Hexabromocyclododecane in sediments from riverine, port, and coastal areas of Kaohsiung, Taiwan: levels, spatial distribution, and potential ecological risk.

The widespread use of hexabromocyclododecane (HBCD), a brominated flame retardant, is a major public health concern because of the toxic, persistent, and bioaccumulative nature of HBCD. However, there is limited information available regarding the distribution and transportation of HBCD in sediments across various environmental settings, spanning from riverine to marine environments in the Kaohsiung area of Taiwan. In this study, we comprehensively investigated the level and distribution of and potential ecological risk posed by HBCD in surface sediments in the Kaohsiung area of Taiwan. In sediment samples from stations on the Love River and Kaohsiung Port area, the concentrations of HBCD ranged from 10.6 to 320.1 µg/kg dry weight (dw) and nondetectable (n.d.) to 58.4 µg/kg dw, respectively. The concentrations of HBCD in sediment collected from the M1, M2, and M3 sites, located in the Cijin coastal area, were 896.2 µg/kg dw, 3.2 µg/kg dw ( 1. The M1 site had the highest risk level (RQ = 5.27). These data suggest that domestic sewage and industrial wastewater discharge pose a potential risk to marine environments. Consequently, timely measures to control HBCD-related risks are required. Our study offers insight into the environmental effects of HBCD contamination of sediment and provides valuable information that can be used to guide environmental policy and safety measures.

Lipid profiling differentiates the effect of ambient microenriched copper on a coral as an advanced tool for biomonitoring.

Copper can be beneficial or harmful to coral at environmentally relevant levels, making environmental monitoring a challenging. Membrane lipids make the cell a dynamic environment according to the circumstances; thus, the lipid profile should be indicative of an environmental/physiological state. To gain more insight into the copper effect on coral health and be a basis of biomonitoring, glycerophosphocholine profiling of coral exposed to microenriched copper levels was conducted in this study. The copper microenrichments resulted in a diacritical effect of decreasing carbonic anhydrase activity, following a supplementation effect, on coral lipid metabolism. Microdifferences in copper levels are critical to determine the coral metabolic state and were therefore included in this study. In addition, an excellent quantitative model correlating the coral lipid variation with the exposed copper levels or the induced physiological effect was obtained to demonstrate its performance for biomonitoring.

Distribution patterns and transportation behavior of alkylphenol polyethoxylate degradation metabolites among river, port area, and coastal water bodies of Kaohsiung City, Taiwan.

In this study, we conducted a comprehensive study of the distribution, transportation behavior and potential ecological risk of alkylphenol polyethoxylates (APnEOs) in the aquatic environments of Kaohsiung City, Taiwan because little information is available regarding the fate of APnEOs in the water bodies of a total environment. At Love River, APnEOs concentrations were much higher at upstream of interception stations L15 (27.33 ± 1.22 µg/L) and L16 (6.31 ± 0.14 µg/L) than at downstream of interception stations L1-L14 (0.69-2.54 µg/L). Additionally, the average ethoxy (EO) chain lengths of APnEOs at L15 and L16 were longer than at L1-L14. These observations were attributed to the sluice between L14 and L15 that intercepts and accumulates untreated sewage from upstream areas and to the infrastructure of the sewage system that prevents domestic sewage from flowing downstream in the river and to the Kaohsiung Port Area. At Kaohsiung Port Area, APnEO concentrations ranging from 0.63 to 6.50 µg/L were measured. The concentration range and average EO chain length of these APnEOs were similar to those of the downstream stretch of the river, which was attributed to the mixing efficiency of the Kaohsiung Port Area and Love River through tidal exchange. At Cijin Coastal Area, APnEO concentrations ranged from 0.14 to 18.77 µg/L. Notably, the APnEO concentration of surface waters was much higher than that of bottom waters. This observation was attributed to the sewage discharged from the ocean outfall buoying up to the surface instead of mixing with surrounding bottom waters. In potential ecological risk, 19 of 39 sampling points exceeded toxic equivalency of 1 µg/L, and approximately 48.7% of the sampling points would exceed the threshold. The result provides insight into the environmental implications of APnEOs contamination in aquatic environments and useful information for environmental policy and ecological risk assessments.

