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Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources
Applied Geochemistry xxx (2017) 1e8
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Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources Eiliv Steinnes*, Syverin Lierhagen Department of Chemistry, Norwegian University of Science and Technology, NO-7491 Trondheim, Norway
a r t i c l e i n f o
a b s t r a c t
Article history: Received 28 January 2017 Accepted 27 March 2017 Available online xxx
Results from a nationwide multi-element survey of natural surface soils in Norway were subjected to robust principal factor analysis. The results confirm and emphasize the importance of atmospheric deposition as a source of given elements. Transboundary atmospheric transport is a major source of elements such as Pb, As, Sb, and Cd to surface soils in the southern part of the country. Another dominant factor associated with atmospheric deposition is airborne substances of marine origin. The significance of marine input for major cations such as Naþ and Mgþþ is confirmed. Trace elements such as Se and Br are also clearly enriched in coastal areas. An additional effect of marine cations not previously demonstrated in the literature appears to be depletion of elements such as Mn, Ba, Eu in surface soils of the coastal regions. © 2017 Published by Elsevier Ltd.
1. Introduction The element composition of surface soils depends on the local mineral matter as well as interactions with the atmosphere and with biota. Plants growing in the soil may strongly influence the element composition by circulating elements between the soil and the green parts, as well as by capturing gaseous and particulate matter from the atmosphere. More over humic matter resulting from dead plant material as well as fungi living in the humus layer may play an important role in the turnover of some elements. In the boreal zone, where the soils are predominantly podzols, the interplay between the organic-rich surface soil and the atmosphere appears to be particularly important. In this paper results for 23 selected elements from a survey of natural surface soils in 2005, covering the entire mainland of Norway, are discussed with respect to their geographical distribution and the possible contribution from different sources of atmospheric deposition. Previous studies have shown long-range atmospheric transport from other parts of Europe to be a significant atmospheric source of trace elements such as Pb and Cd to the southern part of Norway (Steinnes et al., 1992, 2011), and the geographical distribution of these elements in the O horizon of natural soils has appeared to be similar to that of their atmospheric
deposition (Steinnes et al., 1997; 1997; Nygård et al., 2012), whereas their contents in the C horizon do not show a corresponding geographical distribution (Njåstad et al., 1994). The vertical distribution of the same elements in peat cores from ombrotrophic bogs (Steinnes, 1997) supports the view that atmospheric deposition since the industrial revolution in Europe is a main source of these elements to surface soils in the southern part of Norway, and a significant contributing factor for several elements all over the country. In Norway, being a country with a long coast line and large variations in annual precipitation (cfr. Fig. 1), influence from the marine environment may also considerably influence the amount and chemical composition of precipitation may also substantially influence the chemical composition of natural surface soils. Previous studies in Norway have shown that atmospheric transport from ocean to land is a significant source to soils in coastal areas not only for major marine cations such as Naþ and Mg2þ (Låg, 1968) but also for the halogens Cl, Br, and I (Låg and Steinnes, 1976) and even for Se (Låg and Steinnes, 1974, 1978). Results from the present work indicate that deposition of marine cations may also considerably influence the behaviour of some trace elements presumably derived from the local bedrock by depleting their content in the surface soil by cation exchange.
* Corresponding author. E-mail address: [email protected] (E. Steinnes). http://dx.doi.org/10.1016/j.apgeochem.2017.03.013 0883-2927/© 2017 Published by Elsevier Ltd.
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
Fig. 1. Geographical distribution of normal annual precipitation in Norway during the period 1971e2000. The colour ramp from light blue to deep purple indicates the transition from low (below 500 mm) to high (above 4000 mm) annual precipitation. Data and map are from the Norwegian Meteorological Institute. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
2. Materials and methods
2.2. Statistical treatment of data
2.1. Sampling
After a centered log-ratio (clr) transformation of the analytical data (Aitchison, 1986; Bacon-Shone, 2011; Pawlowsky-Glahn and Egozcue, 2016), robust principal factor analysis (in the following referred to as factor analysis) was carried out for the 23 selected elements with the aim to detect hidden multivariate structures in the data. The factor analysis was carried out following the procedures described in Filzmoser et al. (2009), who present an approach to perform PFA with robust methods for compositional data by clr transformation. All statistics and graphics were prepared by use of the R software (R Development Core Team, 2016), the R packages robCompositions (Templ et al., 2011) and StatDA (Filzmoser, 2015).
Samples of the soil O horizon were collected at 464 forest and heathland sites distributed all over Norway. A device developed at the Geological Survey of Norway, sampling a circular soil core of 10 cm diameter was used. The surface litter layer was removed and the upper 3 cm of the mainly organic surface soil was saved for analysis. At each site four sub-samples were obtained within an area of 5 5 m. The sub-samples were combined, dried at room temperature, homogenized, and sieved (2 mm nylon sieve). Weighed samples of about 0.5 g were partially decomposed in an autoclave with 20 mL 7 M nitric acid. After diluting 2 mL of the extract to 10 mL with high-purity water the resulting solutions were analysed for 64 elements by high-resolution ICPMS using a Thermo Finnigan instrument. After primary assessment of data 23 elements (Table 1) were selected for statistical treatment with respect to possible contribution from atmospheric sources. These elements were: Ca, Cd, Pb, S, Se, Yb, W (mass recorded in low resolution mode); Ba, Fe, La, Na, Mg, Mn, Rb, Sb, Sc, Sr, Zn (medium resolution mode) and As, Br, Eu, K (high resolution mode). Further details of the ICPMS analysis and analytical quality control are described in Nordløkken et al. (2015). A more comprehensive presentation of all obtained data will be published elsewhere.
