| 1. |
- Andren, Henrik, et al.
(författare)
-
Sources of mass bias and isotope ratio variation in multi-collector ICP-MS : optimization of instrumental parameters based on experimental observations
- 2004
-
Ingår i: Journal of Analytical Atomic Spectrometry. - : Royal Society of Chemistry (RSC). - 0267-9477 .- 1364-5544. ; 19:9, s. 1217-1224
-
Tidskriftsartikel (refereegranskat)abstract
- In this work, several contributing factors to the observed mass bias in inductively coupled plasma mass spectrometry (ICP-MS) have been identified. Analyses of the isotopic compositions of B deposited on sampler and skimmer cones demonstrate enrichment of [1][0]B on the former and [1][1]B on the latter. Grounding the capacitive discharge system to enhance sensitivity also magnified the level of [1][1]B enrichment on the skimmer cone more than four-fold. This supersonic expansion of the ion beam behind the sampler is confirmed to be an important source of mass bias. Isotopic analyses of the Fe, Zn and Ti leached from used extraction lenses yielded a linear relationship between the levels of lighter isotope depletion and mass ratio. Although consistent with the space-charge effect, the fact that isotopically-heavy deposits were found demonstrates that the ion beam diverges into a relatively wide solid angle in the field-free region behind the skimmer. This severely impairs transmission of, in particular, the lighter isotopes. For a wide range of elements (Li, B, Fe, Ni, Cu, Sb, Ce, Hf and Re), the magnitude of the mass bias was found to be affected by the sample gas flow rate, as well as the distance between the sampler and the end of the torch, i.e., the sampling depth, employed in the Neptune multi-collector ICP-MS instrument. Mathematical analysis of the profiles of intensity variations as a function of these instrumental parameters revealed that the response peaks closer to the torch for the heavier isotopes of all studied elements. Owing to this spatial non-coincidence, tuning for maximum intensity on either isotope will result in sampling from a region where even slight plasma instabilities will be translated into substantial variations in mass bias. Therefore, in-plasma processes also contribute to the degree and temporal stability of mass bias. In light of these findings, recommendations for optimizing multi-collector ICP-MS with respect to obtaining the highest possible precision are presented.
|
|
| 2. |
- Andren, Henrik, et al.
(författare)
-
Variations in instrumental mass discrimination
- 2004
-
Ingår i: 2004 Winter Conference on Plasma Spectrochemistry. - Cambridge : Royal Society of Chemistry. ; , s. 329-
-
Konferensbidrag (refereegranskat)
|
|
| 3. |
- Appelblad, P.K., et al.
(författare)
-
Sources of uncertainty in isotope ratio measurements by inductively coupled plasma mass spectrometry
- 2001
-
Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 73:13, s. 2911-2919
-
Tidskriftsartikel (refereegranskat)abstract
- A model is presented describing the effects of dead time and mass bias correction factor uncertainties, flicker noise, and counting statistics on isotope ratio measurement precision using inductively coupled plasma mass spectrometry (ICPMS) with a single collector. Noise spectral analysis is exploited to enable estimation of the flicker noise parameters. For the instrument used, the flicker noise component exhibited a fairly weak frequency (f) dependence ( f -0.33±0.12), but was directly proportional to the total number of counts, Q. As white noise, determined by counting statistics, is given by Q0.5, the isotope ratio measurement uncertainties will actually cease to improve when Q exceeds a certain threshold. This would suggest that flicker noise could become the limiting factor for the precision with which isotope ratios can be determined by ICPMS. However, under most experimental conditions, uncertainties associated with mass discrimination and dead time correction factors are decisive. For ratios up to ~22 (115In/113In), optimum major isotope count rates are generally below 0.3 MHz, for which precision in the mass discrimination factor is limiting. The model derived could be used as a starting point for determining optimum conditions and understanding the limitations of single-collector ICPMS for precise isotope ratio measurements.
|
|
| 4. |
- Appelblad, Petra K., et al.
(författare)
-
The use of Pt guard electrode in inductively coupled plasma sectorÆeld mass spectrometry: advantages and limitations
- 2000
-
Ingår i: Journal of Analytical Atomic Spectrometry. - : Royal Society of Chemistry (RSC). - 0267-9477 .- 1364-5544. ; 15:4, s. 359-364
-
Tidskriftsartikel (refereegranskat)abstract
- Performance characteristics of inductively coupled plasma sector field mass spectrometry (ICP-SFMS) were studied with a Pt guard electrode (GE) inserted between the torch and load coil. The importance of the optimisation procedure and the matrix effects caused by a seawater matrix were assessed for 20 elements. Oxide and doubly charged ion formation was also investigated. Use of the GE allows a significant increase in ion transmission, by a factor of three to 20, thus resulting in improved instrumental detection limits. The improvement in sensitivity is mass dependent, with the highest gain observed for lower mass elements. Since, for the majority of analytical applications, actual detection limits depend upon blank levels rather on instrumental sensitivity, the most important factor for the determination of elements at ultra-trace levels is the degree of contamination of reagents and containers used. At the same time, significantly greater oxide formation is observed when operating the GE grounded rather than in the floating mode. For example, the BaO+/Ba+ ratio is ten to twelve times higher in the grounded mode. This calls for compromised instrumental parameters and the potential for severe spectral interferences from oxide species, which are often unresolved, even in high-resolution mode. Furthermore, non-spectral interferences from the seawater matrix appear to be more pronounced with the grounded GE, yielding a recovery of Ni of 55% compared with 93% in the floating GE mode. Hence all possible advantages and limitations of the use of the GE should be carefully considered prior to the analysis of real samples.
