Spatiotemporal distribution and potential risks of antibiotics in coastal water of Beibu Gulf, South China Sea: Livestock and poultry emissions play essential effect.

Antibiotics have been the subject of much attention in recent years due to their widespread use and the potential ecological risks and resistance risks. In this study, we conducted an extensive survey of 19 antibiotics in a wide range of waters of the Beibu Gulf during summer and winter (154 samples). The total concentrations of the 19 antibiotics (Σ19ABs, ng/L) were significantly higher in winter (n.d.-364) than in summer (n.d.-70.1) and were mainly concentrated in areas of seagoing rivers (1.50-364). The primary route for antibiotics entering Beibu Gulf was through riverine input. Precisely, florfenicol (FF) (n.d.-278 ng/L) discharged from livestock and poultry farms upstream of Nanliu River, predominantly in swine farming, constitutes the main pollutant in Beibu Gulf throughout the year. The Nanliu River (988 kg/a) accounts for 85% of the gulf's total annual antibiotic emission flux. Source analysis identified livestock and poultry farming, particularly swine farming, as the primary pollution source, contributing 58% in summer. Risk assessment reveals that algae (0.51 ± 0.56) exhibited relatively high sensitivity to antibiotics, presenting a medium-high risk at specific sites in Nanliu River during winter. Additionally, FF discharged from swine farming demonstrates a certain level of antibiotic resistance risk. Therefore, reinforcing control measures for antibiotic discharges from livestock and poultry farming, especially upstream of Nanliu River, can effectively mitigate antibiotic-related risks in the water bodies of Beibu Gulf.

Coral skeletons reveal the impacts of oil pollution on seawater chemistry in the northern South China Sea.

Oil pollution can release trace metals (TMs) with cumulative toxicity into seawater, harming marine ecosystems in the long term. However, the lack of studies has inhibited our understanding of the effects and mechanisms of oil pollution on TMs in seawater. Hence, we investigated the 10-year monthly variation of TMs in Porites coral skeletons from the northern South China Sea (SCS), complemented by spatial distribution of TMs in seawater, sediments and characterization of TMs in fuel oil. The results of principal component-multivariate linear regression showed that the total contribution of oil pollution as a source to TMs in surface seawater was 77.2%, where the residence time of TMs (Ni, V, Cr, Co, Cu, Mn, Fe, and Mo) released from oil spills in surface seawater was approximately 1.4 months. Due to the geochemical nature of the metals, their seasonal variations are controlled by tropical cyclones (Ni, V, Cr, Co, Cu, Mn, Fe, and Mo), winter monsoons (Pb, Cd, Ba, and Zn) and sea surface temperature (Sr). This study shows that coral skeletons can be used as a new tool to study marine oil pollution. This provides valuable reference data for accurately identifying and quantifying the effects of oil pollution on TMs in seawater from a spatial and temporal perspective.

Interannual variation and sources identification of heavy metals in seawater near shipping lanes: Evidence from a coral record from the northern South China Sea.

Heavy metal pollution is a serious environmental problem in the marine ecosystem. Thereinto, marine transportation activities have gradually become an important source of heavy metals in seawater. However, the lack of studies on the temporal dynamics of seawater heavy metals in marine shipping areas has hindered our understanding of the sources and transport mechanisms of heavy metals in seawater of hectic shipping waters. Therefore, we investigated the interannual resolution variation of heavy metals in Porites lutea skeletons during the past 32 years under the rapid development of the shipping sector near Weizhou Island from the northern South China Sea. Results show that most heavy metal concentrations with higher coefficients of variation (≥100 %) in the Porites coral skeletons were higher than those in the uncontaminated or less anthropogenic waters. The results of principal component analysis and multiple linear regression showed that the interannual variations of Ni, V, Cr, Co, Zn, Cu, Mn, Fe and Mo were mainly impacted by marine oil extraction and oil spills generated by shipping activities, accounting for 51.58 %. The effect of sea surface temperature accounts for 13.44 %, and controls the interannual variations of Ba and Sr. The effect of industrial pollution accounts for 13.27 %, and explains the interannual variations of Cd and Y. The fuel consumption of marine shipping accounted for 8.76 %, explaining the interannual variations of Pb. The total contribution of anthropogenic activities reached 73.61 %. The interannual variation of heavy metals indicates that hectic marine shipping activities are the dominant cause of Ni, V, Pb, Cr, Co, Zn, Cu, Mn, Fe and Mo input to surface seawater around Weizhou Island. This provided valuable data for understanding the temporal dynamics and potential sources of heavy metals in the marine environment by using coral skeletons as a high-resolution recording vehicle.

