: a comparison between two leaching methods.

Different alkaline residue materials (fly ash, green liquor dregs, and lime mud) generated from the pulp and paper industry as sealing materials were evaluated to cover aged mine waste tailings (<1% sulfur content, primarily pyrite). The mobility of four selected trace elements (Cr, Cu, Zn, and As) was compared based on batch and column leaching studies to assess the effectiveness of these alkaline materials as sealing agents. Based on the leaching results, Cr, Cu, and Zn were immobilized by the alkaline amendments. In the amended tailings in the batch system only As dramatically exceeded the limit values at L/S 10 L/kg. The leaching results showed similar patterns to the batch results, though leached Cr, Cu, and Zn showed higher levels in the column tests than in the batch tests. However, when the columns were compared with the batches, the trend for Cu was opposite for the unamended tailings. By contrast, both batch and column results showed that the amendment caused mobilization of As compared with the unamended tailings in the ash-amended tailings. The amount of As released was greatest in the ash column and decreased from the dregs to the lime columns. The leaching of As at high levels can be a potential problem whenever alkaline materials (especially for fly ash) are used as sealing materials over tailings. The column test was considered by the authors to be a more informative method in remediation of the aged tailings with low sulfur content, since it mimics better actual situation in a field.

Investigation of biosolids degradation under flooded environments for use in underwater cover designs for mine tailing remediation.

To evaluate the potential suitability of digested sewage sludge (frequently termed biosolids) for use as underwater cover material for mine waste tailings, the degradability of biosolids at 20 - 22 °C under flooded anaerobic conditions was evaluated during incubation for 230 days. Leaching of elements from the flooded anaerobic system was also evaluated. Biosolid degradation was confirmed by the generation and accumulation of CH4 and CO2. Specifically, approximately 1.65 mmoL gas/g biosolids was generated as a result of incubation, corresponding to degradation of 7.68% of the organic matter, and the residue was stable at the end of the laboratory experiment. Under field conditions in northern Sweden, it is expected that the degradation rate will be much slower than that observed in the present study (Nason et al. Environ Earth Sci 70:30933105, 2013). Although the majority of biosolid fractions (>92%) were shown to be recalcitrant during the incubation period, long-term monitoring of further degradability of residue is necessary. The leaching results showed that most of the metals and metalloids leached from the biosolids at day 230 were below the limit value for non-hazardous waste, although Ni was the only element approximately three times higher than the limit value for inert material at the landfill site. In conclusion, biosolids have potential for use as covering material for underwater storage of tailings based on their biodegradability and leaching of elements.

Sedimentary records of δ(13)C, δ(15)N and organic matter accumulation in lakes receiving nutrient-rich mine waters.

Organic C and total N concentrations, C/N ratios, δ(15)N and δ(13)C values in (210)Pb-dated sediment cores were used to reconstruct historical changes in organic matter (OM) accumulation in three Swedish lakes receiving nutrient-rich mine waters. Ammonium-nitrate-based explosives and sodium cyanide (NaCN) used in gold extraction were the major N sources, while lesser amounts of P originated from apatite and flotation chemicals. The software IsoSource was used to model the relative contribution of soil, terrestrial and littoral vegetation, and phytoplankton detritus in the lake sediments. In one lake the IsoSource modelling failed, suggesting the presence of additional, unknown OM sources. In two of the lakes sedimentary detritus of littoral vegetation and phytoplankton had increased by 15-20% and 20-35%, respectively, since ~1950, when N- and P-rich mine waters began to reach the lakes. Today, phytoplankton is the dominating OM component in these lake sediments, which appears to be a eutrophication effect related to mining operations. Changes in the N isotopic composition of biota, lake water, and sediments related to the use of ammonium-nitrate-based explosives and NaCN were evident in the two studied systems. However, N isotope signals in the receiving waters (δ(15)N~+9‰ to +19‰) were clearly shifted from the primary signal in explosives (δ(15)N-NO3=+3.4±0.3‰; δ(15)N-NH4=-8.0±0.3‰) and NaCN (δ(15)N=+1.1±0.5‰), and direct tracing of the primary N isotope signals in mining chemicals was not possible in the receiving waters. Systems where mine waters with a well known discharge history are a major point source of N with well-defined isotopic composition should, however, be suitable for further studies of processes controlling N isotope signatures and their transformation in aquatic systems receiving mine waters.

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: a field evaluation.

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation.

The role of bacterial consortium and organic amendment in Cu and Fe isotope fractionation in plants on a polluted mine site.

