Geochemistry of freshwater calcareous sediments and longevity impacts of their application to acidic soils of eastern Lithuania/Geochemine gelavandeniu kalkinguju nuosedu sudeties variacija ir ju naudojimo palikimas rugstiems ryty lietuvos dirvozemiams.
Lithuania is located in the humid zone, where mean annual precipitation (748 mm) exceeds mean evapotranspiration (512 mm) (Kilkus et al. 2006) and soil acidification is an ongoing natural process (Bolan et al. 2003). In the mid-1960s, before the introduction of large-scale agricultural technologies, acid soils (pH in KCl [less than or equal to] 5.5) covered 41% of agricultural land, which has a national territory of 11,660 [km.sup.2]. However, in some Western and Eastern Lithuanian administrative districts, where there had been limited human intervention, 70-93% of soils had a pH value of < 5 (Savickas 1973). Therefore, natural calcareous materials (lime and marl) were valued by farmers, as soil additives, for their positive effects on the chemical and biological activity of the soil and for their marked effect on soil structure (Dodgshon 1978). For instance, field experiments (since 1984) using calcareous sapropels in Eastern Lithuania demonstrate their long-term effect on luvisol pH that is evident for > 20 years (Baksiene, Janusiene 2005; Baksiene et al. 2006). Other experiments (since 1948) in western Lithuania show the application of calcareous tuff and travertine has a lasting effect on the neutralising of albeluvisols acidity and increasing of crop production (Ozeraitiene et al. 2006). Along with many neighbouring countries (e.g. Aaby 1979 (Sweden); Bartosh 1969a, 1969b; Danilans 1957 (Latvia); Mannil 1964 (Estonia); Irion, Muller 1968 (Germany)), many investigations of quaternary natural calcareous sediments have been carried-out and, once detailed descriptions and depositional maps were created (1950-1960), a geochemical basis for their use in soil conditioning (liming) was determined (Savickas 1957). Since pure calcium carbonate CaC[O.sub.3] rarely exists in natural calcareous deposits, for practical purposes, sediments consisting of > 85% of CaC[O.sub.3] are normally considered to have high-calcium content. As such, the calcareous sediments in Eastern Lithuania were intensively excavated in the 1960's (Gasiuniene, Kadunas 1997). Compared to the industrial lime dusts (95-98% CaC[O.sub.3]) (used in Lithuania since 1976), natural calcareous deposits have greater compositional variability and are often enriched with organic matter (OM). Therefore, the physicochemical characteristics of calcareous sediments may influence soil toxicity one such characteristic is sediment OM content (Lacey et al. 1999). Transport of trace metals from the soil to a plant involves chemical, physical and biological processes (such as diffusion, adsorption, absorption, plant growth, transpiration rate, amongst others) in the soil, the soil rhizosphere and in the plant itself (Baltrenaite, Butkus 2007). To date, there are no known national Lithuanian archives that record the analytical purity and geochemical composition of freshwater calcareous sediments and no documented studies into the limitations and impacts of their use. Therefore, this work aims to: (i) assess the characterisation and distribution of freshwater limestone deposits; and (ii) evaluate the impact of their previous agricultural use in the acidic soil regions of Eastern Lithuania.
2. Materials and methods
2.1. Desktop study
Existing documentation on freshwater calcareous deposits, their excavation and applications in Lithuania are limited. Available information from the national geological survey, accessible land use archives and noted recommendations of soil studies have been combined with regional soil acidity maps to identify those sites used in this study (Vilnius, Moletai and Trakai district municipalities (Fig.1)). Soil acidity is sizeably pronounced in these locations and represents more than half of the total agricultural soils in the districts (Table 1).
[FIGURE 1 OMITTED]
A soil auger was used to define the depositional extent of the calcareous deposits at each site (mainly grasslands) and to interrogate their vertical structure. Selected individual profiles were then excavated, their morphology described and sediment samples collected for laboratory analyses (Fig. 2). To quantify the vertical variability of deposit geochemical composition more detailed sampling was done at the site Balsys (Z. Ezerai) (each 10-15 cm in relation to changes in profile morphology, from depth of 25 to 270 cm).