Occurrence, distribution, source identification, and risk assessment of organophosphate esters in the coastal waters of Beibu Gulf, South China Sea: Impacts of riverine discharge and fishery.

As emerging pollutants, the environmental geochemistry of organophosphate esters (OPEs) in the coastal zone with multiple functional areas are still less recognized. This study investigated spatiotemporal distribution, sources and risks of 11 widely used OPEs in surface waters from seagoing rivers and multiple coastal functional areas of the Beibu Gulf. The results indicated that significantly higher ∑11OPEs (total concentrations of 11 OPEs, ng/L) occurred in summer (34.2-1227) than in winter (20.6-840), as a result of the high emission caused by climate reasons. In general, higher ∑11OPEs occurred in rivers (41.2-1227) than in the coast (34.2-809) in summer, especially in the urban rivers, while in winter, higher ∑11OPEs occurred in the coast (23.4-840 vs 20.6-319 in rivers) because of obviously higher ∑11OPEs in marine fishery areas (99-840). Source identification revealed that fishery activity, especially fishing vessels, and urban rivers were the main sources of OPEs in the Beibu Gulf. For the individual OPE, only tri-n-butyl phosphate (TNBP) may have ecological risks to aquatic organisms in a few sites, but if considering the additive effects, the OPEs mixtures would pose a high risk to algae and low to medium threats to crustaceans and fish.

Natural component geniposide enhances survival rate of crayfish Procambarus clarkii infected with white spot syndrome virus.

White Spot Disease (WSD), caused by white spot syndrome virus (WSSV), is an acute and highly lethal viral disease of shrimp. Currently, there are no commercially available drugs to control WSD. It is urgent and necessary to find anti-WSSV drugs. Natural compounds are an important source of antiviral drug discovery. In this study, the anti-WSSV activity of natural compound geniposide (GP) was investigated in crayfish Procambarus clarkii. Results showed that GP had a concentration-dependent inhibitory effect on WSSV replication in crayfish at 24 h, and highest inhibition was more than 98%. In addition, GP significantly inhibited the expression of WSSV immediate-early gene ie1, early gene DNApol, late gene VP28. The mortality of WSSV-infected crayfish in control groups was 100%, while it reduced by 70.0% when treated with 50 mg/kg GP. Co-incubation, pre-treatment and post-treatment experiments showed that GP could prevent and treat WSSV infection in crayfish by significantly inhibiting WSSV multiplication. Mechanistically, the syntheses of WSSV structural proteins VP19, VP24, VP26 and VP28 were significantly inhibited by GP in S2 cells. Furthermore, GP could also suppress WSSV replication by blocking the expression of antiviral immunity-related factor STAT to reduce ie1 transcription. Moreover, GP possessed anti-inflammatory and anti-oxidative activity in crayfish. Overall, GP has the potential to be developed as a preventive or therapeutic agent against WSSV infection.

Natural component plumbagin as a potential antibacterial agent against Streptococcus agalactiae infection.

