Polychlorinated diphenyl sulfides: preparation of model compounds, chromatography, mass spectrometry, NMR, and environmental analysis

Abstract

Some polychlorinated diphenyl sulfides were prepared by chlorination of diphenyl sulfide with sulfuryl chloride and by Friedel-Crafts-type reaction from 1,2-dichlorobenzene and sulfur. Individual isomers from the reaction mixtures were isolated by reversed-phase high-performance liquid chromatography. Mass spectra show the degree of chlorination of different compounds, and 'H and I3C NMR spectra verify their structures. Three trichloro isomers were shown to be 2,2',4-, 2,4,4'-, and 2,4',6-trichlorodiphenyl sulfides and two symmetric tetrachloro isomers bis(2,4-dichlorophenyl) and bis(3,4dichlorophenyl) sulfides. Chlorine-induced 13C NMR substituent chemical shifts (SCS) have been calculated and compared with the experimental ones in the case of bis(2,4-dichlorophenyl) sulfide. Four stack gases from a waste incinerator and six pulp mill effluents from two bleaching plants were screened for the polychlorinated diphenyl sulfides. Trichlorodiphenyl sulfides were found from five pulp mill effluent samples and tri-and tetrachlorodiphenyl sulfides from two stack gas samples.

Polychlorinated Diphenyl Sulfides: An Emerging Class of Persistent, Bioaccumulative, and Toxic Substances in the Environment

“…Tetra-CDPS congeners including 2,2',4,4'-tetra-CDPS and 3,3',4,4'-tetra-CDPS were found in stack gas samples from a waste incinerator (Sinkkonen et al 1993). These tri-and tetra-CDPS congeners were also detected in fly ash from metal reclamation at 300-850 o C, indicating their potential formation from these high-temperature processes (Sinkkonen et al 1994b).…”

“…Route (I) was reported by Zhang X et al (2011). Route (II) was proposed by Sinkkonen et al (1993). (e.g., partition coefficient) of all these analogs experimentally.…”

Polychlorinated Diphenylsulfides Activate Aryl Hydrocarbon Receptor 2 in Zebrafish Embryos: Potential Mechanism of Developmental Toxicity

“…Polychlorinated diphenyl sulfides (PCDPSs) are a group of chlorinated aromatic compounds comprising 209 theoretical congeners like polychlorinated biphenyls (PCBs). They have been extensively employed as high-temperature resistant lubricants, additives in flame retardants, and insulating media, as well as being widely used as acaricides on fruit and tea crops (known as Tetrasul, mainly 2,4,4′,5-TCDPS) in many countries like China and the USA. − Due to their considerable persistence and environmental mobility properties, , PCDPSs have been frequently found in various environmental matrices, such as dust from metal recycling plants, gas and fly ash from waste incineration (tri- and tetra-CDPSs), wastewater from pulp and paper mill (tri-CDPS isomers), fruits (2,4,4′,5-TCDPS), tea leaves (2,4,4′,5-TCDPS), and water and sediment samples from the Elbe river in Germany (4,4′-DCDPS) and the Yangtze river in China (mono- to hepta-CDPSs, total concentrations ranging from 0.18 to 2.03 ng/L and 0.10 to 6.90 ng/g in surface water and sediment, respectively) . The bioconcentration and bioaccumulation potentials of PCDPSs were also revealed by modeling calculations. , These findings have raised concerns about their potential adverse effects on human and ecosystem health.…”

Down-Regulation of hspb9 and hspb11 Contributes to Wavy Notochord in Zebrafish Embryos Following Exposure to Polychlorinated Diphenylsulfides

“…Polychlorinated diphenylsulfides (PCDPSs) (Figure A) are a group of halogenated aromatic compounds comprised of 209 theoretically possible congeners with structural similarities to polychlorinated diphenyl ethers (PCDEs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). They have been widely used as lubricants, flame retardants, insulating media, and acaricides − in many countries like China and the U.S. To date, PCDPSs have been frequently found in a variety of environmental matrices, including industrial wastewater and dust, , waste incineration ash, natural waters, , and even crops like fruits and tea leaves, ranging from monochloro- to heptachloro-diphenyl sulfide congeners. However, due to the lack of pure authentic standards for PCDPS and/or the shortcomings of purification and analytical methods, most previous studies on concentrations of PCDPSs in environmental matrices were based on qualitative reporting.…”