Development and validation of the DGT technique using the novel cryogel for measuring dissolved Hg(II) in the estuary.

The complex seawater matrix has significantly influenced the determination of estuarine dissolved Hg(II), hindering its monitoring and risk assessment in maricultural areas. In this work, SiO2-SH-DGT assembled by the sulfhydryl-modified silica cryogel (SiO2-SH cryogel) as the novel binding phase was developed to tackle this problem. The uniform dispersion of the cryogel into binding gel was advantageous for achieving remarkable and comparable capacity, which endowed the estimated diffusion coefficient (D) to be 1.39-3.08 times of the existing research. The SiO2-SH-DGT performance was independent of pH (3-9), ionic strength (10-800 mM), fulvic acid at low content, and seawater matrix (Na+, K+, Ca2+, Cl-), but the high content of Mg2+ did interfere with the Hg(II) accumulation, which manifested as competitive adsorption and diffusion. Therefore, the calibrated model was established by calibrating accumulated mass (M') and diffusion coefficient (D') based on the Mg2+ concentration, its high accuracy was further verified in the lab. Finally, SiO2-SH-DGT was deployed in the three typical aquaculture areas in Beibu Gulf, field trials achieved the actual Hg(II) level to be 1.52-5.38 ng/L with consideration of the diffusion boundary layer. The finding could provide new thought and technical support for metal pollution monitoring in estuary maricultural areas.

Prevalence and distribution of domoic acid and cyclic imines in bivalve mollusks from Beibu Gulf, China.

Beibu Gulf is an important shellfish aquaculture area in the northwest of the South China Sea, China. In this study, the toxin profile and spatial-temporal distribution of domoic acid (DA) and 10 lipophilic phycotoxins were systematically analyzed in the bivalve mollusks collected in Beibu Gulf from October 2018 to October 2020. Neurotoxin DA was first detected in the mollusks from the investigative regions with a prevalence of 17.7%, peaking at 401 µg kg-1. Cyclic imines (CIs) including gymnodimine-A (GYM-A, 46.6%) and 13-desmethyl-spirolide-C (SPX1, 15.8%) predominated the lipophilic phycotoxins in shellfish, peaking at 10.1 µg kg-1 and 19.6 µg kg-1, respectively. Gymnodimine-A partially accompanied by SPX1 was detected in all batches of shellfish samples, suggesting that Alexandrium ostenfeldii and Karenia selliformis were possible sources of CIs-group toxins in Beibu Gulf. During the investigative period, relatively higher levels of DA occurred in shellfishes from March to August, while slightly higher contents of CIs in mollusks appeared in October and December. Spatial distribution of the targeted phycotoxins demonstrated that shellfishes tended to accumulate relatively higher contents of toxins in Lianzhou, Qinzhou and Tieshan bays.

Control of phytoplankton by oysters and the consequent impact on nitrogen cycling in a Subtropical Bay.

Although there has been growing interest in using oysters to remediate estuarine eutrophication since the 1980s, the role of oysters in remediation remains controversial. In this study, we took advantage of the intensive oyster farming in a nutrient-enriched estuary to evaluate the control of phytoplankton blooms by oysters. Observing the phytoplankton density variations in March and October, we found that despite doubled nutrient levels in March, oysters kept the phytoplankton density low. This is the first estuary-scale evidence that oysters can effectively suppress phytoplankton blooms. Measuring the isotopic signals in seawater revealed the significant impact of pelagic nitrogen cycling in the estuary. In March, oysters facilitated NO3- removal in the water column by enhancing the coupled phytoplankton assimilation-oyster filtration and denitrification in the sediments. While in October, the oysters-related nitrification could outcompete the removal processes, adding a significant amount of NO3- to the water column. Our study illustrates the influence of massive oysters on pelagic nitrogen cycling in an "oyster-remediated" estuary, providing implications for restoring oyster reefs to mitigate the symptoms of estuarine eutrophication.

Pollution and ecological risk assessment, and source identification of heavy metals in sediment from the Beibu Gulf, South China Sea.

The Beibu Gulf is an important passageway between China and the Association of Southeast Asian Nations, where there has been an increase in pollution of heavy metals (HMs). High concentrations of Pb, Cr, Cd, Cu, Zn, As, and Hg in surface sediment were found in Qinzhou Bay, Fangchenggang, and other coastal areas. Stochastic geo-accumulation analyses identified the pollution to be "uncontaminated"; however, it had an 18% probability of deterioration. The Cd, Hg, and As pollution were relatively serious. Principal component analysis, positive matrix factor model, and mercury isotopes demonstrated that the HMs could mainly be attributed to industrial sources including petrochemical, coal-fired, metal and metalloid processing, leather tanning, and human activities: anthropogenic sources accounted for approximately 70% of all the contaminations. This study demonstrates the contribution of terrigenous input to HMs even at a low level and provides basic data for the coordinated development of land and marine resources.

