The Survey and Measurement Of Residues Of Lindane Organochlorine

Document Sample
The Survey and Measurement Of Residues Of Lindane Organochlorine Powered By Docstoc
					The Survey and Measurement Of Residues Of Lindane (Organochlorine
Pesticides) In Four Species Of the most consumed Fishes in Caspian sea (Iran)

Department of Experiential sciences, Islamic Azad University of Sari, Sari, Iran


Pesticides are compounds that used by human being, especially farmers for controlling

biotical factors for a long time and can bring a lot of environmental Problems. Among these

compounds organochlorine insecticide sprays have high half-life, the property of maintaining

for a long time and high lipophilicity characteristic .due to having chronic consequences that
resulted from consuming of this compounds, It is necessary to evaluation and analysis in

environment especially in foods and also in fishes which have high fat and can carry this kind

of insecticide sprays, so we have investigated the remaining of chloride oregano insecticide

sprays such as lindane in the four thre most consumed kinds of fishes in the Caspian Sea. In

this investigation we have prepared four different kinds of fishes, which arc highly used. and

available in the Caspian Sea (Sefid , koli, kilca and kafal fish) that we selected 100 samples of

fish from the four different hunting region (Chalous and Babolsar city and Khazar Abad and
Miankaleh regions) in 2004. after cleaning, we prepared Hun muscle of the samples, Then

after the process of extraction, we distilled them in Vacuum by means of organic solvent and

at last we evaluated the remaining and reported based on PPM by Gas Chromatography(GC)

with ECD detector. The results of insecticides analyzed in four kinds of fishes and showed

that Kafal in the hunting region of Khazar abad had greatest amount of 0.037 PPM. Kilca

from Chalous had the highest amount of Lindane, 0.029 PPM (P<0.05).in the case of Sefid

and Koli fishes in regions, significant difference was not seen. It is nesserary to mention that

no research has sofar been done to be a criterion for comparison in this area, But,fortunately

the amounts of the insecticide sprays has not reached to standard level in fishes, and it raises

the alarm health.

Key words: Lindane, Organochlorine pesticides , Caspian sea , Fish
 The term organochlorine refers to a wide range of organic chemicals, which contain chlorine
and sometimes several other elements.a range of organochlorine compounds have been used
in Iran, including herbicides, insecticides, fungicides and industrial chemicals such as
polychlorinated biphenyls (PCBs). The compounds are characteristically very stable(1,2,3)
  This characteristic is widely recognised as being a problem in some uses such as pesticides
and transformer oils, because the chemicals can be distributed in the environment especially
river and sea where they persist long after their original use. They degrade slowly and being
fat-soluble, accumulate in the food chain, eventually ending up in the fat of our bodies(4,5).
 Key properties of organochlorines which cause concerns are persistence and toxicity.
While organochlorine pesticides were manufactured for their toxicity, the fact that
they were also persistent had advantages in that they remained effective against target
pests for prolonged periods. Therefore the chlorinated organic compounds held an
important position in pest control in agriculture for a long time, being versatile and,
against some pests, very effective (1,2,6).
 Lindane is an organochlorine insecticide which has been used on a wide range of
soil-dwelling and plant-eating (phytophagous) insects. It is commonly used on a wide
variety of crops, in warehouses, in public health to control insect-borne diseases, and
(with fungicides) as a seed treatment. Lindane is also presently used in lotions,
creams, and shampoos for the control of lice and mites (scabies) in humans(6,7).

  Technical lindane is comprised of the gamma-isomer of hexachlorocyclohexane,
HCH. Five other isomers (molecules with a unique structural arrangement, but
identical chemical formulas) of HCH are commonly found in technical lindane, but
the gamma-isomer is the predominant one, comprising at least 99% of the mixture of
isomers. Lindane may also be found in formulations with a host of fungicides and
insecticides. It is available as a suspension, emulsifiable concentrate, fumigant, seed
treatment, wettable and dustable powder, and ultra low volume (ULV) liquid.

