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Research Article
General Science
Environmental Assessment

Spectrophotometric determination of non-transition


elements (Zn Hg) in environmental sample by the
metal substitution after fractional extraction
Mohammad Nasir Uddin1, Nur Mostaq Shah1, Md. Mujahidul Islam1, Mohammad Amzad
Hossain1

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Abstract
Author and Article Information
Introduction
Materials and Methods
Results and discussion
Discussion
Conclusions
Acknowledgements
Author Contributions
References

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Abstract
Diethyldithiocarbamate (DDTC), the common reagent used for spectrophotometric
determination, forms M(DDTC)2 complexes (M = Cu, Zn, Hg) that are soluble in organic
solvents like CHCl3 or CCl4. Though DDTC complex of Cu(II) shows maximum absorption at
435 nm but that of Hg(II) and Zn(II), being non-transition elements with d 10 electronic
system, shows no absorption in the same region. Again the stability of DDTC complexes is
varied as the metal sequence of Hg> Cu> Zn. Hence from Zn(DDTC)2 zinc is substituted
with the addition of excess copper, and from Cu(DDTC)2 copper is substituted with the
addition of mercury. The subsequent increase or decrease in absorption is equivalent to the
amount of zinc or mercury, respectively. Therefore, based on this substitution
spectrophotometric method has been proposed for the determination of Zn(II), Hg(II) by the
measurement of Cu(DDTC)2. Proposed method has been optimized, validated and applied
to the environmental samples for their simultaneous determination. The LOD and LOQ were
found to be 0.029 g mL-1 and 0.098 g mL-1 respectively for both zinc and mercury
determination.
Keywords

Metal substitution, spectrophotometric determination, nontranstion elements,

environmental sample, fractional extraction

Author and Article Information


Author info

1) Department of chemistry, University of Chittagong, Bangladesh


Recieved
Mar 31 2014AcceptedMay 3 2014PublishedMay 21 2014
Citation

Uddin MN, Shah NM, Islam M, Hossain MA (2014) Spectrophotometric determination

of non-transition elements (Zn Hg) in environmental sample by the metal substitution after
fractional extraction. Science Postprint 1(1): e00021. doi: 10.14340/spp.2014.05A0003

Copyright

2014 The Authors. Science Postprint is published by General Healthcare Inc. This

is an open access article under the terms of the Creative Commons AttributionNonCommercial-NoDerivs 2.1 Japan (CC BY-NC-ND 2.1 JP) License, which permits use
and distribution in any medium, provided the original work is properly cited, the use is noncommercial and no modifications or adaptations are made.
Funding

This research is partially funded by University Grant Commission (UGC,

Bangladesh) under University Revenue Budget Scheme. Ref. 371/P&D/7-28/2012(part 3)


dated 20/05/2012
Competing interest
Donation massage

No conflict of interest.

Any support would be highly appreciated for our further research.

Corresponding author
Address
E-mail

Mohammad Nasir Uddin

Department of chemistry, University of Chittagong, Bangladesh

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Introduction
A variety of metals could enter industrial wastewaters as a result of anthropogenic activity.
Due to corrosion and geological factors some metal ions in complex form being
environmental contaminants could also be present in drinking waters and natural water
bodies and thereby to the soil. By the biological cycle, some of them through the food chain
pass into plants, animals, and man, thus affecting them negatively.
Copper is one of the important and essential nutrients for human health as well as the
growth of animals and plants. Copper is required for normal metabolic processes

. Zinc is

1, 2

most commonly used as an anti-corrosion agent, galvanization as an anode material for


batteries as a substitute for the traditional lead/tin alloy in pipes, in the automotive, electrical,
and hardware industries

3, 4

. Zinc ensures a healthy immune system and takes part in DNA

synthesis as well . Zinc dithiocarbamate complexes are used as agricultural fungicides .


5

Although both zinc and copper are the essential micronutrients and are required by the body
in very small amounts, excess in the human body can cause stomach and intestinal distress
such as nausea, vomiting, diarrhea, and stomach cramps. Mercury and its compounds are
used in medicine. Mercury is used in dental amalgam. It is used as a preservative in
laboratory reagents and related chemicals. Mercury is a heavy metal which is much toxic for
human health. It causes many harmful disease when intake by human body

1, 2

. Mercury

can be inhaled and absorbed through the skin and mucous membranes. The chief sources
of mercury pollution are chlor-alkali plants, paper, pulp, cellulose and plastic industries,
electrical, paint, pharmaceutical industries, etc. Uses of mercury as fungicides, pesticides,
etc., also add mercury to the environment

