ENVIRONMENTAL TOXICITY OF LINDANE AND HEALTH EFECT

M. A. SANDU*, A. VIRSTA

University of Agronomic Sciences and Veterinary Medicine of Bucharest, 59 Marasti Blvd,

District 1, 011464, Bucharest, Romania, Phone: +4021.318.25.64, Fax: +4021.318.25.67

*Corresponding author’s email address: alina.mirela.sandu@gmail.com

Abstract. Persistent organic pollutants are a global concern because of their toxicity,
bioaccumulation, persistence, potential for long-range transport and tendency to accumulate in
fatty tissues. Gamma-hexachlorocyclohexane (γ-HCH or lindane), is an organochlorine
insecticide considered as Persistent Organic Pollutant (POP) and one of the most commonly used
insecticides. Lindane has been used as a broad spectrum pesticide in agricultural, forestry,
veterinary and human health applications and has been found worldwide in air, water, soil and
sediment, as well as in aquatic and terrestrial organisms.
The aim of this study was to review the effect of lindane on human health and ecosystem. The
International Agency for Research on Cancer (IARC) has classified lindane as possibly
carcinogenic to humans and is listed as priority pollutant by the US EPA.

Keywords: Persistent Organic Pollutants, Hexachlorocyclohexane, Lindane, human health.

AIMS AND BACKGROUND

The aim of this study was to review the effect of lindane on human health and ecosystem.

After the Second World War, scientists began to recognize that, certain chemical were capable to

persist in the environment for long time, migrating in air, water, soil and accumulating to levels

that could harm wildlife and human health 1.

These chemical called Persistent Organic Pollutants (POPs) are found in all most areas of the

world, such as deserts, ocean and the poles, where there is no human activity or chemical sources,

demonstrating their ability to travel long distances 2. POPs are mostly lipophilic, bioaccumulating

in fat tissues, and subsequently amplifying in concentration in biota occupying the upper

spectrum on the food chain 3.

In 2001, representatives from 92 countries have agreed to sign the Stockholm Convention on

Persistent Organic Pollutants. The global treaty aimed to restrict and eliminate the production and

subsequent use, trade, release, and storage of POP substances in order to globally protect human

health and the environment 4.

Chemicals currently controlled under the Stockholm Convention and their uses are listed in

Table1.

Table1. Chemicals Currently Controlled under the Stockholm Convention

By -
Compound CAS No. Pesticide Industrial Annex
product
Aldrin 309 - 00 - 2 + Elimination
Chlordane 57 - 74 - 9 + Elimination
Dieldrin 60 - 57 - 1 + Elimination
Endrin 72 - 20 - 8 + Elimination
Heptachlor 76 - 44 - 8 + Elimination
Elimination/unintentional
Hexachlorobenzene ( HCB ) 118 - 74 - 1 + + +
production
Mirex 2385 - 85 - 5 + Elimination
Toxaphene 8001 - 35 - 2 + Elimination
Polychlorinated biphenyls Elimination/unintentional
1336 – 36 - 3 + +
(PCBs) production
DDT 50 - 29 - 3 + Restriction
Polychlorinated dibenzo - p –
+ Unintentional production
dioxins (dioxins)
Polychhlorinated
+ Unintentional production
dibenzofurans (furans)
α - Hexachlorocyclohexane
319 - 84 - 6 + Elimination
(α - HCH )
β - hexachlorocyclohexane
319 - 85 - 7 + Elimination
(β - HCH )
Chlordecone 143 - 50 - 0 + Elimination
Hexabromobiphenyl (HBB) 36355 - 01 - 8 + Elimination
HexaBDE and heptaBDE + + Elimination
Lindane 58 - 89 - 9 + Elimination
Elimination/Unintentional
Pentachlorobenzene ( PeCB ) 608 - 93 - 5 + + +
Production
TetraBDE and pentaBDE + + Elimination
Perfluorooctanesulfonic acid
+ Restriction
(PFOS) and salts
Perfl uorooctanesulfonyl
+ Restriction
fluoride (PFOSF )
Endosulfan 115 – 29 - 7 + Elimination
Lindane and α- and β-HCH were proposed in 2005 by Mexico to be included in the Stockholm
5, 6, 7
Convention POPs list . The Persistent Organic Pollutants Review Committee (POPRC)

recommended the listing of Lindane, α-HCH and β-HCH in Annex A of the Stockholm

Convention in order to achieve the global elimination of these isomers.