3. Results Results from the factor analysis are shown in Table 1. The first four factors show distinct geographical distributions, and may be interpreted as follows: Factor 1 (explaining 33% of the total data variability) shows high negative loadings for elements characteristic of long-range transported aerosols to Norway (Berg et al., 1994). These elements are, as ranged by decreasing values of factor loadings: Pb, Sb, As, Bi, W, Cd. Common for these elements is that they may be volatilized in high-
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
Table 1 Factor loadings from a principal factor analysis of 23 elements. Total cumulative variance explained (TVE) by each of the five factors is shown at the bottom of the table. Element
F1
F2
F3
F4
F5
S Zn Cd Se Sb K W Pb Ca Br Na Sr Rb Eu As Ba Mg Mn La Yb Al Fe Sc TVE (%)
0.45 0.16 0.48 0.25 0.87 0.64 0.55 0.90 0.71 0.41 0.41 0.80 0.01 0.19 0.78 0.17 0.80 0.16 0.09 0.15 0.03 0.06 0.13 32.7
0.70 0.58 0.51 0.40 0.40 0.39 0.34 0.27 0.26 0.18 0.14 0.14 0.11 0.05 0.03 0.00 0.02 0.06 0.66 0.75 0.85 0.91 0.93 54.9
0.16 0.15 0.11 0.61 0.03 0.13 0.14 0.01 0.07 0.74 0.72 0.10 0.50 0.91 0.12 0.94 0.42 0.34 0.12 0.07 0.14 0.02 0.07 74.1
0.18 0.15 0.35 0.43 0.15 0.42 0.19 0.22 0.11 0.39 0.11 0.32 0.47 0.06 0.35 0.07 0.15 0.75 0.05 0.04 0.04 0.03 0.06 79.3
0.03 0.02 0.01 0.17 0.09 0.03 0.02 0.05 0.14 0.15 0.10 0.10 0.24 0.08 0.05 0.06 0.17 0.11 0.59 0.51 0.16 0.05 0.03 82.2
Fig. 2. Geographical distribution of Factor 1 scores and concentration ranges of three elements positively associated with this factor: As, Pb, Cd.
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
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temperature processes, e.g. as an oxide or a halide, in the case of W probably as the trioxide, and be preferentially attached to the smaller-size aerosols available for long-range atmospheric transport (Gladney et al., 1976; Greenberg et al., 1978). The geographical distribution, with high values in areas about 0e100 km from the southern coast, is consistent with trends observed in atmospheric deposition studies in Norway (Schaug et al., 1990; Steinnes et al., 2011) as well as with distributions shown for this group of elements in previous soil surveys (Steinnes et al., 1997; Njåstad et al., 1994; Nygård et al., 2012). The geographical distributions of Factor 1 and the associated elements As, Pb, and Cd are shown in Fig. 2. Factor 2 (explaining 22% of the total data variability) is obviously geogenic, showing very high negative loadings for crustal major elements such as Al and Fe as well as for some trace elements frequently associated with this factor in environmental studies (Sc, La, Yb). The geographical distribution of Factor 1 is shown in Fig. 3 along with corresponding maps for Fe, Al, and Sc. This factor does not show a distinct geographical pattern over the country, which means that it probably does not tell much about geochemical variability in the underlying bedrock. Factor 2 shows a negative correlation with the soil sample weight, which may indicate that it mainly reflects different contents of mineral matter among the
samples. Factor 3 (explaining 19% of the total data variability) shows highly positive loading values for Ba and Rb and negative values for Br, Na, and Se. The latter combination of elements obviously points to the marine environment as a main source, and the association of Se with this group is a confirmation of previous studies of surface soils in Norway (Låg and Steinnes, 1974, 1978) showing a negative correlation of surface soil Se with increasing distance from the Atlantic coast. The geographical distribution of Factor 3 is shown in Fig. 4 along with distribution maps for Na, Br, and Se. The distribution of Factor 3 shows a typical coast - inland gradient with high values in coastal areas and particularly low values in the interior of southern Norway, where precipitation is limited and contains very low levels of marine components. Some elements appearing in Factor 3 with positive sign are present in surface soils as monovalent and divalent cations, and may have been leached from the surface soil horizon by exchange with cations of oceanic origin (e.g. Na, Mg). The fact that Eu appears in this factor indicates that it, as different from the other REE, may be present in the divalent state in the soil humus layer. Separation of Eu from the other lanthanoides after chemical reduction is a well-known observation in geochemistry. Examples of
Fig. 3. Geographical distribution of Factor 2 scores and concentration ranges of three elements positively associated with this factor: Al, Fe, Sc.
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
E. Steinnes, S. Lierhagen / Applied Geochemistry xxx (2017) 1e8
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Fig. 4. Geographical distribution of Factor 3 scores and concentration ranges of three elements positively associated with this factor: Na, Br, Se.
geographical distributions for elements exhibiting this type of behaviour are seen in Fig. 5 in the case of Eu, Ba, and Rb. The observations related to Factor 3 confirm similar geographical trends apparent in samples from a corresponding soil survey in Norway based on sampling in 1995 (Nygård et al., 2012). Factor 4 (explaining 5% of the total data variability) contains the plant nutrient elements Mn and K, and Rb behaving similar with K with respect to plant uptake. This may indicate an association of this factor with plant uptake and productivity. Factor scores are higher in coastal areas in the middle and northern part of Norway than in southern and inland areas. The relations of different elements with the marine environment are illustrated in Fig. 6, where the distributions of selected groups of elements relative to distance from the coastline are plotted as notched boxplots. If the notches of two plots do not overlap, it is considered as “strong evidence” that the two medians differ significantly. It is obvious from the data that elements such as Na, Mg, Br, and Se are appreciably enriched in surface soils in the coastal zone, whereas Ba, Rb, and Eu are depleted. Major crustal elements such as Fe and Ca show no appreciable difference between the coast and inland areas.
4. Discussion While it seems to be a common belief among geoscientists that the element composition of natural surface soils is mainly determined by the local geochemistry, either by particles or “plant pumping” from the underlying mineral soil (Reimann et al., 2007, 2015a) the above results indicate that in Norway abundances of many, if not most, elements in the humic surface horizon are clearly affected by atmospheric chemistry and only moderately influenced by the geochemistry of the subsoil. A lack of obvious correlation between element composition in the subsoil and the corresponding surface soil was also observed by Reimann et al. (2015b) in a recent detailed study of corresponding O and C horizons in natural soils in Nord-Trøndelag county, middle Norway, where element compositions for corresponding samples from the O and C horizons showed limited interconnection. In a recent statistical study results from surveys in Norway of trace elements in terrestrial moss, representing well the atmospheric deposition of many elements, and contents of the same elements in natural surface soils, were compared with data for geographical distribution in Norway of ecological land classes (Nickel et al., 2015). It was shown that the
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
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Fig. 5. Geographical distribution of Factor 4 scores and concentration ranges of three elements negatively associated with this factor: Ba, Rb, Eu.
geographical distribution of Pb and Cd in the surface soil correlated strongly with their atmospheric deposition rates, whereas no appreciable connection with the distribution of land classes was evident on the national scale. In the case of Pb, studies of stable lead isotopes in moss samples, representing atmospheric deposition (Steinnes et al., 2005a), and in soil profiles (Donisa et al., 2005), provide evidence that even in the far north of Norway the relatively low present Pb content in the O horizon is mainly from atmospheric deposition (Steinnes et al., 2005b). The marked contamination of the O horizon with metals from long-range atmospheric transport of pollutants is not a unique finding for Norway. Already more than 30 years ago Reiners et al. (1975) observed elevated contents of Pb in surface soils in remote areas of New England ascribing it to atmospheric transport of pollutants. This influence of long-range transport of atmospheric pollutants has been further documented and discussed in more recent studies in the same region (e.g. Friedland et al., 1984; Richardson et al., 2014; Richardson et al., 2015). In Sweden, which was also until recently substantially exposed to long-range transport of pollutants from other parts of Europe, similar trends as observed in Norway have been reported for temporal and spatial trends of metal deposition (Rühling and Tyler, 2004).
