Investigation of absolute metal uptake efficiency from precipitation in moss
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1 . The Science of the Total Environment Investigation of absolute metal uptake efficiency from precipitation in moss ˇ D. Ceburnis, D. Valiulis Institute of Physics, A. Gostauto ˇ 1, 600 Vilnius, Lithuania Received 4 July 1998; accepted December 1998 Abstract Bioaccumulation of metals in moss was studied by the absolute method using a specially designed moss bag technique. Bulk deposition was collected in open areas along with bulk deposition collected under moss. An absolute uptake efficiency of approximately 60% was obtained, which is in good agreement with the value obtained by a relative method. The absolute uptake efficiency varied between 0 and 9%, hence uptake of metals depends very strongly on microenvironmental conditions which can even cause leaching of metals from moss. The best retained elements were Pb, Ni, Cu and V, while Cd, Cr, Fe and Zn exhibited significantly lower uptake efficiencies. Manganese in all cases showed leaching of the element from moss Elsevier Science B.V. All rights reserved. Keywords: Biomonitoring; Moss; Hylocomium splendens; Pleurozium schreberi; Trace metals; Deposition 1. Introduction Bioaccumulation monitoring methods can be divided into two groups: active and passive. Active monitoring includes the exposure of well-defined species under controlled conditions, whereas passive monitoring refers to the observation or chemical analysis of indigenous plants. The use of mosses as passive biomonitors for atmospheric deposition of metals has been re- Corresponding author, Ecological Spectroscopy Laboratory, Institute of Physics, A. Gostauto ˇ 1, 600 Vilnius, Lithuania. Tel.: ; fax: ; ceburnis@ktl.mii.lt ported in a large number of studies including local investigations as well as regional surveys in different parts of the world, particularly in Western and Northern Europe Ruhling et al., 1987, 199; Ruhling, The moss technique is particularly favourable for estimation of long-term temporal and spatial changes in metal deposition. Mosses are well suited to this purpose because they receive nutrients directly from the atmosphere and efficiently retain a number of elements. At the same time it is still unclear how mosses represent short-term temporal deposition. The moss bag technique, originally introduced by Goodman and Roberts and later modified by Little and Martin has become very $ - see front matter 1999 Elsevier Science B.V. All rights reserved.. PII: S
2 48 D. Ceburnis, D. Valiulis The Science of the Total En ironment popular. Transplant techniques appear to be useful, in particular at relatively high pollutant levels. One distinct advantage compared to the use of indigenous species is that of well-defined exposure time Steinnes, According to Sorteberg the reproducibility of this technique appears not to be very satisfactory concerning parameters such as air concentration and deposition rate. In general the passive biomonitoring method has one major disadvantage: all processes and all sources act at the same time and there is no possibility of separating them and looking for a particular one. Haseloff 198. divided the active biomonitoring into transplantation, test plant and test chamber methods. In the transplantation procedure, suitable organisms mainly mosses and lichens. are transported from unpolluted areas to the polluted site under consideration. The exposure time thus is well defined, but the change in uptake efficiency due to climatic change is not fully known. This method is usually applied to testing either synergistic or single species effects of pollutants on sensitive biomonitors. Although a large number of studies exist, there is still a need for a quantitative comparison of the concentration of environmental chemicals which have accumulated in biomonitors with air pollution measurements at the same site Thomas, 1986.; such a comparison would enable the calibration of the biomonitoring system to be made. The pre-requisites for the quantitative determination of airborne heavy metal pollution using plants are the choice of suitable plant species, knowledge about the effects of genetic variation and microclimate on the accumulation efficiency of the monitoring plants, and the estimation of the accumulation time Thoni and Hertz, The analytical procedure may introduce uncertainties as well and has to be evaluated carefully Wolf et al., A majority of studies dealing with metal uptake efficiency from precipitation in moss Ross, 1990; Berg et al., 1995; Thoni et al., used the passive or non-direct biomonitoring method, using a regression method, for which metal concentrations in moss were compared with metal concentrations in precipitation. A new point of view was proposed in this study for the assessment of metal uptake efficiencies in moss, i.e. direct or absolute evaluation of the uptake process.. Materials and methods A special experiment was carried out to examine possibilities of the active biomonitoring method using feather moss. It is obvious from the literature Ruhling et al., 1987, 199; Steinnes et al., 199; Steinnes, that mosses could truly represent long-time scale atmospheric trace metal deposition. The theoretical relation between the metal concentration in the moss g g dry wt.. and the atmospheric deposition g m time unit. must take into account also the mass g m time unit. of the moss: D C E 1. M where C is concentration in moss, D is deposition rate, M is mass of the moss, and E is uptake efficiency of an individual metal in moss. If three of these four variables are estimated independently, theoretically it is possible to calculate the growth increment of the moss: d m E. c where m is growth increment g m year., d is deposition g m year. and c is metal concentration in the moss corresponding shot g g in annual shot.. The growth increment of the moss or the total mass also could be estimated independently when collecting and weighing annual moss shots or the total moss mass per unit area. Hence, it would be possible to calculate the deposition rate. In both equations a critical parameter is the metal uptake efficiency in the moss which must be evaluated independently or absolutely. The experiment was carried out to study how mosses could reflect short time atmospheric deposition and evaluate metal uptake efficiency in the moss on a real time scale.
