ECOLOGY SCREENING AND MAPPING OF HEAVY METAL POLLUTION OF SOILS BY LASER MASS SPECTROMETRY LUBOMIR SIMEONOV1* AND BIANA

SIMEONOVA2 1 Solar-Terrestrial Influences Laboratory, Bulgarian Academy of Sciences Acad. G. Bonchev Str. Bl.3, 1113 Sofia, Bulgaria 2 Institute of Electronics Bulgarian Academy of Sciences 72 Tzarigradsko Shossee Bul, 1784 Sofia, Bulgaria

Abstract. The present paper discusses an approach for performing an express ecology in-field screening with the help of transportable laser mass spectrometric system of easy-accessible small and medium soil areas, polluted with heavy metals. Presented are results from a demonstration experiment in which the heavy metals elemental and isotopic data, gathered by the laser time-of-flight mass analyzer are arranged according to the map of the places of soil sampletaking, thus providing a satisfactory evidence of the ecological status of the area in respect to further remediation activities.

Keywords: heavy metals, soil pollution, ecological screening, ecological mapping, laser mass spectrometry

1. Introduction The presence of heavy metals in cultural soils is a result mainly of an anthropogenic activity. The magnitude of contemporary production and the introduction of new technologies in different branches of industry and in the living sphere at present time exceeds the potential of the biosphere ecosystem and creates a real hazard for the human being. The gradual contamination of the biosphere with heavy metals is explained by their stability in outer conditions, the solubility in atmospheric water and the ability to be absorbed in soil. For example, the soil
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To whom correspondence should be addressed: simeonov2006@abv.bg
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retention time of Pb in soil is between 150 and 5000 years (McBride, 1989). According to some risk assessment evaluations, the overall contamination with heavy metals will inevitably take the first place in the near future, exceeding the pollution with organic substances and pesticides. In this context, the scientific research for the development of reliable and up-to-date methods and techniques for qualitative and quantitative environmental analysis, combined with effective clean-up technologies is quite actual. The group of heavy metals consists of more than 40 elements, which have a specific gravity greater than 6 g/cm3. From an ecological, toxicological and hygienist point of view, not all the elements from this group are equally important. The metals which have a wide scope of production and implementation in industry and everyday life, usually have high levels of accumulation in the environment and are considered hazardous because of their biological activity and toxicological properties. Especially hazardous are considered Cd, Pb, Hg and As in the first order and also Zn, Ni, Cu, Co, Sn, Sb, Mo, V and CrVI (Ilin, 1992; Trachtenberg et al., 1994). Metals in soil environment exist as components of several different fractions: (1) free metal ions and soluble metal complexes; (2) metal ions, occupying ion-exchangeable sites and absorbed in inorganic soil constituents; (3) organically-bound metals; (4) precipitated or insoluble compounds, oxides, carbonates and hydroxides; (5) metals in the structures of silicate minerals. It is clear, that only metals in fraction (1) and partially from fraction (2) form the hazardous bio-available part of the total presence of metals in soil. Therefore, it is important to evaluate the magnitude of this particular part and to keep this in mind when analysing methods and techniques as conventional AAS (Atomic Absorption Spectroscopy) for example are used in chemical analysis of ecology samples. In this article we present an alternative possibility to apply laser mass spectrometry for express qualitative and semi-quantitative elemental and isotopic analysis of the presence of heavy metals in polluted soils. The investigation is directed for the purposes of ecological screening and mapping in respect to future choice and application of the most appropriate soil remediation approaches and practices for every particular case. The developed approach can be successfully applied also for the evaluation and monitoring of long-term metal deposition in soil in cases of pollution of cultural lands near to heavy industrial complexes as well, as in cases of intentional or criminal releases of pollutants. The method is developed on the basis of a new design concept of traditional laser time-offlight mass spectrometer. The instrument is created as a result of a technological transfer of a space research technique, originally constructed for the purposes of in-field determination of the elemental and isotopic composition of the surface

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layer of small space bodies without atmosphere, like asteroids and planetary satellites (Managadze et al., 1986; Simeonov, 1987). This is probably the smallest laser mass-analyser in terms of its size and whose design features several new elements like a two-stage time-of-flight reflector compartment in a combination with a chevron assembly MCP (micro-channel plate) particle detector with ring configuration. The specially designed construction of the sample lock chamber makes it possible to replace a holder with solid-state (soil) samples during less than one minute without gas leakage and venting the whole analyser vacuum system. The workout of the referred instrumental methodology was focused on several specific aspects: estimation of the instrumental analytical parameters as determination rate, reproducibility of measurement and quantification levels. A special attention was paid to the workout of the sampling strategy (complementary with AAS), clearing aspects as sample-taking, preparation of laser targets from environmental samples and solving of the questions in connection to the reference material. 2. Results and Discussion On Figures 1 and 2 are shown two representative mass spectra, taken with the help of the portable laser time-of-flight mass analyser.

