[Occurrence and Risk Assessment of Microplastics in the Coastal Seawater of Guangdong Province].

Microplastics （MPs） are ubiquitous in the marine environment and have become an emerging pollutant that is attracting great attention. To reveal the pollution characteristics of MPs in surface seawater of coastal waters in Guangdong Province, nine bays （estuaries） were selected from Jiangmen to Shantou. The distribution and compositional characteristics of MPs were investigated through field sampling, oxidation digestion, and visual and compositional identification, and their potential sources were analyzed. The ecological risks were assessed by combining the pollution load index and the polymer risk index. The results showed that MPs were detected in all 30 surface seawater samples from the coastal waters of Guangdong Province, with an abundance range of 70-920 n·m-3 and an average abundance of （295.3 ±175.3） n·m-3. The highest MPs abundance was found in the Pearl River estuary, and the lowest abundance was found in Shenquan bay. The distribution patterns were mainly influenced by human activities and ocean currents. The dominant polymer types included polypropylene （31.2%）, phenol resin （16.0%）, polyethylene terephthalate （15.3%）, and polyethylene （10.9%）. The main shape, color, and size categories of MPs were fiber （57.5%）, transparent （72.0%）, and 0.5-1 mm （32.8%）, respectively. The possible sources of MPs mainly included aquaculture, fishing, navigation, tourism, municipal sewage discharge, and ocean current transportation. The model assessment results showed that the pollution load risk of MPs was relatively low, but the polymer risk was at a medium-high level. This study provides a data basis for the action plan of plastic pollution control in Guangdong Province and supports the prevention and control of marine MPs pollution.

Preparation and Characterization of a Novel Morphosis of Dextran and Its Derivatization with Polyethyleneimine.

Dextran, a variant of α-glucan with a significant proportion of α-(1,6) bonds, exhibits remarkable solubility in water. Nonetheless, the precipitation of dextran has been observed in injection vials during storage. The present study aimed to establish a technique for generating insoluble dextran and analyze its structural properties. Additionally, the potential for positively ionizing IS-dextran with polyethyleneimine was explored, with the ultimate objective of utilizing IS-dextran-PEI as a promising support for enzyme immobilization. As a result, IS-dextran was obtained by the process of slow evaporation with an average molecular weight of 6555 Da and a yield exceeding 60%. The calculated crystallinity of IS-dextran, which reaches 93.62%, is indicative of its irregular and dense structure, thereby accounting for its water insolubility. Furthermore, positive charge modification of IS-dextran, coupled with the incorporation of epichlorohydrin, resulted in all zeta potentials of IS-dextran-PEIs exceeding 30 mV, making it a promising supporting factor for enzyme immobilization.

Mercury isotope compositions in seawater and marine fish revealed the sources and processes of mercury in the food web within differing marine compartments.

Anthropogenic activities and climate change have significantly increased mercury (Hg) levels in seawater. However, the processes and sources of Hg in differing marine compartments (e.g. estuary, marine continental shelf (MCS) or pelagic area) have not been well studied, which makes it difficult to understand Hg cycling in marine ecosystems. To address this issue, the total Hg (THg) concentration, methylmercury (MeHg) concentration and stable Hg isotopes were determined in seawater and fish samples collected from differing marine compartments of the South China Sea (SCS). The results showed that the estuarine seawater exhibited substantially higher THg and MeHg concentrations than those in the MCS and pelagic seawater. Significantly negative δ202Hg (-1.63‰ ± 0.42‰) in estuarine seawater compared with that in pelagic seawater (-0.58‰ ± 0.08‰) may suggest watershed input and domestic sewage discharge of Hg in the estuarine compartment. The Δ199Hg value in estuarine fish (0.39‰ ± 0.35‰) was obviously lower than that in MCS (1.10‰ ± 0.54‰) and pelagic fish (1.15‰ ± 0.46‰), which showed that relatively little MeHg photodegradation occurred in the estuarine compartment. The Hg isotope binary mixing model based on Δ200Hg revealed that approximately 74% MeHg in pelagic fish is derived from atmospheric Hg(II) deposition, and over 60% MeHg in MCS fish is derived from sediments. MeHg sources for estuarine fish may be highly complex (e.g. sediment or riverine/atmospheric input) and further investigations are warranted to clarify the contribution of each source. Our study showed that Hg stable isotopes in seawater and marine fish can be used to identify the processes and sources of Hg in different marine compartments. This finding is of great relevance to the development of marine Hg food web models and the management of Hg in fish.

