Soil pollution and the environment

Contaminated or polluted soil directly affects human health through direct contact with soil or via inhalation of soil contaminants which have vaporized; potentially greater threats are posed by the infiltration of soil contamination into groundwater aquifers used for human consumption, sometimes in areas apparently far removed from any apparent source of above ground contamination (Wikipedia, 2012). Soil quality of the healthy soil cannot be measured directly. For the EU, soil organic carbon content, pH, clay content, sealing, water, nutrient and heat regime in topsoil has been defined as the more appropriate indicator for soil quality. High organic carbon content corresponds to good soil conditions from an agro-environmental point of view: limited soil erosion, high buffering and filtration capacity, rich habitat for soil organisms, enhanced sink for atmospheric carbon dioxide, etc.. Soils with Organic Carbon content between 1 and 10 % can also be considered of high agricultural value, while soils with less the 1% can be considered as affected by severe degradation (desertification) (Figure).

Analytical background

Atomic absorption spectrometry (AAS) and atomic emission spectrometry (AES) are the most widely used techniques for heavy metals quantitative analysis in environmental samples. AAS involves the absorption of radiant energy produced by a special radiation source (lamp), by atoms in their electronic ground state. The lamp emits the atomic spectrum of the analyte elements, i.e., just the energy that can be absorbed in a resonance manner. The analyte elements are transformed in atoms in an atomizer. When light passes through the atom cloud, the atoms absorb ultraviolet or visible light and make transitions to higher electronic energy levels. A monochromator is used for selecting only one of the characteristic wave lengths of the element being determined, and a detector, generally a photomultiplier tube, measures the amount of absorption. The amount of light absorbed indicates the amount of analyte initially present . This method is applicable for the following analytes: Li, Be, B, Na, Mg, Al, P, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Ag, Cd, Sn, Sb, Ba, Hg, Tl, Pb, Th, (Meyers, 1998).
Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) measures the optical emission from excited atoms to determine analyte concentration. High-temperature atomization sources are used to promote the atoms into high energy levels causing them to decay back to lower levels by emitting light. Inductively coupled plasma is a very high excitation source (7000–8000 K) that efficiently desolvates, vaporizes, excites, and ionizes atoms. The wavelengths of photons emitted are element specific. The intensity of emission is generally linearly proportional to the number of atoms of that element in the original sample. ICP-AES and the other atomic emission techniques simultaneously or sequentially measure the concentrations of 20 elements or more at sensitivities equivalent to those of AAS. A second advantage of ICP-AES is its broad dynamic range (Figure) (Ebdon, et al. 1998).

Inductively Coupled Plasma–Mass Spectrometry (ICP-MS) combine of two well-established techniques, namely the inductively coupled plasma and mass spectrometry. An ICP argon plasma is used as ion source, ensuring almost complete decomposition of the sample into its constituent atoms. The ionization conditions within ICP result in highly efficient ionization and importantly, these ions are almost exclusively singly charged. Mass analysis is simply a method of separating ions depending on their mass-to-charge ratio (m/z). Two types of mass analyzers are commonly employed for ICP-MS: the quadrupole and the magnetic sector (Kebbekus and Mitra, 1998). The applications of ICP-MS are similar to those for ICP-AES, although the better sensitivity of the former has resulted in applications such as the determination of ultralow levels of trace elements. It may also be used for determination of total recoverable element concentrations in these waters as well as wastewaters, sludge, and soil samples (Figures ).





Gas chromatography is a powerful separation technique and it is relatively easy to couple the gas effluent to an element-specific determination method such as AAS, AES, or MS without any sample loss. A number of hyphenated techniques based on the combination of GC with AAS, MIP-AES, and ICP-MS have been used in many environmental studies. GC-AAS is normally used for the investigation of volatile or thermally stable compounds such as mercury, tin, and lead alkyl compounds. MIP-AES is an excellent detector for GC capable of detecting virtually all metals and metalloids. Absolute detection limits offered reach the subpicogram level for many elements including Hg, Sn, and Pb and picogram levels are found for most of the others. On the other hand, GCMS is potentially a highly sensitive and selective technique (Adams and Slaets, 2000).
XRF spectrometry uses X-rays as primary excitation source, usually provided by X-ray tubes, or radioisotopes, which cause elements in the sample to emit secondary X-rays of a characteristic wavelength. The elements in the sample are identified by the wavelength/energy of the emitted X-rays while the concentrations are determined by the intensity of the X-rays. Two basic types of detectors are used to detect and analyze the secondary radiation. Wavelengthdispersive XRF spectrometry uses a crystal to diffract the X-rays, as the ranges of angular positions are scanned using a proportional detector. Energy-dispersive XRF spectrometry uses a solid-state detector from which peaks representing pulse-height distributions of the X-ray spectra can be analyzed. Usually, sample preparation required for XRF analysis is minimal compared to conventional analytical techniques. However, for solid samples, since particle size, composition, and element form may affect the analysis. Thirty or more elements may be analyzed simultaneously by measuring the characteristic fluorescence x-rays emitted by a sample. Thermo Scientific Niton XRF analyzers can quantify elements ranging from magnesium (element 12) through uranium (element 92), measuring x-ray energies from 1.25 keV up to 85 keV in the case of Pb k-shell fluorescent x-rays excited with a ¹⁰⁹Cd isotope. These instruments also measure the elastic (Raleigh) and inelastic (Compton) scatter x-rays emitted by the sample during each measurement to determine, among other things, the approximate density and percentage of the light elements in the sample (Figures).