Streptococcus agalactiae, also known as Group B Streptococcus (GBS), can infect humans, terrestrial animals and fish. The emergence of bacterial resistance of S. agalactiae to antibiotics leads to an urgent need of exploration of new antimicrobial agents. In the study, the antibacterial activity of natural component plumbagin (PLB) against S. agalactiae was investigated in vitro and in vivo. The results showed that the minimal inhibitory concentration (MIC) of PLB against S. agalactiae was 8 mg/L. The growth curve assay revealed that PLB could inhibit the growth of S. agalactiae. In addition, the time-killing curve showed that S. agalactiae was killed almost completely by 2-fold MIC of PLB within 12 h. Transmission electron microscopy results showed obvious severe morphological destruction and abnormal cells of S. agalactiae after treated with PLB. The pathogenicity of S. agalactiae to zebrafish was significantly decreased after preincubation with PLB for 2 h in vitro, further indicating the bactericidal activity of PLB. Interestingly, PLB could kill S. agalactiae without inducing resistance development. Furthermore, pretreatment and post-treatment assays suggested that PLB also exhibited the antibacterial activity against S. agalactiae infection in vivo by effectively reducing the bacterial load and improving the survival rate of S. agalactiae-infected zebrafish. In summary, PLB had potent antibacterial activity against S. agalactiae in vitro and in vivo, and it could be an excellent antimicrobial candidate to prevent and control S. agalactiae infection.

Coral-inferred historical changes of nickel emissions related to industrial and transportation activities in the Beibu Gulf, northern South China Sea.

As one of the most abundant metals in heavy oils, Ni has suffered so notably increasing impacts from industrial and traffic activities that anthropogenic Ni emissions have altered natural geochemical processes. The coral Ni/Ca has become a reliable proxy for characterizing marine pollution, but this potential has been unexploited for highlighting oil pollution. Here, we utilized a high-resolution record of geochemical parameters (Ni/Ca, δ18O, and δ13C) in a Porites coral of an offshore island in the northern South China Sea to reconstruct of Ni distribution patterns in surface seawater from 1984 to 2015. The coral Ni/Ca ratios exhibit minor fluctuations, except for multiple mutation peaks (0.20 ± 0.42 µmol/mol) during the period from 1984 to 1993. The ratio was low and stable (0.10 ± 0.09 µmol/mol) from 1994 to 2008, and then increased rapidly with significant variations (1.60 ± 4.56 µmol/mol) from 2009 to 2015. The coral Ni/Ca ratios captured all significant Ni discharges, and this demonstrates its potential for recording oil spill episodes. The historical variations in the contributions of Ni indicate that industrial and traffic activities should be responsible for changes in the anthropogenic input. The leaks and consumptions of petroleum likely account for the primary Ni emission sources.

Oxidation of high iron content electroplating sludge in supercritical water: stabilization of zinc and chromium.

The stabilization of heavy metals (zinc and chromium) and the degradation of organic pollutants during supercritical water (SCW) and supercritical water oxidation (SCWO) treatment of electroplating sludge (EPS) with a high iron content were studied. Experiments were performed in a batch reactor at temperatures in the range from 623.15 to 823.15 K with an oxygen coefficient (OE) from 0 to 2.0, a reaction time of 7 min and pressure of 25 MPa to examine the effect of the operation conditions. Chemical oxygen demand (COD) and total organic carbon (TOC) in raw sludge and liquid products under different reaction conditions were detected. The results indicated that more organic pollutant degradation occurred under supercritical conditions than in subcritical water. Additionally, as the temperature and amount of oxidant increased, the organic pollutant removal rate increased. In addition, the Zn and Cr removal efficiency from sludge was more than 98% under all conditions. Temperatures under 773.15 K had a positive effect, whereas the oxygen ratio was more significant than the other factors above 773.15 K. Furthermore, leaching toxicity tests of the heavy metals in solid products were conducted based on the toxicity characteristic leaching procedure (TCLP). All heavy metals showed greatly reduced leaching toxicity due to their stabilization. The Zn in the EPS is more easily converted into a solid product after SCWO treatment; however, Cr is more difficult to leach from the solid product. Oxides of iron, zinc, and chromium were detected by X-ray diffraction and an electron probe microanalyzer, and the yield of the oxides increased with increasing temperature and oxidant amount. Using the obtained data and analysis results, the effect of Fe on the stabilization of Zn and Cr was studied.

