Airborne compounds

The California Air Resources Board has prepared risk assessments for a number of toxic airborne compounds and mixtures, designated as toxic air contaminants, TACs (Table 16.15). For example, risk assessments for individual compounds such as benzene, benzo[a]pyrene (see Chapter 10), formaldehyde, and vinyl chloride have been carried out, in addition to complex mixtures such as diesel exhaust (California Air Resources Board, 1997a) and environmental tobacco smoke (California Environmental Protection Agency, 1997). These risk assessment documents form the basis for controls imposed as part of the risk management process (e.g., see Seiber, 1996). 

Subsequent studies have shown that the cold, still, sunless Antarctic winter favors the formation of stratospheric ice crystals, and airborne compounds containing chlorine atoms then accumulate on the crystals. Chemical reactions on and within the crystals lead to the formation of Cl2. In September,... 

The use of a passive sampler is characterized by long sampling times, which are needed to allow the airborne compounds to enter the sampler and become trapped on the sorbent surface. Sampling times often exceed several days. The long sampling times show a pitfall of this sampling technique because the sampler is in contact with the air to be sampled for a long time, very volatile compounds may have the chance not only to enter the sampler, but also to leave it on the same way, if their interaction with the sorbent is low. In this case an underestimation of the very volatile substances can be expected. 

In addition to emissions from combustion processes, other potential sources of airborne compounds from... 

Deposition of airborne compounds derived from volcanic eruptions, and the presence of sulfur compounds brought about through hydrothermal activity (i.e., hot springs). 

This book reviews methods for measuring airborne compounds and includes recent developments from experts in the field. Topics range from optical remote sensing to VOC sampling and analysis to visibility research in national parks. 

In spite of the fact that the atmosphere is composed predominantly of relatively inert molecules such as N2 and O2, it is actually a rather efficient oxidizing medium. One reason for the atmosphere s oxidizing capacity arises because the atmosphere contains minute amounts of very reactive molecular fragments, called free radicals. The most important free radical in the chemistry of the troposphere is the hydroxyl (OH) radical, which reacts with nearly every molecular species in the atmosphere. In addition, the atmosphere contains trace amounts of species less reactive than free radicals but nonetheless reactive enough to attack a variety of airborne compounds. Ozone (O3) is one important oxidizer, which also participates in the formation of the hydroxyl radical. 

Coal ash refers to airborne compounds known as fly ash and bottom ash. These compounds are produced by burning coal. They can contain heavy metals that settle out of the atmosphere onto the land and/or into water sources. These heavy metals eventually accumulate in plants and animals that are consumed by humans. Toxicity from heavy metals can result in damage to the nervous system and to vital organs such as the lungs and kidneys. 

In the first survey, head space and bulk air samples are taken to identify possible airborne compounds from the particular operation. For reaction chamber cleans, bulk air samples are taken inside the reaction chamber. Also, a residue sample is taken from the reaction chamber for subsequent head space analysis. For cold trap surveys, air samples are taken inside the trap and at the discharge port. In pump oil surveys, a sample of used oil is taken for a head space analysis and air samples are taken above the used oil as it is transferred. Used oil filters can be evaluated by placing them in a plastic bag, allowing them to off-gas, and then analyzing the head space ofthe bag. Air samples should also be taken near the old oil filter as it is removed. 

Small amounts of these angular fused-ring aromatic hydrocarbons cause cancer in about a month when applied to the skin of a mouse. These compounds are present in the effluent from coal-burning power plants and in automobile exhaust. They are also present in tobacco smoke and in meat cooked over charcoal. The incidence of lung cancer among smokers and inhabitants of large urban areas may partly result from inhaling these airborne compounds in minute amounts over time. 

The OSHA limits, regulations, and recommendations apply to in-plant air quaUty. Improperly filtered exhaust air may cause a plant to be in violation of the EPA standard, therefore these data should not be confused with the EPA limit for airborne lead, 1.5 fig lead/m, measured over a calendar quarter, which pertains to the exterior plant environment and emissions. The installation and proper maintenance of exhaust filtration systems enables most plants to comply with the EPA limits for airborne lead (see Lead compounds, industrial toxicology). 

It is good practice to keep concentrations of airborne nickel in any chemical form as low as possible and certainly below the relevant standard. Local exhaust ventilation is the preferred method, particularly for powders, but personal respirator protection may be employed where necessary. In the United States, the Occupational Safety and Health Administration (OSHA) personal exposure limit (PEL) for all forms of nickel except nickel carbonyl is 1 mg/m. The ACGIH TLVs are respectively 1 mg/m for Ni metal, insoluble compounds, and fume and dust from nickel sulfide roasting, and 0.1 mg/m for soluble nickel compounds. The ACGIH is considering whether to lower the TLVs for all forms of nickel to 0.05 mg/m, based on nonmalignant respiratory effects in experimental animals. 