Lipid profiling of coral symbiosomes in response to copper-induced carbon limitation: A metabolic effect of algal symbionts on the host immune status.

Copper micropollutants are known to constrain coral's assimilation of carbonate, affecting the carbon available to algal symbionts and thus inducing a light stress. However, little is known regarding the physiological relevance of lipid metabolism in coral symbiotic algae in a carbon-limited state. Membrane lipids exhibit multiple physicochemical properties that are collectively responsible for the dynamic structure of cells depending on the physiological demands of the circumstances. To gain insight into lipid metabolism's importance in this regard, glycerophosphocholine (GPC) profiling of symbiosomes in coral (Seriatopora caliendrum) exposed to environmentally relevant copper levels (2.2-7.5 µg/L) for 4 days was performed in this study. Notably, reducing the number of 22:6-processing GPCs and increasing that of lyso-GPCs likely addressed the demands of metabolizing excess light energy, such as affecting the membrane dynamics to promote mitochondrial uncoupling. The decrease in 22:6-processing GPCs additionally protected cellular membranes from elevated oxidative stress, reducing their susceptibility to peroxidation and offsetting oxidized lipid-induced effects on membrane dynamics. The change in plasmanylcholines specifically localized within the symbiosome membrane also met the membrane requirements for responding to oxidative stress conditions. Moreover, increasing the 20:4-possessing plasmanylcholines and lysoplasmanylcholines and reducing the 22:6-possessing plasmanylcholines likely resulted in an imbalance of the immune reaction, influencing the coral-algae symbiosis given the role of such plasmanylcholines in cell signaling. In summary, carbon limitations induced by copper enrichment lead to a shift in the membrane lipid profile of coral symbiosomes, accommodating themselves to light stress conditions while compromising the symbiosis's stability.

Novel Caryophyllane-Related Sesquiterpenoids with Anti-Inflammatory Activity from Rumphella antipathes (Linnaeus, 1758).

Two previously undescribed caryophyllane-related sesquiterpenoids, antipacids A (1) and B (2), with a novel bicyclo[5.2.0] core skeleton, and known compound clovane-2ß,9α-diol (3), along with rumphellolide L (4), an esterified product of 1 and 3, were isolated from the organic extract of octocoral Rumphella antipathes. Their structures, including the absolute configurations were elucidated by spectroscopic and chemical experiments. In vivo anti-inflammatory activity analysis indicated that antipacid B (2) inhibited the generation of superoxide anions and the release of elastase by human neutrophils, with IC50 values of 11.22 and 23.53 µM, respectively, while rumphellolide L (4) suppressed the release of elastase with an IC50 value of 7.63 µM.

An environmentally friendly strategy for determining organic ultraviolet filters in seawater using liquid-phase microextraction with liquid chromatography-tandem mass spectrometry.

Benzophenone-3, benzophenone-8, and 4-methylbenzylidene camphor are used in sunscreens because they can protect the skin from UV radiation. The widespread use of organic UV filters may mean that they directly or indirectly enter seawater during recreational activities or through sewage discharge. In this study, a simple and efficient method using 1-octanol:isooctane (2:8, v/v) as an extraction solvent and liquid chromatography-electrospray tandem mass spectrometry was developed to measure trace levels of organic UV filters in seawater samples. This proposed method proved to be a highly sensitive, low-cost, and green analytical tool that requires minimal sample preparation. The method was validated and it exhibited favorable performance as well as acceptable accuracy (67 to 115%), precision (2.1 to 7.3%), coefficients of determination (0.9952 < R2 < 0.9987), sensitivity (limits of quantification [3.3 to 5.7 ng L-1]), and an acceptable matrix effect (87 to 99%). This methodology was successfully applied to analyze seawater taken from Kenting National Park located in the Hengchun Peninsula of southern Taiwan. Benzophenone-3 was detected at all sampling sites and at a higher concentration than the other organic UV filters. The highest concentration of benzophenone-3 was 514.6 ng L-1 in a sample collected from Baisha Beach.

