Exercício II: Tente a partir do texto a seguir estabelecer em itens a estrutura que reconstitui as idéias

apresentadas. Antes de o autor iniciar a redação do texto a seguir, ele montou uma estrutura e é esta estrutura que
voce deve recriar.

CHEMICAL AVAILABILITY OF MERCURY IN STREAM SEDIMENTS

FROM THE ALMADÉN AREA, SPAIN
The contamination of the environment by mercury has been a matter of large concern
throughout the world for decades. Mercury has some unique properties that make it useful for
many industrial applications but, at the same time, highly toxic mercury compounds can cause
serious kidney injury, central nervous disorders and even death. Since the early 1960s, the
growing awareness of environmental mercury pollution has stimulated the development of
more accurate, precise and efficient methods for the determination of mercury and its
compounds in a wide range of matrices. Special attention has been paid to the determination
of mercury in aquatic systems, because this element tends to accumulate in bottom anaerobic
sediment what seems to be the first step in the aquatic bio-magnification processes [1].
The area of Almadén is located in the Central Spain and forms part of a large
geological anomaly of the Mediterranean basin (Figure 1). The Almadén mining operation is
the largest (1/3 of the total world production) and the oldest (more than 2000 years) mercury
mine/refining operation in the world. Almadén’s extensive cinnabar deposits and mining
activities constitute a “natural laboratory” for the study of the mercury exchanges and
transformations. The long-term mercury exposition in Almadén probably yielded a steady
state cycling and organification rate. In spite of the importance of this area for the
environment knowledge of mercury contamination, only a few studies have been conducted in
the region to evaluate the environmental impact and potential hazards related to mercury
contamination [2-5]. Recently, an integrated program to assess the distribution of total and
monomethylated mercury in the aquatic environment of the Almadén area has been carried
out [6]. As part of this study, a sediment survey was performed with the goal of evaluating
mercury availability and harm for the environment in the Almadén region.
The determination of total mercury content is carried out to assess the extent of the
metal contamination accumulated and provide an overview of the long-term potential toxicity
effects. However, the total determination is not enough for understanding the environmental
impacts and pathways of the different species present in the environment [7]. This mercury
can exist in a large number of different physical and chemical forms with a wide range of
properties. The most common chemical forms are: elemental mercury (Hg 0), divalent
inorganic mercury (Hg2+), methylmercury (CH3Hg+) and dimethylmercury ((CH3)2Hg).
Transportation and bioavailability of mercury as well as its physico-chemical and
toxicological properties are highly dependent on the chemical form it is present in the
environment [7-9]. Therefore, the analytical question ‘How much?’ of a trace element is
increasingly being replaced by the question ‘In which form?’ is the trace element present.
Answer the latter question is the subject matter of chemical speciation. There is no generally
accepted definition of the term but a broad definition can be given as the process of
identifying and quantifying the different species, forms or phases in which an element occurs
[10]. The species can be defined (a) functionally e. g. as “available species”, (b) operationally,
according to the reagent or procedures used in their isolation or, (c) as a specific chemical
compound or oxidation state of an element, for instance as “methylmercury” or “mercuric
mercury” [11, 12].
Operationally defined speciation procedures often involves the use of single or
sequential extractants to release species associated with particular sediment phases. In
sequential extraction, the sample is treated with a succession of reagents intended to dissolve
different sediment phases [13]. One of the first methods was described by Tessier et al. [14]
and has been thoroughly applied since then, with minor modifications, to a wide range of
samples. Due to its specific chemical characteristics, the speciation procedures applied to
other metals have shown to be unsuitable for mercury. The proposed methods for mercury
sequential extraction focused only on mercury instead of aiming at all heavy metals and have
accounted for its chemical characteristics [15-18].
Because of the varying levels of toxicity of mercury forms, knowledge of speciation is
crucial for establishing environmental issues. Of particular interest is methylmercury, not only
because it is highly toxic but also because mercury can be methylated within the environment
(specially marine and freshwater sediments) and accumulated in the tissues of fish,
considerably bio-magnifying in the food chain [7, 19].
A number of papers on the analytical technique for organomercury measurement in
environmental samples have appeared during the past twenty years. They have been reviewed
in several articles and monographs [19, 20]. Methods for methylmercury analysis are
classified according to the isolation technique and the detection system. The most widely
employed method for the extraction and separation of methylmercury in sediments is still the
classic Westöö technique [21, 22]. Other methods are acidic-leaching [23-26], alkaline
digestion [27-31] or steam distillation [29-33] followed by one- or two-step separation, (e.g.
solvent extraction), ion exchange, distillation or aqueous derivatization (hydride generation or
ethylation). Quantification can then be undertaken by electron capture, atomic fluorescence
and atomic emission or absorption spectrometry. On-line hyphenated system combining
derivatization by ethylation or hydride generation, pre-concentration by cryogenic trapping,
separation by thermal desorption, gas chromatography and detection by quartz furnace atomic
absorption spectrometry provides low detection limits and improved selectivity and sensitivity
for mercury speciation [34-36].
In the present work, three different methods of total extraction were applied for
sediments from the Almadén area with the aim of inter-comparing their results and
establishing if they are suitable for specific samples from cinnabar mining areas. The next
step was to identify which phase would bear mercury and if this mercury would be available
to be remobilize in the environment. In this case, a sequential extraction was applied. Finally,
we would identify if mercury is methylated and to what extent. A mercury speciation
procedure was applied to answer these questions.