Thiuram Sulfides. These compounds, (8) and (9), are an important class of accelerator. Thiurams are produced by the oxidation of sodium dithiocarbamates. The di- and polysulfides can donate one or more atoms of sulfur from their molecular stmcture for vulcanization. The use of these compounds at relatively high levels with litde or no elemental sulfur provides articles with improved heat resistance. The short-chain (methyl and ethyl) thiurams and dithiocarbamates ate priced 2/kg. Producers have introduced ultra-accelerators based on longer-chain and branched-chain amines that are less volatile and less toxic. This development is also motivated by a desire to rninirnize airborne nitrosamines. 

Retarders were originally arenecarboxylic acids. These acidic materials not only delay the onset of cross-linking but also slow the cross-linking reaction itself. The acidic retarders do not function weU in black-fiUed compounds because of the high pH of furnace blacks. Another type of retarder, A/-nitroso diphenylamine [86-30-6] was used for many years in black-fiUed compounds. This product disappeared when it was recognized that it trans-nitrosated volatile amines to give a several-fold increase in airborne nitrosamines. U.S. production peaked in 1974 at about 1.6 million kg. 

The adopted values for TWAs for airborne vanadium, including oxide and metal dusts of vanadium, is 0.5 mg/m the values for fumes of vanadium compounds is 0.05 mg/m. These limits are for normal 8-h workday and 40-h work-week exposures. The short-term exposure limit (STEL) is 1.5 mg/m for dusts (25). A description of health ha2ards, including symptoms, first aid, and organ involvement, personal protection, and respirator use has beenpubhshed (26). 

Barium metal and most barium compounds are highly poisonous. A notable exception is barium sulfate which is nontoxic because of its extreme iasolubihty ia water. Barium ion acts as a muscle stimulant and can cause death through ventricular fibrillation of the heart. Therefore, care must be taken to avoid contact with open areas of the skin. Workers must wear respirators (of type approved for toxic airborne particles), goggles, gloves, and protective clothing at all times. The toxic barium aluminate residue obtained from barium production is detoxified by reaction with a solution of ferrous sulfate and converted iato nontoxic barium sulfate. According to OSHA standards, the TWA value for Ba and Ba compounds ia air is 0.5 mg/m. ... 

The chemical composition of particulate pollutants is determined in two forms specific elements, or specific compounds or ions. Knowledge of their chemical composition is useful in determining the sources of airborne particles and in understanding the fate of particles in the atmosphere. Elemental analysis yields results in terms of the individual elements present in a sample such as a given quantity of sulfur, S. From elemental analysis techniques we do not obtain direct information about the chemical form of S in a sample such as sulfate (SO/ ) or sulfide. Two nondestructive techniques used for direct elemental analysis of particulate samples are X-ray fluorescence spectroscopy (XRF) and neutron activation analysis (NAA). 

In nonindustrial settings, MCS substances are the cause of indoor air pollution and are the contaminants in air and water. Many of the chemicals which trigger MCS symptoms are known to be irritants or toxic to the nervous system. As an example, volatile organic compounds readily evaporate into the air at room temperature. Permitted airborne levels of such contaminants can still make ordinary people sick. When the human body is assaulted with levels of toxic chemicals that it cannot safely process, it is likely that at some point an individual will become ill. For some, the outcome could be cancer or reproductive damage. Others may become hypersensitive to these chemicals or develop other chronic disorders, while some people may not experience any noticeable health effects. Even where high levels of exposure occur, generally only a small percentage of people become chemically sensitive. 

Industrial environments expose individuals to a plethora of airborne chemical compounds in the form of vapors, aerosols, or biphasic mixtures of both. These atmospheric contaminants primarily interface with two body surfaces the respiratory tract and the skin. Between these two routes of systemic exposure to airborne chemicals (inhalation and transdermal absorption) the respiratory tract has the larger surface area and a much greater percentage of this surface exposed to the ambient environment. Or dinary work clothing generally restricts skin exposures to the arms, neck, and head, and special protective clothing ensembles further limit or totally eliminate skin exposures, but breathing exposes much of the airway to contaminants. 

Polonium is extremely toxic at all concentrations and is never beneficial. Severe radiation damage of vital organs follows ingestion of even the minutest concentrations and, for the most commonly used isotope, °Po, the maximum permissible body burden is 0.03/zCi, i.e. 1100 Bq (=1100s ), equivalent to 7 x 10 g of the element. Concentrations of airborne Po compounds must be kept below 4 x 10" " mgm . ... 

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