Hazardous Gases: Risk Assessment on the Environment and Human Health

Chapter 1: Arsenic pentafluoride: Risk assessment, environmental, and health hazard

Om Singh    Department of Chemistry, College of Engineering Roorkee, Roorkee, Uttarakhand, India

Abstract

Arsenic pentafluoride gas is not only extremely toxic and corrosive, but also hazardous to the aquatic environment, and is listed as a potential carcinogen. It is used in the synthesis of electroconductive polymers, semiconductor fabrication, and some chemicals. It causes several health effects, including neurologic and neurobehavioral effects, cardiovascular disease, pulmonary or hepatic fibrosis, hematological effects, etc. Keeping the safety of exposed persons from probable adverse effects, many rules and plans have been identified for numerous inorganic and organic procedures for arsenic by international, federal, and state organizations. This chapter is focused on the risk assessment and environmental and health hazards of arsenic pentafluoride.

Keywords

Arsenopyrite; Risk management; Cloud computing; Carcinogen; Arsenic health risk assessment

Abbreviations

AAS 

atomic absorption spectrometry

AHRA 

arsenic health risk assessment

ATP 

adenosine triphosphate

CC 

cloud computing

DMSA 

dimercaptosuccinic acid

DNA 

deoxyribonucleic acid

EDTA 

ethylenediaminetetraacetic acid

GIC 

general informative criteria

Iips 

International Institute for Population Sciences

Mips 

microprocessor without interlocked pipelined stages

NAD + 

nicotinamide adenine dinucleotide

SDS 

safety data sheet

1.1: Introduction

Arsenic pentafluoride (AsF5) is a colorless, noncombustible gas that is extremely toxic and corrosive. Arsenic and hydrogen fluoride are formed when arsenic pentafluoride is hydrolyzed in the presence of water and a humid environment. This gas is hazardous to the aquatic environment (Greenwood & Earnshaw, 1997). It is heavier than air and is also a potential carcinogen as listed by the International Agency for Research on Cancer. Highly toxic, acute, or chronic health hazards result from this gas if gasped, swallowed, or absorbed by the skin (Cotton, Wilkinson, Murillo, & Bochmann, 1999). Arsenic pentafluoride destroys red blood cells and gives off irritation vapors on inhalation in moist air causing widespread systemic injury.

1.2: Occurrence

Arsenic is present everywhere in the environment containing various sulfur-containing minerals, such as arsenopyrite. This depends basically on the geologic participations from mineral-enduring procedures, whereas volumes in inherent floras and faunas consider race diversity. The naturally high quantity of arsenic is restrained by some species of aquatic plants, such as algae and seaweed, and aquatic organisms, such as shellfish (lobster, crab, barnacle, etc.). However, synthetic sources include lead, zinc, and gold that are result of the smelting of nonferrous metal minerals, mostly copper (Paul, Chakraborty, Ali, & Ray, 2015). Arsenic pentafluoride is formed by the reaction of As and F and other reactions as shown from Eqs. (1.1)–(1.4), respectively:

si1_e    (1.1)

si2_e    (1.2)

si3_e    (1.3)

si4_e    (1.4)

It is a great acceptor as revealed in reaction (1.5). As with sulfur tetrafluoride develops an ionic complex-forming halide complex (Azeem, Brownstein, & Gillespie, 1969).

si5_e    (1.5)

1.3: Physicochemical properties

Arsenic pentafluoride has a trigonal bipyramidal structure with five bonding pairs and zero lone pairs (Greenwood & Earnshaw, 1997) (Fig. 1.1). In the solid state, the axial and equatorial As glyph_sbnd F bond lengths are 171.9 and 166.8 pm, respectively. At room temperature, it is a colorless gas, and at − 53°C, a condensed yellow liquid. It is also formed by the reaction of fluorine with arsenic metal or arsenic trifluoride. Fluoride works as a strong Lewis acid; it is also used for the formation of ionic complexes; and in combination with Bronsted acid forms conjugate superacid. Vapor density measurements show some grade of association, but it is a monomeric covalent compound with a high degree of coordinating ability. Due to its potential high toxicity, safety must be taken in the management of any arsenic compound (Singh, 2017).

Fig. 1.1 Structure of arsenic pentafluoride. Credit: Om Singh.

It is also prepared with graphite and constant intercalation compounds, which show electric conduction similar to Ag.

