CHAPTER 1

INTRODUCTION

(9)
 INTRODUCTION

Environmental pollution and chemical processes control are vitally

concerned with impurities at trace and ultratrace levels in aquatic environment.

The increased concern over the last decade for the heavy metal pollution of natural

waters and sediments is an interesting phenomenon (1-4). Most of the heavy

metal fractions carried to the ocean river discharge is retained in the

estuaries/coastal zone. A wealth of information is available on the distribution of

heavy metals in the terrestrial environment (5-10). Many industrialised areas are
characterised by a high degree of metal pollution and increase in recent decades

of deposition rate has been demonstrated on a regional scale. Thus there is a

continuous demand for the development of the selective, sensitive and rapid

methods for the detection, determination and control of heavy metals (22-73).

Heavy metals

The term heavy metal has found its way into the standard texts (11-13)

although no definition is rendered and even no explanation is provided by the

editors of the “Symposium Proceedings of the First International Conference of

Heavy Metals in the Environment" (14).

Heavy metals are more rigorously defined in a few dictionaries of technical

terms. Lapedes(15) includes those metals where specific gravity is approximately

5 or higher, while Anon(16) adopted the view of metals of Burrell (17) who

(10)
 designated the rectangular block of elements In the periodic table flanked by Tl, Hf,

As and Bi and its comers as the heavy metals’ characteristically have specific

gravities ranging from 4.5 (Ti) to 22.5 (Os).

Heavy metals have a density > 6.0 gm cm'3 and occur naturally in rocks but

concentrations are frequently elevated as a result of contamination. The term

'heavy metal' is imprecise but it is widely used although others such as toxic

metals', 'potentially toxic elements’ and ‘trace metals' are possible alternatives.

Heavy metals belong to the group of elements geochemically described as ‘trace

elements’ because they collectively comprise <1 % of the rocks in the earth’s

crust (18).

‘Nibeer et al. (19) proposed that the term 'heavy metals’ be abandoned in

favour of a classification which separates metal ions into class A (oxygen seeking)

class B (nitrogen/sulphur seeking) and borderline (or intermediate). This

classification is related to atomic properties and solution chemistry of metal ions.

A survey of the numerous papers on analytical, biological, ecological and health

aspects of heavy metal pollution adds that Pb, Mo, Se and Hg are in the list of toxic

heavy metals (20-73).

Heavy metals in the environment

Metals differ from other toxic substances in that they are neither created nor

destroyed by humans. Nevertheless utilization by human influences the potential

(11)
 for health effects In at least two major ways : first by environmental transport that Is

by human or anthropogenic contributions to air, water, soil and food and second by

altering the speclation or biochemical form of the element (74). Metals are

redistributed naturally in the environment by both geological and biological cycles

(Fig-1).

ATMOSPHERE

N
| METAL EMISSION | Fall out Wash out
i
•%

*•
•% •»

* %
• •
*- %
•

kun oil
TERRESTRIAL
SYSTEMS
Irrigation
LAKES
RIVERS
Flow ESTUARIES Mlxin
4 OCEANS

SEDIMENTS SEDIMENTS

Routes of transport of trace elements in the environment (74)

Metals have always been an intrinsic component of the earth’s crust. With

the continuing trend towards an increase of human activities involving heavy

metals, various organisms ih the ecosystem, including man, may become exposed

to concentration of toxic heavy metal presenting a potential threat for survival.

While the nutritional essentiality of several trace metals like Cu, Zn, Mn, Cr has

been well established, heavy metals like Pb, Hg, Se, Mo have mainly been studied

(12)
 B

>
FP1W w the toxic heavy metals and essential

illustrate the way in which that depend on essential

occurrence of these impairments under controlled experimental

t similar abnormalities might occur in free living humans
and animals, under circumstances of increased exposure to toxic elements.

Biological effect of heavy metals

The impact on human health of the biogeochemical cycling of a metal is

determined by Its physical, chemical and biological properties (75). In eliciting

biological responses the following physical properties of a metal appear to be of

special significance.

(0 Natural occurrence and availability

(ii) Volatility of the metal and its salt.

(iii) Adsorption and desorption by tissues

(iv) Transport and diffuse through membranes

(v) Solubility in lipids

(vi) Particle size in the atmosphere

The following chemical properties of metals are of clinical importance

0) Speciation

Ease of formation, transport and stability of alkyis when such derivativesare

00
formed (e.g, mercury, lead).
Redox properties
*

(13)
 (iv) Stability and solubilisation of sulphide sedimentation

(v) Ionic association and dissociation in aqueous media and ion exchange

properties

(vl) Chemical complexlng properties

(vii) Stability and persistence in the environment

The following biological characteristics of metals are largely derived from

their above physico-chemical properties.