  Lindane is a moderately toxic compound via oral exposure, with a reported oral
LD50 of 88 to 190 mg/kg in rats. Other reported oral LD50 values are 59 to 562
mg/kg in mice, 100 to 127 mg/kg in guinea pigs, and 200 mg/kg in rabbits. Gamma-
HCH is generally considered to be the most acutely toxic of the isomers following
single administration. It is moderately toxic via the dermal route as well, with
reported dermal LD50 values of 500 to 1000 mg/kg in rats, 300 mg/kg in mice, 400
mg/kg in guinea pigs, and 300 mg/kg in rabbits. Effects of high acute exposure to
lindane may include central nervous system stimulation (usually developing within 1
hour), mental/motor impairment, excitation, clonic (intermittent) and tonic
(continuous) convulsions, increased respiratory rate and/or failure, pulmonary edema,
and dermatitis. Other symptoms in humans are more behavioral in nature such as loss
of balance, grinding of the teeth, and hyper-irritability. Most acute effects in humans
have been due to accidental or intentional ingestion, although inhalation toxicity
occurred (especially among children) when it was used in vaporizers. Workers may be
exposed to the product through skin absorption and through inhalation if handled
incorrectly. Lotions (10%) applied for scabies have resulted in severe intoxication in
some children and infants. It is reported that single administrations of 120 mg/kg
inhibited the ability of white blood cells to attack and kill foreign bacteria in the blood
of rats, and 60 mg/kg inhibited antibody formation to human serum albumin. It is not
clear whether these effects were temporary, or for how long they may have

 Lindane is very stable in both fresh and salt water environments, and is resistant to
photodegradation. It will disappear from the water by secondary mechanisms such as
adsorption on sediment, biological breakdown by microflora and fauna, and
adsorption by fish through gills, skin, and food.

 Lindane is highly to very highly toxic to fish and aquatic invertebrate species.
Reported 96-hour LC50 values range from 1.7 to 90 ug/L in trout (rainbow, brown,
and lake), salmon, carp, largemouth bass. Water hardness did not seem to alter the
toxicity to fish, but increased temperature caused increased toxicity for some species
and decreased toxicity for others. Reported 96-hour LC50 values in aquatic
invertebrates were: in Daphnia, 460 ug/L; in scuds, 10-88 ug/L; and in Pteronarcys
(stone flies), 4.5 ug/L. The bioconcentration factor for the compound is 1400 times
ambient water concentrations, indicating significant bioaccumulation(8,10).
 The Caspian sea, the largest inland sea in the world, is bordered by five countries: Iran
,Azerbaijan, Turkmenistan, Kazakhstan and Russia. It has no outlets and acts as a reservoir
for water in the region . Environmental pollutants found in the sea probably arrive via the
Mazandaran and Gillan rivers. Industrial complexes along the coast particularly in
mazandaran and Gillan provinces, in Iran, also discharge waste directly into the Caspian
sea(10) .
 It is important to note that the use of almost all the chemicals mentioned above is
now banned in Iran , and that a nationwide plan is being developed for their overall
  The goal of this study was to survey levels of organochlorines ( Lindane) in the
Four species of the most consumed fishes that have been hunted from four central
fishery locations in order to estimate the potential of human exposure(11,12,13).

Material and Methods
 Four commonly consumed fish (Sefid = Rutilus frisikutum , Koli= Clupeonella
 delicatula ,Kafal = Mugila auratus and Kilka = Vimba vimba) were selected to
All samples were collected from Caspian sea in July and August 2004. 100 indi-
 viduals of each fish were collected from four sites (Chalous and Babolsar city and Khazar
 Abad and Miankaleh region). dorsal muscle of the samples were removed and frozen at -
 20癈 and shipped to central laboratory ( Sari city ) for analysis and finally
 concentration of residues of lindane , were determined.