1, 2, 7

. Due to the tremendous applications their

exposure to environment and thereby in food cycle is obvious. Therefore, trace and ultratrace determination of copper, zinc and mercury is of great importance, as some of them
have nutritional significance, whilst others are toxic

4, 8, 9

Atomic absorption spectroscopy (AAS) and inductively coupled plasma-atomic emission


spectroscopy (ICP-AES) have been the method of choice for their analysis because of their
utility, sensitivity and reliability. But these techniques suffer from the limitations of being
rather costly (considering instrument acquisition and maintenance), time-consuming (with
respect to sample preparation), and not always readily available. Contrary, in laboratories of
developing countries like UV-visible spectroscopy is a well-established analytical technique
with mature methods and equipment. It is commonly used in both research and science as
well as in industry in inorganic trace analysis. In these regarding a number of
spectrophotometric reagents as chloro(phenyl)glyoxime , 3-methoxy-4-hydroxy
4

benzaldehyde-4-bromophenylhydrazone

10

, thiosemicarbazone , and so on are reported


11

for copper determination. Both zinc and mercury having d10 electronic systems dont show
electronic transition, and hence dont absorb radiation in visible region. So,
spectrophotometric methods for their determination are quite limited. Use of
thiosemicarbazones, dithiozone or hydrazones as a sensitive colourful reagent has been
reported for the zinc determination

12-14

, whereas diacetylmonoxime isonicotinoylhydrazone,

diphenylthiocarbazone are reported for the mercury determination

15, 16

. However, one of the

most common reagents, diethyldithiocarbamate (DDTC) is used for spectrophotometric


determination of transition elements Cu(II), Ni(II), Mn(II), Pb(II) and V(V)

17

. Copper forms

yellow Cu(DDTC)2 complex which is insoluble in water and is extracted in organic solvent for
spectrophotometric measurement

18

. Hg(II) and Zn(II) give white insoluble complexes with

DDTC which are soluble in CHCl3/CCl4. Sequence of stability of DDTC complex is as Hg>
Cu> Zn. Therefore, an alternative method for their has been proposed based on the metal
substitution followed by the measurement of Cu(DDTC)2 spectrophotometrically. Finally,
present method has been successfully applied for their determination in a number of
environmental water and soil samples.

Materials and Methods


Chemicals and reagents
High-purity carbon tetrachloride, various acids, salts and reagent grade Na-DDTC (Merck)
were used. The standard stock solutions (1000 g mL-1) were prepared by dissolving
appropriate amount of each salt in water. Solutions of a large number of inorganic ions and
complexing agents were prepared from their analytical grade, or equivalent grade, water
soluble salts. Stock solutions and environmental water samples (1000 mL each) were kept
in polypropylene bottles containing 1 mL of concentrated HNO 3.

Instrumentation
A Shimadzu UV Visible spectrophotometer (model UV-1800) with suitable settings quipped
with 1-cm quartz cells was used for measuring the absorbance. The spectral band length
was 1 nm, the wavelength accuracy was 0.5 nm with automatic wavelength correction, and
the recorder was a computer-controlled in the wavelength range 1901100 nm. A Jenway
(England, U.K) (Model-30100) pH meter were used for the measurement of pH. A Thermo
(Model-iCE 3000 C093300131v1.30) AAS spectrophotometer was used for comparing the
results.

Preparation of standards
A 0.1% (5.8410-3M) stock solution of Na-DDTC was prepared by dissolving 0.1 g sodium
diethyldithiocarbamate reagent in approximately 80 mL water heated at 60C. Afterwards,
the volume was made up to 100 mL by adding distilled water in volumetric flask and filtered.
A stock solution (100 g mL-1) of copper, zinc or mercury was prepared by dissolving
appropriate amount of copper sulphate pentahydrate, zinc sulphate heptahydrate or
mercuric chloride (Merck, Germany) in 250 mL of doubly distilled deionized water. The
working standards were prepared by suitable dilutions of this stock solution. The buffer
solutions were prepared by mixing 1M HCl and 1M sodium acetate (pH 13), 0.2M acetic
acid and 0.2M sodium acetate (pH 3.26.0), 1M sodium acetate and 0.2M acetic acid (pH
7.0) and 2M ammonium hydroxide and 2M ammonium chloride (pH 8.012.0). Suitable
portions of these solutions were mixed to get the desired pH. A 100 mL stock solution of
tartrate (0.25M) or ammonium thiocyanate (0.4M) was prepared by dissolving 7.055 g of