Occurrence of microplastics in the seawater and atmosphere of the South China Sea: Pollution patterns and interrelationship.

Microplastic (MP) pollution is a serious global environmental problem, particularly in marine ecosystems. However, the pollution patterns of MPs in the ocean and atmosphere, particularly the sea-air interrelationship, remain unclear. Therefore, the abundance, distribution patterns, and sources of MPs in the seawater and atmosphere of the South China Sea (SCS) were comparatively investigated. The results showed that MPs were prevalent in the SCS with an average abundance of 103.4 ± 98.3 items/m3 in the seawater and 4.62 ± 3.60 items/100 m3 in the atmosphere. The spatial analysis indicated that the pollution patterns of seawater MPs were mainly determined by land-based discharge and sea surface currents, whereas atmospheric MPs were predominantly determined by air parcel trajectory and wind conditions. The highest MP abundance of 490 items/m3 in seawater was found at a station near Vietnam with current vortices. However, the highest MP abundance of 14.6 items/100 m3 in the atmosphere was found in air parcels with low-speed southerly winds from Malaysia. Similar MP compositions (e.g., polyethylene terephthalate, polystyrene, and polyethylene) were observed in the two environmental compartments. Furthermore, similar MP characteristics (e.g., shape, color, and size) in the seawater and atmosphere of the same region suggested a close relationship between the MPs in the two compartments. For this purpose, cluster analysis and calculation of the MP diversity integrated index were performed. The results showed an obvious dispersion between the two compartment clusters and a higher diversity integrated index of MPs in seawater than in the atmosphere, thus implying higher compositional diversity and more complex sources of MPs in seawater relative to the atmosphere. These findings deepen our understanding of MP fate and patterns in the semi-enclosed marginal sea environment and highlight the potential interrelationship of MPs in the air-sea system.

Comparison of Pollution Levels, Biomagnification Capacity, and Risk Assessments of Heavy Metals in Nearshore and Offshore Regions of the South China Sea.

Seawater and fish were collected from nearshore (Pearl River Estuarine, PRE) and offshore (middle of the South China Sea, MSCS) regions of the South China Sea (SCS) to determine the heavy metals (HMs) pollution status and biomagnification characteristics. Results show that Cu in PRE seawater was moderately contaminated. Overall pollution risk of seawater were PRE (3.32) > MSCS (0.56), whereas that of fish was MSCS (0.88) > PRE (0.42). δ13C and δ15N exhibited distinguished characteristics for PRE and MSCS fish, indicating the diverse energy sources, nitrogen sources, and food web structures of nearshore and offshore regions. Cu was biomagnified whereas Pb and Ni were biodiluted in offshore fish. Hg presented significant biomagnification in both of nearshore and offshore fish. Finally, the target hazard quotient of Hg (1.41) in MSCS fish exceeded the standard limit, which was posed by high Hg concentration and consumption rate of offshore fish.

Heavy Metal Pollution and Potential Ecological Risk Assessment in a Typical Mariculture Area in Western Guangdong.

The distribution characteristics, environmental contamination states, and potential ecological risks of chromium (Cr), copper (Cu), arsenic (As), lead (Pb), and cadmium (Cd) in seawater, sediment and breeding feed were studied in a typical mariculture area in western Guangdong of China. Pearson correlation analysis was used to determine metal homology, and the single-factor index, potential ecological risk index, hazard quotient (HQ), and joint probability curve (JPC) were used to evaluate pollution states and ecological risk of metals. Four main statements can be concluded from the results: (1) Pb and Cu showed a similar distribution pattern in the seawater and sediment and their contents in the breeding wastewater exceeded the standard limits in several stations. (2) Cr, Cu, and As have similar sources in the feeds, which may be an important source of metals in water. (3) The risk assessment revealed that the sediment from the studied areas was at a low ecological risk of heavy metal, whereas, water in the pond and outfall was slightly polluted by Pb, and water in the cages and outfall were slightly polluted by Cu. (4) Both the hazard quotient (HQ) and joint probability curve showed the overall risk probabilities (ORPs) in the waters ranked as Cu > Cr > Pb > Cd > As. Although Pb and Cd had HQ values greater than 1, their ORPs were acceptable. This study highlights that multiple evaluation models are more reliable than the single ecological risk assessment for evaluating heavy metal pollution risks in the mariculture area.

Removal and Biodegradation of 17ß-Estradiol and Diethylstilbestrol by the Freshwater Microalgae Raphidocelis subcapitata.