Copper and iron isotope fractionation by plant uptake and translocation is a matter of current research. As a way to apply the use of Cu and Fe stable isotopes in the phytoremediation of contaminated sites, the effects of organic amendment and microbial addition in a mine-spoiled soil seeded with Helianthus annuus in pot experiments and field trials were studied. Results show that the addition of a microbial consortium of ten bacterial strains has an influence on Cu and Fe isotope fractionation by the uptake and translocation in pot experiments, with an increase in average of 0.99 ‰ for the δ(65)Cu values from soil to roots. In the field trial, the amendment with the addition of bacteria and mycorrhiza as single and double inoculation enriches the leaves in (65)Cu compared to the soil. As a result of the same trial, the δ(56)Fe values in the leaves are lower than those from the bulk soil, although some differences are seen according to the amendment used. Siderophores, possibly released by the bacterial consortium, can be responsible for this change in the Cu and Fe fractionation. The overall isotopic fractionation trend for Cu and Fe does not vary for pot and field experiments with or without bacteria. However, variations in specific metabolic pathways related to metal-organic complexation and weathering can modify particular isotopic signatures.

Interaction between nitrogen and phosphorus cycles in mining-affected aquatic systems-experiences from field and laboratory measurements.

The main objectives of this study were to (a) study the interaction between N and P cycles in mining-affected aquatic systems and (b) to quantify release rates of sedimentary soluble reactive phosphorus (SRP) that may be related to this interaction. Sediment cores and water from Lake Bruträsket (Boliden, northern Sweden) were collected and a time series of water sampling and flow measurements was conducted in the Brubäcken stream connected to the lake. Factors affecting SRP release were studied in a sediment incubation experiment and water column experiments. Field and laboratory measurements indicated that pH and dissolved oxygen are two important factors for SRP release. At the end of the low-oxygen incubation, an SRP concentration of 56 µg L(-1) resulted in a sedimentary flux of 1.1 mg SRP m(-2) day(-1). This is ~10 times higher than the flux of 0.12 mg SRP m(-2) day(-1) obtained from depth integration of vertical SRP profiles measured in the lake, and ~100 times higher than the external flux of 0.014 mg SRP m(-2) d(-1) into the lake (based on catchment area). Field measurements indicated that oxidation of organic matter and mining-related chemicals (ammonium and thiosulphates) may result in increased internal SRP flux from the sediment. Increased P loading in the lake as a result of low-oxygen conditions could change water column total nitrogen/total phosphorus ratios from 27 to 17, consequently changing the lake from being P-limited to be co-limited by N and P. The obtained findings point to possible interaction between the cycles of nitrogen (oxygen consumption) and P (flux from sediment) that may be important for nutrient regulation in mine water recipients.

Modelling nitrogen transformations in waters receiving mine effluents.

This paper presents a biogeochemical model developed for a clarification pond receiving ammonium nitrogen rich discharge water from the Boliden concentration plant located in northern Sweden. Present knowledge about nitrogen (N) transformations in lakes is compiled in a dynamic model that calculates concentrations of the six N species (state variables) ammonium-N (N(am)), nitrate-N (N(ox)), dissolved organic N in water (N(org)), N in phytoplankton (N(pp)), in macrophytes (N(mp)) and in sediment (N(sed)). It also simulates the rate of 16 N transformation processes occurring in the water column and sediment as well as water-sediment and water-atmosphere interactions. The model was programmed in the software Powersim using 2008 data, whilst validation was performed using data from 2006 to 2007. The sensitivity analysis showed that the state variables are most sensitive to changes in the coefficients related to the temperature dependence of the transformation processes. A six-year simulation of N(am) showed stable behaviour over time. The calibrated model rendered coefficients of determination (R(2)) of 0.93, 0.79 and 0.86 for N(am), N(ox) and N(org), respectively. Performance measures quantitatively expressing the deviation between modelled and measured data resulted in values close to zero, indicating a stable model structure. The simulated denitrification rate was on average five times higher than the ammonia volatilisation rate and about three times higher than the permanent burial of N(sed) and, hence, the most important process for the permanent removal of N. The model can be used to simulate possible measures to reduce the nitrogen load and, after some modification and recalibration, it can be applied at other mine sites affected by N rich effluents.

Estimation of temporal changes in oxidation rates of sulphides in copper mine tailings at Laver, Northern Sweden.

Tailings containing pyrrhotite were deposited in an impoundment at a copper mine at Laver, Northern Sweden, which operated between 1936 and 1946. Since then the oxidation of sulphides has acidified recipient water courses and contaminated them with metals. Measurements from surface water sampled in 1993, 2001 and 2004-05 from a brook into which the tailing impoundment drains indicate that the amounts of sulphide-associated elements such as Cu, S and Zn released into the brook have decreased over time, while pH has increased. The mass transport of S in the brook during 1993 and 2001 corresponded well with the amount of S estimated to be released from the tailings by oxidation. Secondary precipitates such as covellite and gypsum, which can trap sulphur, were shown in earlier studies to be present in only low amounts. The annual release of elements from the tailings was estimated from the volume of tailings assumed to oxidise each year, which depends on movement of the oxidation front with time. The results indicate that the oxidation rate in the tailings has decreased over time, which may be due to the increased distance over which oxygen needs to diffuse to reach unoxidised sulphide grains, or their cores, in the tailings.