Correspondingly, the O horizon of natural surface soils in Sweden shows substantially higher concentrations of these elements in the south of the country than in the north (Aastrup et al., 1995). Studies of stable lead isotopes in pristine forest soils and lake sediments (Bindler et al., 1999; Br€ annvall et al., 2001; Bindler, 2011) leave little doubt that air pollution and not natural local geological sources is the overriding source of excess Pb in natural surface soil in Scandinavia. The strong influence from the marine environment on the geographical distribution of elements in surface soils indicated from previous studies in Norway is further substantiated by the results presented in this paper. However, there appears to be a lack of closely corresponding studies from coastal areas elsewhere in the world. Many papers deal with related aspects, such as biogenic release of chemical substances from the ocean (Liss et al., 1997; Amouroux et al., 2001), concentrations of marine ions in air (Tørseth et al., 1999) and their deposition on land (Gustafsson and n, 1996), their impact on soil acidification (Kreutzer et al., Franze 1998) or their influence on surface water chemistry in the catchment after deposition (Reynolds et al., 1997; Evans et al., 2001). The research corresponding most closely to the present work appears to be from Hawaii, discussing geographically varying marine
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
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Fig. 6. Boxplots showing concentration ranges of selected groups of elements among coastal and inland sites, respectively (cfr. text).
contributions to the contents of strontium (Chadwick et al., 2009) and strontium (Bern et al., 2015) in surface soils. Corresponding studies from coastal regions in other parts of the world would seem desirable. The main conclusion from the present work, supported by other recent studies in Norway, is that the element composition of organic-rich surface soils depends more on atmospheric supply and substantially less on the composition of the underlying mineral soil than generally assumed in the past. Acknowledgement The authors are indebted to Ola Anfin Eggen for help with the figures and the statistical analysis. References Aastrup, M., Iverfeldt, Å., Bringmark, L., Kvarn€ as, H., Thunholm, B., Hultberg, H., 1995. Monitoring of heavy metals in protected forest catchments in Sweden. Water, Air, Soil Pollut. 85, 755e760. Aitchison, J., 1986. The Statistical Analysis of Compositional Data. Chapman & Hall, London, 416 pp. Amouroux, D., Liss, P.S., Tessier, E., Hamren-Larsson, M., Donard, O.F.X., 2001. Role of oceans as biogenic sources of selenium. Earth Planet. Sci. Lett. 189, 277e283. Bacon-Shone, J., 2011. A short history of compositional data analysis. In: Pawlowsky-Glahn, V., Buccanti, A. (Eds.), Compositional Data Analysis: Theory and Applications, first ed. John Wiley & Sons, Ltd, Chichester (UK), pp. 1e11. Berg, T., Røyset, O., Steinnes, E., 1994. Trace elements in atmospheric precipitation at
7
Norwegian background stations (1989-1990) measured by ICP-MS. Atmos. Environ. 28, 3519e3536. Bern, C.R., Chadwick, O.A., Kendall, C., Pribil, M.J., 2015. Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems. Sci. Total Environ. 514, 250e260. Bindler, R., 2011. Contaminated lead environments of man: reviewing the lead isotopic evidence in sediments, peat, and soils for the temporal and spatial patterns of atmospheric lead pollution in Sweden. Environ. Geochem. Health 33, 311e329. €nnvall, M.L., Renberg, I., Emteryd, O., Grip, H., 1999. Natural lead Bindler, R., Bra concentrations in pristine boreal forest soils and past pollution trends: a reference for critical load models. Environ. Sci. Technol. 33, 3362e3367. Br€ annvall, M.L., Kurrkio, H., Bindler, R., Emteryd, O., Renberg, I., 2001. The role of pollution versus natural geological sources for lead enrichment in recent lake sediments and surface forest soils. Environ. Geol. 40, 1057e1065. Chadwick, O.A., Derry, L.A., Bern, C.R., Vitousek, P.M., 2009. Changing sources of strontium to soils and ecosystems across the Hawaiian Islands. Chem. Geol. 267, 64e76. Donisa, C., Steinnes, E., Sjøbakk, T.E., 2005. Nitric-acid soluble fractions of 21 elements in Norwegian podzols: factors affecting regional differences in vertical distribution. Appl. Geochem 20, 1258e1267. Evans, C.D., Monteith, D.T., Harriman, R., 2001. Long-term variability in the deposition of marine ions in the UK Acid Waters Monitoring Network: impacts on surface water chemistry and significance for trend determination. Sci. Total Environ. 265, 115e129. Filzmoser, P., Hron, K., Reimann, C., Garret, R.G., 2009. Robust factor analysis for compositional data. Comput. Geosci. 35, 1854e1861. Filzmoser, P., 2015. StatDA: Statistical Analysis for Environmental Data. R Package Version 1.6.9. http://CRAN.R-project.org/package¼StatDA. Friedland, A.J., Johnson, A.H., Siccama, T.G., 1984. Trace metal content of the forest floor in the Green mountains of Vermont: spatial and temporal patterns. Water, Air, Soil Pollut. 21, 161e170. Gladney, E.S., Small, J.A., Gordon, G.E., Zoller, W.A., 1976. Composition and size distribution of in-stack particulate material at a coal-fired power plant. Atmos. Environ. 10, 1071e1077. Greenberg, R.R., Zoller, W.H., Gordon, G.E., 1978. Composition and size distribution of particles released in refuse incineration. Environ. Sci. Technol. 12, 566e573. n, L.G., 1996. Dry deposition and concentration of marine Gustafsson, M.E.R., Franze aerosols in a coastal area, SW Sweden. Atmos. Environ. 