PAHs chlorinated

Johnsen, S., Gribbestad, I.S., and Johansen, S. Formation of chlorinated PAH - A possible health hazard from water... 

Polycyclic aromatic hydrocarbons (PAH), which are ubiquitous in the environment, including surface waters, undergo facile chlorination by hypochlorite when dissolved in humus-poor water to give a suite of chlorinated PAH (1660). It is therefore conceivable that this chlorination can occur under natural conditions, but this is yet to be determined. Another new possible source of natural chlorinated PAH is the reported in vitro reaction of benzo [a pyrene diol epoxide, the ultimate carcinogen of benzo aIpyrene with chloride ion to give chlorohydrin DDD, which has been isolated and identified as an intermediate en route to a benzol a pyrene-DN A adduct (1661). However, DDD is not considered to be a natural compound at this time. 

Johnsen S, Gribbestad IS, Johansen S (1989) Formation of Chlorinated PAH - A Possible Health Hazard from Water Chlorination. Sci Total Environ 81/82 231... 

A wide range of structurally diverse compounds is produced during incineration. These include PAHs and related compounds, azaarenes, and chlorinated PAHs from combustion of fossil fuels and natural wildfires. Organic compounds in the atmosphere may exist both in the free (gaseous) state or on particles of various dimensions. Recent concern has been directed to the occurrence in aerosols both of the compounds themselves and of their transformation products (secondary aerosols) (1) for their role in atmospheric chemistry and as determinants of climate (Andreae and Crutzen 1997) and (2) due to health risks since aerosol formation facilitates the transport into and sorption by the lungs. 

Chlorinated PAHs in urban air including the mutagenic 1- and 4-chloropyrene, dichloropyrenes, and 6-chlorobenzo [a] pyrene (Nilsson and Ostman 1993) ... 

DFT Chemical Reactivity Driven by Biological Activity Applications for the Toxicological Fate of Chlorinated PAHs... 

Many POPs and other environmental contaminants have been associated with immunotoxic effects but, in most instances, it remains difficult to assign the effects to pure compounds. For example, immunotoxic effects of PCBs in free-ranging harbor seals have been associated with increasing blubber concentrations of PCBs [33], yet the waters inhabited by these animals are also contaminated with other POPs, including chlorinated pesticides and chlorinated PAHs. Indeed, the PCBs themselves are mixtures of different moieties with varying immunotoxic properties. 

The presence of PAHs in drinking water may be due to the contamination of surface or groundwater used as raw water somces [166]. The chlorination of drinking water which contains PAHs has been related to the formation of oxygenated and chlorinated PAHs, compounds that are even more toxic. 

Putz, M. V, Putz, A. M. (2013b). DFT Chemical Reactivity Driven by Biological Activity Applications for the Toxicological Fate of Chlorinated PAHs. Structure and Bonding 150(2013). 181-232 (DOI 10.1007/978-3-642-32750-6 6). 

Aerobic, Anaerobic, and Combined Systems. The vast majority of in situ bioremediations ate conducted under aerobic conditions because most organics can be degraded aerobically and more rapidly than under anaerobic conditions. Some synthetic chemicals are highly resistant to aerobic biodegradation, such as highly oxidized, chlorinated hydrocarbons and polynuclear aromatic hydrocarbons (PAHs). Examples of such compounds are tetrachloroethylene, TCE, benzo(a)pyrene [50-32-8] PCBs, and pesticides. 

Alkylphenols, ammonia, asbestos, chlorinated paraffins, 4-chloroaniline, cyanide, detergents, di- -butyl phthalate, polyaromatic hydrocarbons (PAHs e.g. anthracene, benzopyrene, methylcholanthrene, /i-naphthoflavone), nitrate, nitrite, petroleum oil, phenol, pentachlorophenol, 4-nitrophenol, dinitro-o-cresol, polychlorinated biphenyls (PCBs especially coplanar), polychlorinated dioxins, polybrominated naphthalenes, /i-sitosterol, sulfide, thiourea, urea, acid water, coal dust... 

Only particular solvents are suitable for certain purposes. The choice depending, for instance, on their residual water content or their acid-base nature if Rf values are to be reproduced [1, 2]. Halogen-containing solvents may not be employed for the determination of chlorinated pesticides. Similar considerations apply to PAH analyses. Pro analyst grades are no longer adequate for these purposes. It is true that it would be possible to manufacture universally pure solvents that were adequate for all analytical purposes, but they would then be too expensive for the final user [3, 4]. 

