Spatiotemporal variations of retinoic acids and their metabolites in the marine environment of Hong Kong.

Excessive intake of retinoic acids (RAs) and the oxidative metabolites, 4-oxo-RAs, can lead to abnormal morphological development in animals. This study investigated spatiotemporal variations of concentrations and compositions of these compounds in Hong Kong's seawater and during algal blooms. Total concentrations of the studied compounds in seawater were up to 0.790 and 0.427 ng/L in dry and wet seasons, respectively, though no significant seasonal variation was observed. Spatially, the Deep Bay Water Control Zone was the most enriched area with the studied compounds owing to its semi-enclosed nature and influence from the Pearl River discharge. During algal blooms, the studied compounds were detected up to 4.74 ng/L. Based on calculated risk quotients, the ecological risk of the studied compounds to Hong Kong's marine ecosystems was low. Nevertheless, the occurrence and distribution of these chemicals in the marine environment should be closely monitored where algal blooms frequently occur.

Concentration-response of six marine species to all-trans-retinoic acid and its ecological risk to the marine environment.

Being a class of vitamin A's main derivatives, retinoic acids (RAs) are important to animals' growth and development. Previous studies demonstrated that exposure of excessive amounts of RAs would lead to malformation and abnormal development in aquatic animals such as amphibians and fishes. Currently, there are only limited toxicity data of RAs available for freshwater species, while those for marine species are seriously lacking. This study aimed to fill such data gap by conducting toxicity tests on six marine species (i.e., one microalga, four invertebrates and one fish) towards the exposure to all-trans-RA (at-RA), which is the most widely distributed RA in the environment. Results showed that the embryo of medaka fish Oryzias melastigma was the most sensitive towards the exposure of at-RA while the gastropod Monodonta labio was the least sensitive. A species sensitivity distribution (SSD) was constructed based on the experimental results generated from the present study. An interim marine-specific predicted no-effect concentration (PNEC) of at-RA was derived at 2300 ng/L. By computing the hazard quotients using the interim marine-specific PNEC and available measured and predicted concentrations of RAs, we found the current levels of RAs posed no immediate risks to the marine environment of Hong Kong. The interim marine-specific PNEC was more than 500-fold of freshwater-specific PNEC (i.e., 3.93 ng/L), indicating that marine species were generally less sensitive than their freshwater counterparts towards RAs. This was the first study to document the concentration-response of various marine species towards at-RA exposure and construct the marine-specific SSD for assessing the ecological risk of at-RA towards the marine environment. Since various forms of RAs and their metabolites often coexist in aquatic environments, further studies should investigate their combined toxicity to an array of marine species of different trophic levels with consideration of chronic exposure scenarios.

Occurrence of retinoic acids and their metabolites in sewage and their removal efficiencies by chemically enhanced primary treatment and secondary biological treatment.

Sewage treatment plants (STPs) are important in densely populated megacities like Hong Kong to control the release of harmful pollutants from households and industries into the receiving water bodies and maintain water quality for supporting various beneficial uses. This study investigated the occurrence of the teratogenic retinoic acids (RAs) and their oxidative metabolites in sewage and sludge of six selected STPs that treat about 87% of all sewage in Hong Kong annually, and compared the removal efficiencies of these compounds from sewage between two major sewage treatment processes, i.e., chemically enhanced primary treatment (CEPT) and secondary (biological) treatment. The total concentrations of the studied RAs in influent, effluent and sludge from the six selected STPs were found between 21.5 and 33.1 ng/L, 12.0-20.4 ng/L, and 4.33-7.02 ng/g dry weight, respectively. The compounds were dominated by all-trans-RA and 13-cis-RA, together accounting for 46.9-65.6%, 38.4-56.7%, and 62.8-82.8% of the total RAs in influent, effluent and sludge, respectively. The studied RAs could not be satisfactorily removed by both treatment processes with removal efficiencies ranging from 25.4% to 47.4% only, without significant difference in their removal between CEPT and secondary treatment. Based on the calculated hazard quotients of all-trans-RA equivalents (0.248-0.521), the treated effluents from all the six STPs exhibited medium ecological risks to the receiving coastal environment. Therefore, continuous monitoring of these compounds and enhancement of treatment technologies of STPs shall be considered in the future to improve the removal efficiencies of these compounds.

Current understanding of potential ecological risks of retinoic acids and their metabolites in aquatic environments.

In animals, retinoic acids (RAs), one of the main derivatives of vitamin A, are crucial for a variety of physiological processes. RAs, including all-trans-RA, 9-cis-RA, 13-cis-RA, and their corresponding metabolites (i.e., all-trans-4-oxo-RA, 9-cis-4-oxo-RA and 13-cis-4-oxo-RA) can be excreted through urination from humans and animals. Sewage treatment plants (STPs) are a significant source of RAs and 4-oxo-RAs into aquatic environments. RAs and 4-oxo-RAs can be identified and quantified by use of liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). RAs and 4-oxo-RAs have been reported in various environmental matrices including rivers, lakes, reservoirs and coastal marine environments as well as in sewage effluents discharged from STPs. Greater concentrations of RAs and 4-oxo-RAs have been observed during blooms of cyanobacteria and microalgae, suggesting that cyanobacteria and microalgae are natural sources of RAs and 4-oxo-RAs in aquatic environments. These potential sources of RAs and 4-oxo-RAs raise concerns about their concentrations and risks in aquatic environments because excessive intake of these chemicals can result in abnormal morphological development in animals. Teratogenic effects were observed in amphibians, fish embryos, gastropods, mammals and birds when exposed to RAs. This review summarizes sources, concentrations, adverse effects and ecological risks of RAs and 4-oxo-RAs in aquatic environments. An interim, predicted no-effect concentration (PNEC) of RAs (in terms of at-RA) for freshwater environments was determined to be 3.93 ng/L at-RA equivalents. Based on limited data on concentrations of RAs in freshwater ecosystems, their hazard quotients were found to range from zero to 16.41, depending on the environmental conditions of receiving waters. Ecological risks of RAs in marine environments are yet to be explored due to the paucity of data related to both their concentrations in marine environment and toxic potencies to marine species. This review updates current knowledge of RAs and 4-oxo-RAs in aquatic environments and calls for more studies on their concentrations and fate in aquatic environments, especially estuarine and coastal marine environments with a view to enabling a comprehensive assessment of their ecological risks around the globe.

Accidental Spill of Palm Stearin Poses Relatively Short-Term Ecological Risks to a Tropical Coastal Marine Ecosystem.

In early August 2017, a serious palm stearin pollution accident occurred in the Pearl River Estuary, South China. While there were already several palm oil related spills around the world, the ecological effects and risks of such accidents to coastal marine environments remain largely unknown. In this study, we found that all seawater and sediment samples collected from six coastal sites were heavily contaminated by palm stearin within 1 week of the accident, and their levels significantly decreased to preaccident levels after four months. Waterborne exposure to palm stearin resulted in growth inhibition to four microalgal species (range of EC50: 9.9-212.6 mg/L) and acute mortality to four invertebrate species (range of LC50: 4.6-409.3 mg/L), while adverse chronic effects of palm stearin on the survival, development, and fecundity of Tigriopus japonicus and on the growth of Oryzias melastigma were observed. On the basis of these results, its interim-predicted no effect concentration was determined as 0.141 mg/L. The hazard quotient of palm stearin greatly exceeded 1 at all sites in August 2017 but returned to <1 at four sites and <2 at the other two sites in November 2017, indicating that its ecological risk was relatively transient and short-term.