A.C.S grade (99%) potassium sodium tartrate tetrahydrate or 3.0428 g of solid ammonium
thiocyanate in deionized water. A 100 mL solution of dilute ammonium hydroxide was
prepared by diluting 10 mL concentrated NH4OH (2830% A.C.S grade) to 100 mL with
deionized water. A 100 mL stock solution of EDTA (4000 g mL-1) was prepared by
dissolving 0.4 g of A.C.S grade (>90%) dehydrated disodium salt of
ethylenediaminetetraacetic acid in 100 mL deionized water. Stock solutions were stored at
4C, protected from light and were used within three months. Bimetallic complexes, [Zn(en) 3]
[HgI4], [Zn(NH3)6][HgI4] and [Zn(An)6][Hg(SCN)4] used as certified materials, were prepared
by the same procedure described by Uddin et al.

19

Procedure for the simultaneous determination of copper, zinc


and mercury
To determine copper, zinc and mercury simultaneously, a mixture of (various volume) 210 4

M Cu(II), Zn(II) and Hg(II) solution was placed in a 25-mL separating flask along with 0.3

mL 0.05 M H2SO4 and 5 mL of the reagent DDTC (5.8410-3 M) solution. Its volume was
made up 15 mL with deionized water. The mixture was stirred at 10 min. The solid product
of M(DDTC)2 (Cu, Zn, Hg) complexes so formed was extracted carefully with the addition of
15 mL (53) CCl4, and organic phase was separated out. pH value of one portion was
adjusted to 5 using acetate buffer. A portion of 5 mL extract was separated out and its
absorbance, which is equivalent to copper, was measured at 435 nm against a blank.
Excess Cu(II) solution of 210-4M was added to remaining portion (10 mL) of extract when
additional Cu(DDTC)2was formed by the replacement of zinc immediately. Organic phase
(10 mL) was further separated after vigorous stirring for 10 min. Another portion of 5 mL
extract was separated out and the absorbance was measured at 435 nm against a blank.
Additional absorbance is equivalent to Zn(II) present in sample. Then known amount of
Hg(II) solution was added to third portion (5 mL) of the extract when its pH value was
adjusted to 10 using ammonium (basic) buffer. The intensity of yellow colour of
Cu(DDTC)2 was reduced immediately and organic phase was further separated after
vigorous stirring for 10 min. The absorbance was measured at 435 nm against a blank.
Reduced absorbance will be equivalent to mercury present in solution. Procedural lay out
for the simultaneous determination of copper, zinc and mercury is given in Figure 1.

Procedural lay out for the simultaneous determination of copper, zinc


and mercury
Figure 1

Results and discussion


Method optimization
Method was primarily optimized for the copper determination. Zinc and mercury
determination was based on the measurement of increase and reduction of absorbance of
Cu(DDTC)2.

Absorption spectra
The absorption spectra of the reagent and the complex are recorded in the wavelength
range 300650 nm at pH 5.0 against CCl4. The typical superimposed UV-vis spectra of
Cu(DDTC)2, Zn(DDTC)2 or Hg(DDTC)2 in CCl4 and reagent blank are presented in Figure 2.
The spectra show that Cu(DDTC)2 complex solution has an absorption maximum at 435 nm,
where as Zn(DDTC)2, Hg(DDTC)2 or the reagent does not have appreciable absorbance at
this wavelength. Therefore, UV-vis spectrophotometric measurements were carried out at a
wavelength of 435 nm for subsequent studies.

Figure 2

The typical superimposed UV-vis spectra of Cu(DDTC)2in CCl4

Black curve after Zn substitution, red curve for Cu(II) in mixture and blue curve after Hg(II) addition.
Bottom green curve is an overlapped one for the Zn(DDTC) 2 or Hg(DDTC)2.

Optimization of reaction conditions


Effect of acid

Acid effect was primarily tested for nitric, sulfuric, hydrochloric and phosphoric acids while
sulfuric acid was supposed to be suitable for Cu(DDTC)2 complex formation. The influence
of sulfuric acid concentration on the reaction was investigated by varying acid values. At
room temperature (25 5)C a constant absorbance was produced for (0.10.8)10 -2 M,
H2SO4.
Therefore, all measurements were peformed at 0.110-2 M H2SO4.

Effect of reagent concentration


The absorbance of the complex solution was measured for different molar excesses (1:1
1:40) of sodium diethyldithiocarbamate leaving copper(II) concentration constant (1.0 g mL 1

). The reagent molar ratios of 1:101:40 produced a constant absorbance. Therefore, 15

fold molar excess of DDTC was used in all the subsequent experiments and greater molar
excess of the reagent was not studied.