[FIGURE 2 OMITTED]
2.3. Laboratory analysis
Using the same approach as the geochemical survey of Lithuania (Kadunas et al. 1999), atomic emission spectrography (AES), calibrated to international standards with low background limits, was used to measure 13 elements of < 1 mm size fraction of each sample and the spectrum lines were deciphered by microdensitometer DM-100.
Total soluble alkalinity titrimetric method for the determination of the basicity of soluted material was applied. The principle of the procedure consists in solution of a test portion in water, filtration of the solution and titration with a standard volumetric solution of hydrochloric acid in presence of methyl orange as indicator (ISO 740:1976). ISO 10694:1995 method (determination of organic and total carbon after dry combustion) for the determination of the amount of organic matter (OM) was applied.
2.4. Data analysis
All data was analysed using Minitab-15 software (Guide to Minitab, 2007), to reveal the basic statistics and to determine non-parametric Kruskal-Wallis tests for inter-site variations and Mann-Whitney test for intra-site variations.
3.1. Availability of freshwater calcareous sediments
Summarising geological surveys, profiles of their litho-logical composition and aerial photography sets, it was determined that quaternary depositions of freshwater calcareous sediments are common in SE Lithuania and are represented by two major types, all containing minimal, if any, magnesium. These beds dominantly are comprised of calcareous tufa and lake limestone. The Geological survey of Lithuania (in 2001) reported 235 freshwater limestone deposits (90 of calcareous tufa and 145 of lake limestone) in Alytus, Vilnius and Utena provinces. The revision showed the major part of these deposits having minimal resources and only small thickness of the useful bed (Geological survey of Lithuania, Annual report, 2001) and unfortunately many have been previously excavated but without records available. For application of these materials, physical properties are very important because it is noticeable that in organic matter rich deposits, natural humidity of materials varies in higher range and can reach up to 75% (organic rich calcareous tuff) (Kacas et al. 1955). Excavation of soft and 'more pure' lake limestone has been prioritized compared to other freshwater limestone. A scheme of the vertical structure of deposits demonstrates favourable conditions of deposit excavation after removal of peat layer (Fig. 2).
[FIGURE 3 OMITTED]
3.2. Variability of freshwater calcareous sediments
In Lithuania the thickness of limestone depositions is relatively thin, with deposit mean values at 0.5-1.0 m. Thickness of investigated depositions varied from 0.3 to 2.7 m. Vertical sectional view of selected lake limestone deposits was found often morphologically uneven, with easily noticeable variation in colour, texture or both (Fig. 2-3). Such lamination is demonstrating cyclic sedimentation of carbonates, for which morphologic variation is found closely related to chemical and agronomical parameters of materials. Visible morphological variation chemically can be related to % of organic matter, concentration of Fe and neutralising values. Inter-site variations were calculated for each parameter and Kuskal-Wallis test (Table 2) demonstrated significant differences between all sites for neutralising value.
While limestone from Savaitiskes contains the lowest amount of OM% and Gineitiskes contain the largest OM%, they significantly differ from the Juodenai and Balsys sites. Balsys and Savaitiskes limestone are similar in Fe concentrations, but differ significantly from Juodenai--which is richest in Fe (0.82%).
There is a growing interest in the geochemical parameters of freshwater carbonates from various environmental disciplines, with recent studies providing new insights into the behaviour of trace elements within tufa systems (Rogerson et al. 2008). Geochemical purity data has been unavailable in Lithuania, and data from other countries (Geochemistry of Sedimentary Carbonates 1990; Jochmann et al. 1997; Hood et al. 2004) has been used.
