Hidenori Matsukami

Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alternatives for PBDEs

Three oligomeric organophosphorus flame retardants (o-PFRs), eight monomeric PFRs (m-PFRs), tetrabromobisphenol A (TBBPA), and polybrominated diphenyl ethers (PBDEs) were identified and quantified in surface soils and river sediments around the e-waste recycling area in Bui Dau, northern Vietnam. Around the e-waste recycling workshops, 1,3-phenylene bis(diphenyl phosphate) (PBDPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), triphenyl phosphate (TPHP), TBBPA, and PBDEs were dominant among the investigated flame retardants (FRs). The respective concentrations of PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs were 6.6-14000 ng/g-dry, <2-1500 ng/g-dry, 11-3300 ng/g-dry, <5-2900 ng/g-dry, and 67-9200 ng/g-dry in surface soils, and 4.4-78 ng/g-dry, <2-20 ng/g-dry, 7.3-38 ng/g-dry, 6.0-44 ng/g-dry and 100-350 ng/g-dry in river sediments. Near the open burning site of e-waste, tris(methylphenyl) phosphate (TMPP), (2-ethylhexyl)diphenyl phosphate (EHDPP), TPHP, and the total PBDEs were abundantly with respective concentrations of <2-190 ng/g-dry, <2-69 ng/g-dry, <3-51 ng/g-dry and 1.7-67 ng/g-dry in surface soils. Open storage and burning of e-waste have been determined to be important factors contributing to the emissions of FRs. The environmental occurrence of emerging FRs, especially o-PFRs, indicates that the alternation of FRs addition in electronic products is shifting in response to domestic and international regulations of PBDEs. The emissions of alternatives from open storage and burning of e-waste might become greater than those of PBDEs in the following years. The presence and environmental effects of alternatives should be regarded as a risk factor along with e-waste recycling.

Compositional Analysis of Commercial Oligomeric Organophosphorus Flame Retardants Used as Alternatives for PBDEs: Concentrations and Potential Environmental Emissions of Oligomers and Impurities

Four commercial oligomeric organophosphorus flame retardants (o-PFRs) were characterized using a refractive index detector and atmospheric pressure photoionization (APPI)-quadrupole time-of-flight mass spectrometry (QTOF-MS) compatible with gel permeation chromatography (GPC). Commercial o-PFRs consisted of approximately 90% or more oligomers and several impurities. Triphenyl phosphate (TPHP), tris(dimethylphenyl) phosphate (TDMPP), tris(2-chloroisopropyl) phosphate (TCIPP), and some new impurities were identified as byproducts of some manufacturing process of commercial o-PFRs for the first time. The concentrations of TPHP, TDMPP, and TCIPP were more than 1 weight %, whereas those of new impurities might be approximately 1 weight % by comparison among their abundances acquired through GPC-APPI-QTOF-MS analysis. Based on their vapor pressure and water solubility estimations, the potential environmental emissions of low molecular weight impurities were expected to be higher than those of oligomers. The presence and environmental emissions of low molecular weight impurities might be regarded as risk factors along with commercial o-PFRs.

Exposure assessment of heavy metals in an e-waste processing area in northern Vietnam