3 D. Ceburnis, D. Valiulis The Science of the Total En ironment Fig. 1. Samplers for the collection of bulk deposition under the moss and ordinary bulk deposition collector. The moss-bag technique was modified for use along with the measurements of trace metals in bulk deposition. Fig. 1 shows the collectors which were used in this experiment. The moss of two species, Hylocomium splendens and Pleurozium schreberi, collected in the immediate vicinity to precipitation collectors, gently cleaned from major extraneous material not destroying the structure of moss. and placed on the plastic net with the mesh size of 1 mm. This prevented large material from getting into the sampler while the rainwater simply passed the net. The experiment was carried out at three different locations in Lithuania during summer autumn The first location was in Preila, the Lithuanian background monitoring station on the Baltic seashore. The second was in Vilnius suburbs, a forested area where the Institute of Physics is located. The third was in the Aukstaitija Integrated Monitoring Station situated in the most eastern Lithuanian region Fig... All locations Fig.. A map representing sampling stations. were rather similar because of surrounding coniferous forests. At every location two ordinary bulk precipitation samplers and 10 collectors for collection of precipitation under the moss five collectors of each species. were placed. All precipitation collector material which was in contact with precipitation or mosses was nitric acid washed plastic. Samples were taken once per month, immediately acidified and analyzed for trace metals. Absolute metal uptake efficiency was calculated under the following equation: ž D b / D E 1 m 100% 3. where E is absolute uptake efficiency, Dm is deposition, calculated from precipitation under the moss, and Db is deposition calculated from the bulk collector. Table 1 Analytical results for quality control precipitation samples Metal Sample 1 Sample Sample 3 Sample 4 Certified Measured Certified Measured Certified Measured Certified Measured Cr Ni Cu Zn Cd Pb
4 50 D. Ceburnis, D. Valiulis The Science of the Total En ironment Analytical quality control was performed using standard reference materials obtained from an intercalibration exercise HELCOM-EMEP- PARCOM-AMAP field intercomparison of heavy metals in Precipitation Table 1 provides results for measured vs. certified values. 3. Results and discussion Elemental uptake efficiency values were found to vary significantly month by month. Table shows metal uptake efficiencies in the moss at different locations. At two stations Preila and Vilnius. moss bags were changed monthly while the same bags were used at the third station. No significant difference was obtained which confirms that the metal uptake process in the moss is passive and independent of whether mosses are alive or partly dead. The highest efficiency observed was 9% while in approximately 15% of cases it was 0%. High negative values for Mn clearly show severe continuous leaching of the element from the moss. Estimation of uptake efficiency in species Hylocomium splendens and Pleurozium schreberi showed that there was no significant difference between two moss species Fig. 3. with the exception of Cr, Zn and Mn. The higher uptake efficiency of Cr in Hylocomium splendens is possibly caused by more effective trapping of dust particles due to surface roughness. Leaching of Mn from Hylocomium splendens was much more effective compared to Pleurozium schreberi. The uptake efficiency of Zn in Hylocomium splendens was a little lower than in Pleurozium schreberi. This is also most likely because of the more efficient leaching from Hylocomium splendens. These results correspond very well to the results presented in the author s previous study ˇ Ceburnis et al., using a relative uptake efficiency estimation method. Metal concentration analysis has shown that for almost all the investigated metals, leaching is important and has a significant influence on the uptake of metals Fig. 4.. Fig. 4 illustrates three groups of elements. The first includes Pb, V, Ni and Fe and these metals do not seem to be seriously affected by the leaching process. Under normal conditions uptake efficiency for these metals is rather stable. For Cd, Cu and Zn leaching is an important process. Cadmium occurs in this group possibly because of the analytical un- Table Metal uptake efficiencies at different locations a. Month Ratio E % Pb Ni Cu Cr Cd V Zn Fe Mn Preila June July August September Rugst. July August September Vilnius July August September Median a Ratio represents the bulk precipitation amount divided by the precipitation amount collected under the moss.