Figure 1. Representative spectrum of a soil sample with the presence of Cd and Pb, polluted by industrial waste waters taken with the help of the portable laser mass analyser. The abscissa shows the arrival time in sec of the elements from H to Pb on the detector of the instrument.

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On Figure 2 is shown a part of a mass spectrum in the mass range from 1 to 70 a.m.u. The elemental and isotopic identification of the time-of-flight peaks is achieved with a specially computer programme, which performs a 5-fold estimation based on the natural isotopic abundances of the Periodic System of Elements. An option of the computer programme allows the calculation of the isotopic abundances in percentage in relation to the detected intensities in every separate laser shot mass spectrum.

Figure 2. Representative mass spectrum in the mass range from 1 to 70 a.m.u. of a soil sample polluted by industrial waste waters with the presence of Mg, Al, Fe, Ni and Cu. The mass spectrum is taken with the help of the portable laser mass analyser.

The special application of the portable laser mass spectrometer for the purposes of the express ecologic screening and mapping of heavy metal pollution of soil is illustrated on Figures 3 and 4. As it is shown on Figure 3 the investigated soil area is divided in by a grid into separate equal parcels, where the crossing points of the screen are the measuring points, or the places of sample-taking. Each crossing point gets a laser shots number, ten laser shots/mass spectra per point, so these laser shot numbers are related to the measuring location. On Figure 4 is presented a plot of the detected elements in isotopic resolution in relation to the places where the samples are taken. This simple operation allows in a fast way conclusions about the degree of heavy metal contamination

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101/110 111/120 121/130 131/140

1/10 11/20 21/30 31/40 41/50 51/60 61/70 71/80 81/90 91/100

Figure 3. An example of a grid or a screen over contaminated soil area under investigation with numbers of laser shots on points of sample-taking.

Figure 4. A plot of the estimated distribution of detected elements in isotopic resolution (y-axis) over the laser shot number or place of sample-taking (x-axis).

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of the soil area to be made. The results for particular metals as Cu, Zn, Cd and Pb were verified independently by AAS and the check showed a satisfactory agreement. A look on the distribution plot notes, that the mass numbers 2730 and 39 40 are evidently present in nearly all laser shots/mass spectra. They originate from Al (mass 27), Si (masses 2830), K (masses 39, 41) and Ca (masses 40, 42, 43, 44). These elements belong to the soil matrix. In great number of mass spectra there are signals of mass number 52 and 75. They indicate contamination with Cr and As. Another evidence for contamination is by mass numbers 6370, which originates from the presence of Cu and Zn. Separate signals in the mass region 110140 demonstrate some local distribution of Cd and Sn. Finally, Pb is found by mass numbers 206208 in many places, but is distinguished in local distributions. With this simple demonstration, which can be accomplished with the portable modification of the above described laser mass analyzer even directly in fields, a fast conclusion about the heavy contamination is possible, when needed. This would help to separate the harmful soil areas with metal contamination in respect to the country local Maximum Permissible Levels. The approach saves money and time in comparison to conventional and analytically more precise laboratory methods and gives a satisfactory and fast information for the decision-makers how to proceed with the remediation practices. References
McBride M.B. Advances of Soil Science, 10, 1989, 156. Trachtenberg, I.M., V.G. Kolesnikov, V.P. Lukovenko. Heavy metals in the environment, Science and Technics Publ., Minsk, 1994, 1123. Ilin V.V. Heavy metals in the system soil-plant. Science Publ. Novosibirsk, 1992, 105124. Managadze, G.G., R.Z. Sagdeev, L. Simeonov. Proc. Of the Phobos Study, 1988, 163186. Simeonov, L. Comp. Rend. Acad. Bulg. Sci., 40, 1987, 6770.