Arsenic

1. Introduction

Arsenic, a metalloid and naturally occurring element, is one of the most abundant elements
in the earth’s crust and is found throughout our environment. Arsenic is used as an insecticide
and herbicide or preservative for wood due to its germicidal power and resistance to rotting
and decay. Arsenic is also used in medicine, electronics, and industrial manufacturing. In the
environment, arsenic and its compounds are mobile and cannot be destroyed. However,
interaction with oxygen or other molecules present in air, water, or soil, as well as with
bacteria that live in soil or sediment can cause arsenic to change form, attach to different
particles, or separate from these particles. The environmental presence of arsenic derives
from both natural and anthropogenic sources. Many common arsenic compounds can
dissolve in water, thus arsenic can contaminate water bodies. Arsenic contamination in the
environment is causing a significant global human health problem. They are found to be
associated with detrimental health effects such as hyperpigmentation, keratosis, various
types of cancer and vascular diseases. 9

2. Laws and Regulations related to arsenic

In Malaysia, there are some laws and regulations related to Arsenic. First, there is an act which
is Environmental Quality (Clean Air) Regulations 1978 p.u.(a) 280. The regulation 4 is New
Installations within Residential Areas not Permitted without Prior Approval. According to this
regulation, any equipment or facility used in the manufactures, packing or repacking of
industrial chemicals, in the process of which mercury, antimony, arsenic, cadmium, zinc, lead,
copper or any compound thereof is emitted cannot be installed without approval. Next, based
on the same regulation, the stack gas emission standard for arsenic from industry is not more
than 0.025 gm/Nm3.

The next regulation in Malaysia related to arsenic is extracted from Environmental Quality
(Industrial Effluents) Regulations 2009. From fifth schedule [paragraph 11(1) (a)], there is the
acceptable conditions for discharge of industrial effluent for mixed effluent of standards A
and B. Standard A is for discharge upstream of any raw water intake, and Standard B for
discharge downstream of any raw water intake. For arsenic, the acceptable conditions for
discharge for mixed effluents of standard A is 0.05 mg/L whereas for standard B is 0.10 mg/L.2
Furthermore, according to Environmental Quality (Control of Pollution From Solid Waste
Transfer Station and Landfill) Regulations 2009 (PU(A) 433). From regulation 13 second
schedule, there is the acceptable conditions for discharge of leachate. For arsenic, the
acceptable condition for discharge of leachate is 0.05 mg/L. Next, based on Malaysia food
regulation 1985 regulation 38 fourteenth schedule, there is a list of maximum permitted
proportion of metal contaminant in specified food. The amount of arsenic permitted in
specified food can be observed at table below. 10

Table 1: Malaysia Food Regulation 1985 Fourteenth Schedule (Regulation 38) - Maximum
Permitted Proportion of Metal Contaminant in Specified Food10

Metal Contaminant [Maximum permitted proportion in milligram per kilogram (mg/kg)]

(1) (2) (3) (4) (5) (6)
Food Arsenic Lead Mercury Cadmium Antimony
(As) (Pb) (Hg) (Cd) (Sb)
Flavouring substance 1 2 0.05 1 1
Baking powder, cream 2 2 0.05 1 1
of tartar
Milk and milk product 0.5 0.02 0.05 1 1
Sweetening substance:
i. Sweetening 1 0.5 0.05 1 1
substance
other than
glycerol,
molasses,
saccharin and
sorbitol
1 2 0.05 1 1
ii. Molasses

Honey 1 2 0.05 1 1
Meat and meat product 1 2 0.05 1 1
other than edible
gelatin
Edible gelatin 2 2 0.05 1 1
Edible fat and edible 0.1 0.1 0.05 1 1
oil
Vegetable product and 1 2 0.05 1 1
fruit product other than
vegetable juice and
fruit juice
 Vegetable juice and 0.1 0.5 0.05 1 0.15
fruit juice
Pulp, tomato, paste 2 # 0.05 1 1
and puree
Tea, tea dust, tea 1 2 0.05 1 1
extract and scented tea
Coffee, chicory and 1 2 0.05 1 1
related product
Cocoa and cocoa 1 2 0.05 1 1
product
Spice other than curry 5 2 0.05 1 1
powder
Curry powder 1 2 0.05 1 1
Sauce 1 2 0.05 1 1
Pickle 1 1 0.05 1 1
Alcoholic beverage 0.2 0.5 0.05 1 0.15
other than wine
Vinegar 0.2 0.5 0.05 1 0.15
Soft drink:
i. Requiring 0.5@ 1@ 0.05@ 1@ 0.15@
dilution
ii. For direct
consumption 0.1 0.2 0.5 1 0.15
Any food for which no 1 2 0.05 1 1
other limit is specified,
excluding water and
food additive*