30, 977e989. Kreutzer, K., et al., 1998. Atmospheric deposition and soil acidification in five coniferous forest ecosystems: a comparison of the control plots of the EXMAN sites. For. Ecol. Manag. 101, 125e142. Liss, P.S., Hatton, A.D., Gill, M., Nightingale, P.D., Turner, S., 1997. Marine sulphur emissions. Phil. Trans. R. Soc. Lond. B 352, 159e169. Låg, J., 1968. Relationships between the chemical composition of the precipitation and the content of exchangeable ions in the humus layer of natural soils. Acta Agric. Scand. 18, 148e152. Låg, J., Steinnes, E., 1974. Soil selenium in relation to precipitation. Ambio 3, 237e238. Låg, J., Steinnes, E., 1976. Regional distribution of halogens in Norwegian forest soils. Geoderma 16, 317e325. Låg, J., Steinnes, E., 1978. Regional distribution of selenium and arsenic in humus layers of Norwegian forest soils. Geoderma 20, 3e14. €der, W., Steinnes, E., Uggerud, H.T., 2015. Nickel, S., Hertel, A., Pesch, R., Schro Correlating concentrations of heavy metals in atmospheric deposition with respective accumulation in moss and natural surface soil for ecological land classes in Norway between 1990 and 2010. Environ. Sci. Pollut. Res. 22, 8488e8498. Njåstad, O., Steinnes, E., Bølviken, B., Ødegård, M., 1994. Nationwide Mapping of Element Composition of Natural Soil: Results from Samples Collected in 1977 and 1985 Obtained by Emission Spectrometry. Geological Survey of Norway, Trondheim. Report no. 94.027, 114 pp. (in Norwegian). Nordløkken, M., Berg, T., Flaten, T.P., Steinnes, E., 2015. Essential and non-essential elements in natural vegetation in Southern Norway: contribution from different sources. Sci. Total Environ. 502, 391e399. Nygård, T., Steinnes, E., Røyset, O., 2012. Distribution of 32 elements in organic surface soils: contributions from atmospheric transport of pollutants and natural sources. Water, Air, Soil Pollut. 223, 699e713. Pawlowsky-Glahn, V., Egozcue, J.J., 2016. Spatial analysis of compositional data: a historical review. J. Geochem. Explor. 164, 28e32. R Development Core Team, 2016. R: a Language and Environment for Statistical Computing. R Foundation for Statistical Computing, Vienna, Austria. URL. http:// www.R-project.org/. Reimann, C., Arnoldussen, A., Englmayer, P., Finne, T.E., Garrett, R.G., Koller, F., Nordgulen, Ø., 2007. Element concentrations and variation along a 120-km transect in southern Norway e anthropogenic vs. geoogenic vs. biogenic element sources and cycles. Appl. Geochem 22, 851e871. Reimann, C., Englmaier, P., Fabian, K., Gough, L., Lamothe, P., Smith, D., 2015a. Plant biogeochemical plant-soil interaction: variable element composition in leaves of four plant species collected along a south-north gradient at the southern tip of Norway. Sci. Total Environ. 506e507, 480e495. Reimann, C., Fabian, K., Schilling, J., Roberts, D., Englmaier, P., 2015b. A strong enrichment of potentially toxic elements (PTEs) in Nord-Trøndelag (central Norway) forest soil. Sci. Total Environ. 536, 130e141. Reiners, W.A., Marks, R.H., Vitousek, P.M., 1975. Heavy metals in subalpine and
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
8
E. Steinnes, S. Lierhagen / Applied Geochemistry xxx (2017) 1e8
alpine soils of New Hampshire. Oikos 26, 264e275. Reynolds, B., Fowler, D., Smith, R.I., Hall, J.R., 1997. Atmospheric inputs and catchment solute fluxes for major ions in five Welsh upland catchments. J. Hydrol. 194, 305e329. Richardson, J.B., Friedland, A.J., Kaste, J.M., Jackson, B.P., 2014. Forest floor lead changes from 1980 to 2011 and subsequent accumulation in the mineral soil across the Northeastern United States. J. Environ. Qual. 43, 926e935. Richardson, J.B., Donaldson, E.C., Kaste, J.M., Friedland, A.J., 2015. Forest floor lead, copper and zinc concentrations across the Northeastern United States: synthesizing spatial and temporal responses. Sci. Total Environ. 505, 851e859. Rühling, Å., Tyler, G., 2004. Changes in the atmospheric deposition of minor and rare elements between 1975 and 2000 in south Sweden, as measured by moss analysis. Environ. Pollut. 2004 (131), 417e423. Schaug, J., Rambæk, J.P., Steinnes, E., Henry, R.C., 1990. Multivariate analysis of trace element data from moss samples used to monitor atmospheric deposition. Atmos. Environ. 24A, 2625e2631. Steinnes, E., 1997. Trace element profiles in ombrogenous peat cores from Norway: evidence of long range atmospheric transport. Water, Air, Soil Pollut. 100, 405e413. Steinnes, E., Rambæk, J.P., Hanssen, J.E., 1992. Large scale multi-element survey of
atmospheric deposition using naturally growing moss as a biomonitor. Chemosphere 25, 735e752. Steinnes, E., Allen, R.O., Petersen, H.M., Rambæk, J.P., Varskog, P., 1997. Evidence of large-scale heavy-metal contamination of natural surface soils in Norway from long-range atmospheric transport. Sci. Total Environ. 205, 255e266. Steinnes, E., Åberg, G., Hjelmseth, H., 2005a. Atmospheric deposition of lead in Norway: spatial and temporal variation in isotopic composition. Sci. Total Environ. 336, 105e117. Steinnes, E., Sjøbakk, T.E., Donisa, C., Br€ annvall, M.L., 2005b. Quantification of pollutant lead in forest soils. Soil Sci. Soc. amer. J. 69, 1399e1404. Steinnes, E., Berg, T., Uggerud, H.T., 2011. Three decades of atmospheric deposition in Norway as evident from analysis of moss samples. Sci. Total Environ. 412e413, 351e358. Templ, M., Hron, K., Filzmoser, P., 2011. robCompositions: an R-package for robust statistical analysis of compositional data. In: Pawlowsky-Glahn, V., Buccianti, A. (Eds.), Compos. Data Anal. Theory Appl. John Wiley & Sons, Chichester (UK), pp. 341e355. Tørseth, K., Hanssen, J.E., Semb, A., 1999. Temporal and spatial variations of airborne Mg, Cl, Na, Ca, and K in rural areas of Norway. Sci. Total Environ. 234, 75e85.