(0 Toxicity to man

(ii) Rat© of accumulation in th© food chain-bioaccumulation and

biomagnification.

(iii) Retention time in living organisms

(iv) Biological transformation ©.g. methylation

From th© view point of health, metals can be divided into the following four

major groups

0) Metals essential to life processes e.g. copper, zinc, chromium, manganese,

iron and cobalt

(ii) Metals probably not essential to living systems e.g. barium, aluminium,

lithium and zirconium

(iii) Metals toxic to some life processes e.g. tin and arsenic

(iv) Metals highly toxic to the system e.g. mercury, lead and cadmium.

(14)
Lead

For years lead has been recognised as a health hazard to man and animals.

Lead occurs naturally and Is distributed widely at varying levels in soils, plants and

animal tissues (76-80). The common sources of lead in the environment are lead
#

based pigments In paints, lead containing pesticides, discarded wet cell batteries.

shooting ranges or waterfowl hunting sites, putty, plumbing installations or repair

sites, manufacturing fillers, untaxed whiskey, liniments and lotions, water pipes,

auto exhausts and used motor oil (71). Other sources of lead have been

vegetation contamination resulting from highway traffic or close proximity to a

smelter (71,81-84). Lead recycling plants are also a constant source of

environmental lead.

Characterisation of effects

The environmental contamination from lead to date is not known to have

caused any teratogenic effects. However, the treatment of chick embryos with

lead salt has shown to produce a toxic effect on the morphogenesis of the lead

primordlum hydrocephalus and anterior meningoceles (85-87). The addition of

25 ppm of lead to the drinking water of breeding can cause early deaths of the

offspring (88). Lead levels in the foetal blood and amniotic fluid were found to be

55% of that of the maternal blood In a goat infused for 2 h with lead chloride (89).

The inclusion of tetraethyl lead as gasoline additive in the 1920's was a

landmark event, as this decision resulted in a steep increase in lead emrtted into

(15)
 the environment (90). The modem studies on the effects of developmental

exposure to lead have been extensively reviewed (91-95). IQ was the outcome

variable used in meta analyses of modem lead studies (96-97) although this

method of analysis has been criticized as invalid in part because non identical end

points are combined (98).

Occupational exposure to lead still poses a threat to the health of workers,

resulting in peripheral neuropathy function (99,100). Environmental sources of

lead are producing intellectual impairment in children at levels that had come to be

regarded as normal (101). Occupational exposure limits have become more

stringent over recent years. In New Zealand, the Occupational Safety and

Health Service of the Department of Labour now recommends that workers with

a sustained PbB of 54 //g/dl or above should be suspended (102). Recent

epidemiological studies suggest that children with PbB levels as low as 10 /d!

are impaired, relative to children with lower PbB levels (103). Lead levels in blood

and milk from urban Indian cattle and buffalo ranged between 0.03 and 0.68 ppm

for milk and in blood it ranged between 0.10 and 0.99 ppm (104,105). Inorganic

lead can act as a cumulative poison (106) and may be absorbed through the skin

via sweat gland (107). Speciation of lead in environmental and biological samples

has been reviewed (108). The toxicity of the alkyl lead diminished in the
sequence (109),

=
R*Pb > RaPb+ > R2Pb+2 [R C2H5>CHJ,

(16)
but tho ionic species are more persistent in the environment (110). Efforts to

control lead exposure require accurate information on PbB levels in specific

populations. In the United States PbB levels have shown a substantial decline in

the entire population probably due to the elimination of leaded gasoline

in 1986 (111).

AIR PARTICULATE

10 pg Pb

WATER 15pg MAN EXCRETED

(SOLUBLE & Pb 25 fig Pb stored 200 fig Pb
COMPLEXED) in the bones

FOOD 200 pg Pb
(COMPLEXED)

Daily lead balance for a city resident (112)

Molybdenum

Molybdenum occurs in the earth’s crust in an abundance of 10~*% mainly

as molybdenite (113). In recent years research on molybdenum compounds has
greatly increased because of their academic interest and developing technical

applications as lubricant additives (molybdenum disulphide and sulphur

(17)
complexes), corrosion inhibitor pigments, smoke suppressants, and hetero¬

geneous catalysts (molybdenum trioxide and molybdates). Recognition of the

central role of molybdenum in a number of metalloenzymes (nltrogenase, nitrate

reductase, xanthine oxidase) and the problem of molybdenum toxicity in ruminants

have stimulated research in both molybdenum biochemistry and inorganic

chemistry (114).