Effect of temperature and time


The effect of temperature on the reaction was not studied due to the lake of instrumental
facilities and experiments were carried out at room temperature (25 2C). Reaction
between Cu and DDTC was allowed to proceed at room temperature for varying period of
time when reaction goes to almost completion within 1 min. However, for higher precision
the reaction was allowed to proceed for quite longer time of 10 min.

Extraction parameters for the complex, Cu(DDTC)2


Effect of the aqueous phase volume
The volume of the aqueous phase is an important factor for the extraction of metal ions as
Cu(II)-DDTC is sparingly soluble in aqueous phase

20

. The aqueous phase volume was

changed from 5 mL to 30 mL for 1 g mL-1 of Cu(II). The absorbance was found to be


decreased with the increase of aqueous phase volume. Hence total aqueous volume was
always confined to maximum volume 15 mL throughout all experiments.

Optimum extraction period


The efficiency of Cu(DDTC)2 extraction in organic phase depends on the extraction period.
Optimum extraction period was checked for various period of time containing for 1 g mL 1

of Cu(II). Constant absorbance was obtained after 10 min. and it was remained constant

up to studied period of 30 min.

Effect of pH on the extraction of the complex exchange reaction


The influence of pH on the exchange reaction, replacement of zinc by copper or copper by
mercury and subsequent extraction in organic phase, was investigated by carrying out the
reaction in buffer solution of varying pH values.
The effect of pH on the color intensity is studied in the pH range 112. The optimum pH
value for the replacement of zinc by the copper from Zn(DDTC)2 is attained at pH 4 and
remains constant up to 8 (Figure 3). Hence, pH 5.0 was chosen for further studies as
convenient. In case of copper replacement by mercury forming Hg(DDTC) 2, optimum pH
value for the highest recovery of mercury was obtained at 10 as shown in Figure 4. It is
assumed that the reaction to form this complex could have competed against hydroxide
precipitation above pH 10.0 and at acidic pH, as the sulfur atom in the chelating site of
DDTC has more affinity power with proton at a higher concentration of protons.

Summary for the optimization of variables of the proposed spectrophotometric method is


presented in Table 1.

Effect of pH on the extraction of the Cu(II)-DDTC complex in organic


phase
Figure 3

Effect of pH on the extraction of the Hg(II)-DDTC complex in organic


phase
Figure 4

Summary for the optimization of variables of the proposed


spectrophotometric method
Table 1

Composition of the complex


Jobs method of continuous variation and the molar-ratio method

21

were applied to

ascertain the stoichiometric composition of the complex, Cu(DDTC)2 and the stoichiometry
was found to be 1:2 (Copper: Ligand).

Method validation
Validation parameters

Method was validated in terms of ICH analytical performance parameters

22

; precision,

accuracy, specificity, limit of detection, limit of quantitation, linearity and range, suitability
and robustness. To assess the method validation its accuracy and precision were checked
analyzing synthetic mixture and certified reference materials. The result of Zn and Hg
estimation was compared to that of calculated values. The metal content in the biological
samples were determined by AAS and results were compared to the developed method.

Preparation of calibration curves

The calibration curve was constructed with ten standard solutions containing 0.0116.0 g
mL-1 of copper, zinc or mercury according to the general procedure. Triplicate measurement
was taken for each concentration levels. The curve was constructed by plotting absorbance
against corresponding concentrations. The linearity range, regression equation and
coefficient of determination (r2) were obtained by the method of least squares. The
calibration curves are shown in Figure 5 for zinc and copper, respectively. The straight line
obeyed the equation y = 0.264x + 0.087 and y = 0.209x + 0.070 for zinc and copper,
respectively. The liner plot, between the absorbance obtained after mercury addition and the
amount of mercury added, is drawn and the straight line obeyed the equation y = -0.065x +
1.140.
Alternatively, it was drawn plotting reduced absorbance against amount of mercury added
when the straight line obeyed the equation y = 0.065x + 0.174. Figure 6 shows the
calibration curve constructed by plotting absorbance (-ve slope) and reduced absorbance
(+ve slope) against corresponding concentrations of mercury (g mL -1). For all equations
coefficient of determination (r2) was better than 0.998. According to the Beers law linearity
range of 0.0214 g mL-1 was obtained for zinc and that for Cu(II) alone was 0.0212 g
mL-1. Linearity range for mercury was obtained 0.0215 g mL-1. The analytical sensitivity,
the calibration sensitivity, which is the slope of the analytical curve, the limit of detection,
and the limit of quantitation as well as other analytical characteristics are calculated from the
data obtained for calibration curve. Molar absorption coefficients and Sandals sensitivity
were calculated using linearity equation. Table 2 shows the parameters of the performance
for the proposed spectrophotometric method for determination of mercury and zinc content.