Chromatographic purification for the determination of dissolved silicon isotopic compositions in natural waters by high-resolution multicollector inductively coupled plasma mass spectrometry.

A procedure is described for accurate Si isotope ratio measurements by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). Dissolved silicon was preconcentrated and separated from other elements present in natural surface waters using anion-exchange chromatography. The optimized procedure provides virtually complete elimination of major inorganic constituents while maintaining Si recovery in excess of 97%. High-resolution capabilities of MC-ICPMS used in this study allow interference-free measurements of 28Si and 29Si isotopes using conventional solution nebulization sample introduction without aerosol desolvation. Owing to the magnitude of polyatomic ion contributions in the region of mass 30, mostly from 14N16O+, measurements of the 30Si isotope can be affected by tailing of the interference signals, making exact matching of analyte and nitric acid concentrations in all measurement solutions mandatory. Isotope abundance ratio measurements were performed using the bracketing standards approach and on-line correction for mass-bias variations using an internal standard (Mg). Uncertainties, expressed as 95% confidence intervals, for replication of the entire procedure are better than +/-0.18/1000 for delta29Si and +/-0.5/1000 for delta30Si. For the first time with MC-ICPMS, the quality of Si isotope abundance ratio measurements could be verified using a three-isotope plot. All samples studied were isotopically heavier than the IRMM-018 Si isotopic reference material.

Measurement of iron and zinc isotopes in human whole blood: preliminary application to the study of HFE genotypes.

Multi-collector inductively coupled plasma--sector field mass spectrometry was applied to the measurement of Fe and Zn isotopes in human whole blood samples. For the Fe present in the blood of healthy adults, enrichment of the lighter isotopes relative to a standard material was observed, in agreement with earlier studies. The level of fractionation was found to be lower in hemochromatosis patients exhibiting homozygous (C282Y/C282Y) mutation of the HFE gene. On the one hand, this reinforces the hypothesis that Fe fractionation in blood decreases with enhanced dietary absorption. On the other hand, this contradicts predictions made on the basis of determinations of Fe fractionation in blood samples collected from subjects characterized by milder HFE mutations. In healthy subjects, the Zn in blood is depleted in lighter isotopes, consistent with the limited number of prior observations. As for Fe, the Zn isotopic composition exhibited a tendency toward lower levels of fractionation in the blood of subjects with hereditary hemochromatosis with homozygous mutation (C282Y/C282Y) of the HFE gene. The results therefore suggest that both Fe and Zn isotopic signatures in whole blood, at least to some extent, reflect polymorphisms in the HFE gene.

Sequential extraction of sulfide-rich tailings remediated by the application of till cover, Kristineberg mine, northern Sweden.

A sequential extraction has been carried out on sulfide-rich mine tailings. The purpose was to investigate how elements released by oxidation are secondarily retained in the tailings and the possible consequences of the remediation. After investigating the solid tailings, seven samples were chosen for sequential extractions. Two samples were oxidised, situated just above the oxidation front; two samples from just below the former oxidation front with increased concentrations of several elements; two unoxidised samples were from an intermediate depth, and the deepest sample was from the tailings-peat boundary at the bottom of the impoundment. Five phases were extracted: adsorbed/exchangeable/carbonate; labile organics; amorphous Fe-oxyhydroxides/Mn-oxides; crystalline Fe-oxides; and organics/sulfides. The addition from dried porewater to the extracted fractions has been calculated and considered as minor. In the oxidised tailings, the sulfide fraction still dominates for elements such as Fe, S, Cd, Co, Cu, Hg and Zn, although the concentrations are low compared to the unoxidised tailings. Generally, the second most important fraction is the adsorbed/exchangeable/carbonate fraction. Below the oxidation front, the sulfide content of the tailings sharply increases. In the secondary enrichment zone, the total element concentrations increase compared with the deeper unoxidised samples, mainly due to secondary retention. For some elements, secondary retention is greater than the total amount extracted for the deeper unoxidised samples. In the secondary enrichment zone the adsorbed/exchangeable/carbonate fraction represents approximately 20 wt.% or more for Cd, Co, Mn, Ni and Zn. The amorphous iron oxyhydroxide or the crystalline iron oxide fractions are less important at this level, although for As, Ba and Cu the amorphous iron oxyhydroxide fraction represents up to 20 wt.%. At the lower border of the enrichment zone, the total concentration for most metals is lower, but the importance of the adsorbed/exchangeable/carbonate fraction is further enhanced for Cd, Cu, Ni and Zn. These elements have 35-60 wt.% of the total amount from this fraction. For As, Cd, Cu, Ni and Pb, the secondary fractions extracted (extractions A-D) represent between 60 and 80 wt.% of the total content. At greater depth in the impoundment the relative importance of the adsorbed/exchangeable/carbonate fraction decreases, whilst the importance of amorphous iron oxyhydroxide and crystalline iron oxide fractions increases. The adsorbed/exchangeable/carbonate fraction is the most easily remobilised fraction. A raised groundwater table previously situated below the enrichment zone may result in the release of secondarily retained metals.