The regulation of chemical discharges into the environment is increasing

dramatically and will continue to do so in the 1990's. General aspects of

molybdenum in the environment are reviewed (115). Additional studies and

reviews further explore the impact of molybdenum in the environment (116-117).

Fem (118) found that molybdenum produced no embryocidal or teratogenic

effects upto 100 mg/kg . However Schroedar (88) demonstrated that 10 ppm in the

drinking water of breeding mice caused a significant increase in young deaths in

Fi and F3 generations and in dead litters in F3 generations. Colmano (119)

postulated that molybdenum may be an inhibitor of cellular fission, evoking nuclear

and chromosomal polyploidy and abnormal mitosis . He further hypothesised that

molybdenum may activate the uncontrolled pattern observed in some neoplastic

growths. Jeter and Davis (120) found no effect on the fertility or gestation of
female rats given high doses of molybdenum. Mills and Fell (121) found severe

demyelinzation of the central nervous system In the new bom lamb from lambs

(18)
who, during pregnancy, were maintained on diets high in molybdenum. However,

affected lambs were also found to have a low content of copper in their livers.

Workplace exposure for insoluble molybdenum compounds in the United

State is currently controlled at 10 mg/m 3 (122) which is the same as the TLV-TWA

for nuisance dusts. Soluble molybdenum compounds in the work place are

controlled at 5 mg/m3 (122).

There are no human or animal studies implying accumulation of

molybdenum in the body during the life cycle (123). Utilizing animal models, the

inhibitory effect of molybdenum on oesophageal, fore stomach, and mammary

carcinogenesis has been demonstrated in the laboratory studies (124-126). The

most widely studied environmental problem with molybdenum is its impact on

ruminants that graze on forage with a high molybdenum content (127).

The clinical signs of molybdenum toxicity in animals are primarily due to

copper deficiency. Evidence indicates that cattle are the most susceptible to

molybdenum toxicity of any species followed by sheep. Horses grazed the “teart”

pastures of Somerset without showing any clinical signs of toxicity. Rabbits (128),

Guinea pigs, rats, pigs and chickens (129) are comparatively tolerant to

molybdenum.

Information on the toxic effects of molybdenum in humans is scarce.

Mertz (130) suggests that a dietary intake of more that 10mg/d of molybdenum is

10

(19)
 dangerous to human health, but that intakes of upto 1.5 mg/d do not appear to

have an effect except for an increase in copper urinary excretion, in adult humans

with a normal copper intake (1.5 - 2.5 mg/d) Mertz proposed that a dietary
molybdenum intake of 0.5 -1.0 mg/d can be assumed to be safe. National

Academy of Sciences has estimated an adequate and safe intake of molybdenum

for human beings as 0.15-0.5 mg/d (131).

Selenium

The availability as well as the toxic potential for selenium and selenium

compounds is related to chemical form and most important to solubility. Selenium

occurs in nature and biological systems as selenate (Se6*), selenite (Se4+)

elemental selenium (Se°) and selenide (Se2‘) and deficiency leads to a

cardiomyopathy in mammals including humans (71, 132).

The stability and very low solubility of elemental selenium in aqueous

systems (133,134) indicate that it is a major inert sink for selenium in the aquatic

environment This is important in determining the overall fate of the element

(133,135). Limited data are available regarding the sorption of selenium on soils.

The processess is affected by redox conditions, pH, hydrous oxide content

(particularly iron oxides) clay content, organic materials and presence of

competing anions (133,135-139).

Selenium is an essential animal nutrient but is toxic at high concentrations.

It enters the food chain primarily in the form of selenates (135-137) . Selenium in

li

(20)
food stuffs provides a daily source of selenium (140). Some plants (e.g. locoweed)

can accumulate levels of selenium that are toxic to livestock (135,141). Fish can

accumulate selenium primarily from their diet and very little from water (133).