Lindane - gamma isomer of 1, 2, 3, 4, 5, 6-hexachlorocyclohexane (HCH) - is an organochlorine

insecticide considered as Persistent Organic Pollutant (POP). Technical HCH is an isomeric

mixture that contains eight forms differing only by the chlorine atoms orientation (axial or

equatorial positions) around the cyclohexane ring and they are denoted by the greek letters from

α to θ – Figure 1 8.

Figure 1. Structures of HCH isomers 8

The chemical structure of HCH affects their solubility, volatility, and sorption characteristics,

factors that might be used to explain the relative recalcitrance of γ-HCH. These characteristics are

also influenced by the orientation of the chlorine atoms on the molecule 9.

A list of chemical propertie of Lindane is provided in Table 2.

 Table 2. Chemical characteristics of γ-HCH
Chemical formula C6H6Cl6
Molecular weight 290.9
Melting point (oC) 112.510,11,12; 112–11313
Boiling point (oC) 323.4 at 760 mmHg10
Density (gcm-3) 1.89 at 19oC10
Solubility in water (mg l-1) Insolublee; 0–179;715
Solubility in 100 g ethanol (mg) 6.410,14
Log Kow 3.7210
Log Koc 3.00–3.5710; 3.0415
4.2×10-5 at 20oC10
Vapor pressure (mmHg) 9.4×10-6 at 20oC14
3.1×10-5 at 25oC13
3.3×10-5 at 20–25oC15
EPA toxicity classification Class II
Source: 10 - Source: ATSDR, 1989; 11 - Lide, 2003; 12 - Bintein Devillers, 1996; 13 - Willett et
al., 1998; 14 - Merck Index; 9 - Phillips et al., 2005; 15 - Paraiba Spadotto, 2002.

Technical HCH and Lindane were one of the most extensively used organochlorine pesticides
16
produced mainly after the Second World War until the 1990s . The application of those

organochlorine insecticides during the last decades has resulted in environmental contamination

of global dimensions 17, 18, 19. Lindane it has been used in the past for the protection of crops and
20
control of vector borne diseases (for scabies and lice treatments in humans) and is the only

isomer with insecticidal properties.

Lindane manufacture is an inefficient process, as for each ton of lindane obtained 6–10 tons of

other isomers with no insecticidal properties and mostly considered as waste HCH isomers

(commonly called as ‘muck’; 65–70% of α-HCH, 7–10% of β-HCH, 75% of δ-HCH, 1–2% of ε-

HCH, <2% of η- and θ-HCH 13

, are also produced 6, 20
. These isomers were separated from γ-

HCH and dumped as waste at different spots on the production site, causing serious soil

pollution17. These sites represent now one of the globe’s largest hazardous organic chemical

waste challenges largely unknown to both the public and to the scientific community.
Production and Use

HCH was first synthesized in 1825 by Michael Faraday, but the pesticidal properties were not

identified until 1942 21.

Historical production of technical HCH and Lindane started in the 1950s and occurred in many

European countries as well as in Asia and America 6.

Around 10 Mt of technical HCH has been released to the environment between 1948 and 1997 17.

The amount of global lindane usage has also been estimated by a few scientists. Voldner and Li

(1995) estimates worldwide lindane usage between 1948 and 1993 as 720 kt and Sang et al.

(1999) suggested the global consumption of lindane should be 6,000 kt. Global historical Lindane

use for agricultural purposes between 1950 and 2000 is estimated by Vijgen et al. (2011) at 450

kt.

Global annual Lindane use is given in Figure 2 and shows that the lindane usage worldwide was

highest in the 1960s and the beginning of 1970 22, 23.

