Occurrence Of Organophosphate Flame Retardants Research Articles

Occurrence of organophosphate flame retardants in farmland soils from Northern China: Primary source analysis and risk assessment

Ninety-eight soil samples were collected from farmland soils from Beijing-Tianjin-Hebei core area, Northern China, where agricultural lands were subjected to contamination from intense urban and industrial activities. Twelve organophosphates flame retardants (OPFRs) were analyzed with total soil concentrations ranging from 0.543 μg/kg to 54.9 μg/kg. Chlorinated OPFRs were dominating at mean level of 3.64 μg/kg and Tris(2-chloroisopropyl) phosphate contributed the most (mean 3.36 ± 5.61 μg/kg, 98.0%). Tris(2-ethylhexyl) phosphate was fully detected at levels of 0.041–1.95 μg/kg. Generally, tris(2-butoxyethyl) phosphate and triphenyl phosphate contributed the most to alkyl- (53.6%) and aryl-OPFRs (54.3%), respectively. The levels of ∑OPFRs close to the core urban areas were significantly higher than those from background sites. The occurrence and fate of OPFRs in soil were significantly associated with total organic carbon content and mostly with fine soil particles (<0.005 mm), and a transfer potential from the atmosphere was predicted with logKSA values. Comparable soil levels with poly brominated diphenyl ethers s in other studies suggested that the contamination of OPFRs occurred in farmland soil with an increasing trend but currently showed no significant environmental risk based on risk quotient estimation (<1). This investigation warrants further study on behaviors of OPFRs in a soil system and a continual monitoring for their risk assessment.

Mineral- and Base-Catalyzed Hydrolysis of Organophosphate Flame Retardants: Potential Major Fate-Controlling Sink in Soil and Aquatic Environments.

The ubiquitous occurrence of organophosphate flame retardants (OPFRs) in aquatic and soil environments poses significant risks to human health and ecosystems. Here, we report on the hydrolysis of six OPFRs and three structural analogues in the absence and presence of metal (hydr)oxide minerals. Eight of the target compounds showed marked degradation in alkaline solutions (pH 9-12) with half-lives ranging from 0.02-170 days. Kinetics follow a second-order rate law with apparent rate constants for base-catalyzed hydrolysis (kB) ranging from 0.69-42 000 M-1 d-1. Although hydrolysis in homogeneous solution at circumneutral pH is exceedingly slow (t1/2 > 2 years, except for tris(2,2,2-trichloroethy) phosphate), rapid degradation is observed in the presence of metal (hydr)oxide minerals, with half-lives reduced to <10 days for most of the target OPFRs in mineral suspensions (15 m2/L mineral surface area loading). LC-qToF-MS analysis of transformation products confirmed ester hydrolysis as the active degradation pathway. Values of kB for individual OPFRs are highly variable and correlate with acid dissociation constants (pKa) of the corresponding alcohol leaving groups. In contrast, kinetic parameters for mineral-catalyzed reactions are much less sensitive to OPFR structure, indicating that other factors like mineral-OPFR interactions are rate controlling. Given the documented recalcitrance of OPFRs to biodegradation and photodegradation, these results suggest that mineral-catalyzed hydrolysis may be a major fate-controlling sink in natural environments.

Contamination Characteristics and Human Exposure to Organophosphate Flame Retardants in Road Dust from Suzhou City

The contamination levels and distribution characteristics of four organophosphate flame retardants (OPFRs) in 25 outdoor dust samples collected in Suzhou were quantitatively analyzed by gas chromatography-mass spectrometry (GC-MS). The exposure to OPFRs via ingestion and inhalation of dust were also estimated for adults, children, and professional street sweepers. Four types of OPFRs were detected in all dust samples at different levels; the total OPFRs concentrations ranged from non-detected (ND) to 8901.66 ng·g-1, with a median of 1039.21 ng·g-1. The concentrations of TCPP, TBEP, TDCPP, and TCEP were in the range of 0-6931.46, 0-2021.15, 0-788.44, and 0-62.16 ng·g-1, respectively. The daily intake of ∑OPEs under a high dust ingestion scenario was 125.68, 915.78, and 6314.16 pg·kg-1 for adults, children, and professional street sweepers, respectively. The estimated exposure of children to ∑OPEs was six times higher than that of adults. However, the daily intake of OPFRs via dust inhalation was 3.07E-02, 1.89E-02, and 1.54E-01 pg·kg-1 for adults, children, and professional street sweepers, respectively. These findings indicated that the occurrence of OPFRs in the dust poses a significant risk to children and professional street sweepers.

Occurrence of organophosphate flame retardants in drinking water from China

Several organophosphate flame retardants (OPFRs) have been identified as known or suspected carcinogens or neurotoxic substances. Given the potential health risks of these compounds, we conducted a comprehensive survey of nine OPFRs in drinking water in China. We found total concentrations of OPFRs in tap water ranging from 85.1 ng/L to 325 ng/L, and tris(2-butoxyethyl) phosphate (TBEP), triphenyl phosphate (TPP), and tris(2-chloroisopropyl) phosphate (TCPP) were the most common components. Similar OPFR concentrations and profiles were observed in water samples processed through six different waterworks in Nanjing, China. However, boiling affected OPFR levels in drinking water by either increasing (e.g., TBEP) or decreasing (e.g., tributyl phosphate, TBP) concentrations depending on the particular compound and the state of the indoor environment. We also found that bottled water contained many of the same major OPFR compounds with concentrations 10–25% lower than those in tap water, although TBEP contamination in bottled water remained a concern. Finally, we concluded that the risk of ingesting OPFRs through drinking water was not a major health concern for either adults or children in China. Nevertheless, drinking water ingestion represents an important exposure pathway for OPFRs.