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Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources Eiliv Steinnes*, Syverin Lierhagen Department of Chemistry, Norwegian University of Science and Technology, NO-7491 Trondheim, Norway
a r t i c l e i n f o
a b s t r a c t
Article history: Received 28 January 2017 Accepted 27 March 2017 Available online xxx
Results from a nationwide multi-element survey of natural surface soils in Norway were subjected to robust principal factor analysis. The results confirm and emphasize the importance of atmospheric deposition as a source of given elements. Transboundary atmospheric transport is a major source of elements such as Pb, As, Sb, and Cd to surface soils in the southern part of the country. Another dominant factor associated with atmospheric deposition is airborne substances of marine origin. The significance of marine input for major cations such as Naþ and Mgþþ is confirmed. Trace elements such as Se and Br are also clearly enriched in coastal areas. An additional effect of marine cations not previously demonstrated in the literature appears to be depletion of elements such as Mn, Ba, Eu in surface soils of the coastal regions. © 2017 Published by Elsevier Ltd.
1. Introduction The element composition of surface soils depends on the local mineral matter as well as interactions with the atmosphere and with biota. Plants growing in the soil may strongly influence the element composition by circulating elements between the soil and the green parts, as well as by capturing gaseous and particulate matter from the atmosphere. More over humic matter resulting from dead plant material as well as fungi living in the humus layer may play an important role in the turnover of some elements. In the boreal zone, where the soils are predominantly podzols, the interplay between the organic-rich surface soil and the atmosphere appears to be particularly important. In this paper results for 23 selected elements from a survey of natural surface soils in 2005, covering the entire mainland of Norway, are discussed with respect to their geographical distribution and the possible contribution from different sources of atmospheric deposition. Previous studies have shown long-range atmospheric transport from other parts of Europe to be a significant atmospheric source of trace elements such as Pb and Cd to the southern part of Norway (Steinnes et al., 1992, 2011), and the geographical distribution of these elements in the O horizon of natural soils has appeared to be similar to that of their atmospheric
deposition (Steinnes et al., 1997; 1997; Nygård et al., 2012), whereas their contents in the C horizon do not show a corresponding geographical distribution (Njåstad et al., 1994). The vertical distribution of the same elements in peat cores from ombrotrophic bogs (Steinnes, 1997) supports the view that atmospheric deposition since the industrial revolution in Europe is a main source of these elements to surface soils in the southern part of Norway, and a significant contributing factor for several elements all over the country. In Norway, being a country with a long coast line and large variations in annual precipitation (cfr. Fig. 1), influence from the marine environment may also considerably influence the amount and chemical composition of precipitation may also substantially influence the chemical composition of natural surface soils. Previous studies in Norway have shown that atmospheric transport from ocean to land is a significant source to soils in coastal areas not only for major marine cations such as Naþ and Mg2þ (Låg, 1968) but also for the halogens Cl, Br, and I (Låg and Steinnes, 1976) and even for Se (Låg and Steinnes, 1974, 1978). Results from the present work indicate that deposition of marine cations may also considerably influence the behaviour of some trace elements presumably derived from the local bedrock by depleting their content in the surface soil by cation exchange.
* Corresponding author. E-mail address: [email protected] (E. Steinnes). http://dx.doi.org/10.1016/j.apgeochem.2017.03.013 0883-2927/© 2017 Published by Elsevier Ltd.
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
Fig. 1. Geographical distribution of normal annual precipitation in Norway during the period 1971e2000. The colour ramp from light blue to deep purple indicates the transition from low (below 500 mm) to high (above 4000 mm) annual precipitation. Data and map are from the Norwegian Meteorological Institute. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
2. Materials and methods
2.2. Statistical treatment of data
2.1. Sampling
After a centered log-ratio (clr) transformation of the analytical data (Aitchison, 1986; Bacon-Shone, 2011; Pawlowsky-Glahn and Egozcue, 2016), robust principal factor analysis (in the following referred to as factor analysis) was carried out for the 23 selected elements with the aim to detect hidden multivariate structures in the data. The factor analysis was carried out following the procedures described in Filzmoser et al. (2009), who present an approach to perform PFA with robust methods for compositional data by clr transformation. All statistics and graphics were prepared by use of the R software (R Development Core Team, 2016), the R packages robCompositions (Templ et al., 2011) and StatDA (Filzmoser, 2015).
Samples of the soil O horizon were collected at 464 forest and heathland sites distributed all over Norway. A device developed at the Geological Survey of Norway, sampling a circular soil core of 10 cm diameter was used. The surface litter layer was removed and the upper 3 cm of the mainly organic surface soil was saved for analysis. At each site four sub-samples were obtained within an area of 5 5 m. The sub-samples were combined, dried at room temperature, homogenized, and sieved (2 mm nylon sieve). Weighed samples of about 0.5 g were partially decomposed in an autoclave with 20 mL 7 M nitric acid. After diluting 2 mL of the extract to 10 mL with high-purity water the resulting solutions were analysed for 64 elements by high-resolution ICPMS using a Thermo Finnigan instrument. After primary assessment of data 23 elements (Table 1) were selected for statistical treatment with respect to possible contribution from atmospheric sources. These elements were: Ca, Cd, Pb, S, Se, Yb, W (mass recorded in low resolution mode); Ba, Fe, La, Na, Mg, Mn, Rb, Sb, Sc, Sr, Zn (medium resolution mode) and As, Br, Eu, K (high resolution mode). Further details of the ICPMS analysis and analytical quality control are described in Nordløkken et al. (2015). A more comprehensive presentation of all obtained data will be published elsewhere.
