ABSTRACT
Organophosphate triesters (tri-OPEs) have recently been widely identified in aquatic ecosystems, but information on their organophosphate diester (di-OPE) metabolites is sparsely available. Herein, uniform fishmeal products were collected across the globe (the U.S., China, Europe, South America, and Southeast Asia). Sixteen representative tri-OPEs and eight di-OPEs were investigated to reveal whether industrial production, metabolism, environmental persistence, or physicochemical properties are the key factors influencing their environmental burden and distribution. Tri-OPEs and di-OPEs were 100% detected in fishmeal, with bis(2-chloroethyl) hydrogen phosphate (BCEP) and bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) at discernible levels in marine fauna for the first time. Average concentration of di-OPEs (49.6 ± 27.5 ng/g dw) was of the same order of magnitude as that of tri-OPEs (59.3 ± 92.2 ng/g dw). Geographical-specific distributions of tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), triphenyl phosphate (TPhP), tris(2-butoxyethyl) phosphate (TBOEP), and 2-ethylhexyl diphenyl phosphate (EHDPP) were statistically significant (p < 0.05). Mean concentration ratios ranged from 0.087 for the BCEP-TCEP pair to 507 for the dimethyl phosphate (DMP)-trimethyl phosphate (TMP) pair. Only the TPhP-diphenyl phosphate (DPhP) pair presented a strong positive linear correlation (r = 0.731; p < 0.01), and DPhP was proved a degradation origin. Commercial sources had a significant overall impact on distribution patterns of the DMP-TMP and the dibutyl phosphate (DnBP) - tri-n-butyl phosphate (TnBP) pairs, whereas biotic transformation and abiotic stability profoundly influenced the bis(2-ethylhexyl) phosphate (BEHP)-tris(2-ethylhexyl) phosphate (TEHP), the bis(1-chloro-2-propyl) phosphate (BCIPP)-TCIPP, and the BCEP-TCEP pairs. Di-OPEs are critical to understand environmental behavior of tri-OPEs in marine fauna.
Subject(s)
Flame Retardants , China , Ecosystem , Environmental Monitoring , Esters , Europe , Flame Retardants/analysis , Organophosphates , South AmericaABSTRACT
Nothotsuga longibracteata, a relic and endangered conifer species endemic to subtropical China, was studied for examining the spatial-temporal population genetic variation and structure to understand the historical biogeographical processes underlying the present geographical distribution. Ten populations were sampled over the entire natural range of the species for spatial analysis, while three key populations with large population sizes and varied age structure were selected for temporal analyses using both nuclear microsatellites (nSSR) and chloroplast microsatellites (cpSSR). A recent bottleneck was detected in the natural populations of N. longibracteata. The spatial genetic analysis showed significant population genetic differentiation across its total geographical range. Notwithstanding, the temporal genetic analysis revealed that the level of genetic diversity between different age class subpopulations remained constant over time. Eleven refugia of the Last Glacial Maximum were identified, which deserve particular attention for conservation management.