Zebiihr et al. (29) developed an automated system for determining PAHs, PCBs and PCDD/Fs by using an aminopropyl silica column coupled to a porous graphitic carbon column. This method gives five fractions, i.e. aliphatic and monoaromatic hydrocarbons, polycyclic aromatic hydrocarbons, PCBs with two or more ortho-chlorines, mono-ort/io PCBs, and non-ortho PCBs and PCDD/Fs. This method employed five switching valves and was successfully used with extracts of sediments, biological samples and electrostatic filter precipitates. 

Hydrocarbons. In other publications the historical trend of organic pollutant concentrations, namely polychlorinated biphenys (PCBs), chlorinated pesticides DDT and metabolites DDE, DDD, and polycyclic aromatic hydrocarbons (PAHs), have been reconstructed. For this purpose the sediments of the core sampled in the Lagoon area close to the industrial district were employed (16,17). 

Mere destruction of the original hazardous material is not, however, an adequate measure of the performance of an incinerator. Products of incomplete combustion can be as toxic as, or even more toxic than, the materials from which they evolve. Indeed, highly mutagenic PAHs are readily generated along with soot in fuel-rich regions of most hydrocarbon flames. Formation of dioxins in the combustion of chlorinated hydrocarbons has also been reported. We need to understand the entire sequence of reactions involved in incineration in order to assess the effectiveness and risks of hazardous waste incineration. 

Pyrene is a common PAH contaminant and may occur in drinking water. Chlorination of water with or without bromide that may be present in coastal environments has been examined. Both chlorinated and brominated pyrenes with halogen substituents at the 1,3-, 1,6-, and 1,8-positions were found, and could putatively be produced by reaction of pyrene with hypochlorous acid and hypochlorite (Hu et al. 2006). 

Although these issues have already been briefly noted, they deserve a few additional comments. For freely water-soluble substrates that have low volatility, there are few difficulties in carrying out the appropriate experiments described above. There is, however, increasing interest in xenobiotics such as polycyclic aromatic hydrocarbons (PAHs) and highly chlorinated compounds including, for example, PCBs, which have only low water solubility. In addition, attention has been focused on volatile chlorinated aliphatic compounds such as the chloroethenes, dichloromethane, and carbon tetrachloride. All of these substrates present experimental difficulties of greater or lesser severity. 

CRMs for Contaminants in Environmental Matrices For nearly two decades NIST has been involved in the development of SRMs for the determination of organic contaminants such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and chlorinated pesticides in natural environmental matrices such as fossil fuels (Hertz et al.1980 Kline et al. 1985), air and diesel particulate material (May and Wise 1984 Wise et al. 2000), coal tar (Wise et al. 1988a), sediment (Schantz et al. 1990, 1995a Wise et al. 1995), mussel tissue (Wise et al. 1991 Schantz et al. 1997a), fish oil, and whale blubber (Schantz et al. 1995b). Several papers have reviewed and summarized the development of these environmental matrix SRMs (Wise et al. 1988b Wise 1993 Wise and Schantz 1997 Wise et al. 2000). Seventeen natural matrix SRMs for the determination of organic contaminants are currently available from NIST with certified and reference concentrations primarily for PAHs, PCBs, chlorinated pesticides, polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofiirans (PCDFs) see Table 3.11. 

With suitable adjustments to the temperature, also subcritical water extraction (SWE) or pressurised hot water extraction (PHWE) allows selective extraction of polar (chlorinated phenols), low-polarity (PCBs and PAHs) and nonpolar (alkanes) organic compounds from industrial soils [418]. 

Rhizodegradation Soils, sediments, land application of wastewater Organic compounds (TPH, PAHs, BTEX, pesticides, chlorinated solvents, PCBs) Phenolics releasers (mulberry, apple, osage orange) Grasses with fibrous roots (rye, fescue, Bermuda) for contaminants 0-3 ft deep Phreatophyte trees for 0-10 ft Aquatic plants for sediments... 

Chemicals degraded by WRF include pesticides such as organochlorines DDT and its very toxic metabolite DDE [8, 9] and organophosphate pesticides such as chlorpyrifos, fonofos and terbufos [10] polychlorinated biphenyls (PCBs) of different degrees of chlorine substitution [11-13], some even to mineralization [14, 15] diverse polycyclic aromatic hydrocarbons (PAHs) in liquid media and from contaminated soils or in complex mixtures such as creosote [16-18] components of munition wastes including TNT and its metabolites DNT [19-23], nitroglycerin [24] and RDX [25]. 

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