Yukio Noma

Brominated and organophosphate flame retardants in selected consumer products on the Japanese market in 2008

The concentrations of traditional brominated flame retardants (BFRs) and organophosphate flame retardants (OPFRs) in new consumer products, including electronic equipment, curtains, wallpaper, and building materials, on the Japanese market in 2008 were investigated. Although some components of the electronic equipment contained bromine at concentrations on the order of percent by weight, as indicated by X-ray fluorescence analysis, the bromine content could not be fully accounted for by the BFRs analyzed in this study, which included polybrominated diphenylethers, decabromodiphenyl ethane, tetrabromobisphenol A, polybromophenols, and hexabromocyclododecanes. These results suggest the use of alternative BFRs such as newly developed formulations derived from tribromophenol, tetrabromobisphenol A, or both. Among the 11 OPFRs analyzed, triphenylphosphate was present at the highest concentrations in all the products investigated, which suggests the use of condensed-type OPFRs as alternative flame retardants, because they contain triphenylphosphate as an impurity. Tripropylphosphate was not detected in any samples; and trimethylphosphate, tributyl tris(2-butoxyethyl)phosphate, and tris(1,3-dichloro-2-propyl)phosphate were detected in only some components and at low concentrations. Note that all the consumer products evaluated in this study also contained traditional BFRs in amounts that were inadequate to impart flame retardancy, which implies the incorporation of recycled plastic materials containing BFRs that are of global concern.

Chemical speciation and leaching properties of elements in municipal incinerator ashes

Different chemical properties of bottom ash and fly ash from municipal solid waste incinerators were compared based on the results of the five measuring techniques: (1) total contents and leaching amounts by regulatory leaching test in Japan; (2) leaching properties by pH-dependent leaching test; (3) modeling of pH-dependent leaching test using model compounds; (4) enriched chemical composition compared with bulk composition by an X-ray photoelectron spectrometer (XPS); (5) estimation of chemical states of elements by XPS analysis. The difference between bottom ash and EP ash was clearly found in element content, leaching behavior and release rate. The release rates of many elements in bottom ash were lower than in electrostatic precipitation (EP) ash even in an acidic condition of pH 3 as well as at the inherent pH of 12. Corresponding to the relatively complicated components in bottom ash, leaching patterns depending on pH were not simple. Comparison between the pH-dependent pattern of Ca in a sample and in model compounds resulted in the estimation of some Ca compounds in ash. The surface analysis by XPS showed results that Na, Cl, Zn, Pb and S were enriched in EP ash and Fe and Ti were rarely found in the surface of ash. Possible chemical states of Na, Ca, K, Cl and S were estimated by a new method of comparing binding energies of standard compounds and their mixtures.

HRGC/HRMS Analysis of Chloronaphthalenes in Several Batches of Halowax 1000, 1001, 1013, 1014 and 1099

Chloronaphthalene (CN) congeners and homologue groups have been quantified in up to three batches of several types of technical CN formulations of the Halowax series (Halowax 1031, 1000, 1001, 1013, 1014 and 1099), to elucidate possible batch-to-batch compositional variations. Using isotope dilution and HRGC/HRMS a relatively large variation in CN congeners and homologues composition among the batches of particular types of the Halowax formulations could be noted, and also when compared to the composition declared by the manufacturer. Depending on the type of the Halowax formulation and its batch in total up to 54 peaks from chloronaphthalenes (Agilent Ultra 2 liquid phase), which represented 70 of 75 CN congeners theoretically possible, could be found in these mixtures. These congeners represented all CN homologue groups from mono- to octaCN but some co-eluted. A co-eluting congeners were such as: 1,4-/1,6- (nos. 5/7), 1,5-/2,7- (nos. 6/12), 2,6–1,7- (nos. 11/8) of diCNs; 1,3,6-/1,3,5- (nos. 20/19), 1,3,7-/1,4,6- (nos. 23/24), 1,6,7-/2,3,6- (nos. 25/26) of triCNs; 1,2,5,7-/1,2,4,6-/1,2,4,7- (nos. 37/33/34), 1,3,6,8-/1,2,5,6- (nos. 45/36), 1,2,3,5-/1,3,5,8- (nos. 28/43), 1,2,3,4-/1,2,3,7- (nos. 27/30), 1,2,5,8-/1,2,6,8- (nos. 38/40) of tetraCNs; 1,2,3,5,7-/1,2,4,6,7- (nos. 52/60), 1,2,3,5,8-/1,2,3,6,8- (nos. 53/55) of pentaCNs; 1,2,3,4,6,7-/1,2,3,5,6,7- (nos. 66/67), 1,2,3,4,5,7-/1,2,3,5,6,8- (64/68) and 1,2,4,5,6,8-/1,2,4,5,7,8- (nos. 71/72) of hexaCNs. Absent in the Halowaxes were CN congeners such as 1,3,8-triCN (no. 22) (<0.0002 mg/g), 1,3,6,7-tetraCN (no. 44), 1,2,3,6-TetraCN (no. 29), 1,2,3,6,7-pentaCN (no. 54) and 1,2,3,6,7,8-hexaCN (no. 70) (<0.0005 mg/g).