Determination of sulfamonomethoxine in tilapia (Oreochromis niloticus × Oreochromis mossambicus) by liquid chromatography-tandem mass spectrometry and its application pharmacokinetics study.

A precise and reliable analytical method to measure trace levels of sulfamonomethoxine (SMM) and N4-acetyl metabolite in tilapia samples using liquid chromatography-tandem mass spectrometry was developed. Optimized chromatographic separation was performed on C18 reversed-phase columns using gradient elution with methanol and 5 mmol/L of an ammonium acetate aqueous solution (adjusted to pH 3.5 using formic acid). This study investigated the pharmacokinetic properties and tissue distribution of SMM and its major metabolite N4-acetyl sulfamonomethoxine (AC-SMM) in tilapia after a single dose of 100 mg kg-1 body weight of orally administered SMM. Blood and tissues were collected between 0.5 and 192 h with 14 total sampling time points. SMM was rapidly absorbed, and extensively distributed in the bile and liver through systemic circulation. Enterohepatic circulation of SMM was observed in the tilapia body. Acetylation percentages were 45% (blood), 90% (liver), 62% (kidney), 98% (bile), and 52% (muscle). High concentrations of AC-SMM accumulated in the tilapia bile. At 192 h, AC-SMM concentration in the bile remained at 4710 µg kg-1. The ke value of AC-SMM (0.015 h-1) in the blood was lower than that of SMM (0.032 h-1). This study demonstrated effective residue monitoring and determined the pharmacokinetic properties of SMM and AC-SMM in tilapia.

Using lipidomic methodology to characterize coral response to herbicide contamination and develop an early biomonitoring model.

The use of omics technologies to profile an organism's systemic response to environmental changes can improve the effectiveness of biomonitoring. In cell physiology, the dynamic characteristics of membranes can be used to identify lipid profiles that detect environmental threats and assess the health problems associated with them. The efficacy of this approach was demonstrated by profiling glycerophosphocholines (GPCs, a major membrane lipid class) in the coral Seriatopora caliendrum after exposure to Irgarol 1051. A quantitative biomonitoring model for this photosystem II herbicide was developed by correlating variations in coral lipid profile with herbicide exposure levels and degree of photoinhibition. After 4 days of exposure, the predominant changes correlated with photoinhibition were an increase in lyso-GPCs and saturated GPCs and a decrease in phosphatidylcholines with unsaturated C18 chains or a polyunsaturated C22 chain. A time-course experiment showed that most of these lipid changes occurred opposite to the initial response and that the persistent changes can be attributed to photosynthetic shortages and the membrane accommodation of photoinhibition-induced oxidative conditions. These changes can help predict risk factors leading to coral bleaching. In this study, the application of a lipidomic methodology to characterize the adaptation of coral to ambient contamination serves as a basis for advancing environmental monitoring and assessment.

Lipidomics as a diagnostic tool of the metabolic and physiological state of managed whales: A correlation study of systemic metabolism.

Integrating multifactor blood analysis is a key step toward a precise diagnosis of the health status of marine mammals. Variations in the circulating lipid profile reflect changes in the metabolism and physiology of an individual. To demonstrate the practicability of lipid profiling for physiological assessment, the phosphorylcholine-containing lipids in the plasma of long-term managed beluga whales (Delphinapterus leucas) were profiled using a lipidomics methodology. Using a multivariate analysis, the mean corpuscular volume, cholesterol, potassium, and γ-glutamyltranspeptidase levels were well modeled with the lipid profile of the female whales. In the models, the correlated lipids provided information about blood parameter-related metabolism and physiological regulation, in particular relating to cholesterol and inflammation. In the males, the levels of cholesterol, triglycerides, blood urea nitrogen, creatinine, plasma iron, and segmented neutrophil were well modeled with the lipid profile. In addition to providing information about the related metabolism and regulation, through a cross-linked analysis of the blood parameters, the correlated lipids indicated a parallel regulation involved in the energy metabolism of the male whales. Lipidomics as a method for revealing the context of physiological change shows practical potential for the health care of managed whales.