Our testing is exploring much wider inter-site geochemical variations compared to neutralizing values of sediments. Results indicated that the elements which contribute to concentration ranges can be divided into three groups (Table 3)- [less than or equal to] 10, 10-100, [greater than or equal to] 100. Group one: manganese (Mn) and barium (Ba), group two: boron (B), nickel (Ni), copper (Cu), chromium (Cr), lead (Pb) and vanadium (V) and group three: cobalt (Co) and silver (Ag). The first group are sediments showing the presence of Ba and Mn in their highest concentrations (mean 364.4 ppm and 518.9 ppm accordingly) with maximum of 1600 ppm for Mn. Both these elements demonstrate the widest range of statistical parameter variation. B, Ni, Cu, Cr, Pb, and V varied in the range of 0.6 (V) to 50 (B) ppm, with mean values at 6.7 (V) -10.6 (B) ppm.
To illustrate intra-site vertical variation, profile data from the site of Balsys (each 10-15 cm in relation to changes in profile morphology, from depth of 25 to 250 cm) has been assessed statistically (Table 4). All tested elements presented in vertical variation of geochemical composition appear to be greater for bothhigh and lower concentration in presented elements. Ba (ranging between 180--H0 ppm) and Mn (ranging between 20-190 ppm) demonstrate highest concentrations among other deposits.
3.3. Impacts and longevity of freshwater calcareous sediment applications to soil
In contaminated soils, the total metal content often represents a long-term, multiscore input of metal pollutant elements with complex historical background (Van Oort et al. 2006). The higher concentrations of heavy metals in Central Europe topsoil are found directly related to human activities. Cd, Cu, Hg, Pb, Zn present high correlations with agriculture (r = 0.7) and with quaternary limestone (r = 0.41) (Lado et al. 2008).
All too often, soil-liming benefits are emphasised without mentioning its important environmental and ecological roles. Liming can prevent the uptake of radionuclide and heavy metals by plants (Lietuvos dirvozemiai 2001). Otherwise, soils and groundwater face greater pollution risk. Moreover, acidifying reactions of solutions in the landscape entail an increased aggressiveness of chemical toxic substances, suppression of microbiological processes, disturbances of metabolism and nutrients exchange, spreading of endemic diseases and degradation of material values. Increasing the pH of a soil by adding CaC[O.sub.3] changes the solubility of most mineral elements substantially, the several distinct patterns observed being governed by, for example, ionic properties and charge, affinity for organic compounds, and pH-dependent formation and solubility of complexes. Inversely related to pH are soil solution concentrations of Al, B, Ba, Bi, Cs, Ce, Eu, Ga, Ge, Fe, Li, K, Rb, Na, Th and Ti (Tyler, Olsson 2001).
Our studies have revealed that quality of lake limestone deposits have been acceptable for their former agricultural use irrespective of geological genesis of deposit, geographical location, deposit thickness and vertical variability. On average, neutralizing capacity recorded at 49% demonstrates it was a favourable material for former acid soil liming applications.
According to recommended application rates and periodicity of liming we model the concentrations of elements in topsoil layer. Investigating applications of former lake limestone to soil ranging in amount equal to 5 t per ha CaC[O.sub.3] single application and three liming cycles within 15-years demonstrate negligible concen trations of HN controlled elements have been introduced. Their levels are as low as 0.59% of MPC if we speculate for Zn concentrations at the level of detection. Ba is the second highest modelled concentration element, demonstrating about 50% lower values at 0.29% of MPC. Mn, Ag, B, Co, Cr, Cu, Ni, Pb, V and speculated at detection limit Mo and Sn, all range below 0.12% of MPC.