By-side impurities in chloronaphthalene mixtures of the Halowax series: all 209 chlorobiphenyls.

Abstract All seven Halowax formulations examined were contaminated with chlorophenols (CPhs). The total CPhs content of the CN mixtures ranged from 1050 to 34,200 ng/g. The absolute concentration of CPhs decreased with an increase of degree of chlorination (% Cl) of the Halowax 1031 (27%), 1000 (35%), 1001 (49%), and 1099 (51%), respectively, but remained relatively constant for higher chlorinated Halowax 1099 (51%), 1013 (54%), 1014 (59%), and 1051 (70%). 2,4,6-TrCPh and 2,4-DiCPh did contaminated all seven Halowax formulations and PeCPh remained undetected (<90 ng/g) only in Halowax 1099, while less frequently occurred 2,6-DiCPh and followed by 3-/4-MoCPh, 2,5-DiCPh, 2-MoCPh, 2,3-DiCPh, and 2,3,4,6-TeCPh. The CPh congeners such as 3,4-DiCPh, 3,5-DiCPh, 2,3,4-TrCPh, 2,3,5-TrCPh, 2,3,6-TrCPh, 2,4,5-TrCPh, 3,4,5-TrCPh, 2,3,4,5-TeCPh, and 2,3,5,6-TeCPh were undetected in any of the Halowax formulation examined. The profile (%) of higher chlorinated CPh homologues like PeCPh in the Halowaxes followed somehow a degree of chlorination (Cl %) of the parent mixture, i.e., increased from 14, 22, 43, 55, 52 to 80%, respectively, but exception was free of PeCPh the Halowax 1099. And contrary, for a lower chlorinated DiCPhs and TrCPhs their relative proportions decreased but again an exception was Halowax 1099. The fingerprint profiles of 2,4,6-TrCPh, 2,4-DiCPh, and PeCPh, which were usually the most abundant congeners varied and were less consisted when compared to the CPh homologue group profiles, and also more depended on the type of technical Halowax mixture. Due to absence of 2,4,5-TrCPh but presence of 2,4-DiCPh, 2,6-DiCPh, 2,4,6-TrCPh, and PeCPh, which, respectively, are indicative congeners for CPhs obtained by alkaline hydrolysis of chlorobenzenes or phenol chlorination using gaseous chlorine, just co-occurrence of phenol impurity in technical naphthalene is suggested as a solely source of CPhs in the Halowax mixtures.

Chloronaphthalenes Composition of Several Batches of Halowax 1051

Halowax 1051 is the highest chlorinated technical chloronaphthalene mixture among seven known formulations of the Halowax series. Octa- and heptaCN homologue groups are the main CN constituents of Halowax 1051 with declared 90% and 10% contents, respectively. In this study, using an isotope dilution technique and HRGC/HRMS, octaCN and heptaCNs contents of six batches of Halowax 1051 were between 82–93% and 6.2–17%, respectively. Also mono- to hexaCNs were found in Halowax 1051, and their content more or less varied according to the batch; also, the abundance of a particular CN congeners varied. Tetra-, penta- and hexaCNs have been found in all six batches of Halowax 1051 examined, and their contents varied between 0.0024–0.77%, 0.031–0.22%, and 0.21–0.82%, respectively. TriCNs have been found in three of six batches, and mono- and diCNs in two of six batches with 0.0020–0.40, 0.0017–0.25 and 0.0012–0.34% for positive findings, respectively. 2,3-DiCN (no. 10), 1,8-diCN (no. 9) at < 0.0002 mg/g, 1,6,7-/2,3,6-triCNs (nos. 25/26), 1,3,8-triCN (no. 22) at < 0.0002 mg/g, 1,3,6,7-tetra (no. 44), 1,2,3,6-tetra- (no. 29), 1,2,7,8-tetraCN (no. 41) and 1,2,3,6,7,9-hexaCN (no. 70) at < 0.0005 mg/g have not been found in Halowax 1051.

