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Arsenic

Brief History of Arsenic


Discovery

History is convoluted

Not sure who first discovered

Greeks and Romans had slaves mine for


arsenic

Used in Alchemy
www.en.wikipedia.com

Albertus Magnus

German chemist

First to isolate in 1250 AD

General Information of
Arsenic

Chemical Formula = As

Atomic Number = 33

Molecular Weight = 74.92 grams

Color = lead gray, gray, white

Hardness of 3.5

Similar to calcite or flourite

Talc is 1 and diamond is 10

Nonmagnetic

Metallic

Poor conductor of heat & electricity


http://periodictable.com/Elements/033/index.html

Inorganic vs. Organic


Arsenic
Inorganic

Organic

Occurs

Mainly

naturally in soil and many


minerals and ores that contain copper
and lead
When heated, arsenic rises up
smokestack as a fine dust
Cannot
Used

be used in agriculture

to pressure treat wood

Arsenate

V is found in water

Can

found in marine organisms

still be used on agriculture


Primarily cotton

Improve

properties when added


to an allow or metal
Greatest

use in lead acid

batteries
Semiconductors
Arsenate

http://www.finegardening.com/design/articles/pressure-treated-wood-in-beds.aspx

and LEDs

III found in water

Uses of Arsenic

Poison of Kings

Marsh and Reinsch Tests

Bronze alloy

Lead alloy

Medicinal uses

Syphili, yaws, psoriasis, and other viruses

Industrial uses

Ammunition production, pigments, insecticides, rat


poison, wood preservative, semiconductors, &
others

http://biologyze.com/tag/arsenic-and-bacteria/

Environmental Sources
of Arsenic

Marine animals

In drinking water

~200 mineral species

Most common is arsenopyrite

http://deepbluehome.blogspot.com/2010/10/deep-blue-home-snapshot-20002010.html

Emitted from volcanoes

http://ebt2010.blogspot.com/2010/07/understand-whatsarsenic-and-how-it.html

http://www.ecowaternorthwest.com/arsenic.php

Anthropogenic Sources
of Arsenic

Reduction of Arsenic Trioxide


(As2O3 - Arsenite) with
charcoal

As2O3 is created during the


metal smelting process
http://www.ehow.com/how_6160537_preserve-pressure-treated-wood.html

Industrial uses

Ammunition production,
pigments, insecticides, rat
poison, wood
preservative,
semiconductors, & others

http://www.indiamart.com/alchemylaboratories/
analytical-reagents.html

http://serc.carleton.edu/woburn/issues/pesticides.html

Mechanism

Inorganic

Arsenate exists in +5 oxidation state

Arsenite exists in +3 oxidation state

Mechanism (Continued)

Organic As methylated (both in +3


oxidation state)

Monomethylarsonous acid (MMAIII)

Dimethylarsinous acid (DMAIII)

Mechanism (Continued)
+ 5 oxidation state (pentavalent)

Arsenate

Monomethylarsonous acid (MMAIII)

Dimethylarsinous acid (DMA III)


Arsenite

+ 3 oxidation state (trivalent)

Mechanism (Continued)

In general, As terrorizes the metabolic


processes of the mitochondria

http://www.phschool.com/science/biology_place/biocoach/cellresp/overview.html

Mechanism (Continued)

Pentavalent toxicity

Very similar to phosphate

Can substitute for inorganic phosphate in


glycolytic and cellular respiration pathways

Mechanism (Continued)

Pentavalent toxicity

ADP-phosphate = ATP

ADP-arsenate = biologically useless

High energy phosphate bonds are lost

Stopping the production of ATP will stop all


processes that require ATP

Mechanism (Continued)

Trivalent toxicity

Reacts readily with thiol-containing molecules


(-SH functional group)

Amino acid cysteine contains thiol group

Cysteine rich proteins are vulnerable to As


binding

Mechanism (Continued)

Trivalent toxicity

Pyruvate Dehydrogenase (PDH)


requires lipoic acid cofactor a
dithiol

As inhibits this enzyme by binding


to the cofactor

The citric acid cycle cannot


proceed because the pathway is
terminated
http://upload.wikimedia.org/wikipedia/commons/0/0b/Citric_acid_cycle_with_aconitate_2.svg

Mechanism (Continued)

Oxidative Stress

Reductase enzymes are present in the cell to


reduce reactive oxygen species (ROS)

As binds and inhibits some of these reductases,


resulting in the accumulation of ROS

ROS can bind/damage DNA and other cellular


components

Part of As carcinogenicity

Mechanism (Continued)

Carcinogenicity

Researchers have yet to fully elucidate


carcinogenic mechanisms of As

It is widely accepted that As is a carcinogen


and several mechanisms have been proposed

Mechanism (Continued)

