Regime shift in a coastal pelagic ecosystem with increasing human-induced nutrient inputs over decades.

Human-induced nutrient inputs to global coastal waters are leading to increasing nutrients and escalating eutrophication. However, how aquatic ecosystem functioning responds to these changes remains insufficiently studied. Here we report the long-term changes in the nutrient regime and planktonic ecosystem functioning in the Daya Bay, a typical subtropical semi-enclosed bay experiencing rapid economic and social development for several decades. Time-series (from 1991 to 2018) data with a mostly quarterly resolution were collected to depict long-term changes in dissolved inorganic nutrients and plankton abundances, based on which we constructed simplified abundance size spectra (SASS) and plankton abundance ratios to describe the functioning of the planktonic ecosystem. The results revealed a long-term increase in system productivity but a decrease in integrated energy transfer efficiency of the planktonic ecosystem, with rising concentrations of dissolved inorganic nitrogen (DIN). Shifts in the nutrient regime and planktonic ecosystem functioning were detected at a tipping point or threshold around 2006-2007. The shifts were characterized by abrupt changes in the trends of nutrient (phosphate, ammonia, nitrite) concentrations, nutrient ratios (DIN/phosphate, silicate/phosphate), plankton abundance, and total plankton biomass. Compared to the nutrient regime, the planktonic ecosystem functioning shifted several years later. Overall, this study indicates that the pelagic ecosystem regime can shift significantly in response to long-term increasing input of human-induced nutrients in coastal waters such as the Daya Bay. The regime shifts may have profound implications for fishery production, and ecosystem management in the bay.

Carbon export from submarine groundwater discharge in a semi-enclosed bay: Impact for the buffering capacity against coastal ocean acidification.

Submarine groundwater discharge (SGD) serves as an important pathway for the transport of dissolved carbon from land to ocean, significantly affecting the coastal biogeochemical cycles. However, the impact of SGD-derived dissolved carbon on the coastal carbon budget remains poorly understood. This study first quantified SGD and associated dissolved organic carbon (DOC), dissolved inorganic carbon (DIC) and total alkalinity (TA) fluxes in Daya Bay using mass balance models based on radium isotopes (223Ra, 224Ra, 226Ra and 228Ra). We then constructed carbon mass balance models to evaluate the impact of SGD-derived carbon on the buffering capacity against coastal ocean acidification. The estimated SGD fluxes ranged from 0.80 × 107 to 2.64 × 107 m3d-1. The DIC, DOC and TA fluxes from SGD were 17.90-36.44 mmol m-2d-1, 0.93-2.13 mmol m-2d-1, and 21.19-28.47 mmol m-2d-1, respectively. Based on carbon mass balances, the DIC flux from SGD was 19-39 times the riverine input, accounting for 27.16 % ∼ 37.64 % of the total carbon source. These results suggest that SGD is a major contributor to DIC, significantly affecting the coastal carbon budget. Furthermore, the average TA:DIC ratio of groundwater discharging into Daya Bay was approximately 1.13. High TA exports enhance the buffering capacity of the coastal ocean and contribute bicarbonate to the ocean, playing a significant role in the ocean carbon sequestration process. This study demonstrates the importance of SGD-derived dissolved carbon in the assessment of coastal carbon budgets.

Occurrence, distribution, and ecological risks of polyhalogenated carbazoles in sediments from Daya Bay and Pearl River Estuary, China.

Polyhalogenated carbazoles (PHCZs) are a group of emerging organic pollutants attracting increasing concern. In this study, 32 sediment samples were collected from the Pearl River Estuary (PRE) and adjacent Daya Bay (DYB) in China and were investigated for the occurrence and distribution of PHCZs. Total concentration of sedimentary PHCZs (∑PHCZs) ranged from 0.79 to 3.08 ng/g in PRE and 0.89 to 1.95 ng/g in DYB, both containing 3,6-dichlorocarbazole as the main component. Higher concentrations of ∑PHCZs were found in the rivers-mouth and inner part of the PRE indicating their main origins from anthropogenic activities. Notably, concentrations of brominated carbazoles (BCZs) gradually increased offshore, which suggests the potential bio-transformation of BCZs under a saline environment. The toxic equivalent of PHCZs was estimated at 0.13-0.34 pg TEQ/g suggesting limited dioxin-like effects on local organisms.