Litterfall-derived organic matter enhances mercury methylation in mangrove sediments of South China.

Mercury (Hg) contamination in mangrove ecosystems has received increasing attention in recent years. Although many studies have investigated methylmercury (MeHg) contamination and its relationship to a number of environmental factors in mangrove sediments, the production of MeHg in this carbon-rich ecosystem has not been fully evaluated. In this study, we measured the total mercury (THg) and MeHg concentrations in the sediments collected from seven mangrove forests in China. In addition, we examined the origin and quality of sedimentary organic matter (OM), trying to evaluate their influence on the MeHg accumulation in mangrove sediments. We found that litterfall played an important role in regulating THg and MeHg contents in mangrove sediments. THg and MeHg concentrations in the mangrove sediments were positively correlated to OM content and the labile fraction of the OM. Multiple evidence (stable carbon isotopes, monosaccharide compositions, and biogenic silica) suggested that OM in mangrove sediments was dominated by input from litterfall. THg and MeHg concentrations were elevated at the sediments with higher input of mangrove OM. We observed that addition of mangrove litter stimulated the production of MeHg under anaerobic conditions. Overall, our results suggested that litterfall acted as a source of inorganic Hg, labile carbon, and low-molecular-weight OM which greatly favor the Hg methylation. Our study provides new insights into the MeHg production in mangrove sediments.

Isotopic Composition Reveals the Impact of Oyster Aquaculture on Pelagic Nitrogen Cycling in a Subtropical Estuary.

To offset estuarine eutrophication, interest is increasing in restoring oyster reefs and expanding oyster aquaculture. However, ecosystem-scale evidence is lacking on oyster assemblages' impacts on estuarine pelagic nitrogen (N) cycling. Using a multiple-isotope approach and isotope-mixing model, we examined the sources, transformations, and influence of intensive oyster aquaculture on N pollution in a subtropical estuary. The salinity-dependent NO3- and NH4+ concentrations and their correlations with isotopic signals (δ15N-NO3-, δ18O-NO3-, δ15N-NH4+) indicated the nutrient spatial distribution in low-salinity areas was largely regulated by mixing between freshwater and seawater. However, the intensive oyster aquaculture greatly increased nitrification in the estuary. In high-salinity areas where oyster assemblages were absent, the assimilation of NO3- by phytoplankton became dominant and sharply increased the δ15N-NO3- and δ18O-NO3-. Soil organic nitrogen and fertilizer, domestic sewage, and wastewater treatment plants were the major NO3- sources in the estuary, while internal nitrification contributed 20.6% to the NO3- pool. Oyster biodeposits comprised up to one-third of the particulate organic matter in the water column, and as much as 47.3% of the NH4+ pool could be from the oysters. Our study shows that oysters significantly contribute to the pelagic nutrient pools and N transformations, adding an important dimension to our understanding of oyster assemblages' impacts on estuarine N cycling.

Evaluation of different strategies to minimize the matrix effects on LC-MS/MS analysis of multiple lipophilic shellfish toxins in both acidic and alkaline chromatographic conditions.

Lipophilic shellfish toxins (LSTs) accumulated by shellfish pose a potential threat to consumer health. A mandatory routine monitoring of LSTs has been adopted for seafood products by liquid chromatography-mass spectrometry (LC-MS) in many countries. In this study, two methods developed on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) under acidic and alkaline chromatographic conditions were assessed for the determination of multiple LSTs. Different strategies including matrix solid-phase dispersion (MSPD), solid phase extraction (SPE) and sample dilution were applied and evaluated the matrix effects of mussel, scallop, clam, and oyster samples on the signal response of mass spectrometry. Results showed that the alkaline method achieved a lower limit of detection (LOD) and more robust compared to the acidic method. The obvious signal suppression of OA and DTX1 (55%-76%) and signal enhancement of PTX2 (27%-34%) occurred in the crude extracts of shellfish under acidic chromatography. In the alkaline method, no remarkable matrix effects of crude extracts were found except for the scallop matrix on the signal intensity of DTX1, AZA3 and GYM-A (121%-130%). Clean-up methods MSPD, SPE and sample dilution obviously reduced the inhibition of shellfish matrices on the signal response of OA and DTX1, however, which were still subject to signal inhibition under acidic condition. Sample dilution was more effective than SPE and MSPD in minimizing the matrix interference in both acidic and alkaline methods. Furthermore, sample dilution in combination with the alkaline chromatography was the most effective method. Bivalve mollusks harvested from Beibu Bay, South China Sea, were generally contaminated by GYM-A and SPX1 at low concentrations.