Sex-Specific Bioamplification of Halogenated Organic Pollutants during Silkworm (Bombyx mori) Metamorphosis and Their Adverse Effects on Silkworm Development.

A partial life cycle test was performed with silkworms (Bombyx mori) exposed to different levels of halogenated organic pollutants (HOPs). The aims were to investigate the fate of HOPs during metamorphosis and the adverse effects of HOP exposures on silkworm development. Contaminant exposures resulted in decreased body weights, increased development times, and reductions of fecundity in silkworms. Assimilation efficiencies of HOPs decreased with an increasing octanol-water partition coefficient (log KOW). From the larvae to the pupae stage, bioamplification factors (BAmFs) exhibited concentration-dependent results, in which there was a positive correlation with the log KOW at the high concentrations but no correlation at the low concentrations. From the pupae to the moth stage, BAmFs were linearly negatively correlated with the log KOW for males, but a parabolic correlation with the log KOW was more suitable for females. Regarding reproductive activities, female moths selectively transferred low log KOW HOPs to eggs by the oviposition except for highly halogenated lipophilic pollutants. However, BAmFs of male moths during mating showed no correlation with the log KOW, although highly halogenated lipophilic pollutants had the highest BAmF values. The sex-specific bioamplification processes and special behaviors of highly halogenated lipophilic pollutants deserve further research.

Structures, Single-Molecule Magnets, and Fluorescent Properties of Four Dinuclear Lanthanide Complexes Based on 4-Azotriazolyl-3-hydroxy-2-naphthoic Acid.

Four isostructural dinuclear lanthanide complexes based on 4-azotriazolyl-3-hydroxy-2-naphthoic acid (H3ATNA) and 3-hydroxy-2-naphthoic acid (H2NA) ligands, {[Ln2(HATNA)2(HNA)2(H2O)4]·6DMF} (Ln = Dy (1), Tb (2), Sm (3), Eu (4); DMF = N, N-dimethylformamide) have been prepared and characterized by X-ray diffraction crystallography, dc/ac magnetic characterization, and fluorescent spectrometry. The crystallographic data reveal dinuclear lanthanide cores of complexes 1-4, bridged by phenoxo and µ1,3 carboxyl groups. Each nine-coordinated Ln(III) ion is located in a slightly distorted monocapped square antiprism. The ligand of H3ATNA displays a unique antenna effect in complex 4. Complexes 1-3 display only two ligand-centered fluorescent emissive peaks around 450 and 600 nm, and complex 4 shows four characteristic Eu(III)-centered emission bands at 593, 618, 653, and 698 nm under excitation at 348 nm. Complex 1 exhibits single-molecule magnet behavior that is rationalized through ab initio calculations.

Bioaccumulation of Persistent Halogenated Organic Pollutants in Insects: Common Alterations to the Pollutant Pattern for Different Insects during Metamorphosis.

Few studies have examined the accumulation and fate of persistent halogenated organic pollutants (HOPs) in insects. We measured HOPs, including dichlorodiphenyltrichloroethanes (DDTs), polychlorinated biphenyls, and halogenated flame retardants, in insects from four taxonomic groups collected from an e-waste site. Dragonfly larvae collected from a pond contained the highest concentrations of all chemicals except DDTs, while the litchi stinkbugs contained the lowest. Different insect taxa exhibited different contaminant patterns which could be attributed to their habitats and feeding strategies. Bioaccumulation factors for dragonfly larvae and biomagnification factors for moth and grasshopper larvae were significantly positively correlated with the octanol-water partition coefficient of the chemicals (log KOW < 8). Common nonlinear correlations between the ratio of larval to adult concentrations and log KOW were observed for all taxa studied. The ratio of concentrations decreased with increasing values of log KOW (log KOW < 6-6.5), then increased (6 < log KOW < 8) and decreased again (log KOW > 8). This result implies that the mechanism that regulates organic pollutants in insects during metamorphosis is common to all the taxa studied.

Bioamplification and Biomagnification of Polycyclic Aromatic Hydrocarbons and Halogenated Organic Pollutants in Moths from an Electronic Waste Recycling Site.

Samples of Asota caricae (larvae, pupae, and adults) and its host plant leaf (Ficus hispida), larvae of Aloa lactinea, and mixed adult moths were collected from an electronic waste (e-waste) recycling site in south China. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and polybrominated diphenyl ethers were found to exhibit concentrations of 420-1300, 100-860, and 7.6-49 ng/g dry weight, respectively. The different chemical compositions among the samples of the three groups indicated that at least two exposure scenarios occurred among the moths in the study area. A complex relationship between bioamplification factors and the octanol-water partition coefficient (log KOW ) was observed during metamorphosis, in which a positive relationship was evident for 5 < log KOW < 7, whereas an inverse relationship occurred for log KOW values outside of this range. The biomagnification factors (BMFs) calculated from the larvae of Asota caricae to the host plant were negatively correlated with log KOW for all chemicals, differing completely from those obtained in previous studies. However, after metamorphosis, the correlation between BMF and log KOW was found to coincide with that in previous studies. These results indicate that the biotransformation of pollutants in organisms played a key role in determining whether or not biomagnification occurred in organisms and highlight the potential application of the metabolic rate of chemicals in screening-level risk assessments of new chemicals. Environ Toxicol Chem 2022;41:2395-2403. © 2022 SETAC.

Organophosphorus flame retardants in fish from Rivers in the Pearl River Delta, South China.