Selenium is added to fertilizers or animal feed in the form of sodium selenite or

sodium selenate, which are absorbed more readily by plants (142). Selenium has

produced loss of fertility and congenital defects and is considered embryotoxic and

teratogenic on the basis of animal experiments (143,144). Selenium sulphide

produced an increase in hepato cellular carcinomas and adenomas, but selenium

sulphide suspension and selsun<ÿ®ÿ>an antidandruff shampoo containing 2.5

percent selenium sulphide, applied to the skin of Swiss mice did not produce

dermal tumours (45,146). Selenium is an essential trace element in the

selenoenzyme glutathione peroxidase. The activity of glutathione peroxidase in

red blood corpuscles correlated well with the selenium concentration upto 100 //g/L

(147,148). The transition from essential trace quantities to toxic quantities of

selenium in terms of intake in food is summarised below (148).

Low selenium area with Keshan disease 11 figld

Selenium adequate area 116 figld
National Academy of Science, Food and Nutrition Board 50-200 figld
“Safe and adequate" range

Lowest Observed Effect Level (LOEL) 3200 figld

High selenium area with chronic selenosis 4990 figld

Required selenium levels for good health are between 0.04 and 0.1 ppm

(149). In general, levels of selenium of 5-10 mg/kg of food are considered

12

(21)
 toxic (150). In a study carried out in Canada on people working in selenium

production, if the TLV was exceeded slightly (upto 0.6 mg/m3) for limited periods,

no symptoms resulted (151). In Germany the limit in drinking water is 0.008 mg/L
(152) and in the United States, the EPA recommends a maximum contamination

level (MCL) of 0.01 mg/L. Average intake per day in North-Eastern United State

has been estimated at 62 /zg/ day (153) Canada 110-220 (154), New Zealand

25(155), Netherlands 110, France 166 and Italy 141 (156).

PLANTS j HYDROSPHERE | ATMOSPHERE

SOILS~[* SEDIMENTS

|IGNEOUS ROCKS|

Jj MOLTEN ROCKS [

Geochemical cycle of selenium (53)

Mercury

No other metal better illustrate, the diversity of effects caused by different

biochemical forms than does mercury.

The major source of mercury is the natural degassing of the earth's

crust, including land areas, rivers and the ocean, and is estimated to be in the

order of 25,000 to 150,000 tons per year (157-159).

13

(22)
 Toxicity to various forms or salts of mercury is related to cationic mercury

per se whereas solubility, biotransformation, and tissue distribution are influenced

by valence state and anionic component (160-162). With chronic exposure to

mercury vapour the major effects are on the central nervous system (163).

Mercurous compounds of mercury are less corrosive and less toxic than mercuric

salts, presumably because they are less soluble.

Methyl mercury is the most important form of mercury in terms of toxicity,

and health effects from environmental exposures. Most of what is known about

methyl mercury toxicity is from detailed epidemiologic studies of exposed

populations (157).

Two major epidemics of methyl mercury poisoning have occurred in Japan,

in Minamata bay and in Niigata. The largest recorded epidemic of methyl mercury

poisoning took place in the winter of 1971-1972 in Iraq (164).

For persons in the general population, it is estimated that daily mercury

exposure is about 1 from air, less than 2 from water, and about
20 /*g/day from food, but may be upto 75 /*g/day depending on the amount of fish

in the diet. The recommended standard (time-weighted average) for permissible

exposure limits for inorganic mercury in air in the workplace is 0.05 mg Hg/m3

(165). Mercury levels in hair may also be co-related with severity of clinical

symptoms (57).

14

(23)
AIMS AND SCOPE

With the better understanding of the phenomenon of toxicity of trace

elements and continuous diminutions in the maximum allowable limits of (166)

contaminants in the effluents, the need for development of sensitive, selective,

rapid, field adaptable and economical analytical methods for the detection and

determination of elements at trace levels has been growing.

A review of the literature work of the last five years for the reagents used

for the determination of lead molybdenum, selenium and mercury is given in

Tables 1-4 .

Various analytical methods are available for the determination of heavy

metals viz. spectrography, polarography, spectrometry, chromatography, and

colorimetry (238-243). Although these methods have a limited use and are

expensive. Colorimetry is still in practice. Organic reagents viz., dithizone,

/3-d i ketones, diethyl ammonium diethykiithiocarbamate, most common reagents

used for extraction of heavy metals (244,245). Some of these reagents are
sensitive but no systematic study has been made and several diverse ions are

interfering in their determination.

With the horizon of complexation abilities and salient properties of

calix(6)arenes increasing, there is increase in the number of reports, monographs

15

(24)
 and patents. Most of the recent applications are associated with their properties as

molecular receptors (246).