In sample matrices such as typical mining samples, metal and precious metal alloys, it is necessary to measure both lighter elements that emit lower energy x-rays (that are easily absorbed) as well as heavier elements that emit much higher energy x-rays (that penetrate comparatively long distances through the sample). Thermo Scientific Niton XRF analyzers compensate for all of these effects in order to determine the actual concentration of elements in multi-element samples from the modified fluorescence x-ray spectrum that these samples produce in the XRF analyzer. To do this, NITON employ multiple methods to determine the true composition of these complex samples from their x-ray spectra. These include: Fundamental Parameters (FP) analysis; Compton Normalization (CN); Spectral matching (“fingerprint”) empirical calibrations; User-definable empirical calibrations.
Electroanalysis is a broad spectrum of techniques that can be distinguished by the variable that is controlled: voltage or current. The usual practice is to apply one of these variables to a solution containing the analyte species and measure one of the other variables. From a plot of the measured variable versus the applied variable, information regarding the concentration and identity of electroactive species in solution is determined. Of the many electrochemical techniques, only a few are routinely used for environmental analysis: voltammetry, direct-current DC, polarography, and potentiometry (Alloway,1995).
Spectrophotometry is based on the simple relationship between the molecular absorption of UV-VIS radiation by a solution and the concentration of the colored species in solution. The basic components of a spectrophotometer include a light source, a monochromator, which isolates the desired source emission line, a sample cell, a detector-readout system, and a data-processing unit. Spectrophotometric measurements are based on the Beer-Lambert law, which describes a linear dependence of absorbance on the concentration (Gauglitz,1994).
The chemical and physical associations of toxic elements with their environment can strongly influence their distribution, mobility, and biological availability; therefore, there is an increasing need for metal speciation analysis in environmental samples (for review see refs. 45–50). The ma-in environmental applications involve speciation analysis of redox and organometallic forms of antimony and arsenic, redox forms of chromium, protein-bound cadmium, organic forms of lead such as alkyllead compounds, organomercury compounds, inorganic platinum compounds, inorganic and organometallic compounds of selenium, organometallic forms of tin, and redox states of vanadium (Sarkar, 2002).
Direct heavy metal speciation analysis can also be carried out using separation and preconcentration of particular metal species by either chromatographic methods, coprecipitation, ion exchange, separation with chelating resins, or solvent extraction. Biological substrates such as algae, plant-derived materials, bacteria, yeast, fungi, and erythrocytes can be used for metal preconcentration and direct speciation analysis (Glidewell and Goodman, 1995).
Immunoassay technology relies on an antibody that is developed to have a high degree of sensitivity to the target compound. This antibody’s high specificity is coupled within a sensitive colorimetric reaction that provides a visual result. Immunoassays offer significant advantages over more traditional methods of metal detection; they are quick, inexpensive, simple to perform, and can be both highly sensitive and selective. Antibodies that recognize chelated forms of metal ions have been used to construct immunoassays for Ni(II), Cd(II), Hg(II), and Pb(II) (Blake, et al. 1998).
Polynuclear Aromatic Hydrocarbons (PAHs) are among the most frequently monitored environmental contaminants. Standard and official methods for the analysis of PAHs are found in compendia for air, drinking water, waste water, solid waste, and food analysis. Many of these methods specify HPLC, usually with UV and fluorescence detection, as recommended analytical procedure. YMC PAH columns are optimized for the HPLC analysis of PAHs. The chromatogram shows 16 PAH compounds, listed as target pollutants by the EPA. The YMC PAH columns achieve baseline resolution and excellent peak symmetry for all 16 target analytes. The YMC PAH columns provide narrow symmetrical peak shapes and their resolving ability leads to an easy identification and quantification for PAHs. Their optimized selectivity results in a separation with enough space for wavelength changes by the use of fluorescence detectors(Figure).

 

Prof. Tamás János, Dr. Kovács Elza (2008)

Debreceni Egyetem a TÁMOP 4.1.2 pályázat keretein belül