Higher ecological risks and lower bioremediation potentials identified for emerging OPEs than legacy PCBs in the Beibu Gulf, China.

The production and use of organophosphate esters (OPEs) as substitutes for traditional halogenated flame retardants is increasing, resulting in greater global concern related to their ecological risks to marine environments. In this study, polychlorinated biphenyls (PCBs) and OPEs, representing traditional halogenated and emerging flame retardants, respectively, were studied in multiple environmental matrices in the Beibu Gulf, a typical semi-closed bay in the South China Sea. We investigated the differences in PCB and OPE distributions, sources, risks, and bioremediation potentials. Overall, the concentrations of emerging OPEs were much higher than those of PCBs in both seawater and sediment samples. Sediment samples from the inner bay and bay mouth areas (L sites) accumulated more PCBs, with penta- and hexa-CBs as major homologs. Chlorinated OPEs were prevalent in both seawater and sediment samples from the L sites, whereas tri-phenyl phosphate (TPHP) and tri-n-butyl phosphate (TNBP) were predominant at the outer bay (B sites) sediment samples. Source identification via principal component analysis, land use regression statistics, and δ13C analysis indicate that PCBs were mainly sourced from the atmospheric deposition of sugarcane and waste incineration, whereas sewage inputs, aquaculture, and shipping activity were identified as sources of OPE pollution in the Beibu Gulf. A half-year sediment anaerobic culturing experiment was performed for PCBs and OPEs, and the results only exhibited satisfactory dechlorination for PCBs. However, compared with the low ecological risks of PCBs to marine organisms, OPEs (particularly trichloroethyl phosphate (TCEP) and TPHP) exhibited low to medium threats to algae and crustaceans at most sites. Given their increasing usage, high ecological risks, and low bioremediation potential in enrichment cultures, pollution by emerging OPEs warrants close attention.

Sources and distribution of sedimentary organic matter along the northern Bering and Chukchi Seas.

In this study, lignin-derived phenols were used to determine the sources and distribution of sedimentary organic matter along the northern Bering Sea and Chukchi Sea of the Arctic Ocean. The lignin parameter syringyl/vanillyl (S/V) and cinnamyl/vanillyl (C/V) ratios are used to indicate vegetation sources; and the ratios of vanillic acid/vanillin, (Ad/Al)v and syringic acid/syringaldehyde, (Ad/Al)s are used as indicators of lignin diagenesis. Results showed the predominance of woody gymnosperm signal at the easternmost location in the northern Bering Sea, a mixture of refractory non-woody angiosperm and fresher gymnosperm tissues in the Chukchi Sea, and signal of fresher woody gymnosperm tissues in the northernmost locations in the Chukchi Sea. The lignin materials showed gradual increase in decomposition stage during transport along the northern Bering Sea. Hydrodynamic sorting process, which is the retention of coarser materials nearshore and transportation of finer particles farther offshore, most probably occurred along the east coast of the northern Bering Sea. In Chukchi Sea, the non-woody angiosperm tissues could have originated from the Canadian Arctic and gymnosperm tissues could be from the Russian Arctic side. The fresher materials in the northernmost Chukchi Sea could have been transported here via the ice-rafting process. Detection of fresh lignin materials and the occurrence of lignin decomposition mean that this region could be sensitive to the impact of climate change.

Distribution and sources of microplastics in the Beibu Gulf using in-situ filtration technique.

The Beibu Gulf is a vital link between China and the ASEAN nations, and microplastic contamination is rising due to fast growth, coastal life, fisheries, and mariculture. The abundance, distribution, and source analyses were conducted at 25 sample points for this study. According to this study, the average MPs was 0.25 ± 0.05 items/m3, ranging from 0.01 items/m3 to 0.89 items/m3. Fibers, white, cellulose, and 0.33-1 mm were abundant in shape, color, composition, and size, respectively. Multi-statistics-based source analysis indicated land-based inputs (packing materials, textile materials, fisheries, and mariculture) were dominant in the Beibu Gulf. In this study, we also acknowledged a comprehensive comparison and convenience between plankton pumps and other conventional designs to collect microplastic samples from water. We suggested that using a uniform design could elevate the data quality of microplastics.

The distribution and enrichment of trace elements in surface and core sediments from the Changjiang River Estuary, China: Evidence for anthropogenic inputs and enhanced availability of rare earth elements (REE).

Huge amount of trace metals emitted through manmade activities are carried by the Changjiang River into the East China Sea. Most of them deposit in the Changjiang River Estuary and threaten the regional aquatic environment. In this study, major and trace elements of 34 archive surface sediments and two cores are examined. Sequential extraction procedures were also performed on surface sediments from 12 sites. We found that Tl, Tm, Er show distinct accumulation in surface sediments in the order of Tm > Tl > Er. Particularly, abnormally elevated HREE are observed mainly in those sites near the mouth of the estuary. Most elements exhibit an obvious reduction in the upper 30 cm of core B8, reflecting a decrease of sediment discharge from Changjiang River runoff. The increase of some trace elements recorded in the upper 20 cm of core C3 demonstrates a distinct local anthropogenic input in recent years.

Organic matter degradation in surface sediments of the Changjiang estuary: Evidence from amino acids.