Calibration curve constructed by plotting absorbance against


corresponding concentrations (g mL-1) of zinc (red) and copper (blue)
Figure 5

Calibration curve constructed by plotting absorbance (blue) and


reduced absorbance (red) against corresponding concentrations of
mercury (g mL-1)
Figure 6

Parameters for the performance of the proposed spectrophotometric


method for determination of mercury and zinc content
Table 2

Accuracy and precision


For accuracy check of the method standard mixtures having 1, 5, 8 g mL -1 of zinc and
mercury were analyzed. The recovery was 94.0102.0% (Table 3) for both intra- and inter
day analyses of standards. The results indicate that found values are very concordant
indicating the good accuracy of the proposed method. The precision of the method was
expressed in terms of percentage relative standard deviations (RSD) for five replicate
measurements in the same day within-day repeatability (RSD). The procedure was repeated
at same concentration levels on five consecutive days to determine between-day
repeatability. RSD did not exceed 4.43% (Table 3) proving the high precision of the
proposed method.

Determination of zinc and mercury in standard mixture for the intra


and inter-day accuracy and precision study
Table 3

Sensitivity
The sensitivity calculation of the method is based on the standard deviation of the response
(Sxy) and the slope of the calibration curve (a). The limit of detection were calculated from
calibration graph by the formula; LOD = 3Sxy/a, and the limit of quantification; LOQ =
10Sxy/a. The results are presented in Table 2. The lower detection limit and quantification
limit were found to be 0.029 g mL-1 and 0.098 g mL-1 respectively for both zinc and
mercury determination.

Robustness
The influence of small variation in the method variables; (DDTC) concentration, buffer pH,
reaction and extraction period on its analytical performance shows the robustness of the
method. Small variation in the method variables did not significantly affect the procedures;
recovery values were (99.87101.41) (0.260.66)% for zinc and (99.07103.11) (0.24
1.40)% for mercury.

Ruggedness
A pre-validated AAS method was used as a reference method for determination of zinc and
mercury in whole blood and urine samples as to get inter method variation as the test of
ruggedness. Whole blood and urine samples were digested according to the previously

reported procedure

18

. Inter method variations in percentage of error in measurements of

zinc and mercury by the proposed method and AAS has been shown in Figure 7. No
significant differences were found between the calculated and theoretical values of t- and Ftests at 95% confidence level proving similar accuracy and precision in the determination of
metals by both methods.

Inter method variations in percentage of error in measurements of


proposed method and AAS
Figure 7

Suitability
For at five different concentration levels of standard within 1.010.0 g mL -1maximum
wavelength (435.52 0.33) of absorption was checked. Their relative standard deviation
was found to be 0.077%. Molar absorptivity calculated for the four different concentrations
gave straight line parallel to concentration axis (x-axis) when plotted.

Effect of diverse ions


The determination of Zn(II) or Hg(II) was carried out in presence of various anions and
cations using the above described general procedure. The tolerance limit of a foreign ion is
taken as the amount that caused an error in the absorbance value of 10%. Large amounts
of commonly associated cations and anions do not interfere in the present method. Among
the various ions studied, all the anions and the cations Pb(II), Te(IV), U(VI), Na(I), K(I), Li(I),
Th(IV), W(VI), Ce(VI), Ti(IV), Al(III) do not interfere even when present in more than 100 fold

excess. Copper(II), nickel(II), cobalt(II), mercury(II), cadmium(II), iron(III) and iron(II) ions
interfered seriously at all proportions. Interference from Co, Ni, Cr, Mn, Bi, Pb, Cd can be
eliminated using EDTA as masking agent up to 50 fold excess. Selective extraction of zinc
was performed from thiocyanate solution in 0.5 M HCl medium followed by its back
extraction with an ammoniacal solution. If excess iron is present in the sample, it is
necessary to add 1300 g mL-1 NaF/NaI before their extraction. EDTA has been selected to
be suitable masking agent for the determination of copper and zinc, and ascorbic acid for
the determination of mercury.

Application
The present method was successfully applied to the determination of zinc and mercury in
series of synthetic mixtures of various compositions and a number of certified materials as
the validation check. Copper, zinc and mercury were determined in environmental water and
soil samples. Samples were prepared for the metal analysis according to the procedure
mentioned below.