Notes:
1. *The maximum permitted proportion of metal contaminant in food additive, other than
flavouring substance, colouring substance and edible gelatin, shall be governed by good
manufacturing practice.

2. “@” indicates level before dilution.

3. Major sources of the selected pollutant

a) Natural Sources3

i. Arsenic Minerals in the Environment - The greatest concentrations of these minerals occur
in mineralized areas associated with the presence of cadmium, lead, silver, gold, antimony,
phosphorus, tungsten and molybdenum

ii. Arsenic Occurrence and Concentrations in Rock-Forming Minerals

 Sulfide Mineral: As chemistry of arsenic has some similarities to that of sulfur, the
greatest concentrations of the element tend to occur in sulfide minerals, of which
pyrite is the most abundant
 Oxide Minerals: High arsenic concentrations are also found in many oxide minerals
and hydrous metal oxides, either as part of the mineral structure or as sorbed species
 Phosphate and Other Minerals: Arsenic concentrations in phosphate minerals are
variable but can reach high values, up to 1000 mg/kg in apatite

iii. Arsenic Occurrence and Concentrations in Rocks

 Igneous Rocks: Arsenic concentrations in igneous rocks are usually low

 Sedimentary Rocks: concentration of arsenic in sedimentary rocks is typically in the
range 5–10mg/kg

iv. Groundwater Contamination

 The occurrence, origin and mobility of arsenic in groundwater are primarily influenced
by local geology, hydrogeology, and geochemistry of the aquifer sediments. Elevated
arsenic concentrations may arise from natural weathering and leaching of arsenic
from geological materials containing arsenic, drainage from thermal springs and
geysers, as well as atmospheric deposition
 Arsenic Enrichment in Areas of Geothermal Activity: Many geothermal systems have
been, or will be, developed to generate energy from steam and hot water reservoirs
beneath the earth’s surface. Therefore, the potential exists for further mobilization
and exposure to arsenic from such development.
b) Anthropogenic Sources3

i. Metal acquisition and processing: Ore production and processing, metal melting in iron
works; Metal-treatment admixture in bronze, lead, and copper alloy production; Galvanizing
processes; Battery plate production

ii. Energy: High-temperature oil and coal burning; Operation of power plants

iii. Agriculture and livestock: Use of arsenical insecticides; Debarking trees (process of
removing bark from wood), soil sterilants, feed additives; compost and dung surplus (arsenic
from animal feeding)

iv. Wood preservatives

v. Medicine: Pharmaceutical substances: antisyphilitic drugs (treat syphilis: Syphilis is a

bacterial infection usually spread by sexual contact); treatment of amebiasis (an infection of
the intestines with a parasite called E. histolytic. It results in diarrhoea with blood or mucus),
and sleeping sickness ( Sleeping sickness is an infection caused by tiny parasites carried by
certain flies. It results in swelling of the brain)

vi. Waste material: Waste incineration; Household waste disposal

vii. Other industrial uses/sources: Glassware and ceramics production; Use in decoloring
agents; Electronics industries; Solar cells, semiconductor applications, light-emitting diodes
(digital watches); Dyes and colors; Oil and solvent recycling; Cement works

3. Impact of Arsenic on ecology system, human health and economy

Arsenic (As) a persistent inorganic element, classified as the most toxic and carcinogenic
contaminant by several national and international environmental and health organizations,
currently poses a severe threat to the human and environmental health.