5 D. Ceburnis, D. Valiulis The Science of the Total En ironment Fig. 3. A comparison of metal uptake efficiency in two moss species Hylocomium splendens and Pleurozium schreberi. Manganese values are 10-fold. certainties due to the extremely low concentrations in precipitation under the moss in many cases. For Mn and Cr, leaching is a dominant process. Comparing these data with the data showing the influence of a secondary source not anthropogenic. to the metal concentrations in the moss Ceburnis ˇ et al., 1998., it becomes rather clear that some metals such as Cr, Zn and Mn enter the moss from non-atmospheric sources and are probably associated with crust or dust particles which can be washed away rather quickly under unfavourable conditions. Fig. 5 shows that one of these conditions could be the intensity of precipitation. For the intensity of precipitation it was assumed a variable defined as ratio of the precipitation amount in the open field collector against the precipitation amount in the moss-bag collector. Fig. 5 shows that the heavier the rain the less metal uptake efficiency is obtained. For Fig. 5 the uptake efficiency was averaged for all Fig. 4. Trends of the bulk metal concentration vs. metal concentration in the precipitation under moss. Concentration scale for Mn is 10-fold.
6 5 D. Ceburnis, D. Valiulis The Science of the Total En ironment Fig. 5. Absolute uptake efficiency in moss vs. the precipitation ratio. metals for a particular precipitation intensity. Equilibrium is possibly reached when the bulk precipitation amount exceeds the precipitation amount under the moss by approximately five times. It is evident that when precipitation passes moss slowly the uptake process is more effective. On the contrary, when the precipitation passes very fast, for example during the rain-shower, the uptake process is minimal and even leaching occurs because of the strong flow. This could partly explain the findings of Steinnes et al where lower Mn concentrations near the sea coast were attributed to the sea salt effect. Nevertheless, the sea salt effect was identified during laboratory experiments Gjengedal et al., It must be taken into account that near the seashore rain-showers are very common and therefore leaching could be more efficient. The latter could be confirmed from Table which shows that the highest leaching values were obtained for the coastal site in Preila. Another interesting observation is observed within the data. According to Table we can calculate that the median retention of the precipitation amount by moss is approximately 65%. We can assume that 65% of rainwater which gets onto the moss is evaporated and metals which are present in that amount of rainwater are taken up completely. This is true for short falls of light rain. In this case the flow of rainwater through the moss is so slow that water can easily evaporate without passing through the moss. Even during heavy rain the last portion of water is retained by moss completely since moss can hold a significant amount of water, especially after a dry period. When the water starts to get through the moss, the time span for passing is too short for metals to be taken up. According to our experimental data Table. the least amount of rainwater which was retained by moss was approximately 33%. It is evident from Table that the best uptake for elements exhibit approximately 60% of the uptake efficiency which support the latter suggestion. In relating these calculations with the leaching process an overall picture of the uptake process becomes rather comprehensive. According to our experiment the estimated uptake efficiency values are of the lowest level and could be higher if somehow to avoid leaching of metals. On the other hand as the values from the relative and absolute methods correspond well to each other we conclude that the leaching must also occur in naturally growing moss. Table shows that, on average, approximately 60% of metals are retained in the moss. A similar value was also obtained from other experiments Ross, 1990; Berg et al., 1995; Ceburnis ˇ et al., when comparing moss concentrations and deposition rates. Another interesting observation is that for a majority of elements the uptake