By-Side Impurities in Chloronaphthalene Mixtures of the Halowax Series: All 75 Chlorodibenzo-p-Dioxins

Abstract A by-side chlorodibenzo-p-dioxins (CDDs) has been identified as impurity in concentration between 1.5 and 370 ng/g in the Halowax formulations of all type. Halowax 1014 was relatively richer in number of CDD congeners detected when compared to six other CN formulations examined. Amongst the mono- to tri-CDDs, the most prevalent in the Halowaxes were 1- and 2-MoCDD, and especially they were abundant in the formulations of a lower than a higher degree of chlorination. Amongst the tetra- to octaCDD only 1,2,3,4-/1,2,4,6-/1,2,4,9-/ 1,2,3,8-TeCDD, 1,2,3,4,6,7,8-HpCDD and OcCDD were found in all the Halowaxes, and 1,2,3,4,6,7,9-HpCDD remained undetected only in Halowax 1099 and 1013, while most of TeCDDs, PeCDD, and HxCDDs were absent in a majority of the formulations examined. The compositional profile of 1,2,3,4-/1,2,4,6-/1,2,4,9,-/1,2,3,8-TeCDD and OcCDD congeners found in the Halowaxes seem to indicate, that after an initial in situ formation of mono- and di-CDDs during CNs synthesis, a further increase of reaction time, temperature, and pressure can lead to successive chlorination of the already established chlorodibenzo-p-dioxin molecule, and so to enrichment in 1,2,3,4-/ 1,2,4,6-/1,2,4,9,-/1,2,3,8-TeCDD but also OcCDD content for most of the final products obtained. Nevertheless, also due to the co-synthesis of chlorophenols in the Halowaxes, their condensation reactions could also contribute to the formation of CDDs. In term of dioxin-like toxicity the most potent due to CDDs content was Halowax 1014 with 0.95 ng TCDD TEQ/g, and between 0.00068 and 0.058 ng/g were for other formulations. A rough estimation made implies that a net CDDs production due to manufacture of the technical CNs in the XX century could reach an amount between 3.0 and 12.6 kg, while for most toxic dioxin-like constituents between 5.25 and 24 g TCDD TEQ, For the worst case scenario and involvement of Halowax 1014 only the net total CDDs production was estimated to be 1.5 kg, and for highly-toxic congeners 71 g TCDD TEQ. All these figures are much lower when compared to co-production of CDFs.

Chlorobiphenyl constituents of Aroclor 1268, Chlorofen, Clophen T 64, KC-600, and KC-1000 technical formulations

All 209 chlorobiphenyls (CBs) theoretically possible and potentially present in relatively highly chlorinated types of technical CB formulations of Aroclor 1268, Chlorofen, Clophen T 64, KC-600, and KC-1000 have been quantified using isotope dilution techniques and high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). CB constituents of Aroclor 1268, Chlorofen, Clophen T 64, KC-600, and KC-1000 could be separated, detected, identified and quantified as “bulk CBs,” using a capillary column (60 m length × 0.25 mm i.d.) coated by 8% phenyl polycarborane-siloxane (HT-8PCB, SGE, Australia) liquid phase for GC coupled to HRMS, into 111, 78, 126, 137, and 148 peaks, respectively, which covered 140, 100, 158, 169, and 180 possible CB congeners. 87, 60, 99, 110, and 121 peaks represented single CB congeners in Aroclor 1268, Chlorofen, Clophen T 64, KC-600, and KC-1000, respectively, while 34, 18, 27, 27, and 27 peaks represented 53, 40, 59, 59, and 59 co-eluting CBs. After enrichment procedures using multilayer silica beds, alumina beds, and carbon-impregnated silica beds in glass columns, all four planar non-ortho CBs and all eight mono-ortho CBs (but with the exception of CB no. 123 in Chlorofen) could be quantified in all five technical CB formulations examined. The planar non- and mono-ortho CBs content of Aroclor 1268, Chlorofen, Clophen T 64, KC-600 and KC-1000 were 6.2, 7.0, 47, 120, 470 μ g/g and 220, 410, 34,000, 12,000, 5900 μ g/g, respectively, and their 2,3,7,8-tetrachlorodibenzo-p-dioxin toxicity equivalents (2,3,7,8-TeCDD TEQs) were 31, 390, 710, 260, 1900 ng-TEQ/g and 35, 99, 5900, 2600, 8900 ng-TEQ/g, and the total 2,3,7,8-TeCDD TEQs of planar CBs were 66, 490, 6600, 2900, and 11,000 ng-TEQ/g.