Natural steroidal and synthetic non-steroidal estrogens such as 17ß-estradiol (E2) and diethylstilbestrol (DES) have been found in natural water, which can potentially endanger public health and aquatic ecosystems. The removal and biodegradation of E2 and DES by Raphidocelis subcapitata were studied in bacteria-free cultures exposed to single and mixture treatments at different concentrations for 96 h. The results showed that R. subcapitata exhibited a rapid and strong ability to remove E2 and DES in both single and mixture treatments by biodegradation. At the end of 96 h, the removal percentage of single E2 and DES achieved 82.0%, 80.4%, 74.6% and 89.9%, 73.4%, 54.1% in 0.1, 0.5, and 1.5 mg·L-1, respectively. With the exception of the 0.1 mg·L-1 treatment at 96 h, the removal capacity of E2 was more efficient than that of DES by R. subcapitata. Furthermore, the removal percentage of mixture E2 and DES achieved 88.5%, 82.9%, 84.3% and 87.2%, 71.8%, 51.1% in 0.1, 0.5, and 1.5 mg·L-1, respectively. The removal percentage of mixed E2 was significantly higher than that of the single E2. The presence of DES could accelerate the removal of E2 from the mixture treatments in equal concentrations. In addition, the removal was mainly attributed to the biodegradation or biotransformation process by the microalgae cells rather than simple sorption and accumulation in the cells. The microalgae R. subcapitata demonstrated a high capability for the removal of the E2 and DES indicating future prospects for its application.

Tissue distribution, bioaccumulation characteristics and health risk of antibiotics in cultured fish from a typical aquaculture area.

The negative impacts of residual antibiotics in the environment on ecosystem and human health are big concerns. However, little information is available on the antibiotic bioaccumulation in aquaculture farms. In this study, the bioaccumulative potentials of 21 antibiotics in the plasma, bile, liver and muscle of cultured fish from a typical aquaculture area were systematically investigated. RESULTS: indicated that antibiotic distribution in the cultured fish was mainly influenced by species and specific substances. The mean values of log bioaccumulation factors (Log BAFs) for the detected antibiotics were in the range of 0.43-3.70, 0.36-4.75, -0.31-4.48, and 0.23-4.33 in the fish plasma, bile, liver and muscle tissues, respectively. For grass carp, both ciprofloxacin and enrofloxacin showed high transportability from the plasma to the muscle and liver. The correlations of various antibiotic concentrations between the plasma and the other three tissues indicated that the concentrations of ciprofloxacin and enrofloxacin in the fish tissues could be predicted by their concentrations in the plasma. Based on the calculated hazard quotients, human health risk evaluation of antibiotic exposure by fish consumption indicated that the consumption of these cultured fish posed low risks to human health.

Removal and Biodegradation of Nonylphenol by Four Freshwater Microalgae.

The removal and biodegradation of nonylphenol (NP) by four freshwater microalgae, including three green algae (Scendesmus quadriauda, Chlorella vulgaris, and Ankistrodesmus acicularis) and one cyanobacterium (Chroococcus minutus) were studied in bacteria-free cultures exposed to different concentrations of NP for 5 days. All four algal species showed a rapid and high ability to remove NP (including bioaccumulation and biodegradation). Among these species, A. acicularis (Ankistrodesmus acicularis) had the highest NP removal rate (83.77%) at 120 h when exposed to different NP treatments (0.5-2.5 mg·L-1), followed by C. vulgaris (Chlorella vulgaris) (80.80%), S. quadriauda (Scendesmus quadriauda) (70.96%) and C. minutus (Chroococcus minutus) (64.26%). C. vulgaris had the highest NP biodegradation percentage (68.80%) at 120 h, followed by A. acicularis (65.63%), S. quadriauda (63.10%); and C. minutus (34.91%). The extracellular NP contents were lower than the intracellular NP contents in all tested algae. The ratio of the extracellular NP content and the intracellular NP content ranged from 0.04 to 0.85. Therefore, the removal of NP from the medium was mainly due to the algal degradation. These results indicate that A. acicularis and C. vulgaris are more tolerant to NP and could be used for treatment of NP contaminated aqueous systems effectively by bioremoval and biodegradation.

Occurrence, source analysis and risk assessment of androgens, glucocorticoids and progestagens in the Hailing Bay region, South China Sea.

