**3. History**

182 Pesticides in the Modern World - Risks and Benefits

more toxic than As V (Yousef, El-Demerdash, and Radwan 2008). From biological and toxicological view, arsenic compounds can be classified into three major groups: Inorganic arsenic compounds, organic arsenic compounds and arsine gas (Hardman et al. 1996). The metalloid is found mostly as yellow complex sulfides. Organic arsenic is non-toxic whereas inorganic arsenic is toxic. The inorganic forms of arsenic are yellow (AS2S3, orpiment), red (AS2S2 realgar) and grey to silver white (FeAsS, arsenopyrite) (Waxman and Anderson 2001).

a) Orpiment

 c) Arsenopyrite Fig. 1. Orpiment, realgar and arsenopyrite - from left to right- (Photographs from the Ohio

State University Newark)

b) Realgar

Arsenic and arsenic compounds are known since the ancient times. As early as 500 B.C. the ancients knew about arsenic, whose name comes from the Greek word "arsenikon" for potent or bold, which means orpiment form Latin auripigmentum. In the 16th an 17th centuries, red and white arsenic were put into amulets that were worn around the neck and close to the heart to ward off the plaques (Cullen 2008). Most arsenic is found in conjunction with sulfur in minerals such as arsenopyrite (AsFeS). Because of the association with ore and the stability of As in form like AsFeS, As was used as a "pathfinder element" in geochemical exploration for gold (Jones 2007).

Fig. 2. Acidum Arsenicosum Anhydricum bottle, Global Antiques

Arsenic – Pesticides with an Ambivalent Character 185

For centuries arsenic has been used for different purposes. Arsenic was an ingredient of a lot of consumer products e.g. wallpapers, toys, food wrappers, cosmetics, pigments in paints – known as "Paris green". William Withering, an english doctor, who discovered 1775 digitalis was a proponent of therapies with arsenic. He argued:" Poison in small doses are the best

Arsenic-containing compounds have been used for cancer-treatment in both tradition Western and Chinese medicine. The first use of arsenic in the treatment of leukemia was in 1865 by Lissauer (Lissauer and H. 1865). With the development of modern medicine against

Arsenic exposure occurs from inhalation, absorption through the skin and by ingestion. Arsenic is mainly transported in the environment by food, which contains both organic and inorganic As, but mostly accrue as relatively no-toxic organic compounds (arsenobentaine and arsenocholine). Seafood, fish and algae are the richest organic sources (Edmonds and Francesconi 1987). The following table shows an overview of the arsenic content of various

Concentrations of arsenic vary in the environment, e.g. 0,03-025 ppm in soil, 0,023-0,35 ppm in plants, up to 55 ppm in groundwater, 0,0001-0,08 ppm in seawater, 4-170 ppm in fish, 0,008-0,85 ppm in wine and up to 0,00049 or 0,63 mg/m³ in urban air (2004; Jones 2007; Rahman 2006; Basu et al. 2001). Contamination of arsenic in ground water is a global problem and millions of people are at a risk of arsenicosis. People from countries in Asia (Taiwan, Bangladesh, West Bengal (India) and South America (Chile and Córdoba) get presented to inorganic arsenic in ground water with very high concentration. The arsenic poisoning from drinking As-contaminated underground water was often triggered by the introduction of deep tube-pump wells to replace surface water. The World health organization (WHO) and US environment protection agency (EPA) had set up the standard for drinking water known as maximum contamination level (MCL) which is 10 µg/l (Effelsberg 1992). The WHO recommended 0.01 mg/l of arsenic in drinking water as an allowable ranger for human consumption. Millions of people are compelled to use the drinking water higher arsenic level than MCL worldwide. In addition there are industrial exposures for workers, e.g. semiconductor workers and famers handle with arsenical

It was found an increase in the prevalence of skin lesions at 0,005 mg As/l in the drinking water, which is a lower level than the drinking water quality standard of WHO (Yoshida,

medicines; and the best medicines in too large doses are poisonous (Aronson 1994).

**Food Estimates of daily intake (µg/d)** 

Table 2. Estimated of daily arsenic intake from diet (Sorvari et al. 2007)

herbicides. Arsenic has been used as feed additives e.g. poultry feeds.

cancer the use of arsenic in the western world diminished.

Milk 1,39 Fruits and vegetable 0,46 Meat 2,14 Cereals and bakery wares 6,57 Fish 34,9 Eggs 0,13 Sweeteners 0,2 Beverages 4,67

**4. Epidemiology** 

foods.

Through the centuries Arsenic was a common method of homicide. The death of the French emperor Napoleon Bonaparte, on 5 May 1821 was believed to be a victim after drinking arsenic-tainted wine that was served him (Leslie and Smith 1978; Lin, Alber, and Henkelmann 2004). Arsenic was a popular murder weapon because of the odorless and tasteless properties and the poisoning result in symptoms that can be confused with other natural disorders. In the Middle ages arsenic was a favorite poison and has been called the Poison of Kings and the King of Poison (Vahidnia, van, V, and de Wolff 2007).

Arsenic was also used as healing agents. The Greek physicians such as Hippocrates and Galen popularized it use for treating skin ulcers and tumors such as superficial epitheliomas. Arsenic has been used as topical pastes, as vapor inhalation, intravenous injection, orally in liquid or in solid form. A paste of the sulfides were used for treatment of neuralgia, rheumatism, arthritis and skin disease (Shen et al. 1997). Also Fowler´s solution, a 1% arsenic trioxide preparation, was widely used during the 19th century. Fowler´s original recipe was described as "64 grains arsenic oxide, 64 grains purest vegetable alkali, distilled water half pound. Heat until clear. Cool. Add half pound spirit of lavender and make up to 15 oz with water." (Cullen 2008).

Fig. 3. Fowler´s Solution made by Wisconsin Pharmacal Co

It was used to treat diseases like leukemia, Hodkin´s disease and pernicious anemia. The first organic arsenical used therapeutically was Salvarsan, which was developed by Paul Ehrlich 1907. It was used to treat syphilis, until penicillin became available in the 1940s. A model representation from Salvarsan and a picture of Ehrlich adorned the 200 Deutschmark banknote.

Fig. 4. German 200 Deutschmark banknote with hologram and Paul Ehrlich

For centuries arsenic has been used for different purposes. Arsenic was an ingredient of a lot of consumer products e.g. wallpapers, toys, food wrappers, cosmetics, pigments in paints – known as "Paris green". William Withering, an english doctor, who discovered 1775 digitalis was a proponent of therapies with arsenic. He argued:" Poison in small doses are the best medicines; and the best medicines in too large doses are poisonous (Aronson 1994).

Arsenic-containing compounds have been used for cancer-treatment in both tradition Western and Chinese medicine. The first use of arsenic in the treatment of leukemia was in 1865 by Lissauer (Lissauer and H. 1865). With the development of modern medicine against cancer the use of arsenic in the western world diminished.