Survey of selected personal care products in surface water of coral reefs in Kenting National Park, Taiwan.

Kenting National Park (KNP) located in the Hengchun Peninsula in southern Taiwan is a popular tourist spot, annually attracting millions of visitors, who engage in water sport and amusement activities. In this region, sewage is directly discharged into the marine environment. In this study, the concentrations of five organic UV filters [benzophenone (BP), 2,4-dihydroxy benzophenone (BP-1), 2-hydroxy-4-methoxy benzophenone (BP-3), 2,2'-dihydroxy-4-methoxy benzophenone (BP-8), and 4-methylbenzylidene camphor], five preservatives [methylparaben (MeP), ethylparaben, propylparaben (PrP), butylparaben, and benzylparaben], one disinfectant [triclosan (TCS)], and twenty-four detergent derivatives [nonylphenol (NP), nonylphenol ethoxylates (NP2EO-NP12EO), octylphenol (OP) and octylphenol ethoxylates OP2EO-OP12EO] were detected in seawater and river water samples collected from eight beaches in KNP and two major river estuaries in the Hengchun Peninsula. BP-3 was detected at all sampling sites and was higher in concentration than the other organic UV filters. The highest concentration of BP-3 was 1233 ng/L collected from Wanlitong Beach. MeP and PrP were the main preservative components in seawater. The highest total content of preservative agents was 164 ng/L collected from Houwan Beach. Moreover, NP was detected at all sampling sites, with the highest concentration found at Sail Rock Beach (26.5 ng/L). The highest concentration of OP was 113 ng/L in the Boli River estuary. The widespread use of personal care products (PCPs) has resulted in the release of their major ingredients into natural ecosystems. Therefore, the potential long-term effects of multi-PCPs at low concentration exposure to on the coral reef ecosystem in KNP must be considered and monitored.

Persistent organic pollutants in Antarctic notothenioid fish and invertebrates associated with trophic levels.

Notothenioid fish and invertebrate samples from Antarctica were collected in the austral summer of 2009, and analyzed for persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), and polybrominated diphenylethers (PBDEs), as well as δ13C and δ15N stable isotopes for trophic level determination. In this study, the POP levels in the Antarctic biota samples were found to be ranked in the following order: OCPs > PAHs >> PBDEs. The POP levels in notothenioid fish and krill correlate to trophic levels; however, the POP concentrations in intertidal benthic invertebrates are higher than in notothenioid fish implying that specific biogeochemical factors may affect bioaccumulation in the Antarctica ecosystem. Biomagnification of POPs may have a smaller role than bioconcentration in Antarctica environment. In addition to the source, transport, exposure, and absorption for each group of POPs in the short food chain in Antarctica, the biological variation among species, interaction habitats, diet and metabolism are also factors for future studies on contaminant bioaccumulation.

Modeling the effects of Irgarol 1051 on coral using lipidomic methodology for environmental monitoring and assessment.