In developing countries, inappropriate recycling of e-waste has resulted in the environmental release of toxicants, including heavy metals, that may have deleterious health effects. In this study, we estimated daily metal intakes in five households in a Vietnamese village located in an e-waste processing area and assessed the health risk posed by exposure to the metals. Garden soil, floor dust, 24-h duplicate diet, and ambient air samples were collected from five households in northern Vietnam in January 2014. All samples were acid-digested, and contents of Cd, Cu, Mn, Pb, Sb, and Zn were measured by using ICP mass spectrometry and ICP atomic emission spectroscopy. In addition, the soil, dust, and diet samples were subjected to an bioaccessibility extraction test to determine bioaccessible metal concentrations. Hazard quotients were estimated from bioaccessible metal concentrations, provisional tolerable weekly intakes, and reference doses. Garden soil and floor dust were estimated to be mainly contributors to daily Pb intake, as indicated by calculations using bioaccessible metal concentrations and the U.S. Environmental Protection Agency soil plus dust ingestion rate. Diet was suggested to contribute significantly to daily Cd, Cu, Mn, Sb, and Zn intake. Estimated metal exposures via inhalation were negligible, as indicated by calculations using International Atomic Energy Agency reference inhalation rates. The maximum hazard quotients were calculated as 0.2 (Cd), 0.09 (Cu), 0.3 (Mn), 0.6 (Pb), 0.2 (Sb), and 0.5 (Zn), on the basis of bioaccessible metal concentrations. The contributions of Cd, Cu, Mn, Sb, and Zn except Pb to potential noncancer risk for adult residents of the five households in the e-waste processing area may be low.

Pilot-scale incineration of wastes with high content of chlorinated and non-halogenated organophosphorus flame retardants used as alternatives for PBDEs

Chlorinated and non-halogenated organophosphorus flame retardants (OPFRs) including tris(2-chloroisopropyl) phosphate (TCIPP), diethylene glycol bis(di(2-chloroisopropyl) phosphate) (DEG-BDCIPP), triphenyl phosphate (TPHP), and bisphenol A bis(diphenyl phosphate) (BPA-BDPP) have been used increasingly as alternatives to polybrominated diphenyl ethers and other brominated flame retardants. For this study, five batches of incineration experiments of wastes containing approximately 1% of TCIPP, DEG-BDCIPP, TPHP, and BPA-BDPP were conducted using a pilot-scale incinerator. Destruction and emission behaviors of OPFRs were investigated along with the effects on behaviors of unintentional persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), and pentachlorophenol (PCP). Incineration conditions were chosen according to current regulations for waste incinerators in Japan and UNEP. The OPFRs in the input materials were mainly destroyed in the primary combustion with destruction efficiencies greater than 99.999%. Concentrations of the OPFRs in the exhaust gases and ash were, respectively, <0.01-0.048 μg m(-3) and <0.5-68 μg kg(-1). Almost all of the total phosphorus in the input materials was partitioned into the ash, but less into final exit gases, indicating negligible emissions of volatile phosphorus compounds during incineration. Inputs of chlorinated OPFRs did not affect the formation markedly. Destruction and emission behaviors of unintentional POPs were investigated. Emissions of such POPs in exhaust gases and the ash were lower than the Japanese and international standards. Results show that even in wastes with high contents of chlorinated and non-halogenated OPFRs, waste incineration by the current regulations for the waste incinerators can control environmental emissions of OPFRs and unintentional POPs. Incineration is regarded as a best available technology (BAT) for waste management systems.

Early-life exposure to Tris(1,3-dichloroisopropyl) phosphate induces dose-dependent suppression of sexual behavior in male rats: EARLY-LIFE TDCIPP EXPOSURE SUPPRESSES SEXUAL BEHAVIOR IN MALE RATS

Exposure to endocrine‐disrupting chemicals may adversely affect animals, particularly during development. Tris(1,3‐dichloroisopropyl) phosphate (TDCIPP) is an organophosphate with anti‐androgen function in vitro that is present in indoor dust at relatively high concentrations. In male rats, androgens are necessary for the development of reproductive organs, as well as the endocrine and central nervous systems. However, we currently do not know the exact effects of TDCIPP exposure through suckling on subsequent reproductive behavior in males. Here, we show that TDCIPP exposure (25–250 mg kg–1 via oral administration over 28 consecutive days post‐birth) suppressed male sexual behavior and reduced testes size. These changes were dose‐dependent and appeared first in adults rather than in juveniles. These results demonstrate that TDCIPP exposure led to normal body growth and appearance in juveniles, but disrupted the endocrine system and physiology in adults. Therefore, assays should be performed using adult animals to ensure accuracy, and to confirm the influence of chemical substances given during early mammalian life.