Impact on Ecology System4

Water and land-living plants and animals show a wide range of sensitivities to different
chemical forms of arsenic. Their sensitivity is modified both by biological factors and by their
surrounding physical and chemical environment. In general, inorganic forms of arsenic are
more toxic to the environment than organic forms and, among inorganic forms, arsenite is
more toxic than arsenate. This is probably because the way in which the various forms are
taken up into the body differs and once taken up, they act in different ways in the body. The
reason why arsenite is toxic is thought to be because it binds to particular chemical groups -
sulfhydryl groups - found on proteins. Arsenate, on the other hand, affects the key energy
producing process that take place in all cells.

Arsenic compounds cause short-term and long-term effects in individual plants and animals
and in populations and communities of organisms. The nature of the effects depends on the
species and time of exposure. The effects include death, inhibition of growth, photosynthesis
and reproduction, and behavioural effects. Environments contaminated with arsenic contain
only a few species and fewer numbers within species. However, Arsenic compounds are not
thought to pose a threat at a wider global environmental scale.

Impact on Human Health7

People are exposed to elevated levels of inorganic arsenic through drinking contaminated
water, using contaminated water in food preparation and irrigation of food crops, industrial
processes, eating contaminated food and smoking tobacco.

Acute Effect

The immediate symptoms of acute arsenic poisoning include vomiting, abdominal pain and
diarrhoea. These are followed by numbness and tingling of the extremities, muscle cramping
and death, in extreme cases.

Long-term Effect

After about five years of exposure to high levels of inorganic arsenic (for example, through
drinking-water and food), the effects can be observed in the skin which includes pigmentation
changes, skin lesions and hard patches on the palms and soles of the feet and might lead to
skin cancer.

In addition to skin cancer, long-term exposure to arsenic may also cause cancers of the
bladder and lungs. The International Agency for Research on Cancer (IARC) has classified
arsenic and arsenic compounds as carcinogenic to humans, and has also stated that arsenic
in drinking-water is carcinogenic to humans.
Developmental effects, diabetes, pulmonary disease, and cardiovascular disease. Adverse
pregnancy outcomes and infant mortality, with impacts on child health

Impact on Economy1

Figure 1: Economic impacts of arsenic pollution

Arsenic toxicity is causing the social and health hazards to the affected people in the study
area which is West Bengal, India and at the same time, it is creating a lot of economic
problems. Job opportunities of people with arsenical skin manifestation appear to be
shrinking and they also lose their jobs and the diseases thought to be the spreading one.
The arsenical affected people in the study area are often victimized by matchmakers,
moneylenders or by tricksters in different ways, which cause extreme financial uneasiness.
Due to poverty drop out, difficulties of medical expenditure, selling of assets are also very
common in arsenical affected village that create further economic crisis.
4. Sampling and analytical techniques required to determine/quantify arsenic
Sampling technique6
Sampling for arsenic in air is dependent on the operation. If the operation being sampled
has the potential for producing inorganic arsenic vapour and arsine, a sampling train,
sampling media II is used to capture the vapour and particulate whereas sampling media I is
only for particulate arsenic. Sampling can be accomplished using one of two different
approaches:
Table 2: Different approaches for arsenic air samples
Suspected Form Sampling Media Flow Rate (L/min)
Particulate ( + Vapour) I 2
Particulate + Vapour + Arsine II 0.5

Sampling Procedure:
i. Place an MCE filter and a cellulose backup pad in each two- or three-piece cassette.
The backup pad should be chemically-treated if volatile inorganic arsenic compounds
are suspected. Seal each cassette with a gel band.
ii. Attach calibration sampling media to the pump using flexible tubing. Depending on
the sampling media in use, follow the sampling scheme shown:

Figure 2: Sampling scheme of air samples of arsenic

 iii. Calibrate each personal sampling pump with prepared sampling media in-line to
within ±10% of the recommended flow rate of 2 L/min (Sampling Media I) or 0.5
L/min (Sampling Media II). Remove the calibration media and attach new sampling
media to the calibrated pump.
iv. Place the sampling media/pump assembly in appropriate positions on the employee
or the workplace area.
v. If possible, collect full-shift samples. All samples should be taken for at least 240 min.
The minimum recommended air volume is 480 L (120-L for Sampling Media II). Take
samples to cover the workshift.
vi. If the filter becomes overloaded while sampling, prepare and use another filter
cassette. Take consecutive samples using shorter sampling periods if overloading
occurs.
vii. Place plastic end caps on each sampling media after sampling.