Coral is commonly selected as a bioindicator of detecting a variety of adverse factors such as photosystem II herbicide Irgarol 1051, through measuring pan-type biomarkers. To improve the effectiveness of biomonitoring, omic technologies have recently been applied to model the systemic changes in an organism. Membrane lipids create a dynamic cell structure based on the physiological state, which offers a distinct lipid profile to specifically detect environmental threats and assess the associated health risk. To demonstrate the potential of a lipidomic methodology for biomonitoring, the glycerophosphocholine (GPC) profiles of the coral Seriatopora caliendrum were observed during 3 days of Irgarol (0.1-2.0 µg/L) exposure. The lipid profile variations were modeled based on the Irgarol dose and the coral photoinhibition levels to develop an excellent quantitative model. The predominant changes correlated with the photoinhibition, decreasing the lyso-GPCs and GPCs with lower unsaturated chains and increasing GPCs with highly polyunsaturated chains, can be related to the consequence of blocking the photosynthetic electron flow based on the associated physiological roles. Other dose-specific lipid changes led to the partial exchange of PC(O-16:0/20:5) for PC(16,0/20:5) as a first-line response to counteract the membrane opening caused by Irgarol. Increased levels of the GPCs with 20:4 or 22:6 chains, which can promote mitochondrial functionality, confirmed an elevated respiration level in the coral exposed to Irgarol levels of >0.5 µg/L. Notably, plasmanylcholines with 20:4 or 22:6 chains and phosphatidylcholines with 22:6 or 22:5 chains, which can alter their membrane material properties to mitigate organelle pre-swelling and swelling in different ways, formed in the coral exposed to the 0.5 and 2.0 µg/L Irgarol levels. Such coral adaptations further predict the health risks associated with altered physiological conditions. In this study, the lipidomic methodology is demonstrated as a potential tool for environmental monitoring and assessment.

Membrane lipid profiles of coral responded to zinc oxide nanoparticle-induced perturbations on the cellular membrane.

Zinc oxide nanoparticles (nZnOs) released from popular sunscreens used during marine recreation apparently endanger corals; however, the known biological effects are very limited. Membrane lipids constitute the basic structural element to create cell a dynamic structure according to the circumstance. Nano-specific effects have been shown to mechanically perturb the physical state of the lipid membrane, and the cells accommodating the actions of nZnOs can be involved in the alteration of the membrane lipid composition. To gain insight into the effects of nanoparticles on coral, glycerophosphocholine (GPC) profiling of the coral Seriatopora caliendrum exposed to nZnOs was performed in this study. Increasing lyso-GPCs, docosapentaenoic acid-possessing GPCs and docosahexaenoic acid-possessing GPCs and decreasing arachidonic acid-possessing GPCs were the predominant changes responded to nZnO exposure in the coral. A backfilling of polyunsaturated plasmanylcholines was observed in the coral exposed to nZnO levels over a threshold. These changes can be logically interpreted as an accommodation to nZnOs-induced mechanical disturbances in the cellular membrane based on the biophysical properties of the lipids. Moreover, the coral demonstrated a difference in the changes in lipid profiles between intra-colonial functionally differentiated polyps, indicating an initial membrane composition-dependent response. Based on the physicochemical properties and physiological functions of these changed lipids, some chronic biological effects can be incubated once the coral receives long-term exposure to nZnOs.

Intra-Colonial Functional Differentiation-Related Modulation of the Cellular Membrane in a Pocilloporid Coral Seriatopora caliendrum.

Scleractinian corals have displayed phenotypic gradients of polyps within a single genotypic colony, and this has profound implications for their biology. The intrinsic polymorphism of membrane lipids and the molecular interactions involved allow cells to dynamically organize their membranes to have physicochemical properties appropriate for their physiological requirements. To gain insight into the accommodation of the cellular membrane during ontogenetic shifts, intra-colony differences in the glycerophosphocholine profiling of a pocilloporid coral, Seriatopora caliendrum, were characterized using a previously validated method. Specifically, several major polyunsaturated phosphatidylcholines showed higher levels in the distal tissue of coral branches. In contrast, the corresponding molecules with 1-2-degree less unsaturation and plasmanylcholines were expressed more highly in the proximal tissue. The lipid profiles of these two colonial positions also contrasted sharply with regard to the saturated, monounsaturated, and lyso-glycerophosphocholine ratios. Based on the biochemical and biophysical properties of these lipids, the associated modulation of cellular membrane properties could be related to the physiological requirements, including coral growth and aging, of the functionally differentiated polyps. In this study, the metabolic regulation of membrane lipids involved in the functional differentiation of polyps within a S. caliendrum colony was identified.

Natural Caryophyllane Sesquiterpenoids from Rumphella antipathies.

Two new natural caryophyllane-type sesquiterpenoids, 1 and 2, were isolated from the gorgonian coral Rumphella antipathies. Standard spectroscopic techniques were used to determine the structures of caryophyllanes 1 and 2.