Determination of zinc and mercury in synthetic mixtures


Several synthetic mixtures of varying compositions containing zinc or mercury and diverse
ions of known concentrations were prepared and metal content was determined by the
present method using a suitable masking agent and the results, both accuracy and
precision, were calculated. The results are shown in Table 4. The accurate recovery was
achieved in all solutions with maximum RSD value of 1.36% for zinc and 1.70% for mercury
of their triplicate measurements. It is indicated that zinc and mercury can be measured
eliminating possible interferences from diverse ions.

Determination of zinc and mercury (n = 3) in synthetic mixture by the


proposed spectrophotometric method
Table 4

Determination of zinc and mercury in reference materials


20 mg of each synthetic complex or 0.1 g of an alloy and amalgam was accurately weighed
and acid decomposition

18

was performed in a 50 mL Erlenmeyer flask. The solution was

carefully evaporated to dense white fumes to drive off the oxides of nitrogen and then
cooled to room temperature (25 5)C. After suitable dilution with deionized water, solution
was neutralized with a dilute NH4OH solution. The resulting solution was filtered if
necessary. An aliquot of 2 mL decomposed solution was taken into a calibrated flask and
the metal content was determined under general procedure using suitable masking agent.
The average percentage recovery and RSD values for five replicate analyses were in good

agreement with the certified values (Table 5) indicating good accuracy and precision of the
measurements.

Analysis of certified substances for the determination of zinc and


mercury
Table 5

Determination of zinc and mercury in water and soil samples


250 mL of industrial (KY steel, PHP steel, berger paint, ship breaking Chittagong urea
fertilizer limited, battery waste water, ystern refinary) or battery water was mixed with 10 mL
of conc. HNO3, 2 mL of conc. H2SO4 and 2 drops HClO4 acid in a distillation flask. The
sample was digested until a paste was formed. Other water (250 mL) samples (Tap water,
Karnafuli river water and Bay of Bangle water) were pre-concentrated by simple
evaporation. Ammonia buffer solution was added to precipitate iron as hydroxide. The
resulting solution was then filtered and quantitatively transferred into a 50 mL calibrated
flask and made up to the mark with deionized water. 2 g of soil sample was placed into a
250 mL flask. 0.2 mL of sulfuric acid, 1 mL of nitric acid and 1 mL of perchloric acid were
added. The mixture was heated to 180C for 3 hrs on a hotplate. After cooling, 1 g of
ammonium chloride and 20 mL of 0.5 N HCl were added, evaporated to approximately 10
mL and filtered into 50 mL plastic bottles through an ashless 5B filter paper. Ammonia buffer
solution was added (not exceeding pH 8) to this solution to precipitate iron as hydroxide. An
aliquot (2 mL) of pre-concentrated environmental water or acid digested soil sample was
pipetted into a calibrated flask and the copper, zinc and mercury content was determined

under the general procedure using suitable masking agent. Triplicate measurements
possess good precision (RSD not greater than 6%) (Table 6).

Determination of copper, zinc and mercury in environmental samples


by the proposed method
Table 6

Discussion
Zn(II) and Hg(II) complex formed with DDTC have no absorption whereas copper gives
yellow insoluble complexes which has maximum absorption at wavelength 435 nm. Method
is primarily optimized for copper determination using DDTC. Cu(DDTC) 2is more stable than
Zn(DDTC)2. Zinc can be determined by a quantitative displacement Cu(II) followed by the
extraction of Cu(DDTC)2 with a carbon tetrachloride and measuring the increased
absorbance. Again, Hg(DDTC)2 is more stable than Cu(DDTC)2. Addition of He replaces the
copper form Cu(DDTC)2 and thereby absorbance is reduced. Mercury determination is
based on the measurement of reduced absorbance. Difference between two measurements
gives the zinc or mercury contents present in mixture. Therefore, copper, zinc and mercury
have been simultaneous determined after fractional extraction followed by their
spectrophotometric measurement.
Robustness, ruggedness and suitability of the method indicated the reliability of the
proposed method during its routine application for the analysis of zinc and mercury. The
absorbance of the Cu(DDTC)2 complex remains stable for at least 72 h. This allowed the
process of large batches of samples and their comfortable measurements convenient. This
gives the high throughput property to the proposed method when applied for analysis of
large number of samples in quality control/analytical laboratories. The results of samples
analyses by the spectrophotometric method showed the satisfactory accuracy and precision
within analytical agreement. The pH value should not be lower than 4 due to the fast
decomposition of dithiocarbamates at these experimental conditions. On the other hand, pH
value over 10 would accelerate the Cu(OH)2 precipitation. The results of biological analyses
by spectrophotometric method were found to be in excellent agreement with those obtained
by AAS.
In deep-well water zinc was 0.01g mL-1 but in Chittagong WASA water it was present 5.07
g mL-1 which is too much larger than deep well water. The large amount of the zinc and
copper was also obtained in steel industry area water samples. For example the amount of
Zn in PHP Steel area was 337.16 g mL-1 but in KY Steel area it was 10.43 g mL-1. Higher
values for both zinc and copper concentration were detected for the water and soil samples
collected from ship breaking yard. In case of industrial sample battery waste water contain