|
|
| 5. |
- Augustsson, Anna, et al.
(författare)
-
Managing health risks in urban agriculture: The effect of vegetable washing for reducing exposure to metal contaminants
- 2023
-
Ingår i: Science of the Total Environment. - : Elsevier B.V.. - 0048-9697 .- 1879-1026. ; 863
-
Tidskriftsartikel (refereegranskat)abstract
- A common, yet poorly evaluated, advice to remove contaminants from urban vegetables is to wash the produce before consumption. This study is based on 63 samples of chard, kale, lettuce and parsley that have grown near a heavily trafficked road in the third largest city in Sweden, with one portion of each sample being analysed without first being washed, and the other portion being subjected to common household washing. Concentrations of 71 elements were analysed by ICP-SFMS after a sample digestion that dissolves both the plant tissues and all potentially adhering particles. The results show that the washing effect, or the fraction removed upon washing, varies significantly between elements: from approximately 0 % for K to 68 % for the ∑REEs. Considering traditional metal contaminants, the efficiency decreased from Pb (on average 56 % lost) to Co (56 %) > Cr (55 %) > As (45 %) > Sb (35 %) > Ni (33 %) > Cu (13 %) > Zn (7 %) > Cd (7 %), and Ba (5 %). A clear negative correlation between the washing effect and the different elements' bioconcentration factors shows that the elements' accessibility for plant uptake is a key controlling factor for the degree to which they are removed upon washing. Based on the average washing efficiencies seen in this study, the average daily intake of Pb would increase by 130 % if vegetables are not washed prior to consumption. For the other contaminant metals this increase corresponds to 126 % (Co), 121 % (Cr), 82 % (As), 55 % (Sb), 50 % (Ni), 16 % (Cu), 8 % (Zn), 7 % (Cd) and 5 % (Ba). The advice to wash vegetables is therefore, for many elements, highly motivated for reducing exposure and health risks. For elements which are only slightly reduced when the vegetables are washed, however, advising should rather focus on reducing levels of contamination in the soil itself.
|
|
| 6. |
- Augustsson, Anna, et al.
(författare)
-
Trace and major elements in food supplements of different origin : implications for daily intake levels and health risks
- 2021
-
Ingår i: Toxicology reports. - : Elsevier. - 2214-7500. ; 8, s. 1067-1080
-
Tidskriftsartikel (refereegranskat)abstract
- As the use of food supplements increases, voices are being raised questioning the safety of these products. As a contribution to understanding the trace and major elemental composition of food supplements and their potential health risks, this study presents concentrations of 71 elements in 138 supplements, categorised into synthetic products and three groups of products with natural ingredients. Concentrations were converted into average daily doses (ADDs) and compared to tolerable daily intakes (TDIs). For elements where we found significant ADDs relative to the TDI a comparison was also made to the normal dietary intake. Our main findings are that: 1) Most elements display highly variable concentrations in food supplements; more so than in normal foodstuff; 2) For ten of the analysed elements some products rendered ADDs > 50% of the TDI. Half of the elements were essential (Fe, Mn, Se, Mo, Zn), and as such motivated in food supplements. The other half (As, Pb, Cd, Al, Ni) represent non-essential and highly toxic elements, where the occurrence in food supplements ought to be viewed as contamination. Although none of these toxic metals were declared on any product’s table of content, several products gave high ADDs - in several cases even exceeding the TDIs; 3) The risk of reaching high ADDs for the toxic elements is strongly associated with products that contain marine ingredients (e.g. algae, mussels etc), and to some degree products of terrestrial plant-based origin. The health of consumers would benefit if food regulatory frameworks were updated to better address the risks of food supplements occasionally being contaminated with different toxic metals, for example by setting maximum permissible concentrations for a longer list of elements.
|
|
| 7. |
- Augustsson, Anna, et al.