Adsorption of trace elements on pyrite surfaces in sulfidic mine tailings from Kristineberg (Sweden) a few years after remediation.

Laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) has been used to determine the elemental composition of the surface and interior layers of pyrite grains from the mine tailings from Kristineberg (northern Sweden) in order to determine concentration gradients between these two layers. The pyrite grains were collected from oxidized and unoxidized zones within the tailings. The aim of this study was to assess the role of pyrite surfaces as sites for the attenuation of solutes from the mine-tailings porewater. The normalized intensities of Cu, Zn, Ag, Sb, Ce, Pb and Bi are highest at the surface of each grain (within the surface layer drilled by the LA) and decrease towards the interior. The surface adsorption of Cu, Zn and Pb is more pronounced within the unoxidized than within the oxidized zone of the tailings. Copper exhibits a distinct concentration peak at the surface of the pyrite grains below the pre-remediation oxidation front. Silver, Sb, Bi, As and Au are preferably adsorbed within the uppermost layer of the oxidized zone in the tailings, where the pH is as high as 6.2. The conversion of intensity signals of the elements to concentration values in ppm was accomplished using an external calibration against an in-house pyrite standard.

Multielemental analysis of Mn-Fe nodules by ICP-MS: optimisation of analytical method.

Two acid digestion procedures (microwave-assisted and room temperature) were developed for the quantitative analysis of ferromanganese nodules by inductively coupled plasma double focusing sector field mass spectrometry (ICP-SFMS). Different compositions of the acid mixture, dilution factors and corrections for spectral interferences were tested. A combination of nitric, hydrochloric and hydrofluoric acids is necessary for complete sample digestion, with lowest acid to sample ratios (v/m) of 15 and 1.5, respectively, for the last two acids. Sample dilution factors higher than 2 x 10(4) should be used in order to decrease matrix effects and provide robust long-term instrumental operation. In spite of high dilution, method detection limits in the sub-microg g(-1) range were obtained for 54 out of 71 elements tested, due to the high detection capability of ICP-SFMS, as well as the special care taken to ensure the purity of reagents, to clean the instrument sample introduction system and to minimise sample handling. Owing to the presence of unresolved (at the resolution available) spectral interferences, accurate determination of Au, Hg, Os, Pd, Re and Rh is impossible without matrix separation. The accuracy of the entire analytical method was tested by the analysis of two nodule reference materials. The results generated agreed to within +/-2% for about 10, within +/-10% for more than 40 and within +/-20% for about 50 of 53 elements for which certified, recommended or literature values are available. A precision better than 3%, expressed as the between-digestion relative standard deviation (n = 4), was obtained for the majority of elements, except in cases limited by low analyte concentrations.

High spatial resolution analysis of ferromanganese concretions by LA-ICP-MS†.

A procedure was developed for the determination of element distributions in cross-sections of ferromanganese concretions using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The effects of carrier flow rates, rf forward power, ablation energy, ablation spot size, repetition rate and number of shots per point on analyte intensity were studied. It is shown that different carrier gas flow rates are required in order to obtain maximum sensitivities for different groups of elements, thus complicating the optimisation of ICP parameters. On the contrary, LA parameters have very similar effects on almost all elements studied, thus providing a common optimum parameter set for the entire mass range. However, for selected LA parameters, the use of compromise conditions was necessary in order to compensate for relatively slow data acquisition by ICP-MS and maintain high spatial resolution without sacrificing the multielemental capabilities of the technique. Possible variations in ablation efficiency were corrected for mathematically using the sum of Fe and Mn intensities. Quantification by external calibration against matrix-matched standards was successfully used for more than 50 elements. These standards, in the form of pressed pellets (no binder), were prepared in-house using ferromanganese concentrates from a deep-sea nodule reference material as well as from shallow-marine concretions varying in size and having different proportions of three major phases: aluminosilicates, Fe- and Mn-oxyhydroxides. Element concentrations in each standard were determined by means of conventional solution nebulisation ICP-MS following acid digestion. Examples of selected inter-element correlations in distribution patterns along the cross-section of a concretion are given.