3. Results Results from the factor analysis are shown in Table 1. The first four factors show distinct geographical distributions, and may be interpreted as follows: Factor 1 (explaining 33% of the total data variability) shows high negative loadings for elements characteristic of long-range transported aerosols to Norway (Berg et al., 1994). These elements are, as ranged by decreasing values of factor loadings: Pb, Sb, As, Bi, W, Cd. Common for these elements is that they may be volatilized in high-
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
Table 1 Factor loadings from a principal factor analysis of 23 elements. Total cumulative variance explained (TVE) by each of the five factors is shown at the bottom of the table. Element
F1
F2
F3
F4
F5
S Zn Cd Se Sb K W Pb Ca Br Na Sr Rb Eu As Ba Mg Mn La Yb Al Fe Sc TVE (%)
0.45 0.16 0.48 0.25 0.87 0.64 0.55 0.90 0.71 0.41 0.41 0.80 0.01 0.19 0.78 0.17 0.80 0.16 0.09 0.15 0.03 0.06 0.13 32.7
0.70 0.58 0.51 0.40 0.40 0.39 0.34 0.27 0.26 0.18 0.14 0.14 0.11 0.05 0.03 0.00 0.02 0.06 0.66 0.75 0.85 0.91 0.93 54.9
0.16 0.15 0.11 0.61 0.03 0.13 0.14 0.01 0.07 0.74 0.72 0.10 0.50 0.91 0.12 0.94 0.42 0.34 0.12 0.07 0.14 0.02 0.07 74.1
0.18 0.15 0.35 0.43 0.15 0.42 0.19 0.22 0.11 0.39 0.11 0.32 0.47 0.06 0.35 0.07 0.15 0.75 0.05 0.04 0.04 0.03 0.06 79.3
0.03 0.02 0.01 0.17 0.09 0.03 0.02 0.05 0.14 0.15 0.10 0.10 0.24 0.08 0.05 0.06 0.17 0.11 0.59 0.51 0.16 0.05 0.03 82.2
Fig. 2. Geographical distribution of Factor 1 scores and concentration ranges of three elements positively associated with this factor: As, Pb, Cd.
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temperature processes, e.g. as an oxide or a halide, in the case of W probably as the trioxide, and be preferentially attached to the smaller-size aerosols available for long-range atmospheric transport (Gladney et al., 1976; Greenberg et al., 1978). The geographical distribution, with high values in areas about 0e100 km from the southern coast, is consistent with trends observed in atmospheric deposition studies in Norway (Schaug et al., 1990; Steinnes et al., 2011) as well as with distributions shown for this group of elements in previous soil surveys (Steinnes et al., 1997; Njåstad et al., 1994; Nygård et al., 2012). The geographical distributions of Factor 1 and the associated elements As, Pb, and Cd are shown in Fig. 2. Factor 2 (explaining 22% of the total data variability) is obviously geogenic, showing very high negative loadings for crustal major elements such as Al and Fe as well as for some trace elements frequently associated with this factor in environmental studies (Sc, La, Yb). The geographical distribution of Factor 1 is shown in Fig. 3 along with corresponding maps for Fe, Al, and Sc. This factor does not show a distinct geographical pattern over the country, which means that it probably does not tell much about geochemical variability in the underlying bedrock. Factor 2 shows a negative correlation with the soil sample weight, which may indicate that it mainly reflects different contents of mineral matter among the
samples. Factor 3 (explaining 19% of the total data variability) shows highly positive loading values for Ba and Rb and negative values for Br, Na, and Se. The latter combination of elements obviously points to the marine environment as a main source, and the association of Se with this group is a confirmation of previous studies of surface soils in Norway (Låg and Steinnes, 1974, 1978) showing a negative correlation of surface soil Se with increasing distance from the Atlantic coast. The geographical distribution of Factor 3 is shown in Fig. 4 along with distribution maps for Na, Br, and Se. The distribution of Factor 3 shows a typical coast - inland gradient with high values in coastal areas and particularly low values in the interior of southern Norway, where precipitation is limited and contains very low levels of marine components. Some elements appearing in Factor 3 with positive sign are present in surface soils as monovalent and divalent cations, and may have been leached from the surface soil horizon by exchange with cations of oceanic origin (e.g. Na, Mg). The fact that Eu appears in this factor indicates that it, as different from the other REE, may be present in the divalent state in the soil humus layer. Separation of Eu from the other lanthanoides after chemical reduction is a well-known observation in geochemistry. Examples of
Fig. 3. Geographical distribution of Factor 2 scores and concentration ranges of three elements positively associated with this factor: Al, Fe, Sc.
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
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Fig. 4. Geographical distribution of Factor 3 scores and concentration ranges of three elements positively associated with this factor: Na, Br, Se.
geographical distributions for elements exhibiting this type of behaviour are seen in Fig. 5 in the case of Eu, Ba, and Rb. The observations related to Factor 3 confirm similar geographical trends apparent in samples from a corresponding soil survey in Norway based on sampling in 1995 (Nygård et al., 2012). Factor 4 (explaining 5% of the total data variability) contains the plant nutrient elements Mn and K, and Rb behaving similar with K with respect to plant uptake. This may indicate an association of this factor with plant uptake and productivity. Factor scores are higher in coastal areas in the middle and northern part of Norway than in southern and inland areas. The relations of different elements with the marine environment are illustrated in Fig. 6, where the distributions of selected groups of elements relative to distance from the coastline are plotted as notched boxplots. If the notches of two plots do not overlap, it is considered as “strong evidence” that the two medians differ significantly. It is obvious from the data that elements such as Na, Mg, Br, and Se are appreciably enriched in surface soils in the coastal zone, whereas Ba, Rb, and Eu are depleted. Major crustal elements such as Fe and Ca show no appreciable difference between the coast and inland areas.
4. Discussion While it seems to be a common belief among geoscientists that the element composition of natural surface soils is mainly determined by the local geochemistry, either by particles or “plant pumping” from the underlying mineral soil (Reimann et al., 2007, 2015a) the above results indicate that in Norway abundances of many, if not most, elements in the humic surface horizon are clearly affected by atmospheric chemistry and only moderately influenced by the geochemistry of the subsoil. A lack of obvious correlation between element composition in the subsoil and the corresponding surface soil was also observed by Reimann et al. (2015b) in a recent detailed study of corresponding O and C horizons in natural soils in Nord-Trøndelag county, middle Norway, where element compositions for corresponding samples from the O and C horizons showed limited interconnection. In a recent statistical study results from surveys in Norway of trace elements in terrestrial moss, representing well the atmospheric deposition of many elements, and contents of the same elements in natural surface soils, were compared with data for geographical distribution in Norway of ecological land classes (Nickel et al., 2015). It was shown that the
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
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Fig. 5. Geographical distribution of Factor 4 scores and concentration ranges of three elements negatively associated with this factor: Ba, Rb, Eu.
geographical distribution of Pb and Cd in the surface soil correlated strongly with their atmospheric deposition rates, whereas no appreciable connection with the distribution of land classes was evident on the national scale. In the case of Pb, studies of stable lead isotopes in moss samples, representing atmospheric deposition (Steinnes et al., 2005a), and in soil profiles (Donisa et al., 2005), provide evidence that even in the far north of Norway the relatively low present Pb content in the O horizon is mainly from atmospheric deposition (Steinnes et al., 2005b). The marked contamination of the O horizon with metals from long-range atmospheric transport of pollutants is not a unique finding for Norway. Already more than 30 years ago Reiners et al. (1975) observed elevated contents of Pb in surface soils in remote areas of New England ascribing it to atmospheric transport of pollutants. This influence of long-range transport of atmospheric pollutants has been further documented and discussed in more recent studies in the same region (e.g. Friedland et al., 1984; Richardson et al., 2014; Richardson et al., 2015). In Sweden, which was also until recently substantially exposed to long-range transport of pollutants from other parts of Europe, similar trends as observed in Norway have been reported for temporal and spatial trends of metal deposition (Rühling and Tyler, 2004).