Application of enzyme-hydrolyzed cassava dregs as a carbon source in aquaculture.

As a kind of tropical agricultural solid waste, cassava dregs had become a thorny nonpoint source pollution problem. This study investigated the feasibility of applying cassava dregs as a substitute for sucrose in biofloc technology (BFT) systems. Three types of biofloc systems (using three different carbon sources sucrose (BFT1), cassava dregs (BFT2) and enzyme-hydrolyzed cassava dregs (BFT3) respectively), and the control were constructed in this experiment in 200L tanks with a C/N ratio of 20/1. The comparison of the water quality indicators (The total ammonia nitrogen (TAN), nitrite (NO2--N), nitrate (NO3--N), chemical oxygen demand (COD)), biofloc for the above four groups was performed, and the results indicated that BFT3 showed greater potential to the formation of biofloc, which was beneficial for the water quality control. So the shrimp survival rate was the highest and the feed conversion rate was the lowest in BFT3. Besides, the high-throughput sequencing results showed that the relative abundance of heterotrophic bacteria in the top 30 dominant microbial communities in BFT3 was higher than those in BFT1 and BFT2 by 20.70% and 1.19%, respectively, which could decrease TAN to improve the water quality. Overall, the results had proved that the cassava dregs of enzymes hydrolysis could be used as an ideal and cheap carbon source in BFT.

Species-specific profiles and risk assessment of perfluoroalkyl substances in coral reef fishes from the South China Sea.

The contamination profiles of sixteen perfluoroalkyl substances (PFAS) were examined in coral reef fish samples collected from the South China Sea (SCS) where no information about this topic was available in the literature. The results revealed that six PFAS were found in coral reef fish samples from the SCS. Perfluorooctane sulfonate (PFOS) was the most predominant PFAS contaminant detected in most of the samples, with the highest concentration value of 27.05 ng/g wet weight (ww) observed in Cephalopholis urodelus. Perfluoroundecanoic acid (PFUnDA) and Perfluorotridecanoic acid (PFTrDA) were the second and third dominant PFAS, respectively. Mean PFOS concentrations in muscle of seven coral reef fish varied from 0.29 ng/g ww in Lethrinus olivaceus to 10.78 ng/g ww in Cephalopholis urodelus. No significant linear relationship was observed between PFOS levels and coral reef fish traits (length, weight) collected in this region. Average daily intake of PFOS for the seven coral reef fishes ranged from 0.79 ng/kg/d for Lethrinus olivaceus to 29.53 ng/kg/d for Cephalopholis urodelus. The hazard ratio (HR) values for human consumption of PFOS-contaminated coral reef fishes ranged from 0.04 to 1.48, with Cephalopholis urodelus having the highest HR value of 1.18 (higher than 1) among the species, indicating frequent consumption of Cephalopholis urodelus might pose potential health risk to local population. The present work have provided the first hand data of PFAS in coral reef fishes in the SCS and indirectly demonstrated the existence of low level PFAS pollution in the SCS in China.

Occurrence, sources and transport of antibiotics in the surface water of coral reef regions in the South China Sea: Potential risk to coral growth.

Laboratory research has indicated that antibiotics had negative effects on coral growth by disturbing natural microbiota; however, no field studies have reported antibiotic contamination levels and their influence on coral growth in natural coral reef regions (CRRs). This study investigated antibiotic occurrence and sources in the surface water from CRRs that have suffered from rapid coral degradation and evaluated their risk to coral growth. These regions are in the South China Sea, including four coastal and two offshore CRRs. The results show that 13 antibiotics were detected in the coastal CRRs with concentrations ranging from 10-2-100 ng L-1, while 5 antibiotics occurred in offshore CRRs (300-950 km from the mainland), with concentrations ranging from 10-2 to 10-1 ng L-1. Their concentrations decreased gradually from the coast to offshore in the transport process. However, Yongxing Island, which is approximately 300 km from the mainland, was an exception with relatively higher concentrations than the surrounding reefs because of the ever-increasing human activity on the island. The presence of anthropogenic contaminants antibiotics in CRRs may be a potential risk to coral growth.