Analytical Technique6
The analysis of arsenic is performed with an atomic absorption spectrometer (AAS) utilizing
a heated graphite atomizer (AAS-HGA). Compared to arsine generation procedure, the AAS-
HGA procedure offers following advantages:

i. a simple digestion procedure

ii. increased ability to analyze other analytes from the same sample
iii. a decrease in sample loss and an increase in sample throughput

This method uses a HGA with a Zeeman/L'vov configuration to analyze arsenic and reduce
background contributions. Zeeman electromagnet technique assists in minimizing
background without the use of continuum sources such as the deuterium arc. The L'vov
platform is a pyrolytically-coated graphite support inserted into a graphite tube offers a
more uniform temperature distribution inside the graphite tube, increased sensitivity, and
less opportunity for matrix effects from molecular formation and absorption during
atomization.
Analysis procedure:

i. Set up the spectrometer and HGA according to the AAS-HGA standard operating
procedure.
ii. Inject an aliquot of a standard into the HGA and measure the absorbance of the
standard using peak height or area. The standard concentration should be within the
linear range.
iii. Analyze samples and blanks. Analyze a standard after every four or five samples.
Standard readings should be within 10 to 15% of the readings obtained at the
beginning of the analysis.
iv. If any samples exceed the linear range, dilute with diluting solution to bring them
into the working range.

Summary

 Arsenic is an abundant pollutant that can be found throughout the environment

 Arsenic is highly toxic in its inorganic form
 Arsenic can be originated from two types of sources which are natural sources and
anthropogenic sources
 Some laws and regulations related to arsenic has been implemented in Malaysia to
minimize the exposure of arsenic to the public
 From impact of arsenic on environment, we can see that it can be harmful to water
and land-living plants and animals but cannot pose threat at a global environment
scale
 Arsenic can have acute and long-term health effect towards human health such as
skin, bladder and lung cancer
 Sampling technique using sampling train which is sampling media I or sampling
media II depending on whether operation being sampled has the potential to
produce arsine
 Analysis of arsenic is performed with an atomic absorption spectrometer (AAS)
utilizing a heated graphite atomizer (AAS-HGA)
References

1. Abhijit Das, J. R. S. C. Different Economic Impacts Of Arsenic Pollution 2019, p. 19.

https://shodhganga.inflibnet.ac.in/bitstream/10603/162997/12/12_chapter%205.pdf.

2. Environment, D. o., Environmental Requirements: A Guide For Investors. Putrajaya,

2010. http://www.doe.gov.my/eia/wp-content/uploads/2012/03/A-Guide-For-
Investors1.pdf.

3. Garelick, H.; Jones, H.; Dybowska, A.; Valsami-Jones, E., Arsenic pollution sources.
Rev Environ Contam Toxicol 2008, 197, 17-60.

4. GreenFacts Arsenic: 6. What are the effects of arsenic on the environment?

https://www.greenfacts.org/en/arsenic/l-2/arsenic-6.htm#0.

5. Hernandez, S. Sena's Chemistry Blog: I am Arsenic.

http://senab102.blogspot.com/2015/09/i-am-arsenic.html.

6. Labor, U. S. D. o. Sampling and Analytical Methods: Inorganic Arsenic In Workplace

Atmospheres - ID105.
http://www.aresok.org/npg/nioshdbs/oshamethods/inorganic/id105/id105.html#8.12.

7. Organization, W. H. Arsenic. https://www.who.int/news-room/fact-

sheets/detail/arsenic.

8. Point, A. Arsenic: Properties and Occurrence - Assignment Point.

https://www.assignmentpoint.com/science/geographic-minerals/arsenic-properties-
occurrence.html.

9. Registry, A. f. T. S.; Disease ATSDR - Public Health Statement: Arsenic.

https://www.atsdr.cdc.gov/phs/phs.asp?id=18&tid=3.

10. Services, I. L. B., Food Regulations 1985. Kuala Lumpur : International Law Book
Services, 1994.: Kuala Lumpur, 1994.