The low inter-site differences displayed by our data suggest geochemical variations can not be assessed with confidence. Intra-site variability could be large enough to mask inter-site variability in sediment geochemistry. Previous findings on freshwater limes applications disclaim direct risks of soil pollution (relating to hygiene norm) by higher heavy metals and rare elements accumulation in soil. However, this does not eliminate the effect on the large variety of forms of life sensitive to eco-toxic concentration for any substance. In spite of this, results do not correspond to the risk of accumulation in crops and transport to ground waters as long-term effect on soil pH exists, because it is one of the main parameters of mobility of selected elements. Whole-catchment liming experiments clearly demonstrate that liming produces a long-term effect on water quality (Traaen et al. 1997). Latest results of long-term field experiments on calcareous sapropels (Baksiene, Janusiene 2005; Baksiene et al. 2006) in Eastern Lithuania (lasting since 1984) demonstrate that their effect on luvisol pH is evident for more than 20 years. Other experiments in Western Lithuania (since 1948) show that application of calcareous tuff and travertine has, at least for 55 years, a lasting effect on neutralising of albeluvisols acidity and increasing of crop production (Ozeraitiene et al. 2006).
Geochemical evaluation of soils in long-term field experiments conclude statistically reliable deviations of Co, Cu and Sr total concentrations as compared to the background levels of 18 elements tested (Marcinkonis et al. 2005). Assessment of trace elements enrichment or depletion, using total concentrations of Al, Fe and V (control topsoil and B horizon) as reference elements show Sr accumulation, which means that Sr concentrations have profoundly changed during decades of soil fertilization and liming in Lithuanian soils (Marcinkonis 2008). Concentration of some elements in soils can be efficiently controlled by the application of phytoremediation technique. According to the mathematical modelling results of soil remediation with regard to heavy metals obtained by Jankaite (2009), it has been shown that when soil is cleaned with grassy vegetation, copper concentrations decrease and, therefore, we can draw a conclusion that a selected mixture of grassy vegetation may be applied for the removal of heavy metals from soil.
It is surmised that lake limestone is a pure liming material, and because of its long-lasting pH regulating effect, which might have indirect influence on accumulation of HN controlled elements, when applied with mineral and organic fertilizers.
Three general conclusions can be drawn from this work:
(i) Freshwater calcareous sediments are geochemically diverse even in between layers of the same deposit, and tested calcareous materials are especially rich in total manganese (3500 ppm) and total barium (490 ppm);
(ii) Long-term and intensive use of calcareous freshwater lake limestone for soil liming appears harmless, from a direct soil pollution viewpoint; and
(iii) Former applications of freshwater calcareous sediment offer indirect influences on long-term soil pH-regulating effects.
Financial support from the Lithuanian State Science and Studies Foundation (project No.T-60/06) is gratefully acknowledged. Finally, the first author gratefully acknowledges receipt of a Lady Wulfrun visiting fellowship from the former School of Engineering and the Built Environment (now School of Technology) at University of Wolverhampton, UK.
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Saulius MARCINKONIS. Dr, Senior Researcher in Soil Chemistry at the Department of Soil Chemistry, Voke Branch of Lithuanian Research Centre for Agriculture and Forestry. Doctor of Biomedical Sciences (Agronomy), Lithuanian Institute of Agriculture, 2000. Publications: author/co-author of ~30 scientific papers. Research interests: soil chemistry, degradation, soil pollution, re-vegetation.
Bronislavas KARMAZA. Dr, Senior Researcher of the Quaternary Research Section at the Institute of Geology and Geography. His main research trend is the Lithuanian Pleistocene glaciolacustrine, glaciofluvial sediments: their structure and composition, geological heritage and application of distant methods for the research of exogenous Quaternary sediment processes, archaeological camps and settlements. Publications: author/co-author of ~20 scientific papers. Research interests: geochemistry, land degradation, soil pollution.
Colin A. BOOTH. Dr, Associate Professor of Sustainability, is Associate Head of Research and Scholarship in the Faculty of Environment and Technology at the University of the West of England, Bristol (UK). Publications: author/coauthor of ~100 scientific papers and chapters. Research interests: sustainability, environmental management, climate change mitigation and adaptation strategies, water resources management, and built environment studies, urban pollution, coastal and estuarine science.
