Polybrominated dibenzo-p-dioxins/furans and their chlorinated analogues in sediments from a historical hotspot for both brominated flame retardants and organochlorine pesticides.

Polybrominated dibenzo-p-dioxin/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) in the environment are closely related to their precursors, brominated flame retardants (BFRs) and organochlorine pesticides (OCPs). However, their change trends following the regulation of BFRs and OCPs remain incompletely characterized. Here, we examined PBDD/Fs and PCDD/Fs in sediments from a historical hotspot for both BFRs and OCPs, namely the Pearl River Delta (PRD), China. PBDD/Fs showed ubiquity in these samples but significantly lower concentrations than PCDD/Fs. Spatially, the occurrence of PBDD/Fs was positively correlated with local development levels and sediments from highly urbanized/industrialized areas showed higher and increasing PBDD/F concentrations. Polybrominated diphenyl ether (PBDE)-related products/industries were the greatest PBDD/F contributors to the PRD, followed by bromo-phenol/benzene-related products/industries. PCDD/Fs in PRD sediments showed significant positive correlations with local grain planting area, yield, and pesticide consumption. The historical use of pentachlorophenol (PCP)/PCP-Na and biomass open-burning were the leading PCDD/F sources of the PRD agricultural/rural areas, where the concentrations and toxic equivalent quantities (TEQs) of PCDD/Fs in sediments changed very little over the past decade. Anthropogenic thermal processes involved in metallurgy, waste incineration, and vehicles were the greatest PCDD/F contributors in the PRD urban/industrial areas, where the PCDD/F concentrations in sediments almost doubled over the last decade. This finding indicates the increasing PCDD/F contributions of industrial and municipal activities in the PRD, despite the implementation of strict emission standards. Over sixty percent of the samples showed TEQs that surpassed the low-risk threshold specified for mammalian life by the U.S. EPA (2.5 pg TEQ g-1) and warrant continuous attention.

Spatiotemporal transitions of organophosphate esters (OPEs) and brominated flame retardants (BFRs) in sediments from the Pearl River Delta, China.

Recent regulations on the use of brominated flame retardants (BFRs, especially polybrominated diphenyl ethers, PBDEs) have led a sharp increase in the use of organophosphate esters (OPEs), which have become the subject of widespread environmental concern. To gain insights into their environmental transitions, we investigated the spatiotemporal trends and sources of 25 OPEs and 23 BFRs (21 PBDEs and two alternative BFRs) in sediments from the Pearl River Delta (PRD), the second economic/industrial region of China. Among them, PBDEs showed higher mean concentrations than OPEs and alt-BFRs in PRD sediments, a continual increase in most PRD areas, and positive correlations with most local socioeconomic parameters. The source analysis results indicated that all of these changes resulted from the substantial use/stock of PBDEs (especially deca-BDE) in this region, and BDE-209 displayed debromination in most sediments. OPEs demonstrated obvious increases in sediments from all major PRD rivers, especially those located in less-developed regions. This distribution might be related to the large-scale industry relocation from the central PRD area to its vicinities. Unexpectedly, decabromodiphenyl ethane (DBDPE), an important deca-BDE substitute, presented considerable declines in the PRD sediments while several novel OPEs showed considerably high proportions, especially aryl-substituted OPEs, which merit further screening analysis.

Occurrence of Dechlorane series flame retardants in sediments from the Pearl River Delta, South China.

Dechlorane series flame retardants (DECs), e.g. Dechlorane plus (DP), have reportedly showed an increase in consumption since the phase-out of traditional brominated flame retardants (BFRs). Here we investigated DP and 7 structural analogues, as well as its 2 dechlorinated products in 76 surficial sediments from the Pearl River Delta (PRD), one of the three important manufacturing bases of China. The concentration of Σ8DECs varied from 28.1 to 38,000 pg g-1 dw in the PRD sediments, dominated by DP and Mirex. Spatially, sedimental DP concentrations were significantly and positively correlated with the municipal gross domestic product (GDP), population and sewage discharge of the PRD cities, but were insignificantly related to their industrial outputs. This indicates that DP in the PRD sediments mainly originated from urban activities instead of industrial ones. Although Mirex has been restricted for several decades, it demonstrated ubiquity in the PRD and considerably high levels in several termite control hot-spots (up to 34,200 pg g-1), implying its massive historical use in this subtropical region. Other DECs, however, exhibited quite low abundances, implying their limited applications in this region. In comparison to the historical data, sedimental DP concentrations presented an increasing trend in most rivers in the PRD except the West River. The fractions of anti-DP (fanti) showed insignificant deviations from its technical value, suggesting that no obvious anti-DP transformation occurred in most PRD sediments. However, anti-Cl11-DP, an important dechlorination product of anti-DP, was ubiquitously found in the PRD sediments, and its concentrations were significantly and positively associated with those of anti-DP. Therefore, anti-Cl11-DP in the PRD sediments was deemed as the impurity co-emitted with anti-DP rather than its dechlorination byproduct. Considering its ubiquity, increasing trend and persistence, DP in the PRD environments merits continuous concerns.