Sample preparation and analysis
  The sample preparation and analysis protocols are similar to those described in
Vidar and Anuschka ,1998 .Briefly, approximately 5 g of dorsal muscle from Samples
fish was thawed and homogenised w ith 60 g of anhydrous sodium sulphate in a
mortar until a free-flowing powder was obtained. The sample was extracted with 225
ml of 1: 1 methylene chloride/hexane. Extracted sample was injected to Gas
chromatography in electron capture detector (ECD) . OC levels ( Lindane) were
measured using the internal
standard method in conjunction with the corresponding external standards using
selected ion monitoring mode(8,13,14,15).

Result and Discussion:

   The Amounts of lindane Contents in all Samples of four Examined fishes (Sefid ,
Kafal , Kilca and Koli) of Caspian Sea Were Measured and Represented in Table 1.

Table 1. The average quantities of Lindane Contents (ppm) in four Speices of fishes
under study in the Caspian Sea.

       Region                    Kind of fish   Mean of Lindane(ppm)
                         Sefid                         0.024
                         Koli                          0.029
                         Kafal                         0.025
                         Kilca                         0.018
                         Sefid                         0.031
                         Koli                          0.015
                         Kafal                         0.018
                         Kilca                         0.018
                         Sefid                         0.030
                         Koli                          0.023
     Khazar abad
                         Kafal                         0.031
                         Kilca                         0.022
                         Sefid                         0.027
                         Koli                          0.023
                         Kafal                         0.022
                         Kilca                         0.026

   According to Table 1, Residues of lindane in Kafal fish Samples had maximum
amounts (0.037 ppm) in Khazar abad Region. In Chalus Region, Kilca fish presented
the greatest quantity of lindane (0.029 ppm). In the case of Sefid and Koli fishes
significant difference was not seen.
   Statistical analysis (One–way ANOVA) , indicatad a significant difference
regarding lindane (P< 0.05 , Sig 0.082) among fishery sites.
   The results presented that difficulty of poisonous residues is very serious and
important and Since researches in the case of Caspian sea fishes is Very Little, to
compare with this Study, then, there is a requirement to complete Survey in Caspian
sea (Mazandaran Province) and Southern Coasts of Caspian sea(16,17).
   Other Study in North Atlantic indicated that means of DDT (0.002 ppm), lindane
(0.002 ppm), Dieldrin (0.006 ppm) and Endosulphan (0.007 ppm) in Liver Samples
(in Shirbit fish), that these Levels ware lower than quantities proposed by WHO (0.05
ppm)(15,16,) .
   Quantities of lindane in Caspian sea (Table 1) was lower than WHO Standard
Levels (0.05ppm) But in comparison to all regions and other poisons , Presented
higher quantities for great use by farmers in Northern Province in Iran (Southern
coasts of Caspian sea) and great distribution by agriculture center in Mazandaran
among Farmers(17)
   There is evidence that the population of seals in the Caspian Sea is declining and
fertility rates are decreasing. Further studies on contaminants in live animals and
biomarker responses that may indicate reproductive interference are needed before we
can conclude that the high levels of lindane insecticides in this population are
lexicologically important (18,19 ).
   Additionally, chemical analysis has demonstrated the presence of highly toxic
contaminants such as the lindane. No long-term monitoring data exist for these
compounds, which may affect fish and wildlife at extremely low concentrations
(23,24,25,26). New approaches and technologies, capable of detecting chemical
exposure and its effects at all levels of biological organization, will be required to
monitor and assess highly toxic chemicals and those that do not accumulate in fish
and wildlife before concentrations reach harmful levels(20).


 The authors would also like to thank Eng.Mr. Khaki , Mr Rezaee and Mr. Mohsen
Emami(Islamic Azad University of Sari ) for all their help .