Organic matter degradation is a key component of the processes of carbon preservation and burial in seafloor sediments. The aim of this study was to explore organic matter degradation state within the open-shelf Changjiang Estuary of the East China Sea, using an amino acids-based degradation index (DI) in conjunction with information about organic matter source (marine versus terrestrial), bottom water oxygenation state, and sediment grain size. The relative molar percentages of 17 individual amino acids (characterized using principal component analysis) in surface sediments indicate that organic matter is degraded to varying extents across the estuary seabed. Sediments with DI >0 (relatively labile) were found mostly within a coastal hypoxic area. Sediments of DI less than -1 (relatively refractory) were found near the Changjiang River mouth and the northern and southern parts of the central shelf. We consider DI to be a more reliable indicator of degradation than simple ratios of AAs. DI was inversely correlated with the proportion of terrestrial organic material (Ft) in the sediments, indicating that relatively fresh/labile organic matter was generally associated with marine sources. DI was significantly correlated with Ft and bottom water apparent oxygen utilization (AOUbot) together. The parameter DI and the (labile) amino acid tyrosine were highest in hypoxic areas, suggesting the presence of relatively fresh organic matter, probably due to a combination of marine-source inputs and better preservation of organic matter in the silt and clay sediments of these areas (as compared to sandy sediments). Less degraded organic matter with high amino acids was also favorable to benthic animals. Overall, sedimentary estuarine organic matter was least degraded in areas characterized by marine sources of organic matter, low-oxygen conditions, and fine-grained sediments.

Determination triazine pesticides in cereal samples based on single-hole hollow molecularly imprinted microspheres.

Single-hole hollow molecularly imprinted microspheres (h-MIMs) were prepared by hard template method and applied to extract six triazine pesticides in cereal samples, followed by HPLC-MS/MS detection. The synthesis mechanism of the h-MIMs has been studied. The h-MIMs exhibited bigger specific surface area and much higher binding capacity than the molecularly imprinted polymers prepared by precipitation polymerization (p-MIPs) and surface polymerization (s-MIPs). Besides, the adsorption rate of h-MIMs to prometryn was significantly higher than that of p-MIPs and s-MIPs. Owing to the hollow structure of the h-MIMs, more binding cavities were located on the inner and outer surfaces of the h-MIMs, which could facilitate the removal of template molecules from the polymers and the rebinding of the target molecules to the polymers. Under the optimal conditions, the detection limits of triazines are in the range of 0.08-0.16ngg(-1). At the spiked level (5ngg(-1)), the recoveries of triazines are in the range of 81±4% to 96±4%. The proposed method was successfully applied to determine six triazines in five cereal samples. Atrazine was found in two rice samples and a wheat sample with the contents of 5.1, 6.7 and 5.6ngg(-1), respectively. Ametryn and prometryn were found in a maize sample with the contents of 7.6 and 7.3ngg(-1), respectively.

A green method using a micellar system for determination of andrographolide and dehydroandrographolide in human plasma.

A method based on cloud point extraction (CPE) coupled with high-performance liquid chromatography separation and ultraviolet (UV) detection was developed to determine andrographolide and dehydroandrographolide in human plasma. The nonionic surfactant Triton X-114 was chosen as the extraction medium. Variable parameters affecting the CPE efficiency were evaluated and optimized, such as concentrations of Triton X-114 and NaCl, pH, equilibration temperature and equilibration time. A Zorbax SB C18 column (250 × 4.6 mm i.d., 5 µm) was used for separation of the two analytes at 30°C. The UV detection was performed at 254 nm. Under the optimum conditions, the limits of detection of andrographolide and dehydroandrographolide are 0.032 and 0.019 µg/mL, respectively. The intra-day and inter-day precisions expressed as relative standard deviation ranged from 3.2 to 7.3% and from 2.9 and 8.6%. The recoveries of andrographolide and dehydroandrographolide were in the range of 76.8-98.6% at three fortified concentrations of 0.1, 0.5 and 1.0 µg/mL. This method was efficient, environmentally friendly, rapid and inexpensive for the extraction and determination of andrographolide and dehydroandrographolide in human plasma.

Construction of a hyperbranched supramolecular polymer as a bifunctional antioxidative enzyme model.

A HBSP has been designed as a novel bifunctional enzyme model with SOD and GPx activity by host/guest-directed self-assembly of MnTPyP-M-Ad and 6-Te-diCD. The structure of the host/guest complex was elucidated by (1) H NMR spectra, and the HBSP was characterized by SEM, DLS and measurement of catalytic properties. In the bifunctional enzyme model, the Mn(III) porphyrins act as efficient SOD active sites and the tellurol moieties endow GPx activity. The SOD-like activity (IC(50) ) of this new supramolecular catalyst was found to be 1.05 × 10(-7) M, which corresponds to 2.82% of the activity of the native SOD enzyme. Besides this, the hyperbranched supramolecular polymer also shows a higher GPx activity (ν(0 ) = 21.7 × 10(-6) M · min(-1) ) than other supramolecular enzyme models.

Determination of xanthohumol in beer based on cloud point extraction coupled with high performance liquid chromatography.

A method based on coupling of cloud point extraction (CPE) with high performance liquid chromatography separation and ultraviolet detection was developed for determination of xanthohumol in beer. The nonionic surfactant Triton X-114 was chosen as the extraction medium. The parameters affecting the CPE were evaluated and optimized. The highest extraction yield of xanthohumol was obtained with 2.5% of Triton X-114 (v/v) at pH 5.0, 15% of sodium chloride (w/v), 70 degrees C of equilibrium temperature and 10 min of equilibrium time. Under these conditions, the limit of detection of xanthohumol is 0.003 mg L(-1). The intra- and inter-day precisions expressed as relative standard deviations are 4.6% and 6.3%, respectively. The proposed method was successfully applied for determination of xanthohumol in various beer samples. The contents of xanthohumol in these samples are in the range of 0.052-0.628 mg L(-1), and the recoveries ranging from 90.7% to 101.9% were obtained. The developed method was demonstrated to be efficient, green, rapid and inexpensive for extraction and determination of xanthohumol in beer.