Carcinogenicity

ROS accumulation

DNA Excision Repair and DNA Ligase inhibited by


Arsenic

Co-mutagenic effect with ROS, UV radiation, XRays, and other chemicals

DNA methylation alterations

Also noted as a tumor promoter in mouse ovarian


cancers

http://www.biol.unt.edu/~jajohnson/DNA_sequencing_process

Health Effects and


Symptoms

Acute As poisoning

Nausea

Vomiting

Blood in the urine

Cramping muscle

Hair loss

Stomach pain

Convulsions

Organ failure

Comma to death (interferes with glycolysis)

Health Effects and


Symptoms

Chronic arsenic poisoning

High oxidative stress

affect the structure of function of cardiovascular


system

Increases the risk of cancer

Vitamin A deficiency

Night blindness

Heart disease

Skin color change

Eye inflammation

Hyperkeratosis and hyperpigmentation

Blushed complexion

http://wewinwater.com/2011/09/03/addressing-arsenic-poisoning-in-bangladesh/

Health Effects and


Symptoms

Bangladesh

77 million people (1/2 population of crowded


Bangladesh) may have been exposed to toxic
levels of arsenic.

More than 20% of deaths are caused by


arsenic.

Groundwater is contaminated with As

http://www.who.int/topics/arsenic/en/

Health Effects and


Symptoms

United Kingdom (1990 and 1991)

In UK, 6000 people had the arsenic poisoning


and 70 of them died.

The beer contained 15ppm of arsenic

Glucose (ingredient of beer) is contaminated


to arsenic

Contaminated during the refining process

http://www.beer100.com/beercalories.htm

Health Effects and


Symptoms

Japan (1955)

In Japan, 12,130 children suffered from the arsenic


poisoning and 130 of them died.

Milk from Tokushima factory was contaminated to


arsenic

Symptoms

loss of appetite, vomiting, diarrhea, boil, skin


color changed to black, anemia, hypertrophy of
the liver

Aftereffect

blurred vision, hard of hearing, low score in


school record, abnormal brainwave, epilepsy,
headache, dizziness, cold hands and feet

http://romanianrecipes.wikia.com/wiki/Milk

Health Effects and


Symptoms

Arsenic and ADHD study (Roy et al 2010)

526 6-7 years old children in Torreon Mexico

Urinary arsenic levels were measured

No significant relationship found between any


measure of urinary arsenic and parents ratings
of behavior

However, higher urinary arsenic was associated


with high scores on Cognitive Problem exams

Health Effects and


Symptoms

Pre- and Postnatal Arsenic Exposure and Body


Size a cohort study (Saha et al 2012)

Purpose - to assess potential effects of early


lifeAsexposureon weight and length of children from
birth to 2 years of age

2372 children born in Bangladesh.

Measured arsenic concentrations in urine (U-As) with


child body weight and length

Compared to girls in the first quintile of U-As (<16


g/L), those in the fourth quintile (26-46 g/L) were
almost 300 g lighter and 0.7 cm shorter.

Postnatalarsenicexposurewas associated with lower


body weight and length among girls, but not boys.

Arsenic Regulation &


Legislation

EPA

Proposed a maximum contaminant level (MCL)


of 5mcg/L in 2000 and established at 10mcg/L
on Jan 22, 2001

This rule became enforceable on Jan 23, 2006

This standard protects public health based on


the best available science and ensures that
the cost of the standard is achievable

Arsenic Regulation &


Legislation

FDA

Currently only has a standard for maximum levels of As in


bottled water

No inorganic As regulations in Europe and U.S. in relation to food

Only China has a regulatory limit (150 ppb)

Today, FDA is testing apple juice and trying to determine an


appropriate level

Apple juice containing >23 ppb of organic arsenic represent a


potential health risk

Arsenic Regulation &


Legislation

Organic Food

Organic food is not exempt from being


contaminated by toxic chemicals

Organic standard do not prohibit the presence of As

Two brands of organic infant formula 20 times


more As than other regular brands

Institute for Agriculture and Trade Policy (IATP) and


FDA move toward regulating As contaminant levels
in the food supply

References
http://www.sciencedirect.com/science/article/pii/S037842740200084
X
http://emedicine.medscape.com/article/812953-overview#a0104
http://www.sciencedirect.com/science/article/pii/S001393511100073
9
http://www.ncbi.nlm.nih.gov/pubmed/22504586
http://www.who.int/bulletin/archives/78(9)1093.pdf
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1026413/pdf/westjme
d00133-0060.pdf
http://www.ehjournal.net/content/5/1/31
http://www.weitzlux.com/arsenic/historyofarsenic_403021.html
http://webmineral.com/data/Arsenic.shtml
http://drugstoremuseum.com/sections/level_info2.php?
level_id=150&level=3
http://www.weitzlux.com/arsenic/historyofarsenic_403021.html
http://www.greenfacts.org/en/arsenic/l-3/arsenic-2.htm#0p0
http://water.epa.gov/lawsregs/rulesregs/sdwa/arsenic/regulations.cfm
http://www.foodqualitynews.com/Legislation/Congressrepresentatives-urge-FDA-to-move-on-inorganic-arsenic-levels
http://www.foodqualitynews.com/Legislation/US-rice-arsenic-levelregulations-imperative-report

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