The occurrence and spatial distribution of 40 steroids in the environmental matrices of the Hailing Bay region, South China Sea, were investigated by rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS). Seventeen, 14 and 11 of 40 steroids were detected with the concentrations ranging from 0.04 (testosterone) to 40.00 ng/L (prednisolone), 1.33 (4-hydroxy-androst-4-ene-17-dione) to 1855 ng/L (androsta-1,4-diene-3,17-dione) and <0.19 (androsta-1,4-diene-3,17-dione) to 2.37 ng/g (progesterone) in the seawater, the municipal sewage discharged effluent and the sediment samples, respectively. The concentrations and risk quotients (RQs) of the steroids detected in the water samples decreased in the order of municipal sewage discharge site>wharves~aquaculture zones~tourism areas>offshore areas. The distribution of steroids in the marine environment was significantly correlated with the levels of chemical oxygen demand (COD) and ammonium nitrogen (NH4-N). Source analysis indicated that untreated municipal sewage was the main source of steroids in the marine environment. Furthermore, progesterone was found to be a reliable chemical indicator to surrogate different steroids in both the water and sediment phases based on the correlation analysis.

Antibiotics in the coastal environment of the Hailing Bay region, South China Sea: Spatial distribution, source analysis and ecological risks.

In this study, the occurrence and spatial distribution of 38 antibiotics in surface water and sediment samples of the Hailing Bay region, South China Sea, were investigated. Twenty-one, 16 and 15 of 38 antibiotics were detected with the concentrations ranging from <0.08 (clarithromycin) to 15,163ng/L (oxytetracycline), 2.12 (methacycline) to 1318ng/L (erythromycin-H2O), <1.95 (ciprofloxacin) to 184ng/g (chlortetracycline) in the seawater, discharged effluent and sediment samples, respectively. The concentrations of antibiotics in the water phase were correlated positively with chemical oxygen demand and nitrate. The source analysis indicated that untreated domestic sewage was the primary source of antibiotics in the study region. Fluoroquinolones showed strong sorption capacity onto sediments due to their high pseudo-partitioning coefficients. Risk assessment indicated that oxytetracycline, norfloxacin and erythromycin-H2O posed high risks to aquatic organisms.

Ecotoxicity of two organophosphate pesticides chlorpyrifos and dichlorvos on non-targeting cyanobacteria Microcystis wesenbergii.

Organophosphate pesticides (OPs), as a replacement for the organochlorine pesticides, are generally considered non-toxic to plants and algae. Chlorpyrifos and dichlorvos are two OPs used for pest control all over the world. In this study, the dose-response of cyanobacteria Microcystis wesenbergii on OPs exposure and the stimulating effect of OPs with and without phosphorus source were investigated. The results showed that high concentrations of chlorpyrifos and dichlorvos caused significant decrease of chlorophyll a content. The median inhibitory concentrations (EC50) of chlorpyrifos and dichlorvos at 96 h were 15.40 and 261.16 µmol L(-1), respectively. Growth of M. wesenbergii under low concentration of OPs (ranged from 1/10,000 to 1/20 EC50), was increased by 35.85 % (chlorpyrifos) and 41.83 % (dichlorvos) at 120 h, respectively. Correspondingly, the highest enhancement on the maximum quantum yield (F v/F m) was 4.20 % (24 h) and 9.70 % (48 h), respectively. Chlorophyll fluorescence kinetics, known as O-J-I-P transients, showed significant enhancements in the O-J, J-I, and I-P transients under low concentrations of dichlorvos at 144 h, while enhancements of chlorophyll fluorescence kinetics induced by low concentrations of chlorpyrifos were only observed in the J-I transient at 144 h. Significant decreases of chlorophyll content, F v/F m and O-J-I-P transients with OPs as sole phosphorus source were found when they were compared with inorganic phosphate treatments. The results demonstrated an evidently hormetic dose-response of M. wesenbergii to both chlorpyrifos and dichlorvos, where high dose (far beyond environmental concentrations) exposure caused growth inhibition and low dose exposure induced enhancement on physiological processes. The stimulating effect of two OPs on growth of M. wesenbergii was negligible under phosphate limitation.

Antibiotics in typical marine aquaculture farms surrounding Hailing Island, South China: occurrence, bioaccumulation and human dietary exposure.

The occurrence, bioaccumulation, and human dietary exposure via seafood consumption of 37 antibiotics in six typical marine aquaculture farms surrounding Hailing Island, South China were investigated in this study. Sulfamethoxazole, salinomycin and trimethoprim were widely detected in the water samples (0.4-36.9 ng/L), while oxytetracycline was the predominant antibiotic in the water samples of shrimp larvae pond. Enrofloxacin was widely detected in the feed samples (16.6-31.8 ng/g) and erythromycin-H2O was the most frequently detected antibiotic in the sediment samples (0.8-4.8 ng/g). Erythromycin-H2O was the dominant antibiotic in the adult Fenneropenaeus penicillatus with concentrations ranging from 2498 to 15,090 ng/g. In addition, trimethoprim was found to be bioaccumulative in young Lutjanus russelli with a median bioaccumulation factor of 6488 L/kg. Based on daily intake estimation, the erythromycin-H2O in adult F. penicillatus presented a potential risk to human safety.