Literature survey on calix(6)arenes indicate that they are still finding new

applications as molecular receptors for highly selective ion complexation. Agrawal

et. al having a major contributions in hydroxamic acid chemistry have brought forth

new molecules with supra molecular assests by fusing versatile hydroxamic acid

with flexible molecular baskets calix(6)arenes. Introducing a chelating group into

the calix(6)arene will enhance the complexation properties of calix(6)arenes.

Hydroxamic acids are bidentate ligands with the functional group (1).

R’_ N— OH CoH3 N — OH

R — C(I)=0 C«H5 — C O
(II)
=

These acids have remarkable versatility for the organic and inorganic

analysis (247-271).

PRESENT INVESTIGATION

The present thesis describes the synthesis of N-phenyl calix(6)arene

hydroxamic acid. Calix(6)arenes are synthesised by reacting p-hydroxy benzoic

acid and formaldehyde in o-xylene medium. The N-phenyl calix(6)arene

hydroxamic acid is synthesised by reacting N-phenyl hydroxylamine with acid

chloride of caljx(6)arene at low temperature in diethyl ether medium containing

16

(25)
 Table 1
Complexation studies of lead with various reagents

Beer's law (ppm)

S.No. Reagent Technique pH/Acidlty/ Sandell’s sensitivity (ÿtg cm ) Remarks Ref.
Solvent Molar absorptivity (Lmol*1 cm'1)
Detection limit (ppm)
1 Didecylaminoethyl-0- ext., photo. detn in air natural and 167
tridecylammonium iodide 285 waste water, soil, dyes
3.4 x104 and dry milk

2 Purpurin (1,2,4-trihydroxy spec. different samples 168

anthraquinone) 575
MIBK 2.8 x104
3 Tetraethyl ammonium ext.,spec. soil, potato, fish 169
(26)

benzene samples and apples.

dithiocarboxylate
4 1-phenyl-3-methyl-4- ext., AAS MIBK 170
benzyl-pyrazolone 1x 10-4 %
94-104
5 12-membered oxathia, 18 ext. soft picrates 171
membered thia crown radiometric and hard
detection nitrates
6 Nitrilotriacetic acid pseudo rate const. 172
polarog.
K*=2 x 103 cms*1
7 1-phenyl propane-1-pentyl simultaneous detn of 173
sulfonyl hydrazone-2- adsorptive Ni, Co, Cd, Pb and Cu,
oxime volm. RSD at cones.
.0006-0.012 7.81 ppb is 2.7-5. 2% to
natural waters
 8 Dithizone ext., alk.pH 0-40 av. recovery of Pb in 174
AAS 5% HN03 spiked water samples
CHClj was 97% coeff. of
variation
4.7 % at 10ÿg/L
3.1 at % 20
2.7 % at 30 fxg/L
9 Dithizone + Tween 20 spec. 480 nm 0-0.4 detn lead in human 175
hair, recovery was
1.3x10* 99-102%
10 Ammonium pyrrolidinyl FAAS with along with lead used for 176
dithio carbamate + reverse flow Cu, Fe, and Mn. free
Diethyldithio carbamate injection MIBK from interferences from
ext. 3.3 alkali metal ions alkali
earth metal ions, Zn*2,
« Ni*2 and PO4- did not
interfere with the detn.
(27)

11 Thenoyl trifluoro acetone ext. , AAS the stability const (/S) of 177
(TTA) + DB-18-C-6 the adduct Pb(TTA)2
o-dichloro DBI8C6 detd by curve
benzene fiting method as
log >3=4.2, detn of Pb in
natural waters
12 Diethyl dithio carbamate Flame AAS preconc. through 178
sorption of diethyl
diothiocarbamate
complexes. Detn of Cu,
Cd, Zn and Pb in tap
water, corresponding
RSD (n=10) were 15,9,
5 and 6.5%
 13 Crown and thiacrown liq.liq. ext. the compositions of the 179
extracted species were
p-nonyl detd
phenol
14 Qxa-thia and thiacrown ext. ext. ofSr(ll), Ag(l) and 180
ethers lead(ll) _
15 [3-(2-arsono-5-carboxy spec 620 0-2 analyse Cu alloys with 181
phenyl-azo)-6-(4-methyl- RSD of 0.97 - 1 .35%
2,6-dibromo phenyl azo)- 4.2 x 104
4,5-dihydroxy-2,7-
napthalene disulphonic
acid, KAtA-DBMI
(28)

