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Determination of Anionic Surfactants Using Atomic W Absorption Spectrometry and Anodic Stripping Voltammetry
Determination of Anionic Surfactants Using Atomic W Absorption Spectrometry and Anodic Stripping Voltammetry
Atomic absorption spectroscopy (AAS) and anodic strip- has been shown to impair feeding behavior (7 ). While the
ping voltammetry (ASV) are techniques typically restricted more active marine adults (such as fish) are more susceptible
to metal analysis. An experiment developed for our under- to the presence of anionic surfactants than less active adults
graduate teaching program demonstrates the utility of these (such as crustaceans), the developmental stages of all forms
techniques for the determination of organic species, in this case, of marine life are extremely susceptible to even trace levels
the indirect analysis of anionic surfactants. The method involves of these compounds. In particular, invertebrate and fish
formation of an extractable complex between the synthetic sur- larvae show susceptibility to anionic surfactant concentra-
factant anion and the bis(ethylenediamine)diaquacopper(II) tions of 0.05 mg L{1 (8) and 0.16 mg L{1 (9), respectively.
cation. This complex is extracted into chloroform and then
back-extracted into dilute acid. The resulting Cu(II) ions are Analysis of Anionic Surfactants
determined by AAS and ASV. Students are required to deter- The APHA standard method for the determination of
mine the concentration of a pre-prepared “unknown” anionic anionic surfactants is the Methylene Blue Active Substances
surfactant solution and to collect and analyze a real sample (MBAS) method (10). This method employs the methylene
of their choice. blue cation, which forms a 1:1 ion pair with the surfactant
The experiment was designed as a final-year under- anion. The ion pair is extracted into chloroform and deter-
graduate laboratory for the subject Analytical Chemistry mined spectrophotometrically. Unfortunately, the MBAS
within our Environmental Science degree. It demontrates method lacks specificity because many sulfonates and simple
the following analytical principles: inorganic anions such as cyanate, nitrate, thiocyanate, sulfide,
indirect analysis and chloride also form extractable compounds with methylene
blue, resulting in positive interferences. For this reason, the
compleximetric analysis
MBAS method for anionic surfactants was replaced as the
liquid–liquid (solvent) extraction Australian standard method by a method that uses the
back extraction (into dilute acid) bis(ethylenediamine)diaquacopper(II) cation as the extracting
analytical recovery agent (11). This ion permits selective quantitative extraction of
analysis using flame-AAS and ASV, two of the most surfactant anions into an organic solvent (1). The surfactant
popular methods for trace metal analysis anion reacts with the aquated bis(ethylenediamine)copper(II)
ion (12) and is extracted into chloroform as a neutral inner
In their write-up, students are expected to discuss each
sphere complex (eq 1). The [Cu(en)2(RSO2O)2](org) com-
of the above principles and make a critical comparison of
plex is back-extracted with dilute acid, releasing free Cu(II)
metal analysis by AAS and ASV. The experiment expands on
into the aqueous phase. The copper concentration is then
a previous publication in this Journal for the determination
determined using AAS and ASV.
of anionic surfactants, which employed a colorimetric end-
point for the analysis (1). [Cu(en)2(H2O)2]2+(aq) + 2RSO2O{(aq) →
(1)
[Cu(en)2(RSO2O)2](org) + 2H2O(aq)
Background
en = ethylenediamine (H2NCH2CH2NH2)
Anionic surfactants are widely used for industrial and R = hydrocarbon group (C12H25C6H4)
domestic purposes, including laundry powders, dish-washing
liquids, shampoos, emulsifiers for industrial solvent cleaners, In contrast to the Australian standard method for anionic
and agricultural and horticultural chemical delivery systems. surfactant analysis, which utilizes flame AAS, the instrumen-
Although most anionic surfactants in use today are biode- tation required by ASV is simpler and more robust, without
gradable and essentially nontoxic to humans (2), a need still the need for specialized gases and extraction systems. The
exists for effective monitoring of these compounds. Aside from simple instrumentation means that very little operator ex-
the visual pollution (in the form of foaming) associated with pertise is needed, making it ideal for undergraduate students.
surfactant use, the environmental impact of surfactant release Unlike ASV, flame-AAS cannot be used to measure copper
in natural water systems can be much more serious. For ex- concentrations below 0.02 ppm, and the calibration curve
ample, several authors have reported impaired respiratory for ASV generally extends over more orders of magnitude
function in fish caused by damage to the gill epithelium at than AAS. Of its spectroscopic competitors, only flameless
concentrations below 3 mg L{1 (3–6 ). In addition, damage to AAS is able to achieve the same sensitivity as ASV, but at a
chemoreceptors of fish at concentrations as low as 0.5 mg L{1 much higher cost.