Steroids in marine aquaculture farms surrounding Hailing Island, South China: occurrence, bioconcentration, and human dietary exposure.

The occurrence, bioconcentration, and human dietary exposure via seafood consumption of 24 steroids were investigated by rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS) in six typical marine aquaculture farms surrounding Hailing Island, South China. Ten, 9, 10, 15 of 24 steroids were detected at concentrations ranging from <0.1 (testosterone) to 40 ng/L (prednisolone), from 0.1 (4-androstene-3,17-dione) to 2.4 ng/g (progesterone), from 0.3 ng/g (testosterone) to 21.4 ng/g (epi-androsterone), and from <0.1 (testosterone) to 560 ng/g (cortisol) (wet weight) in the water, sediment, feed and biota samples, respectively. Synthetic steroids (androsta-1,4-diene-3,17-dione, 17α-boldenone, 17ß-boldenone, 17ß-trenbolone, prednisolone, norgestrel) were detected in the feed samples, clearly demonstrating the illegal use of steroids in the feed. The field bioconcentration factors (BCFs) of steroids calculated in different aquatic organisms ranged from 93.8 to 4000. The estimated daily intakes (EDIs) of androgens, glucocorticoids, and progestagens via consumption of seafood (i.e., shrimps, crabs, mollusks, and fish) for different age groups were in the range of 33.4-134, 2061-8566, and 40.4-155 ng/d for children (2-5 years), youth (6-18 years), and adults (>18 years), respectively. Even though no significant risk from dietary exposure arises from individual steroid, elevated risk to humans can result from the occurrence of multiple steroids in the seafood raised in the aquaculture farms, especially for the sensitive populations, such as pregnant women and children.

Brominated flame retardants in mangrove sediments of the Pearl River Estuary, South China: spatial distribution, temporal trend and mass inventory.

Sediments were collected from three mangrove wetlands in the Pearl River Estuary (PRE) of South China to investigate spatial and temporal distributions of polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Concentrations of ΣPBDEs, DBDPE and BTBPE in mangrove sediments of the PRE ranged from 1.25-206, 0.364-34.9, and not detected-0.794 ng g(-1) dry weight, respectively. The highest concentrations of ΣPBDEs, DBDPE and BTBPE were found at the mangrove wetland from Shenzhen, followed by Zhuhai and Guangzhou, showing the dependence on the proximity to urban areas. PBDEs were the predominant brominated flame retardants (BFRs) in mangrove sediments. The concentrations of ΣPBDEs, DBDPE and BTBPE in sediment cores showed an increasing trend from the bottom to top layers, reflecting the increasing usage of these BFRs. The inventories of ΣPBDEs, DBDPE and BTBPE in mangrove sediments were 1962, 245, and 4.10 ng cm(-2), respectively. This is the first study to report the occurrence of DBDPE and BTBPE in mangrove ecosystems.

Effects of glycerol on the fluorescence spectra and chloroplast ultrastructure of Phaeodactylum tricornutum (Bacillariophyta).

Responses of the photosynthetic activity of Phaeodactylum tricornutum (Bacillariophyta) to organic carbon glycerol were investigated. The growth rate, photosynthetic pigments, 77 K fluorescence spectra, and chloroplast ultrastructure of P. tricornutum were examined under photoautotrophic, mixotrophic, and photoheterotrophic conditions. The results showed that the specific growth rate was the fastest under mixotrophic conditions. The cell photosynthetic pigment content and values of Chl a/Chl c were reduced under mixotrophic and photoheterotrophic conditions. The value of carotenoid/Chl a was enhanced under mixotrophic conditions, but was decreased under photoheterotrophic conditions. In comparison with photoautotrophic conditions, the fluorescence emission peaks and fluorescence excitation peaks were not shifted. The relative fluorescence of photosystem (PS) I and PS II and the values of F685/F710 and F685/F738 were decreased. Chloroplast thylakoid pairs were less packed under mixotrophic and photoheterotrophic conditions. There was a strong correlation between degree of chloroplast thylakoid packing and the excitation energy kept in PS II. These results suggested that the PS II activity was reduced by glycerol under mixotrophic conditions, thereby leading to repression of the photosynthetic activity.