VO
 Table 2
Complexation studies of molybdenum with various reagents

Beer’s law (ppm)

S. No. Reagent Technique pH/Acidity/ Sandeli’s sensitivity (pg cur) Remarks Ref.
Solvent Molar absorptivity (L mol'1 cm'1)
Detection limit (ppm)
1 Thiocyanate +Sodium ext., spec. 468 0-2.6 detn of Mo in steels, 182
dithionite HCI 0.0053 flue dust
et.acetate 1.79 x 104dm3 mol"1 cm'1
2 Alizarin Red S + Hexa spec. 4.7 vegetable tissues 183
decyltrimethyl ammonium fluorometric and pharmaceuticals
bromide
3 O-nitrophenyl fluorone spec. 531 0-0.32 detn of alloy, steel 184
(O-NPF) 0.3-0.6 mol/L
N>
o + HCI 1.63x10*
(29)

Cetyl pyridinium bromide

4 3,4-dimethoxyphenyl spec. 526 0-0.53 185
fluorone + Tween-80 0.18-0.34
mol/L HCI 1.16x10s
5 3-hydroxy-2-(4- ext,spec. 411 0-2.3 detn in steel, waters 186
methoxyphenyl)-6- acetic acid, 0.0011 and flue dust
methyl-4H-chromen-4- 1,2 dichloro- 5.61 x 104 dm3 mol'1 cm'1

6
one
Sulfocyanate + Crystal
violet
spec — h
ethane
600 0-0.28 187

5.38x10*
 7 N’-hydroxy-N1, N2- ext., spec. 470 0.5 -9.6 steels and synthetic 188
diphenyl benzamidine 4-6 M HCI matrices
-(ÿThiocyanate Amyl ale. in
benzene
8 3,5-dibromo-4-amino spec. 530 steels and alloys 189
phenyl fluorone 0.2 -0.8
mol/L HCI 1.56x10®
9 2-(3,5-dibnomo- spec. 2.4 -3.5 618 composition of 190
2pyridylazo)-5 complex is Mo(VI) :
diethylamino phenol + 4.8 x104 3,5-diBr-PADP :
Hydroxylamine 0-2.5 Hydroxylamine
hydrochloride hydrochloride 1:1:1
10 Morin polarog. 2.1 detn of Mo in spectral 191
grade W03
(30)

1.88x1O'10 Mo mol/L

11 Dibromohydroxyphenyl photo. 532 0-0.8 detn of Mo in steels 192

fluorone +Cetyl 0.3 -0.7
pyridinium chloride mol/L HCI 1.19x10®

12 4-(5-bromo-2- ext., spec. 4.0 536 0-0.80 detn of Mo in alloys 193

thiazolylazo)pyro catechol steels
diphenyl guanidine CHCI3 6.33 x104

13 4-(2- benzothiazolylazo spec. 4.8 572 0-22 194

pyrogallol+ Cetyl trimethyl
ammonium bromide) 8.6 x 104
 14 O 0-bis(2- spec. 503 RSD(n=8) at 100 195
ethylhexyl)dithio- /<m-Mo(VI) was 0.5%
phosphorlc acid +
Micellar solution of
Triton X-100
15 Thiazolyl blue ext., photo. 470 0.1 -15 analysis of six lettuce 196
samples
1,2- 5.7 X103
dichloroethane
16 4,5-dibromo-213,7- spec. 3-4 541.5 0-0.6 RSD was 0.91- 197
trihydroxy-9-piperonyl-6- 3.17%
fluorone [4,5-dibromo- 8.1 x 104
PIF1
to
to 17 Pyrocatechol violet GFAAS 313.3 0.01 -0.1 RSD (n=6) at 0.3 g 198
- 0.6HCIM cone. was 3% analysis of
natural water
(31)

samples
18 Acetyl acetaldehyde-O- photo. 435 0-3.2 detn Mo in steel with 199
aminophenol acetal RSD of 4. 7
9.6 x103

19 2-(5-bromo-2-pyridylazo)- spec. 595 0-2.5 analyse soft 200

5-dimethyl magnetic alloys with
aminophenol/hydroxyl- 4.3 x104 RSD of 1.4-2.5%
amine
 Table 3-
Complexation studies of selenium with various reagents

5S
Beer's law (ppm)
S. No. Reagent Technique pH/Acldlty/ A mex Sanded sensitivity cm-2) Remarks Ref.
Solvent Molar absorptivityfLmol'1 cm'1)
Detection limit (ppm)