Some of the physical properties of arsenic pentafluoride are shown in Table 1.1 (Fischer & Thompson, 1978).

Table 1.1

1.4: Physiological role

Metabolic processes in organisms can be influenced by hydrogen fluoride or fluoride ions released after hydrolysis of arsenic pentafluoride. After absorption, As(V) reacts with As(III), which is subsequently methylated and eliminated via the urine. However, the corrosiveness of this gas does not induce the intake of doses augmenting the physiological elimination of arsenic and fluoride. The gas reacts with macromolecules in tissues, metabolized via some pathways after the delay. The whole mechanism is still a topic of research (Jaishankar, Tseten, Anbalagan, Mathew, & Beeregowda, 2014).

1.5: Uses

Arsenic pentafluoride is used to make electroconductive polymers, semiconductor fabrication, and general synthetic chemicals (Vogel, 1977). Intercalation compounds of graphite such as graphite/AsF5 have been suggested for use both as extremely electronically conducting constituents (Fischer & Thompson, 1978) and chemical catalysts (Foley, Zeller, Falardeau, & Vogel, 1977; Olah, Kaspi, & Bukala, 1977; Selig & Gani, 1975). There is documentation showing that arsenic pentafluoride oxidizes graphite but with an uncertainty of the extent of oxidation and amount of AsF3 (Ebert, Mills, Scanlon, & Selig, 1981). The compounds formed are considered among the most highly anisotropic of any general informative criteria (McRae, Mareche, Lelaurain, & Furdin, 1987).

1.6: Risk assessment

A number of health effects, including neurologic and neurobehavioral effects, heart disease, pulmonary or hepatic fibrosis, hematological effects, etc., can result postexposure to this gas. Therefore, some important points in risk assessment should be kept in mind (Singh, 2017):

•Cloud computing (CC) might fill the gaps between radio communication and environmental or health interference.

•The intangible outline of a cloud-based pronouncement support structure for arsenic encompasses substance health risk analysis (CC-AHRA).

•Risk assessment clarifies how the CC-AHRA may support uncovered societies in considering the danger of cancer due to arsenic contact from drinking water.

•The CC-AHRA may support water organization and system, investigator, and private initiative production with well-versed judgments for mitigating health hazards due to arsenic ingestion.

1.7: Hazardousness

Arsenic pentafluoride is a hazardous gas that destroys red blood cells often affecting the lungs, skin, kidneys, and liver. When the poisoning becomes acute, symptoms lead to diarrhea, nausea, hematuria, cramping muscles, alopecia, colic pain, convulsions, headache, delirium, vomiting, body ache, angina, and pain in the abdomen or loins.

While arsenic pentafluoride has not been recognized as a congenital abnormality or a multiplicative hazard, arsenic and definite compounds are teratogens and might lead to reproductive damage, such as productiveness and interference with menses (Kim & Kim, 2015).

With the help of certain mechanisms, arsenic and its metabolites interrupt adenosine triphosphate (ATP) production. Arsenic also prevents pyruvate dehydrogenase by opposing phosphate, which separates oxidative phosphorylation at the level of the citric acid cycle, and hence prevents energy-linked reduction of NAD+, mitochondrial exhalation, and ATP synthesis. Arsenic can alter DNA-mending enzyme activity, and interfere with DNA methylation designs and cell production (Casarett, Klaassen, & Watkins, 2003; Kitchin & Wallace, 2008).

Arsenic is absorbed by inhalation or ingestion, but when it comes in contact with the skin it is absorbed in a smaller amount. After inhalation or ingestion, it is distributed all over the body and reduces to arsenite. Arsenic or its metabolites are eliminated in urine. Arsenic binds with metal and forms protein metallothionein, which reduces the noxious effects of arsenic by acting as an antioxidant (Pokhrel, Bhandari, & Viraraghavan, 2009).

1.8: Treatment

In concern with how to handle AsF5 toxicity, treatment of arsenic poisoning can be done with the help of chelation therapy. Some chelating agents are dimercaprol, ethylenediaminetetraacetic acid, or dimercaptosuccinic acid. For less severe cases, charcoal tablets and a high sulfur diet can be used (Pokhrel et al., 2009).

1.9: Risk management

•Due to probable adverse effects in exposed persons, many rules and plans have been identified for numerous inorganic and organic procedures for arsenic by international, federal, and state organizations.

