Metal reclamation produces sulphur analogues of toxic dioxins and furans

Sinkkonen, Seija; Vattulainen, A.; Aittola, Jussi-Pekka; Paasiv́irta, Jaakko; Tarhanen, Juhani; Lahtiperä, Mirja

doi:10.1016/0045-6535(94)90072-8

Cited by 42 publications

(24 citation statements)

References 14 publications

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“…Pentachlorodibenzothiophenes and other higher chlorinated PCDBTs were not detected (Sinkkonen et al, 1994). There is probably some transfer of these chlorinated sulfides into the air.…”

Section: Pulp and Paper Industrymentioning

confidence: 92%

“…Thus the global thia-arenes, where some 58% is BNT), then upper estimates of the emissions of thia-arenes and BNT become 0.003 and 0.0018 Gg S a -1 . Chlorinated sulfur compounds are also found, typically tri-, tetra-and pentachloro DBTs (Aittola et al, 1996;Sinkkonen et al, 1994), particularly at aluminium reclamation plants. If we assume a molecular weight of 322 and emissions relative to PAHs estimated by Becker et al (1999), we get upper estimates of 0.0016 Gg S a -1 .…”

Section: Aluminium Industrymentioning

confidence: 99%

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Anthropogenic contributions to global carbonyl sulfide, carbon disulfide and organosulfides fluxes

Lee

Brimblecombe

2016

Earth-Science Reviews

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Previous studies of the global sulfur cycle have focused almost exclusively on oxidized species and just a few sulfides. This focus is expanded here to include a wider range of reduced sulfur compounds. Inorganic sulfides tend to be bound into sediments, and sulfates are present both in sediments and the oceans. Sulfur can adopt polymeric forms that include S-S bonds. This review examines the global anthropogenic sources of reduced sulfur, updating emission inventories and widening the consideration of industrial sources. It estimates the anthropogenic fluxes of key sulfides to the atmosphere (units Gg S

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“…Pentachlorodibenzothiophenes and other higher chlorinated PCDBTs were not detected (Sinkkonen et al, 1994). There is probably some transfer of these chlorinated sulfides into the air.…”

Section: Pulp and Paper Industrymentioning

confidence: 92%

Section: Aluminium Industrymentioning

confidence: 99%

Anthropogenic contributions to global carbonyl sulfide, carbon disulfide and organosulfides fluxes

Lee

Brimblecombe

2016

Earth-Science Reviews

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“…PCTA/DTs are PCDD/Fs analogues in which the oxygen atoms are substituted by the sulfur atoms. PCDT/TAs were never intentionally synthesized for commercial purposes, but are known to be produced as byproducts from the chemical processes that are similar to those resulting in the formation of PCDD/Fs, such as combustion, emissions from municipal and hazardous waste incinerators as well as industrial incinerators [ 10 , 11 ]. Buser reported the concentrations of PCDTs in fly ash was to be up to 55 ng/g, at or 1 magnitude below the concentrations of the PCDDs and PCDFs [ 10 ].…”

Section: Introductionmentioning

confidence: 99%

Mechanistic and Kinetic Studies on the Homogeneous Gas-Phase Formation of PCTA/DTs from 2,4-Dichlorothiophenol and 2,4,6-Trichlorothiophenol

Shi

et al. 2015

IJMS

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Polychlorinated thianthrene/dibenzothiophenes (PCTA/DTs) are sulfur analogues compounds to polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs). Chlorothiophenols (CTPs) are key precursors to form PCTA/DTs. 2,4-DCTP has the minimum number of Cl atoms to form 2,4,6,8-tetrachlorinated dibenzothiophenes (2,4,6,8-TeCDT), which is the most important and widely detected of the PCDTs. In this paper, quantum chemical calculations were carried out to investigate the homogeneous gas-phase formation of PCTA/DTs from 2,4-DCTP and 2,4,6-TCTP precursors at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. Several energetically feasible pathways were revealed to compare the formation potential of PCTA/DT products. The rate constants of the crucial elementary reactions were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction over a wide temperature range of 600–1200 K. This study shows that pathways that ended with elimination of Cl step were dominant over pathways ended with elimination of the H step. The water molecule has a negative catalytic effect on the H-shift step and hinders the formation of PCDTs from 2,4-DCTP. This study, together with works already published from our group, clearly illustrates an increased propensity for the dioxin formation from CTPs over the analogous CPs.

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“…PCDT/TAs were never intentionally synthesized for commercial purposes, but are formed as byproducts from the chemical processes that are similar to those resulting in the formation of PCDD/Fs. The major known sources of PCDT/TAs in environment are combustion, emissions from municipal and hazardous waste incinerators as well as industrial incinerators [ 13 , 14 ]. High correlation between concentrations of PCDT/TAs and PCDD/Fs in the environmental samples revealed their similar formation mechanism under the pyrolysis or combustion conditions [ 11 , 15 , 16 ].…”

Section: Introductionmentioning

confidence: 99%

Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

Shi

Zhang

et al. 2015

IJMS

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The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH.

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Metal reclamation produces sulphur analogues of toxic dioxins and furans

Cited by 42 publications

References 14 publications

Anthropogenic contributions to global carbonyl sulfide, carbon disulfide and organosulfides fluxes

Anthropogenic contributions to global carbonyl sulfide, carbon disulfide and organosulfides fluxes

Mechanistic and Kinetic Studies on the Homogeneous Gas-Phase Formation of PCTA/DTs from 2,4-Dichlorothiophenol and 2,4,6-Trichlorothiophenol

Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

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