References :
1- Ware, G. W. Fundamentals of Pesticides: A Self-Instruction Guide. Thompson
Publications, Fresno, CA, 1986.6-2 .
2- M.M. Shereif and K. H. Mancy. (1995) , Organochlorine pesticides and heavy
metals in fish reared in treated sewage effluents and fish grown in farms using
polluted surface waters in egypt. War. Sci. Tech. Vol. 32, No. 11, pp. 153-161.
3- Ingrid .V, Joan .O.(2002). Method for integrated analysis of polycyclic aromatic

hydrocarbons and organochlorine compounds in fish liver, J. Chromatography, (768):

4- Smith, A. G. Chlorinated Hydrocarbon Insecticides. In Handbook of Pesticide
Toxicology. Hayes, W. J., Jr.and Laws, E. R., Jr., Eds. Academic Press Inc., New
York, NY, 1991.6-3
5- Kidd, H. and James, D. R., Eds. The Agrochemicals Handbook, Third Edition.
Royal Society of Chemistry Information Services, Cambridge, UK, 1991 (as
6- U.S. National Library of Medicine. Hazardous Substances DataBank. Bethesda,
MD, 1995.6-18
7- U.S. Agency for Toxic Substances and Disease Registry. Toxicological Profile for
Endosulfan. Draft Report. Atlanta, GA, 1990.6-52

8- Vidar. B, Anuschka. p (1998), Organochlorines in deep-sea fish from the nordfjord

. Chemosphere. 38(2): 275-282.

9- Vidar Berg , Anuschka Polder and Janneche Utne Skaare. (1998) ,
Organochlorines in deep – sea fish from the nordfjord , Chemosphere , Vol. 38, No. 2,
pp. 275-282.

10-Hall.A.J ,1999 ,Organochlorine contaminants in Caspian and harbour Seal blubber
,Environment pollution ,106:203-212.
11- M.D. Stephenson , M. Martin and R.S . Tjeerdema, 1995 , Long-Term Trends in
DDT, Polychlorinated Biphenyls, and Chlordane in California Mussels. Arch.
Environ. Contam. Toxicol., 28, 443-450 .

12- Gudrun Hilbert, Lone Lillemark, Steen Balchen and Carsten Schriver Hojskov.
(1998), Reduction of organochlorine contaminants from fish oil during refining.
Chemosphere, Vol. 37, No. 7, pp. 1241-1252.

13- J. Falandysz, K. Kannan, S. Tanabe and R. Tatsukawa, Organochlorine pesticides
and polychlorinated biphenyls in cod-liver oils: North Atlantic, Norwegian Sea, North
Sea Baltic Sea, Ambio 23, 288- 293 (1994).

14- Ingrid Vives, Joan O.Grimalt .(2002), Method for integrated analysis of
polycyclic aromatic hydrocarbons and organochlorine compounds in fish liver ,
Journal of Chromatography B, 768 , 247-254.
15- Juhler-Rk ; Lauridsen-MG ; Christensen-MR ; Hilbert-G .(1999), Pesticide
residues in selected food commodities: results from the Danish National pesticide
monitoring program 1995-1996. J-AOAC-Int. 1999 Mar-Apr ; 82(2) : 337-58.

16 Dogheim-SM ; Gad-Alla-SA; el-Syes-Sm ; and (1996), Orqanochloring and
organophosphorus pesticide residues in food from Egyptian local markets. J-AOAC-

17-Morion, B. (1989) Pollution of the coastal waters of Hong Kong. Marine
   Pollution Bulletin 20, 310-318.

18-Wolfe, D. A., Champ, M. A., Cross, F. A., Kester, D. R., Park, P. K. and
Swanson, R. L. (19S4) Marine pollution research facilities in the People's Republic of
China. Marine Pollution Bulletin 15, 207-212.

19-Bunck, C.M., R.M. Prouty, and A.J. Krynitsky. 1987. Residues of organochlorine
pesticides and polychlorobiphenyls in starlings (Sturnus vulgaris) from the continental
United States, 1982. Environmental Monitoring and Assessment 8:59-75.

20-Lemly, A.D. 1993. Guidelines for evaluating selenium data from aquatic
monitoring and assessment studies. Ecotoxicology and Environmental Safety 26:181-

mikesanye mikesanye