•Treatment approaches as well as chemical precipitation (clotting procedures), ion exchange, reverse osmosis/electrodialysis, use of activated carbon or alumina, and oxidation have been suggested for arsenic elimination in contaminated water.

•CC, an internet-based, manageable, economical, and on-demand calculating facility, has appeared as a key constituent in real-time administrative progressions. It permits user to access, examine, and assess data anywhere (Mondal, Majumder, & Mohanty, 2006).

1.10: Current research

The following current research or experimental work has been recognized in different science areas (Ebert & Selig, 1977):

•AsF5 is a poisonous gas that can be used in the making of electroconductive polymers. Also, the AsF5 molecule can compromise various health problems, for example, nervous system syndrome. Therefore, the assessment of AsF5 gas is essential but there are concerns about public health and environmental pollution. Recently, scientific research reported a novel Kagome phosphorene nanosheet (Kagome-PNS) for the study of the performance of AsF5 molecules using the density-functional theory method. The Kagome-PNS can be skillfully used as a chemical sensor to identify the molecule of AsF5 gas (Nagarajan & Chandiramouli, 2020).

•Current progress in the assessment of arsenic by arsine generation and atomic absorption spectrometry with argon–hydrogen combustions has provided very sensitive and fast analyses of trace quantities.

•The technique is useful to investigate environmental pollution (H2O, soil, and wastewater), steel, and silicate rocks. For rock examination, the sample is decayed by H2SO4, HNO3, HF acids, and KMNO4 solution; frequent fuming is required to eliminate fluoride, but the process is time consuming (Wahed et al., 2006).

•The process can be practically functional for the assessment of arsenic in rocks, soils, deposits, and numerous reserves. All researches can be admitted to the cloud/Internet component of the CC-AHRA through a web portal.

•Various nanomaterial-based trace element sample pretreatment procedures have been established in the past for simplifying actions and growing the analytical presentation of the approaches (Mumuni & Peacock, 2001).

•Solid-phase abstraction, particularly that use microprocessor without interlocked pipelined stages/International Institute for Population Sciences, provides the important involvement of element preconcentration and speciation examination in biological, food, environmental examination, etc. (Horwitz, 1979).

1.11: Safety measures

The following are some of the safety measures that should be followed (Kim & Kim, 2015):

•For eye protection, immediately wash the eye and internal surface of the eyelid with water for a few minutes and keep the eye open if required.

•Preferably wear a fire prevent lab coat, pants, and closed-toe shoes.

•Contact with skin, eyes, and clothing should be avoided.

•Wash the hands immediately after handling the product.

•Move immediately to fresh air in case of accidental inhalation of the gas.

1.12: Handling and storage (Jaishankar et al., 2014)

Handling

•Gas cylinders must be handled in sealed material.

•The cylinder should not be heated in any way to enhance the rate of the product.

•In a mandate to protect subatmospheric (< 760 Torr) packages, the temperature of the cylinder must not be more than 24°C.

•If the temperature is greater than 24°C, the container may be pressurized, which advances the chance of seepage or contact with hazardous vapors (Mondal et al., 2006).

Storage

•Arsenic pentafluoride should be stored according to all recent guidelines and ethics (Saunders & Wheeler, 1991).

•Keep the gas in a dry, cool, and ventilated area with a noncombustible infrastructure.

•Protect the gas container from contact with sunlight, mechanical losses, and temperatures below 55°C.

•Gas containers should be stored away from oxygen or other extremely oxidized or combustible materials.

•Gas cylinders should have exit plugs and valves with protective caps in the vessel.

1.13: Precautions

There are different precautions for handling arsenic pentafluoride (Horwitz, 1979):

•Wash hands immediately after handling.

•Wear protective gloves, clothes, eyeglasses, and face covers.

•Do not drink or smoke.

•Choose outdoor or well-ventilated areas.

•Be familiar with all relevant information.

•Use respiratory protection.

References

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Casarett L.J., Klaassen C.D., Watkins J.B. Casarett and doull's essentials of toxicology. New York: McGraw-Hill/Medical Pub. Div; 2003.25 Chapter 1.

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Ebert L.B., Mills D.R., Scanlon J.C., Selig H. Magnetic resonance of intercalation compounds of graphite: Questions of ionicity and mobility of inserted species. Materials Research Bulletin. 1981;16(7):831–840.