higher amount of copper and Yestern Refinery water sample contain higher value of
mercury. Therefore, respective responsible authorities in Bangladesh should have an
attention to control environmental pollution due to zinc exposure.

Conclusions
Among the techniques suitable for the quantification of metal ions, ICP-MS, ICP-AES and
atomic absorption or emission spectroscopy are likely to be the most widely employed. The
choice of any analytical methods depends on the availability of reagents, cost effectiveness
of instruments and the time required for analysis as well as safety and ease of operation.
Thus, simple spectrophotometric techniques, which tend to be less costly and laborintensive, are viable alternative to those methods requiring more sophisticated
instrumentation. A spectrophotometric procedure for the simultaneous determination of
zinc(II) and mercury using diethyldithiocarbamate (DDTC) as ligand is described. In the
presence of a suitable masking agent very good selectivity was achieved for the
simultaneous determination of zinc and mercury. Dithiocarbamates are more suitable than
other complexing reagents because of their selectivity towards Hg(II) and Zn(II). Great
advantage that is interesting also of this method is its selective application to copper, zinc or
mercury determination individually or their simultaneous determination as required.
Therefore, the method described herein has many advantages: it is simple and rapid; it has
high accuracy and sensitivity, use of inexpensive reagents available in any analytical
laboratory. The method is practical and valuable for its wide application.

Acknowledgements
Authors feel pleased to express their gratitude toward authority of University of Chittagong,
Bangladesh and University Grant Commission (UGC), Bangladesh for financial support to
conduct the project. Principal author also acknowledges to the MS students who carried out
the research and Department of Chemistry for giving laboratory facilities.

Author Contributions

Uddin MN: Project director, wrote the article and designed the discussion.
Shah NM, Islam MM, Hossain MA: conducted experiments and analyzed the data.

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Article outline

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Abstract

Keywords

1. Introduction

2. Materials and methods

3. Results and discussions

4. Conclusions

Acknowledgements

References

Figures and tables

1.
Table 1

2.

3.
Table 2

4.

5.
Table 3

6.

7.
Table 4

8.

9.

10.

222222222222222222222222222222222222222222222222222222222
Table 5

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Analytica Chimica Acta


Volume 389, Issues 13, 14 May 1999, Pages 257266

Determination of chromium in airborne particulate matter


by high resolution and laser ablation inductively coupled
plasma mass spectrometry

Chu-Fang Wanga, ,
Ching-Jer China,
Shen-Kay Luob,
Lee-Chung Menb
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doi:10.1016/S0003-2670(99)00162-2
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Abstract
This work presents an optimized sample digestion procedure for determining Cr in airborne
particulate matter by inductively coupled plasma mass spectrometry (ICP-MS). High
resolution (HR) ICP-MS is utilized to examine how the added acid mixture and subsequent
evaporation process influence spectroscopic interference. Experimental results indicate that
a two-step high pressure bomb acid digestion (1st step with HNO 3+HClO4, and 2nd step with
HF) procedure without evaporation is the optimum pre-treatment procedure for determining
Cr by ICP-MS. In addition, laser ablation (LA) ICP-MS is used directly to analyze for Cr in
airborne particulate matter. Results obtained by LA-ICP-MS correlate well with certified
values and values obtained from the conventional acid digestion/HR-ICP-MS method. The
detection limit for Cr in air particles by HR-ICP-MS with the proposed digestion method
is<10 ng g1. Furthermore, LA-ICP-MS provides a rapid direct analytical technique with a
detection limit of 0.05 g/filter.

Keywords

Chromium determination;
Airborne particles;
Microwave digestion;
High-pressure bomb digestion;
High resolution inductively coupled plasma mass spectrometry;
Laser ablation inductively coupled plasma mass spectrometry

Corresponding author. Tel.: +886-3-5715131-4222; fax: +886-3-5727298; e-mail:


cfwang@ins.nthu.edu.tw
Copyright 1999 Elsevier Science B.V. All rights reserved.