Correspondingly, the O horizon of natural surface soils in Sweden shows substantially higher concentrations of these elements in the south of the country than in the north (Aastrup et al., 1995). Studies of stable lead isotopes in pristine forest soils and lake sediments (Bindler et al., 1999; Br€ annvall et al., 2001; Bindler, 2011) leave little doubt that air pollution and not natural local geological sources is the overriding source of excess Pb in natural surface soil in Scandinavia. The strong influence from the marine environment on the geographical distribution of elements in surface soils indicated from previous studies in Norway is further substantiated by the results presented in this paper. However, there appears to be a lack of closely corresponding studies from coastal areas elsewhere in the world. Many papers deal with related aspects, such as biogenic release of chemical substances from the ocean (Liss et al., 1997; Amouroux et al., 2001), concentrations of marine ions in air (Tørseth et al., 1999) and their deposition on land (Gustafsson and n, 1996), their impact on soil acidification (Kreutzer et al., Franze 1998) or their influence on surface water chemistry in the catchment after deposition (Reynolds et al., 1997; Evans et al., 2001). The research corresponding most closely to the present work appears to be from Hawaii, discussing geographically varying marine
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
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Fig. 6. Boxplots showing concentration ranges of selected groups of elements among coastal and inland sites, respectively (cfr. text).
contributions to the contents of strontium (Chadwick et al., 2009) and strontium (Bern et al., 2015) in surface soils. Corresponding studies from coastal regions in other parts of the world would seem desirable. The main conclusion from the present work, supported by other recent studies in Norway, is that the element composition of organic-rich surface soils depends more on atmospheric supply and substantially less on the composition of the underlying mineral soil than generally assumed in the past. Acknowledgement The authors are indebted to Ola Anfin Eggen for help with the figures and the statistical analysis. References Aastrup, M., Iverfeldt, Å., Bringmark, L., Kvarn€ as, H., Thunholm, B., Hultberg, H., 1995. Monitoring of heavy metals in protected forest catchments in Sweden. Water, Air, Soil Pollut. 85, 755e760. Aitchison, J., 1986. The Statistical Analysis of Compositional Data. Chapman & Hall, London, 416 pp. Amouroux, D., Liss, P.S., Tessier, E., Hamren-Larsson, M., Donard, O.F.X., 2001. Role of oceans as biogenic sources of selenium. Earth Planet. Sci. Lett. 189, 277e283. Bacon-Shone, J., 2011. A short history of compositional data analysis. In: Pawlowsky-Glahn, V., Buccanti, A. (Eds.), Compositional Data Analysis: Theory and Applications, first ed. John Wiley & Sons, Ltd, Chichester (UK), pp. 1e11. Berg, T., Røyset, O., Steinnes, E., 1994. Trace elements in atmospheric precipitation at
7
Norwegian background stations (1989-1990) measured by ICP-MS. Atmos. Environ. 28, 3519e3536. Bern, C.R., Chadwick, O.A., Kendall, C., Pribil, M.J., 2015. Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems. Sci. Total Environ. 514, 250e260. Bindler, R., 2011. Contaminated lead environments of man: reviewing the lead isotopic evidence in sediments, peat, and soils for the temporal and spatial patterns of atmospheric lead pollution in Sweden. Environ. Geochem. Health 33, 311e329. €nnvall, M.L., Renberg, I., Emteryd, O., Grip, H., 1999. Natural lead Bindler, R., Bra concentrations in pristine boreal forest soils and past pollution trends: a reference for critical load models. Environ. Sci. Technol. 33, 3362e3367. Br€ annvall, M.L., Kurrkio, H., Bindler, R., Emteryd, O., Renberg, I., 2001. The role of pollution versus natural geological sources for lead enrichment in recent lake sediments and surface forest soils. Environ. Geol. 40, 1057e1065. Chadwick, O.A., Derry, L.A., Bern, C.R., Vitousek, P.M., 2009. Changing sources of strontium to soils and ecosystems across the Hawaiian Islands. Chem. Geol. 267, 64e76. Donisa, C., Steinnes, E., Sjøbakk, T.E., 2005. Nitric-acid soluble fractions of 21 elements in Norwegian podzols: factors affecting regional differences in vertical distribution. Appl. Geochem 20, 1258e1267. Evans, C.D., Monteith, D.T., Harriman, R., 2001. Long-term variability in the deposition of marine ions in the UK Acid Waters Monitoring Network: impacts on surface water chemistry and significance for trend determination. Sci. Total Environ. 265, 115e129. Filzmoser, P., Hron, K., Reimann, C., Garret, R.G., 2009. Robust factor analysis for compositional data. Comput. Geosci. 35, 1854e1861. Filzmoser, P., 2015. StatDA: Statistical Analysis for Environmental Data. R Package Version 1.6.9. http://CRAN.R-project.org/package¼StatDA. Friedland, A.J., Johnson, A.H., Siccama, T.G., 1984. Trace metal content of the forest floor in the Green mountains of Vermont: spatial and temporal patterns. Water, Air, Soil Pollut. 21, 161e170. Gladney, E.S., Small, J.A., Gordon, G.E., Zoller, W.A., 1976. Composition and size distribution of in-stack particulate material at a coal-fired power plant. Atmos. Environ. 10, 1071e1077. Greenberg, R.R., Zoller, W.H., Gordon, G.E., 1978. Composition and size distribution of particles released in refuse incineration. Environ. Sci. Technol. 12, 566e573. n, L.G., 1996. Dry deposition and concentration of marine Gustafsson, M.E.R., Franze aerosols in a coastal area, SW Sweden. Atmos. Environ. 30, 977e989. Kreutzer, K., et al., 1998. Atmospheric deposition and soil acidification in five coniferous forest ecosystems: a comparison of the control plots of the EXMAN sites. For. Ecol. Manag. 