Figure 2. Global annual lindane usage from 1950 to 2000 24

 22
Although many countries, especially developed countries banned Lindane usage in 1970s the

largest share of its use and production was in Europe. This accounted for almost 290 kt,

approximately 63% of the total global Lindane Consumption (Figure 3).

Figure 3. Lindane usage in different continent from 1950 to 2000 - (a) The tonnage (kt) and (b)
the percent of usage to the total global use 24

Additional use of Lindane on livestock, in forestry applications, in human pharmaceuticals has

been estimated at 150 kt 24 bringing the total global use to an estimated 600 kt.

Figure 4 estimates HCH waste quantities in countries with historical HCH/Lindane production

capacity.

Figure 4. Estimate on quantities of stored/deposited HCH waste isomers present in countries 25

Because of the environmental and biological persistence of HCHs, their use has been regulated.
26, 27
Canada and the United States banned technical HCH mixtures in 1971 respectively 1978, .
17
China banned technical HCH in 1983, and the former Soviet Union banned it in 1990 .

However, as of 1992, neither technical HCH nor lindane was banned in several countries; these

include India, Sudan, and Columbia. Lindane is still used in Canada and the United States as a

seed dressing and as a human medicinal.

Reasons for concern

Being a POP, Lindane is nowadays found in air, water, soil and sediment, as well as in aquatic

and terrestrial organisms. Lindane has been shown to be a persistent, toxic and bioaccumulative

chemical, migrate to long distances with air current, deposit in colder regions, and cause

widespread contamination with potential for long-range transport.

Lindanes can bioaccumulate in microorganisms, invertebrates, fish, birds and mammals due to its

high lipid solubility 6. Lindane levels have been measured in human blood, human breast milk

and human adipose tissue in many countries, demonstrating that humans are being exposed to

lindane 6. Several studies have detected HCH residues in regions, like the Arctic, that are free
28
from direct inputs of pesticides demonstrating their capacity for long-range transport. Direct

exposure to lindane can also occur with pharmaceutical treatments for head lice and scabies as

well as in occupational settings in facilities where lindane is formulated into commercial

pesticides. Abandoned pesticide plants and hazardous waste sites are also potential sources of
29
exposure to lindane and other HCH isomers . Lindane has been shown to be neurotoxic,

hepatotoxic, immunotoxic, and have reproductive and developmental effects in laboratory

animals 30.

The International Agency for Research on Cancer (IARC) has classified lindane as possibly

carcinogenic to humans and is listed as priority pollutant by the US EPA. Acute adverse effects
in humans for pharmaceutical uses have only been reported when the pesticide is not used

according to instructions 29.

FATE AND EXPOSURE

Lindane is a persistent organic pollutant with a long half-life in various environmental

compartments 12, 31, 32, 33.

Lindane has the potential to bioaccumulate in organisms and to be transported over long

distances 34.

Figure 5. Pathways for POPs transport 34

Lindane in air

γ-HCH major sources to the atmosphere are considered to be volatilization from treated

agricultural soil, volatilization from plant foliage sprayed and fugitive dust particles from wind

erosion of contaminated soil. Lindane may be emitted also into the atmosphere during the
25
manufacturing and is removed from the atmosphere by rain and dry deposition. The residence
time of γ-HCH in air is 119 days and the removal rates by rainfall is 2.5 per cent per week and

dry deposition is estimated at 3.5 per cent per week 36.

Levels of lindane in the atmosphere are seasonal and dependent of temperature; high summer

concentrations of γ-HCH may be indicative of recent usage as well as the movement of warm

air37.

Lindane in water

Lindane is more soluble in water than other organochlorine compounds and has a tendency to
23
remain in the water column . Contamination of surface water may occur as a result of surface
23
run-off and atmospheric depositions . The major transport pathways for atmospheric inputs to

surface waters are: wet deposition, dry deposition and gas exchange across the air-water

interface. Lindane biodegradation in aquatic systems is considered the most dominant process in

the removal mechanism from water 23. The estimated half-lives of lindane in rivers is 3-30 days,
38
in lakes 30-300 days and groundwater >300 days . Agricultural run-off and point source

discharges are the major contamination route of γ-HCH to surface water 39.