(författare)
-
Urban vegetable contamination - The role of adhering particles and their significance for human exposure
- 2023
-
Ingår i: Science of the Total Environment. - : Elsevier. - 0048-9697 .- 1879-1026. ; 900
-
Tidskriftsartikel (refereegranskat)abstract
- While urban-grown vegetables could help combat future food insecurity, the elevated levels of toxic metals in urban soils need to be met with measures that minimise transfer to crops. The study firstly examines soil/dust particle inclusion in leafy vegetables and its contribution to vegetable metals (As, Ba, Cd, Co, Cr, Cu, Ni, Pb, Sb, and Zn), using vegetable, soil and dust data from an open-field urban farm in southeastern Sweden. Titanium concentrations were used to assess soil/dust adherence. Results showed that vegetables contained 0.05–1.3 wt% of adhering particles (AP) even after washing. With 0.5 % AP, an adult with an average intake of vegetables could ingest approximately 100mg of particles per day, highlighting leafy vegetables as a major route for soil/dust ingestion. The presence of adhering particles also significantly contributed to the vegetable concentrations of As (9-20%), Co (17-20%), Pb (25-29%), and Cr (33-34%). Secondly, data from an indoor experiment was used to characterise root metal uptake from 20 urban soils from Sweden, Denmark, Spain, the UK, and the Czech Republic. Combining particle adherence and root uptake data, vegetable metal concentrations were calculated for the 20 urban soils to represent hypothetical field scenarios for these. Subsequently, average daily doses were assessed for vegetable consumers (adults and 3-6 year old children), distinguishing between doses from adhering particles and root uptake. Risks were evaluated from hazard quotients (HQs; average daily doses/tolerable intakes). Lead was found to pose the greatest risk, where particle ingestion often resulted in HQs>1 across all assessed scenarios. In summary, since washing was shown to remove only a portion of adhering metal-laden soil/dust particles from leafy vegetation, farmers and urban planners need to consider that measures to limit particle deposition are equally important as cultivating in uncontaminated soil.
|
|
| 8. |
- Axelsson, Mikael D., et al.
(författare)
-
High spatial resolution analysis of ferromanganese concretions by LA-ICP-MS
- 2002
-
Ingår i: Geochemical Transactions. - : Springer Science and Business Media LLC. - 1467-4866. ; 3:5, s. 40-47
-
Tidskriftsartikel (refereegranskat)abstract
- 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
|
|
| 9. |
- Bank, Michael S., et al.
(författare)
-
Multi-isotopic composition of brown crab (Cancer pagurus) and seafloor sediment from a mine tailing sea disposal impacted fjord ecosystem
- 2024
-
Ingår i: Journal of Hazardous Materials. - : Elsevier. - 0304-3894 .- 1873-3336. ; 471
-
Tidskriftsartikel (refereegranskat)abstract
- Here we studied accumulation of heavy metals in brown crab (Cancer pagurus) and seafloor sediment from Jøssingfjord, Norway during 2018 to evaluate long-term, legacy pollution effects of coastal mine tailing sea disposal activities. Nickel and copper sediment pollution in the mine tailing sea disposal area was classified as moderate and severe, respectively, under Norwegian environmental quality standards, and highlights the persistent hazard and legacy impacts of heavy metals in these impacted fjord ecosystems. Mercury, zinc, and arsenic had stronger affinities to brown crab muscle likely due to the presence of thiols, and availability of metal binding sites. Our multi-isotopic composition data showed that lead isotopes were the most useful source apportionment tool for this fjord. Overall, our study highlights the importance and value of measuring several different heavy metals and multiple isotopic signatures in different crab organs and seafloor sediment to comprehensively evaluate fjord pollution and kinetic uptake dynamics. Brown crabs were suitable eco-indicators of benthic ecosystem heavy metal pollution in a fjord ecosystem still experiencing short- and long-term physical and chemical impacts from coastal mining sea disposal activities.
|
|
| 10. |
- Baxter, Douglas, et al.
(författare)
-
Revised exponential model for mass bias correction using an internal standard for isotope abundance ratio measurements by multi-collector inductively coupled plasma mass spectrometry
- 2006
-
Ingår i: Journal of Analytical Atomic Spectrometry. - : Royal Society of Chemistry (RSC). - 0267-9477 .- 1364-5544. ; 21:4, s. 427-430
-
Tidskriftsartikel (refereegranskat)abstract
- An internal standard (IS) can be used to account for moderate, matrix-related shifts in mass bias using multi-collector inductively coupled plasma mass spectrometry through the empirical, linear relationship between measured isotope abundance ratios for different elements in ln-ln space. Unfortunately, erroneous mass bias corrected isotope abundance ratios may be returned by the model, requiring artificial adjustment of the true isotope abundance ratio of the IS. Although inadequate correction for peak tailing has been convincingly used to explain this problem, our analysis of the literature describing the development of the mass bias correction model using an IS reveals the presence of a source of systematic error. The origin of this error is purely mathematical and is eliminated in the revised model presented, in which mass bias corrected isotope abundance ratios are independent of the isotopic composition of the IS. An expression for computing the total combined uncertainty in the corrected ratio, incorporating contributions from the linear model, the isotopic reference material, and measurements of analyte element and IS in the sample, is also derived.
|
|