101, 125e142. Liss, P.S., Hatton, A.D., Gill, M., Nightingale, P.D., Turner, S., 1997. Marine sulphur emissions. Phil. Trans. R. Soc. Lond. B 352, 159e169. Låg, J., 1968. Relationships between the chemical composition of the precipitation and the content of exchangeable ions in the humus layer of natural soils. Acta Agric. Scand. 18, 148e152. Låg, J., Steinnes, E., 1974. Soil selenium in relation to precipitation. Ambio 3, 237e238. Låg, J., Steinnes, E., 1976. Regional distribution of halogens in Norwegian forest soils. Geoderma 16, 317e325. Låg, J., Steinnes, E., 1978. Regional distribution of selenium and arsenic in humus layers of Norwegian forest soils. Geoderma 20, 3e14. €der, W., Steinnes, E., Uggerud, H.T., 2015. Nickel, S., Hertel, A., Pesch, R., Schro Correlating concentrations of heavy metals in atmospheric deposition with respective accumulation in moss and natural surface soil for ecological land classes in Norway between 1990 and 2010. Environ. Sci. Pollut. Res. 22, 8488e8498. Njåstad, O., Steinnes, E., Bølviken, B., Ødegård, M., 1994. Nationwide Mapping of Element Composition of Natural Soil: Results from Samples Collected in 1977 and 1985 Obtained by Emission Spectrometry. Geological Survey of Norway, Trondheim. Report no. 94.027, 114 pp. (in Norwegian). Nordløkken, M., Berg, T., Flaten, T.P., Steinnes, E., 2015. Essential and non-essential elements in natural vegetation in Southern Norway: contribution from different sources. Sci. Total Environ. 502, 391e399. Nygård, T., Steinnes, E., Røyset, O., 2012. Distribution of 32 elements in organic surface soils: contributions from atmospheric transport of pollutants and natural sources. Water, Air, Soil Pollut. 223, 699e713. Pawlowsky-Glahn, V., Egozcue, J.J., 2016. Spatial analysis of compositional data: a historical review. J. Geochem. Explor. 164, 28e32. R Development Core Team, 2016. R: a Language and Environment for Statistical Computing. R Foundation for Statistical Computing, Vienna, Austria. URL. http:// www.R-project.org/. Reimann, C., Arnoldussen, A., Englmayer, P., Finne, T.E., Garrett, R.G., Koller, F., Nordgulen, Ø., 2007. Element concentrations and variation along a 120-km transect in southern Norway e anthropogenic vs. geoogenic vs. biogenic element sources and cycles. Appl. Geochem 22, 851e871. Reimann, C., Englmaier, P., Fabian, K., Gough, L., Lamothe, P., Smith, D., 2015a. Plant biogeochemical plant-soil interaction: variable element composition in leaves of four plant species collected along a south-north gradient at the southern tip of Norway. Sci. Total Environ. 506e507, 480e495. Reimann, C., Fabian, K., Schilling, J., Roberts, D., Englmaier, P., 2015b. A strong enrichment of potentially toxic elements (PTEs) in Nord-Trøndelag (central Norway) forest soil. Sci. Total Environ. 536, 130e141. Reiners, W.A., Marks, R.H., Vitousek, P.M., 1975. Heavy metals in subalpine and
Please cite this article in press as: Steinnes, E., Lierhagen, S., Geographical distribution of trace elements in natural surface soils: Atmospheric influence from natural and anthropogenic sources, Applied Geochemistry (2017), http://dx.doi.org/10.1016/j.apgeochem.2017.03.013
8
E. Steinnes, S. Lierhagen / Applied Geochemistry xxx (2017) 1e8
alpine soils of New Hampshire. Oikos 26, 264e275. Reynolds, B., Fowler, D., Smith, R.I., Hall, J.R., 1997. Atmospheric inputs and catchment solute fluxes for major ions in five Welsh upland catchments. J. Hydrol. 194, 305e329. Richardson, J.B., Friedland, A.J., Kaste, J.M., Jackson, B.P., 2014. Forest floor lead changes from 1980 to 2011 and subsequent accumulation in the mineral soil across the Northeastern United States. J. Environ. Qual. 43, 926e935. Richardson, J.B., Donaldson, E.C., Kaste, J.M., Friedland, A.J., 2015. Forest floor lead, copper and zinc concentrations across the Northeastern United States: synthesizing spatial and temporal responses. Sci. Total Environ. 505, 851e859. Rühling, Å., Tyler, G., 2004. Changes in the atmospheric deposition of minor and rare elements between 1975 and 2000 in south Sweden, as measured by moss analysis. Environ. Pollut. 2004 (131), 417e423. Schaug, J., Rambæk, J.P., Steinnes, E., Henry, R.C., 1990. Multivariate analysis of trace element data from moss samples used to monitor atmospheric deposition. Atmos. Environ. 24A, 2625e2631. Steinnes, E., 1997. Trace element profiles in ombrogenous peat cores from Norway: evidence of long range atmospheric transport. Water, Air, Soil Pollut. 100, 405e413. Steinnes, E., Rambæk, J.P., Hanssen, J.E., 1992. Large scale multi-element survey of
atmospheric deposition using naturally growing moss as a biomonitor. Chemosphere 25, 735e752. Steinnes, E., Allen, R.O., Petersen, H.M., Rambæk, J.P., Varskog, P., 1997. Evidence of large-scale heavy-metal contamination of natural surface soils in Norway from long-range atmospheric transport. Sci. Total Environ. 205, 255e266. Steinnes, E., Åberg, G., Hjelmseth, H., 2005a. Atmospheric deposition of lead in Norway: spatial and temporal variation in isotopic composition. Sci. Total Environ. 336, 105e117. Steinnes, E., Sjøbakk, T.E., Donisa, C., Br€ annvall, M.L., 2005b. Quantification of pollutant lead in forest soils. Soil Sci. Soc. amer. J. 69, 1399e1404. Steinnes, E., Berg, T., Uggerud, H.T., 2011. Three decades of atmospheric deposition in Norway as evident from analysis of moss samples. Sci. Total Environ. 412e413, 351e358. Templ, M., Hron, K., Filzmoser, P., 2011. robCompositions: an R-package for robust statistical analysis of compositional data. In: Pawlowsky-Glahn, V., Buccianti, A. (Eds.), Compos. Data Anal. Theory Appl. John Wiley & Sons, Chichester (UK), pp. 341e355. Tørseth, K., Hanssen, J.E., Semb, A., 1999. Temporal and spatial variations of airborne Mg, Cl, Na, Ca, and K in rural areas of Norway. Sci. Total Environ. 234, 75e85.
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