Enhanced heterogeneous photo-Fenton process modified by magnetite and EDDS: BPA degradation.

In this research, magnetite and ethylenediamine-N,N'-disuccinic acid (EDDS) are used in a heterogeneous photo-Fenton system in order to find a new way to remove organic contaminants from water. Influence of different parameters including magnetite dosage, EDDS concentration, H2O2 concentration, and pH value were evaluated. The effect of different radical species including HO· and HO2·/O2·- was investigated by addition of different scavengers into the system. The addition of EDDS improved the heterogeneous photo-Fenton degradation of bisphenol A (BPA) through the formation of photochemically efficient Fe-EDDS complex. This effect is dependent on the H2O2 and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O2·- to generate Fe(II) from Fe(III) species reduction. GC-MS analysis suggested that the cleavage of the two benzene rings is the first degradation step followed by oxidation leading to the formation of the benzene derivatives. Then, the benzene ring was opened due to the attack of HO· radicals producing short-chain organic compounds of low molecular weight like glycerol and ethylene glycol. These findings regarding the capability of EDDS/magnetite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.

Construction of 1D SnO2-coated ZnO nanowire heterojunction for their improved n-butylamine sensing performances.

One-dimensional (1D) SnO2-coated ZnO nanowire (SnO2/ZnO NW) N-N heterojunctions were successfully constructed by an effective solvothermal treatment followed with calcination at 400 °C. The obtained samples were characterized by means of XRD, SEM, TEM, Scanning TEM coupled with EDS and XPS analysis, which confirmed that the outer layers of N-type SnO2 nanoparticles (avg. 4 nm) were uniformly distributed onto our pre-synthesized n-type ZnO nanowire supports (diameter 80~100 nm, length 12~16 µm). Comparisons of the gas sensing performances among pure SnO2, pure ZnO NW and the as-fabricated SnO2/ZnO NW heterojunctions revealed that after modification, SnO2/ZnO NW based sensor exhibited remarkably improved response, fast response and recovery speeds, good selectivity and excellent reproducibility to n-butylamine gas, indicating it can be used as promising candidates for high-performance organic amine sensors. The enhanced gas-sensing behavior should be attributed to the unique 1D wire-like morphology of ZnO support, the small size effect of SnO2 nanoparticles, and the semiconductor depletion layer model induced by the strong interfacial interaction between SnO2 and ZnO of the heterojunctions. The as-prepared SnO2/ZnO NW heterojunctions may also supply other novel applications in the fields like photocatalysis, lithium-ion batteries, waste water purification, and so on.

Seasonal characteristics and current sources of OCPs and PCBs and enantiomeric signatures of chiral OCPs in the atmosphere of Vietnam.

Passive air samplers (PAS) were deployed concurrently at 15 locations (nine urban sites and six rural sites) in Vietnam and exposed for approximately 6 weeks from June 26, 2012 to August 26, 2012 and from December 8, 2012 to February 8, 2013. The concentration, composition and enantiomeric signatures of the target compound and Air Mass Backward Trajectories of the 15 sampling sites are presented and discussed in this study. Relatively clean air mass from ocean and similar concentrations and composition of POPs between the south and north of Vietnam indicate that local emissions is most likely the major source of POPs in Vietnam. Technical DDT and technical HCH were widely used in Vietnam and corresponding quantitative data suggests the sporadic use. The preferential degradation of (+)-α-HCH was found in all sampling sites, which could be a regional characteristic of Vietnam. High trans-/cis-chlordane (TC/CC) ratios indicate the current use of technical chlordane for termite control. PCA estimated that main source of PCBs present in the atmosphere of Vietnam was uncontrolled discarded e-waste.