Saulius Marcinkonis (1), Bronislavas Karmaza (2), Colin A. Booth (3)
(1) Voke Branch of the Lithuanian Research Centre for Agriculture and Forestry, Zalioji a. (2), Traku Voke, LT-02232 Vilnius, Lithuania 2Nature Research Centre, Institute of Geology and Geography, T. Sevcenkos g. 13, LT-03223 Vilnius, Lithuania (3) Faculty of Environment and Technology, University of the West of England, Bristol BS161QY, UK E-mails: (1) firstname.lastname@example.org (corresponding author); (2) email@example.com; (3) firstname.lastname@example.org
Submitted 09 Feb. 2011; accepted 28 Dec. 2011
Table 1. Distribution of acid and exposed to acidification soils (pH in KCl [less than or equal to] 5.5) in East Lithuania (Mazvila et al. 1998) Administrative districts Distribution Vilnius Traki Moletai Total of acid and exposed to % of acid soils from total acidification soils agriculture area Currently acid soils 35.9 33.8 25.8 26.6 Soils exposed to 32.0 21.6 25.1 25.3 acidification Total 67.9 55.4 50.9 51.9 Table 2. Kuskal-Wallis test on major specific calcareous sediments properties in different sites (n = 12) Test results Fe% * (H = 3.04 sites DF = 3 p = 0.385) media rank Z Balsys 0.31 3.0 -1.55 Juodenai 0.82 6.3 1.03 Savaitiskes 0.4 4.0 -0.39 Gineitiskes 0.72 6.5 0.88 OM% * (H = 6.16 sites DF = 3 p = 0.104) media rank Z Balsys 2.61 3.7 -1.03 Juodenai 2.71 5.3 0.26 Savaitiskes 2.24 1 -1.55 Gineitiskes 4.86 8.5 2.05 Neutralizing capacity % * (H = 5.44 DF = 3 sites p = 0.142) media rank Z Balsys 45.21 5.0 0.00 Juodenai 42.87 2.7 -1.81 Savaitiskes 44.71 5.0 0.00 Gineitiskes 50.30 8.5 2.05 * H - Kuskal-Wallis test statistic; DF - degree of freedom; p - significance. Table 3. Descriptive statistics of inter-site geochemical composition variation, ppm (parts per million) (n = 12) Kruskal- Basic statistics Wallis test Standard Elements Mean deviation Minimum Maximum H p Mn 518.9 546.9 80 1600 7.2 0.07 Ba 364.4 112 230 490 7.3 0.06 B 10.6 15.5 1.8 50 4.0 0.26 Ni 9.7 10.4 2 35 5.1 0.17 Cu 7.7 8 1.7 26 2.0 0.57 Cr 7.6 10.9 1.5 35 4.9 0.18 Pb 6.9 2.8 5 13 2.8 0.43 V 6.7 11.7 0.6 37 4.1 0.25 Co 4.2 3.3 1 9 4.9 0.18 Ag 0.1 0.1 0.1 0.3 5.4 0.14 Table 4. Summary statistics of vertical intra-site geochemical composition variation, ppm (parts per million) (n = 10) Summary statistics Mann-Whitney test St. Elements Mean deviation Minimum Maximum * W * p-value Ba 295 71.8 180 410 31 0.108 Mn 110.2 72.6 20 190 20 0.933 Ag 0.1 0 0.1 0.1 0 - B 2.2 0.5 2 3.5 25 0.554 Co 1 0 1 1 0 - Cr 2.1 1.1 1.5 4.5 26.5 0.398 Cu 5.9 3.3 2.7 12 20 0.933 Ni 5.7 2.2 3 10 11 0.108 Pb 4.5 0.7 4 6 30 0.151 V 0.6 0.2 0.5 1 34 0.035 * W-Mann-hitney test statistic; * p-value--significance
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|Author:||Marcinkonis, Saulius; Karmaza, Bronislavas; Booth, Colin A.|
|Publication:||Journal of Environmental Engineering and Landscape Management|
|Date:||Dec 1, 2012|
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