Design of a six-gas NDIR gas sensor using an integrated optical gas chamber.

A non-dispersive infrared (NDIR) gas sensor with an integrated optical gas chamber was designed to accurately detect multiple gas concentrations in a complex polluted environment. This chamber consists of a hexagonal prism shell and a reflection plate. In particular, six dual-channel infrared detectors for sensing different gases and one collimated infrared light source are integrated in the gas chamber. The IR light emitted by the collimated IR light source arrives at these detectors after four reflections. The result of simulation and data collection for optical path length and luminous flux shows that the average optical path length in the chamber is 63 mm, and the effective utilization rate of the luminous flux can reach 78.8%. The highly compact NDIR sensor can detect the concentrations of a mixture of gases (CO, CO2, CH4, H2CO, NH3, and NO with a volume fraction ranging from 0 to 4%).

Brominated and organophosphate flame retardants along a sediment transect encompassing the Guiyu, China e-waste recycling zone.

e-Waste recycling using crude techniques releases a complex, yet incompletely characterized mixture of hazardous materials, including flame retardants (FRs), to the environment. Their migration downstream and the associated risks also remain undocumented. We examined 26 FRs (18 brominated (BFRs: 12 polybrominated diphenyl ether (PBDE) congeners, plus 6 alternatives) and 8 organophosphate esters (OPEs)) in surficial sediments of the Lian River. Sampling encompassed the river's origin, through the Guiyu e-waste recycling zone, to its mouth, as well as associated tributaries. OPE exceeded BFR concentrations in most sediments, despite their far greater water solubilities. Among OPEs, tris(1-chloro-2-propyl) phosphate dominated upstream, but shifted to triphenyl phosphate in Guiyu and downstream sediments. For PBDEs, Deca-BDE dominated upstream, but Penta-BDE prevailed in Guiyu and at many downstream sites. Among emerging alternative BFRs, decabromodiphenyl ethane dominated upstream, transitioning to 1,2-bis(2,4,6,-tribromophenoxy)ethane in Guiyu sediments. Penta-BDE (BDE-47 + -99, 668-204,000 ng g-1, ∑PBDEs 2280-287,000 ng g-1), tetrabromobisphenol A (2,720-41,200 ng g-1), 1,2-bis(2,4,6,-tribromophenoxy)ethane (222-9870 ng g-1) and triphenyl phosphate (4260-1,710,000 ng g-1, OPEs 6010-2,120,000 ng g-1) concentrations in Guiyu sediments were among the highest reported in the world to date. The continuing dominance of these e-waste indicative FRs in sediments downstream of Guiyu suggested that FR migration from Guiyu occurred. Hazard quotients >1.0 indicated that the extreme sediment concentrations of individual FRs posed ecological risks in most Guiyu reach and downstream areas. Simultaneous exposure to multiple FRs likely increased risks. However, risks may be mediated if FRs were associated with strong sorbents, e.g. carbon black from burned debris, hydrophobic polymer fragments, or resided as additives within polymer fragments.

Airborne polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and dechlorane plus (DP) in concentrated vehicle parking areas.

This study investigated polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and dechlorane plus (DP) in air around three concentrated vehicle parking areas (underground, indoor, and outdoor) in a metropolitan of South China. The parking areas showed higher concentrations of PBDEs, PBDD/Fs, and DP than their adjacent urban area or distinct congener/isomer profiles, which indicate their local emission sources. The highest PBDE and DP concentrations were found in the outdoor parking lot, which might be related to the heating effect of direct sunlight exposure. Multi-linear regression analysis results suggest that deca-BDEs without noticeable transformation contributed most to airborne PBDEs in all studied areas, followed by penta-BDEs. The statistically lower anti-DP fractions in the urban area than that of commercial product signified its degradation/transformation during transportation. Neither PBDEs nor vehicle exhaust contributed much to airborne PBDD/Fs in the parking areas. There were 68.1-100 % of PBDEs, PBDD/Fs, and DP associated with particles. Logarithms of gas-particle distribution coefficients (K ps) of PBDEs were significantly linear-correlated with those of their sub-cooled vapor pressures (p Ls) and octanol-air partition coefficients (K OAs) in all studied areas. The daily inhalation doses of PBDEs, DP, and PBDD/Fs were individually estimated as 89.7-10,741, 2.05-39.4, and 0.12-4.17 pg kg(-1) day(-1) for employees in the parking areas via Monte Carlo simulation.