Lindane in soil

In soils and sediments, Lindane is degraded by biotransformation but, the major removal

mechanism of lindane from soil is volatilization 23. The mean half-life of lindane in treated soils

is estimated at 120 days 12

. Has been reported that γ-HCH degrade faster under anaerobic soil
40
conditions . Lindane will stay on the upper layer of the soil and generally, there is very little

movement to lower soil layers 41.

Lindane in plants

Plants are exposed to lindane during direct application, from air and water 42.
Metabolism of Lindane in plants is not well understood and it depends on plant type and lipid

content. For example, carrots are estimated to metabolize lindane with a half-life of 10 weeks, but

in lettuce the metabolic half-life is 3 to 4 days 43.

Lindane in wildlife

Wildlife exposed in the natural environment was found to accumulate Lindane in fatty tissues 32.

Higher levels of γ-HAH were found in the common cormorant (which is a bottom feeder), as

compared to the white pelican (which feeds at the surface), 23. This is due to increased exposure
23
of cormorants since sediments are generally higher in Lindane than surface water . Lindane is

considered to be moderately toxic to birds 42; exposure to high concentrations has been shown to

result in liver toxicity 44.

Highly toxicity of γ-HCH has been reported in different species of fish, acute exposure resulted

in biochemical changes in liver, brain tissue and hyperglycemia 45.

Effects on the liver, kidney, immune system and nervous system have been seen in mammals

following exposure to lindane 35.

HUMAN EXPOSURE

General public exposure to γ-HCH can result from eating food sprayed with Lindane, drynking

water, breathing air and dermal contact with contaminated soil. Almost all human exposure to

Lindane is from dietary intake (>99 per cent), 12, 33, 46.

Lindane can be absorbed by the skin through the use of scabies control lotions 47, 48, 49, 50, 51.

Workers occupationally exposed to HCH through spraying have higher concentrations of Lindane

in their blood and skin lipid samples than the general population 52.

Exposure of children to Lindane is a particular concern. Gamma-HCH has been found in

maternal serum, in placenta, and in umbilical cord 53, 54. HCH isomers have been found in human
 55, 56, 57
breast milk in many areas of the world . The infants of humans and wildlife may be

exposed to Lindane through breast milk 54, 58.

Acute oral exposure of people affects the cardiovascular, gastrointestinal, and nervous system,

causing dizziness, headaches and seizures 59, 60, 64. Inhalation of Lindane includes nose and throat

irritation, anemia, and itchy skin 61.

US EPA (1998a) classified as a possible human carcinogen of low to medium carcinogenic

hazard (Group B2/C). The International Agency for Research on Cancer (IARC) also classifies

Lindane as a possible human carcinogen (Group 2B) 62.

CONCLUSIONS

Lindane, the γ-HCH isomer, is extracted from technical HCH, (which consists of 60-70% α-

HCH, 5-12% β-HCH, 10-15% γ-HCH) and it is the only isomer with pesticidal properties.

Historical usage of lindane worldwide has been investigated from different sources. Global

Lindane use for agricultural purpose between 1950 and 2000 is estimated to be 450 kt, among

which 280 kt was used in Europe, 73 kt in Asian, 64 kt in America, 29 kt in Africa, and 1 kt in

Oceania countries. Although Lindane use in most Europe countries are stopped, the historical

lindane use from 1950 to 2000 in Europe reached approximately 63% of the total global use.

Global Lindane usage was highest in the 1960s and the beginning of 1970.

In this review, the existence of Lindane in environmental systems and its adverse effect on

human health were discussed. Lindane is a persistent organochlorine compound resistant to

environmental degradation, capable of long - range transport and bioaccumulate in animal and

human tissues and can be extremely toxic. Lindane has also been shown to bioaccumulate in the

fatty tissue of organisms and biomagnificate along the food chain.

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