Norcembranoidal diterpenes from the cultured-type octocoral Sinularia numerosa.

A known norcembranoidal diterpene, 5-episinuleptolide (1), along with a new analogue, 4α-hydroxy-5-episinuleptolide (2), were isolated from a cultured-type soft coral Sinularia numerosa. The structures of 1 and 2 were elucidated on the basis of spectroscopic methods and by comparison of the data with those of the related metabolites. Cytotoxicity of metabolites 1 and 2 against a panel of tumor cells is also described. Compound 2 exhibited moderate cytotoxicity toward CCRF-CEM cells with an IC50 value 4.21 µg/mL. Preliminary SAR (structure activity relationship) information was obtained from these two compounds.

A generic and rapid strategy for determining trace multiresidues of sulfonamides in aquatic products by using an improved QuEChERS method and liquid chromatography-electrospray quadrupole tandem mass spectrometry.

A rapid and efficient multiresidue method that involves using improved QuEChERS method and liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS/MS) was developed to measure trace levels of sulfonamides in fish tissue. This proposed method was proven to be a powerful, highly sensitive, and environmentally friendly analytical tool that requires minimal sample preparation. The typical MS/MS fragmentation patterns of the [M+H](+) were 156 m/z, 108 m/z, and 92 m/z. Separation was performed on HC-C18 columns with a gradient elution by using methanol -5mM ammonium acetate containing formic acid (pH 3.5). This method was validated and exhibited favorable performance as well as acceptable accuracy (80.2-93.5%), precision (3.82-8.71%), sensitivity (limits of detection (LODs) 0.43-1.22 µg kg(-1), limits of quantification (LOQs) 1.27-3.71 µg kg(-1); decision limit (CCα) 1.49-10.9 µg kg(-1), detection capability (CCß) 1.71-11.4 µg kg(-1)), and an acceptable matrix effect (-18.2-18.4%). This methodology has been successfully applied in analyzing various fish tissue from local markets.

Determination of cholesterol and four phytosterols in foods without derivatization by gas chromatography-tandem mass spectrometry.

In this study, a method for determination of cholesterol and four phytosterols by gas chromatography coupled with electron impact ionization mode-tandem mass spectrometry without derivatization in general food was developed. The sample was saponified with 7.5% KOH in methanol. After heating on hot plate and reflux for 60 minutes, the saponified portion was extracted with n-hexane/petroleum ether (50:50, v/v). The extracts were evaporated with rotary evaporator and then redissolved with tetrahydrofuran. The tetrahydrofuran layer was transferred into an injection vial and analyzed by gas chromatography on a 30 m VF-5 column. Limit of quantification was 2 mg/kg. Recoveries of cholesterol and four phytosterols from general food were between 91% and 100%.

Rumphellaoic acid A, a novel sesquiterpenoid from the formosan gorgonian coral Rumphella antipathies.

A novel sesquiterpenoid, rumphellaoic acid A (1), was isolated from the gorgonian coral Rumphella antipathies, and was found to possess a carbon skeleton that was obtained for the first time from a natural sources. The structure of 1 was elucidated by spectroscopic methods and this compound and was found to exert a moderate inhibitory effect on the release of elastase by human neutrophils.

Rumphellols A and B, new caryophyllene sesquiterpenoids from a Formosan gorgonian coral, Rumphella antipathies.

Two new marine-derived caryophyllene-type sesquiterpenoids, rumphellols A and B (1 and 2), were obtained from the gorgonian coral, Rumphella antipathies, collected off the waters of Taiwan. Although caryophyllene-type sesquiterpenes are rarely found in marine organisms, compounds of this type could be principal components of R. antipathies. The structures of new Compounds 1 and 2 were determined by analysis of their spectroscopic data, including 1D and 2D NMR experiments. Caryophyllene 1 and 2 were evaluated in terms of their anti-inflammatory activity by examining their inhibitory effects on the generation of superoxide anions and the release of elastase by human neutrophils.