Twelve organophosphorus flame retardants (PFRs) were detected in the muscle of 3 species of fish, mud carp (Cirrhinus molitorella), tilapia (Tilapia nilotica), and plecostomus (Hypostomus plecostomus), from rivers in the Pearl River Delta (PRD) region. The total concentrations of PFRs in the mud carp, tilapia, and plecostomus ranged from 2.3 to 16, 3.4 to 16, and 3.5 to 30 ng/g wet weight (ww), respectively. Generally, tris(2-ethylhexyl) phosphate (TEHP), tris (2-chloro-isopropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP), and tri-n-butyl phosphate (TnBP) were the dominant compounds of the PFRs, collectively accounting for up to 90% of the total PFR levels. Concentrations of PFRs were significantly higher in the plecostomus than in the mud carp and tilapia (p < 0.05), which could be explained by differences in habitat and feeding habits of the fish species. High concentrations of PFRs were found mainly in the Guangzhou section of the Pearl River (site P1, P2, and P3) and site B3, which was similar to our previous study of PFRs in sediment from the Pearl River Delta, indicating a relatively high level of PFRs pollution in these regions. The estimated daily intake (EDI) of total PFRs from consumption of fish was 17 ng/kg bw/day to 98 ng/kg bw/day for adults and children, which was three to four orders of magnitude lower than reference dose values.

Halogenated organic pollutants in aquatic, amphibious, and terrestrial organisms from an e-waste site: Habitat-dependent accumulation and maternal transfer in watersnake.

Dichlorodiphenyltrichloroethanes (DDTs), Polychlorinated biphenyls (PCBs), and halogenated flame retardants (HFRs) were measured in aquatic, amphibious, and terrestrial wildlife collected from an e-waste contaminated pond and its surrounding region. The species-specific bioaccumulation and maternal transfer of chemicals in the watersnake were investigated. Total concentrations of target chemicals ranged from 1.3 × 103 to 4.8 × 105 ng g-1 lipid weight. PCBs were the predominant (72-95%) contaminants, followed by polybrominated biphenyl ethers (PBDEs, 4-27%). The concentrations of PCBs and HFRs except decabromodiphenyl ethane (DBDPE) were higher in aquatic organisms and terrestrial birds than in amphibians and lizards. Relatively high DDT levels were observed in the terrestrial birds and toads, but high DBDPE was found in the aquatic species except for waterbird eggs. Species-specific congeners profiles for PCB and PBDE and isomeric composition for dechlorane plus were observed. These results indicated a habitat-dependent accumulation among different species. Maternal transfer examined by the ratio of egg to carcass for watersnakes indicated multi-linear correlations between maternal transfer potential and octanol-water partition coefficient (log KOW) of chemicals. The same maternal transfer efficiencies were found for chemicals with log KOW between 6 and 8, then the maternal transfer potential rapidly decreased with increasing of log KOW.

Determination of organophosphorus flame retardants in fish by freezing-lipid precipitation, solid-phase extraction and gas chromatography-mass spectrometry.

An analytical method has been developed for measuring 12 organophosphorus flame retardants (PFRs) in fish tissue samples. After the Soxhlet extraction of PFRs with dichloromethane. The experimental parameters of the clean-up were systematically optimized. Methanol was found to be a more effective solvent than acetonitrile used in freezing-lipid precipitation. Methanol (5%) in ultrapure water, was finally selected to perform solid-phase extraction (SPE, Oasis HLB cartridge), with mean lipid removal efficiency of 94% after freezing-lipid precipitation. Further purification followed by 200mg of Z-Sep and C18 dispersant to eliminate the remaining interferences. Quantification was performed using gas chromatography-mass spectrometry in selective ion monitoring mode. The recovery, precision, and the method detection limits (MDLs) were verified by spiking experiments. All chemicals except triethyl phosphate (TEP) showed satisfactory recoveries in the range of 73-107% and 56-108% in the spiked blanks samples and spiked fish tissue samples, respectively. MDLs for PFRs in the biological samples ranged from 0.004 to 0.059ng/g. The proposed method successfully applied to the determination of PFRs in real fish samples with recoveries of four internal standards varying from 75 to 97%. The results demonstrated that the proposed method is highly effective for analyzing PFRs in fish samples.

In ovo uptake, metabolism, and tissue-specific distribution of chiral PCBs and PBDEs in developing chicken embryos.

Fertilized chicken eggs were injected with environmental doses of 4 chiral polychlorinated biphenyls (PCBs) and 8 polybrominated biphenyl ethers (PBDEs) to investigate their uptake, metabolism in the embryo, and distribution in the neonate chicken. PCB95 uptake was the most efficient (80%) whereas BDE209 was the least (56%). Embryos metabolized approximately 52% of the PCBs absorbed. Though some degree of metabolism in the first 18 days, most of the PCBs and PBDEs was metabolized in the last three days, when BDE85, 99, 153, and 209 decrease by 11-37%. Enantioselective metabolism of the (+) enantiomers of PCB95, 149, and 132 and the (-) enantiomer of PCB91 was observed. The enantioselective reactivity was higher with the two penta-PCBs than the two tetra-PCBs. Liver, exhibited high affinity for high lipophilic chemicals, enrich all chemicals that was deflected in other tissues except for some special chemicals in a given tissues. Lipid composition, time of organ formation, and metabolism contribute to the distribution of chemicals in the neonate chicken. The result of this study will improve our understanding on the fate and potential adverse effects of PCBs and PBDEs in the neonate chicken.