Ebert L.B., Selig H. Determination by magnetic resonance of the oxidation state of species intercalated in graphite. Materials Science and Engineering. 1977;31:177–181.

Fischer J.E., Thompson T.E. Graphite intercalation compounds. Physics Today. 1978;31(7):36–45.

Foley G.T., Zeller C., Falardeau E.R., Vogel F.L. Room temperature electrical conductivity of a highly two dimensional synthetic metal: AsF5-graphite. Solid State Communications. 1977;24(5):371–375.

Greenwood N.N., Earnshaw A. Chemistry of the elements. Butterworth; 1997.

Horwitz W. Arsenic and tin in foods: Reviews of commonly used methods of analysis. Food & Agriculture Org; . 1979;Vol. 9.

Jaishankar M., Tseten T., Anbalagan N., Mathew B.B., Beeregowda K.N. Toxicity, mechanism and health effects of some heavy metals. Interdisciplinary Toxicology. 2014;7(2):60–72.

Kim Y.J., Kim J.M. Arsenic toxicity in male reproduction and development. Development and Reproduction. 2015;19(4):167.

Kitchin K.T., Wallace K. The role of protein binding of trivalent arsenicals in arsenic carcinogenesis and toxicity. Journal of Inorganic Biochemistry. 2008;102(3):532–539.

McRae E., Mareche J.F., Lelaurain M., Furdin G. Conductivity anisotropy in AsF5—Intercalated graphite. Journal of Physics and Chemistry of Solids. 1987;48(10):957–963.

Mondal P., Majumder C.B., Mohanty B. Laboratory based approaches for arsenic remediation from contaminated water: Recent developments. Journal of Hazardous Materials. 2006;137(1):464–479.

Mumuni A.R., Peacock C.J. Development of a simple system for the determination of arsenic after hydride generation atomic absorption spectrophotometry. Journal of Applied Sciences and Environmental Management. 2001;5(1).

Nagarajan V., Chandiramouli R. Arsenic pentafluoride surface adsorption studies on Kagome-phosphorene–a DFT outlook. Physics Letters A. 2020;126552.

Olah G.A., Kaspi J., Bukala J. Heterogeneous catalysis by solid superacids. 3. Alkylation of benzene and transalkylation of alkylbenzenes over graphite-intercalated Lewis acid halide and perfluorinated resin sulfonic acid (Nafion-H) catalysts. The Journal of Organic Chemistry. 1977;42(26):4187–4191.

Paul S., Chakraborty S., Ali N., Ray D.P. Arsenic distribution in environment and its bioremediation: A review. International Journal of Agriculture, Environment and Biotechnology. 2015;8(1):189–204.

Pokhrel D., Bhandari B.S., Viraraghavan T. Arsenic contamination of groundwater in the Terai region of Nepal: An overview of health concerns and treatment options. Environment International. 2009;35(1):157–161.

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Selig H., Gani O. Graphite intercalation compounds with xenon oxide tetrafluoride and iodine pentafluoride. Inorganic and Nuclear Chemistry Letters. 1975;11(1):75–77.

Singh S.K. Conceptual framework of a cloud-based decision support system for arsenic health risk assessment. Environment Systems and Decisions. 2017;37(4):435–450.

Vogel F.L. The electrical conductivity of graphite intercalated with superacid fluorides: Experiments with antimony pentafluoride. Journal of Materials Science. 1977;12(5):982–986.

Wahed M.A., Chowdhury D., Nermell B., Khan S.I., Ilias M., Rahman M., et al. A modified routine analysis of arsenic content in drinking-water in Bangladesh by hydride generation-atomic absorption spectrophotometry. Journal of Health, Population and Nutrition. 2006;36–41.

Chapter 2: Arsine: Risk assessment, environmental, and health hazard

Rakesh Kumar Sonia; Om Singhb    a Department of Chemistry, C.C.S University, Meerut, Uttar Pradesh, India

b Department of Chemistry, College of Engineering Roorkee, Roorkee, Uttarakhand, India

Abstract

Arsine is one of the highly toxic forms of arsenic and one of the leading causes of pollution worldwide. The persistent rise of this toxic matter in the atmosphere can create various toxic effects such as hemolysis, loss of blood, and liver and kidney function disturbance. This chapter discusses findings that define the toxicological and environmental issues encountered postexposure of arsine. Also, the chapter gives an account of studies associated with the progress of risk assessment, as well as management of toxic matter while handling and storing the gas.