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1999, Reference Module in Chemistry, Molecular Sciences and Chemical Engineering,
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Article outline

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Abstract

Keywords

1. Introduction

2. Experimental

3. Results and discussion

4. Conclusions

Acknowledgements

References

Figures and tables

1.
Table 1

2.
Table 2

3.

4.

5.
Table 3

ADVERTISEMENT

Analytica Chimica Acta


Volume 392, Issues 23, 21 June 1999, Pages 299306

Determination of arsenic and vanadium in airborne related


reference materials by inductively coupled plasmamass
spectrometry

Chu-Fang Wanga, ,
C.Y. Changa,
C.J. China,
L.C. Menb
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doi:10.1016/S0003-2670(99)00242-1
Get rights and content

Abstract
This study investigated sample digestion techniques and instrumental interference in
determining As and V in airborne related reference materials using inductively coupled
plasma mass spectrometry (ICPMS). Four reference materials, NIST SRM 1648 urban
particulate matter, BCR Reference Material No. 176 city waste incineration ash, NIST SRM
2709 San Joaquin soil, and NIST SRM 1633b coal fly ash were dissolved by acid mixture highpressure bomb digestion. A HNO3+H2O2+HF mixed acid digestion with a low temperature
evaporation procedure is proposed as an effective sample pretreatment method for the
determination of As in all samples. The addition of HF is required especially for dissolving
geologically originated samples such as soil or dust. It was found that, with the proposed
digestion procedure, the determinations of V are still unacceptable for highly chlorinated
samples when using quadrupole ICPMS. It was also proved that sector-field ICPMS is
sufficiently sensitive for the determination of V, and can be utilized as a valid tool to
investigate the amount and direction of biased results obtained from ICPMS.

Keywords

Arsenic determination;
Vanadium determination;
Air particles;
High-pressure bomb digestion;
Inductively coupled plasma mass spectrometry

Corresponding author. Tel.: +886-3-5715131-4222; fax: +886-3-5727298; e-mail:


cfwang@ins.nthu.edu.tw
Copyright 1999 Elsevier Science B.V. All rights reserved.

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Article outline

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Abstract

Keywords

1. Introduction

2. Materials and methods

3. Results and discussion

4. Conclusions

Acknowledgments

References

Figures and tables

1.

Table 1

2.
Table 2

3.

4.

ADVERTISEMENT

Analytica Chimica Acta


Volume 599, Issue 2, 19 September 2007, Pages 170176

Microwave digestionICP-MS for elemental analysis in


ambient airborne fine particulate matter: Rare earth
elements and validation using a filter borne fine particle
certified reference material

Pranav Kulkarnia,
Shankararaman Chellama, b, , ,
James B. Flanaganc,
R.K.M. Jayantyc
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doi:10.1016/j.aca.2007.08.014
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Abstract
NIST standard reference material SRM 2783 was employed to validate a high temperature,
high pressure, two-stage microwave assisted acid digestion procedure using HNO 3, HF and
H3BO3 developed for the analysis of trace elements (including rare earths) in atmospheric
fine particulate matter (PM2.5) prior to inductively coupled plasma mass spectrometry (ICPMS). This method quantitatively solubilized Na, Mg, Al, K, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se,
Rb, Sb, Cd, Cs, Ba, Pb, Th, U and several rare earth elements (REEs) (La, Ce, Pr, Nd, Gd, Dy,
Er, Sm and Eu) from SRM 1648 and SRM 2783. A small amount of HF in the first stage was
required to dissolve silicates necessitating the corresponding addition of H 3BO3 in second
stage to dissolve fluoride precipitates of Mg, La, Ce and Th. The optimized microwave
dissolutionICP-MS method detected Na, Mg, Al, K, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb,
Sr, Cd, Mo, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Gd, Pb, Th and U at trace to ultra-trace levels in
ambient airborne fine particles from three sites in North Carolina. La to light lanthanide
signature ratios suggested that soil and motor vehicles are the dominant REE sources in SRM
2783 and PM2.5 samples collected during this study.

Keywords

Inductively coupled plasma mass spectrometry (ICP-MS);


Microwave digestion;
PM2.5;
Standard reference material (SRM) 2783;
Trace metals;
Rare earth elements
Corresponding author at: Department of Civil and Environmental Engineering,
University of Houston, 4800 Calhoun Road, Houston, TX 77204-4003, United States.
Tel.: +1 713 743 4265; fax: +1 713 743 4260.
Copyright 2007 Elsevier B.V. All rights reserved.

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