7 D. Ceburnis, D. Valiulis The Science of the Total En ironment efficiency under favourable conditions is rather stable and very similar even for some elements which exhibit the secondary source first of all soil erosion. influence Cr, Ni, V, Fe.. The most important thing concerning quantitative reflection of bulk deposition appears to be how efficiently and to what extent elements could be leached or washed out under unfavourable conditions. To prove the latter requires more experimental data. 4. Conclusions Metal uptake efficiency in moss obtained by the absolute method 60%. corresponds well to the value derived from the relative regression. method. It has been defined that intensity of precipitation is one of the main parameters which modify the uptake process. There was no significant difference in uptake efficiency between different elements except Mn. under the most favourable conditions. It has been tested during this experiment that the metal uptake process in moss is a passive one and does not depend whether the moss is alive or dead. It has been shown that there is no significant difference between two moss species Hylocomium splendens and Pleurozium schreberi concerning quantitative uptake of metals. This experiment revealed the main consequence that mosses do not necessary reflect monthly or short-term deposition and do not always hold information about a particular month, so they can hardly be used for that purpose or for monitoring an acute accident. Moss as a living organism is strongly influenced by microclimatic and microenvironmental conditions which have a certain influence on quantitative uptake of metals from precipitation. Moss is a long-term integrator of atmospheric trace metal deposition. References Berg T, Røyset O, Steinnes E. Moss Hylocomium splendens. used as biomonitor of atmospheric trace element deposition: estimation of uptake efficiencies. Atmos Environ 1995;9A: Čeburnis D, Steinnes E, Kvietkus K. Estimation of metal uptake efficiencies from precipitation in mosses in Lithuania. Chemosphere 1998;38: Gjengedal E, Steinnes E. Uptake of metal ions in moss from artificial precipitation. Environ Monit Assess 1990;14: Goodman GT, Roberts TM. Plants and soils as indicators of metals in the air. Nature 1971;31:87 9. Haseloff HP. Bioindikatoren und bioindikation. Biol Zeit 198;1:0 6. Little P, Martin MH. Biological monitoring of heavy metal pollution. Environ Pollut 1974;6:1 19. Ross H. On the use of mosses Hylocomium splendens and Pleurozium schreberi. for estimating atmospheric trace metal deposition. Water Air Soil Pollut 1990;50: Ruhling A, Rasmusen L, Pilegaard K, Makinen A, Steinnes E. Survey of atmospheric heavy metal deposition in the Nordic countries in 1985 monitored by moss analysis. NORD 1987;1. Ruhling A, Brumelis G, Goltsova N et al. Atmospheric heavy metal deposition in Northern Europe. NORD 199;1. Ruhling A, editor. Atmospheric heavy metal deposition in Europe estimation based on moss analysis. NORD 1994;9. Sorteberg S. Evaluation of the moss-bag technique in connection with air pollution studies in Oslo in Norwegian. Thesis, University of Trondheim, AVH, Norway, Steinnes E. Biomonitors of air pollution by heavy metals. In: Pacyna JM, Ottar B, editors. Control and fate of atmospheric trace metals. Kluver Academic Publishers, 1989: Steinnes E, Rambaek JP, Hanssen JE. Large scale multi element survey of atmospheric deposition using naturally growing moss as biomonitor. Chemosphere 199;5: Steinnes E. A critical evaluation of the use of naturally growing moss to monitor the deposition of atmospheric metals. Sci Total Environ 1995; : Thomas W. Representativity of mosses as biomonitor organisms for the accumulation of environmental chemicals in plants and soils. Ecotoxicol Environ Saf 1986;11: Thoni L, Hertz J. Moose als Biomonitoren fur die flachenhafte Abschatzung der Schwermetallbelastung in der Schweiz. VDI Ber 1987;609: Thoni L, Schnyder N, Krieg F. Comparison of metal concentrations in three species of mosses and metal freights in bulk precipitations. Fresenius J Anal Chem 1996; 354: Wolf A, Schramel P, Lill G, Hohn H. Bestimmung von Spurenelementen in Moos und Bodenproben zur Untersuchung der Eignung fur Umweltbelastungen. Fresenius Z Anal Chem 1984;317:
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