Keywords

Stibine; Heinz bodies; Hazard analysis critical control points; Good agricultural practices; Chemical weapon

Abbreviations

ALS 

advanced life support

ATD 

average total dose

CBC 

complete blood count

CDI 

chronic daily intake

CGA PL Compressed Gas Association, Pamphlet

CR 

cancer risk

GAP 

good agricultural practices

HACCP 

hazard analysis critical control points

Hb 

hemoglobin

HI 

hazard index

HQ 

hazard quotient

MOE 

margin of exposure

PRA 

probabilistic risk assessment

PVC 

poly vinyl chloride

USEPA 

United States Environmental Protection Agency

WHO 

World Health Organization

2.1: Introduction

Arsine is a nonirritating, toxic, transparent, and flammable gas with a mild garlic or fish-like odor, which is detectable at levels sufficient to cause poisoning (Plantamura, Dorandeu, Burnat, & Renard, 2011). The general formula of an organoarsenic compound is AsH3 − xRx, (R is aryl or alkyl group), as shown in Fig. 2.1. Arsenic on reaction with acid forms arsine, which is also known as stibine (smells like rotten eggs).

Fig. 2.1 Structure of arsine. Credit: Om Singh.

2.2: Occurrence

Arsine does not occur in nature and was first obtained in 1775 by Scheele. Commercially, it is prepared by electrochemical reduction of arsenic compounds in a solution of Zn3As2 and acid (Eq. 2.1). It can also be synthesized by reacting arsenic trioxide and sodium borohydride catalyzed by zinc in acid (Sengupta, Sawalha, Ohira, Idowu, & Dasgupta, 2010).

   (2.1)

From Eq. (2.1), it can be seen that the nascent hydrogen is responsible for the mitigation of arsenicals to arsine. Despite this known perspective, until now there is no evidence available supporting the essential role of nascent hydrogen in the preparation of arsine.

Another synthetic approach that more sufficiently explains arsine preparation is the thermodynamically favored reaction given in Eq. 2.2:

   (2.2)

2.3: Historical background

Arsine gas was recognized in 1775 by Scheele. In 1815, Cehlen, a German chemist, was the first victim reported to die from accidental exposure to arsine (Elkins & Fahy, 1967), which created havoc in the vicinity.

2.4: Physicochemical properties

Arsine is generally prepared from inorganic arsenic (such as arsenite or arsenate) under definite chemical conditions (Winski, Barber, Rael, & Carter, 1997). Arsine smells like a clove of mild garlic or fish when present at above 0.5 ppm; otherwise it is a colorless, odorless, and flammable gas. It is soluble in water but slightly soluble at 20°C. This gas is 2.7 times denser than air. Arsine is a stable compound but decomposes at room temperature slowly; this decomposition rate is dependent on factors like humidity, presence of light, specific catalysts, etc.

Arsine can react hazardously with halogens like fluorine and chlorine, which can even result in an explosion. It can react with strong oxidizing agents like permanganate and nitric acid and easily oxidizes with concentrated or dilute O2 engagement, represented by reaction (2.3):

   (2.3)

2.5: Physiological role

There are reports of toxicity of arsine in humans showing a dependency on oxidative pressure (Blair et al., 1990; Hatlelid, 1996; Hatlelid, Brailsford, & Carter, 1995; Hatlelid & Carter, 1997; Pernis & Magistretti, 1960) or reaction with sulfhydryl groups (Levinsky, Smalley, Hillyer, & Shindler, 1970; Winski et al., 1997). The following reaction (Eq. 2.4) depicts the hemolytic activity of arsine as postulated by Hatlelid and Carter (1997).

   (2.4)

On the addition of H2As – Hb or H2As–heme, the reaction further leads to the formation of methemoglobin, arsine peroxide, hydrogen peroxide, or arsenic, as shown by Eq. (2.5):

   (2.5)

Moreover, the formed adduct may damage hemoglobin (Hatlelid & Carter, 1997), which can cause restructuring of the protein membrane as well as alter membrane rigidity. This initiates the oxidation of heme iron for the formation of hemin with the help of protein sulfhydryl groups present in the membrane (Hatlelid, 1996). Eventually the overriding number of Heinz bodies and hemin sources rupture the red blood cell (RBC) membrane, hence causing cell fragmentation (Weed & Reed,