1 J-acid ext., spec. 520 0.03-0.3 detn of Se in polluted 201

0.004 water, soil, dust, hair
BuOH 18.5 ±(0.1)x103 and plant materials

2 Butyl Rhodamine B + Kl spec. detn of trace amount of i 202

0.10 mol/LHCI Se in environmental
1.32x10* materials
3 Iodide + Crystal violet spec. 546 detn of Se(IV) in 203
environmental
(32)

1.3 x 10* samples_

4 CTMAB-surfactant cathodic 2.09 detn of Se in marine | 204
volm. -
creature mussel a std j
reference material and
hair sample _ [
5 I Rhodamine B system scattering relation between the 205
intensity of double
scattered light and
cone, of Se(IV) was
established
6 (8-hydroxyqulnoline-5- fluorometry Xn .3 -
0.005 0.1 detn of Se in ref. 206
sutfonic acld)-paliadium(ll) A*m'497 samples
complex
 7 Sodium salt of ext., spec 335 detn of Se in polluted 207
hexamethylene imine 0.0166 water, plant material,
carbodlthloate 4.42x1 03 wheat flour and
medicated shampoo
8 1,2 diamine-4- spec. the obtained results 208
nltro benzene were subject to
stastical anal.
9 2,3-diaminonaphthalene HPLC detn of Se in 209
xibaokang capsules.
The average recovery
was 98.9% ;
RSD-1.16%
10 Thiocyanate + Rhodamine spec. 0-0.06 detn of Se in herbal 210
B system medicine ; interfering
Ions are Na, K and Ca
ts> 11 Brilliant cresyl blue spec. 630 0.0001-0.500 RSD are 2.5, 2.2, and 211
2.0% of 0.10,10.0 and
100.0 ng/ml of Se(IV);
(33)

detn of Se in waste
water
12 Iodide-basic triphenyl scattering 212
methane dye system

13 2,3,Strlphenyl tetrazolium ext

-
.000094 .00086
extseparation of 500 213
chloride 1 M H2SO4 /tg of Se(IV) and Te(IV)
from Cu concentrate
incinerator ash. in Sb
alloys with recoveries
of 98.3 -100.6 and
98.0-101.4% resp.
14 Methyl yellow and H2O2 518 0.0002 -0.5 Se(IV) detn in eggs and 214
wheat
 Table 4
Complexation studies of mercury with various reagents

Beer’s law (ppm )

S. No. Reagent Technique pH/Acldity/ X max Sanded’s sensitivity (ug cm'2) Remarlts Ref.
Solvent Molar absorptivity (Lmol'1 cm'1)
Detection limit (ppm)
1 4,4’-diazobenzene spec. 10 515 0-0.56 detn of Hg(ll) in 215
diazoaminoazo benzene waste water and
1.6 x105 natural water samples

2 5,1 0,15, 20-tetrakis(3- spec. 6.22 0-12.0 std deviation (n=12) 216
chloro-4-sulfophenyl) 0.82%; Zn2+,
porphine 0.025 Cu2*,Mn2+ needed to
be masked ; anal, of
water samples
3 Thiocyanate +Rhodamine spec. 530 detn of traces of Hg 217
6G in cadmium chloride
2.1 x 105 prepn and Buffalo
river sediment
«
(34)

4 5,10,15, 20-tetrakis(3- spec. 425.7 0-12.0 simultaneous detn of 218

<y
chloro-4-sulfophenyl) Zn and Hg; anal, of
f porphine synthetic water
f
! z » \\ samples _
V? *
V *. %r *
*
#
ji* 5 2-hydroxy-1 -
naphthaldehyde-4-
ext., spec.
1.5 M H2SO4
413 0-10.0 detn of Hg in hair
samples
219

V -.4yj>
phenyl-3- CHCI3 2.16 X104
thiosemicarbazone
6 Nicotinaldehyde-4- ext., spec. 3.5 365 0-18 detn of Hg in std. 220
phenyl-3- human hair samples
thiosemicarbazone CHCI3 2.45 x104

7 Brilliant green sulphite spec. 6.5 615 detn of Hg in cleaning 221

solns for contact
lenses and in
0.005-0.013 industrial waste water
W
 8 Antipyrinyldiazoamino-2, spec. 10.2 -12.3 0-0.6 detn of Hg in tap water 222
4-dinitro benzene samples
2.10 x10s