By-side PCDD/Fs in technical PCB formulations of Kanechlor series

The Japanese Kanechlor technical PCB formulations such as KC-300, KC-400, KC-500, KC-600 and KC-1000 have been examined for possible contamination with by-side PCDD/Fs. 75 PCDDs and 135 PCDF have been determined using isotope dilution, separation and enrichment on silica gel impregnated with activated carbon, and final HRGC/HRMS measurement. MonoCDDs to OCDD were absent in KC-300, KC-600 and KC-1000. Tetra- and PentaCDDs occurred at > 1 ng/g in KC-400 and KC-500. The Kanechlors were contaminated with nearly all 135 PCDFsw. In parallel with an increasing degree of chlorination of a particular Kanechlor formulation examined increased also the content of more chlorinated PCDFs. In term of total dioxin-like toxicity and TEQ loads the KC-500 contained highly toxic PCDD/Fs at 270 ng TEQ/g and followed by KC-400 with 269 ng TEQ/g, KC-600 with 188 ng TEQ/g, KC-1000 with 164 ng TEQ/g and KC-300 with 79 ng TEQ/g. From 99.5 to 100% of PCDD/Fs toxicity found in the Kanechlors was from PCDFs.

Behavior of polychlorinated benzenes, PCDD/Fs and dioxin-like PCBs during incineration of solid waste contaminated with mg/kg levels of hexachlorobenzene

Hexachlorobenzene (HCB), one of the well-known Persistent Organic Pollutants (POPs), is present in some pigments and these raw materials with maximum level of several thousand of mg/kg. Considering that these pigments have been used in long-life products, such as car parts, construction materials and electrical and electronic equipments, the articles containing HCB at a concentration of several hundred mg/kg still have to undergo waste management. In this study, we performed a combustion experiment involving solid waste containing 300 mg/kg of HCB as the input material using a pilot-scale incinerator to determine the destruction of HCB and its influence on the behavior of other polychlorinated benzenes (CBzs) and unintentionally produced POPs, such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs). HCB at a concentration of 300 mg/kg in the input material was destroyed mainly in the primary combustion zone. Overall the destruction efficiency of HCB was > 99.9985%. The input concentration of HCB did not significantly affect the formation and destruction or the final emissions of other CBzs, PCDD/Fs and dl-PCBs. These results indicate that incineration, when operated and structured to minimize emissions of dioxin-related compounds, is considered to be one of the Best Available Technologies for the appropriate treatment of waste containing HCB with a concentration in the order of mg/kg.

By-side chlorodibenzo-P-dioxins and chlorodibenzofurans in technical chlorobiphenyl formulations of aroclor 1268, chlorofen, and clophen T 64.

Aroclor 1268, Chlorofen, and Clophen T 64 technical chlorobiphenyl formulations were examined for 75 congeners of chlorodibenzo-p-dioxin (CDD) and 135 congeners of chlorodibenzofuran (CDF) using isotope dilution technique, separation, and enrichment on silica gel impregnated with activated carbon and final high resolution gas chromatography (HRGC)/high resolution mass spectrometry (HRMS) quantification. Three the most highly chlorinated congeners of CDD were found in Aroclor 1268, Chlorofen, and Clophen T 64. In the case of CDF, the number of congeners identified was 108 with 44 coeluting in pairs and 3 in triplicate in Aroclor 1268, 16 with 4 coeluting in pairs in Chlorofen, and 88 with 46 coeluting in pairs and 3 in triplicate in Clophen T 64. The total CDD and CDF concentrations of Aroclor 1268, Chlorofen, and Clophen T 64 were 24, 160, and 8.5 ng/g and 1600, 270,000, and 4000 ng/g, respectively. No mono-to hexa-CDDs could be quantified in Aroclor 1268 (< 0.03 to < 1 ng/g), Chlorofen (< 0.07 to < 0.3 ng/g), or Clophen T 64 (< 0.007 to < 2 ng/g), whereas two hepta-CDDs and octa-CDD were found in all three formulations, and Chlorofen was richer in those compounds, followed by Aroclor 1268 and Clophen T 64.