9 1-(4-antipyrinyl)-3-(2,4 spec. 6.0 -8.5 Hg(ll) in natural water 223

dinitrophenyl)-triazene and urine was detd
directly ; RSD . 3.5 %
10 3-mercapto-1 ,2-propane complex. estn of Hg in 224
diol titrn complexes and
synthetic mixtures ,
relative error :+ 0.41
coefficient of variation
(n=6) ; 0.43%
11 Tetrazol violet spec. Hg(ll) detd in aq.solns
as bromide and iodide
1 x 1 0® for bromide and complexed with

complexes _
1.02x10® for Iodide _
tetrazolviolet TV[HgBr3]
and TVfHg l31
12 p-formyl phenyl spec. 9.5 510 0.02 -0.48 detn of trace Hg in 226
diazoamino benzene + ores
(35)

to
C*
Triton X -100 1.16x10®
13 Thiacrownethers + ext., spec 420 -
0.5 12.0 negligible interferences 227
Bromoc resol green of alkali, alk. earth and
CHCI3 other transition metal;
strong interferences
from Ag (I)_
14 phenylazoamino spec. 9.0 514 0-0.8 detn of Hg in river 228
azobenzene + Triton X - waste water and tea
100 2.0x10® samples

15 Potassium iodide- spec. 7.0 650 0-1.0 The interference of 229

methylviolet-Triton X-305 Cu2+, Cd2+, Bi2*, Pb2+
1.12x10® were eliminated by
sepn with sulfhydryl
cotton fibers, detn of
Hg in biol. materials
and env. samples
 16 Thiocyanate +Basic scattering
triphenyl methane dyes

0.0016-0.006
17 1-(4-anti pyrinyl)-3-(3- spec. 10.5-12.2 0-0.64 231
chlorophenyl)triazene
1.85x10*
18 Batho phenanthroline quencho- 3.8-44 (max) detn of Hg (I I) in 232
disulphonate fluorimetry :288 sewage sludge,
env. water and certified
:444.8 .0.01 -1.0 reference material
19 Triphenyl phosphine complexom 5.6-59 industrial waste water; 233I
sulfide etrically/ acid extract of
AAS toluene medicinal soap and to
two drugs _
20 Reinecke salt Nephelo¬ 400 0.04 -2.4 method applied to 23
to
-4 metric water and mud
samples with
(36)

35 recoveries of
95.3-100.5%
21 Benzothiazolyl spec. 520 0-1.2 Hg(ll) in wastewater 235
diazoaminoazobenzene with RSD of 1.7-4. 2%
1.51 x106
22 p-sulphamoyl spec. 470 0-1 anal, of waste water 236I
benzenediazo with recoveries 93.8-
aminoazobenzene 8.8 x104 94.1%; RSD(n=5) 1.9-
2.2 %
23 1-(2-benzothizotyl) -3-(4- spec. 510 0-0.56 anal, of tap water 237
phenylazophenyl) triazine domestic and industrial
waste water recoveries
of 98- 103%

ext, : extraction ; spec. : spectrophotometry ; photo : photometry ale. : alcohol ; polarog. : polarography ; volm. : voltametry
MIBK : methyl isobutyl ketone ; alk. : alkaline ; preconc. : preconcentration FAAS : flame atomic absorption spectrophotometry
DB-18-C-6 : dibenzo 18-crown-6 , complex, titm : complexo metric titration estn : estimation ; BuOH. butanol ; EL : Ethyl ;
GFAAS : graphite furnace atomic absorption spectrophotometry. anal. : analysis
aqueous suspension of sodium bicarbonate. The synthesised N-phenyl
calix(6)arene is characterised by m.p., UV, NMR and IR spectra.

The simple, selective and sensitive methods have been developed for the

extraction and spectrophotometric determination of the toxic heavy metal ions viz.

lead, molybdenum, selenium and mercury using N-phenyl calix(6)arene

hydroxamic acid as an extractant.

These metals have been extracted with the proper choice of solvents and

judicious adjustment of the pH or acidity of the medium. A detailed study of the

various parameters like effect of pH or acidity, reagent concentration, diverse ions,

and addition of other reagents in the process of extraction have been studied.

The study of the distribution of the heavy metals, lead, molybdenum,

selenium and mercury have been carried out in soil and plants along major

thoroughfare in Ahmedabad city. The heavy metal contents are also determined

in water samples of Sabarmati river. The effect of lead from motor vehicle exhaust

on soils and plants along a busy thoroughfare of National Baroda Ahmedabad

highway has been investigated.

28

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