Insights into the spatial distributions of bacteria, archaea, ammonia-oxidizing bacteria and archaea communities in sediments of Daya Bay, northern South China Sea.

Microbe plays an important role in the biogeochemical cycles of the coastal waters. However, comprehensive information about the microbe in the gulf waters is lacking. This study employed high-throughput sequencing and quantitative PCR (qPCR) to investigate the distribution patterns of bacterial, archaeal, ammonia-oxidizing bacterial (AOB), and archaeal (AOA) communities in Daya Bay. Community compositions and principal coordinates analysis (PCoA) exhibited significant spatial characteristics in the diversity and distributions of bacteria, archaea, AOB, and AOA. Notably, various microbial taxa (bacterial, archaeal, AOB, and AOA) exhibited significant differences in different regions, playing crucial roles in nitrogen, sulfur metabolism, and organic carbon mineralization. Canonical correlation analysis (CCA) or redundancy analysis (RDA) indicated that environmental parameters such as temperature, salinity, nitrate, total nitrogen, silicate, and phosphate strongly influenced the distributions of bacterial, archaeal, AOB, and AOA. This study deepens the understanding of the composition and ecological function of prokaryotes in the bay.

Anthropogenic influences on the sources and distribution of organic carbon, black carbon, and heavy metals in Daya Bay's surface sediments.

The total organic carbon (TOC), total nitrogen (TN), black carbon (BC), δ13CTOC, δ15N, δ13CBC, grain size, and heavy metals of surface sediments collected from Daya Bay were determined to investigate the spatial distributions of these parameters and to evaluate the influences of human activities. Marine organic matter was found to constitute approximately 84.41 ± 7.70 % of these sediments on average. The western and northern regions of Daya Bay exhibited relatively fine grain sizes, weak hydrodynamic conditions, and high sedimentation rates, which favored the burial and preservation of organic matter. The high concentration of organic matter could be attributed to the influence of petroleum and aquaculture industries. Fossil fuels were the main source of BC. The enrichment factor (EF) and geo-accumulation index (Igeo) were used to evaluate the sources and pollution levels of heavy metals. The results revealed that the source and distribution of heavy metals were strongly influenced by human activities, resulting in moderate pollution levels across most regions of Daya Bay. A strong correlation was observed between the Igeo values of heavy metals and BC, TOC, TN, and mean particle grain size (Mz). This suggests that the ability of sediments in Daya Bay to enrich and adsorb heavy metals depends on the sediment grain size, the content and type of organic matter. Importantly, sediments in the inner bay of Daya Bay exhibited a greater capacity to impede the migration of heavy metals compared to those in the outer bay.

The anthropogenic effects on organic matter in sediment core based on Bayesian mixing model: a case study of Daya Bay.

Sediment is an important carrier of evidence about environmental evolution which receives huge volumes of organic material originated from both anthropogenic and natural sources. In this study, based on sedimentary chronology, the vertical trends of particle size distribution, total organic carbon (TOC), total nitrogen (TN), and their stable isotopes (δ13C, δ15N) in the sediment core of the nuclear power sea in southwest Daya Bay were analyzed, and the distribution characteristics and contribution ratios of different sources of organic matter in the sedimentary environment over the past 70 years were resolved using a Bayesian mixing model (MixSIAR). TOC, TN, δ13C, and δ15N ranged from 0.89 to 1.56%, 0.09 to 0.2%, - 22.3 to - 20.6‰, and 4.38 to 6.51‰, respectively. The organic matter in the sediment is controlled by a mixture of terrestrial input and marine autochthonous, the proportion of organic matter from terrestrial sources increases, while that from marine sources decreases in the sediment core, which persists from 1960 to 2000, yet organic matter from marine sources still dominates. The first signs of increased primary productivity occurred in 1960, and it was primarily due to agricultural activity. After the 1980s, the rapid increase in population around Daya Bay, the construction of nuclear power plants, the rise of aquaculture, and the quick expansion of industrial bases were all major factors that changed the ecological environment of Daya Bay.

Distribution and co-occurrence networks of the bacterial community in sediment cores from the subtropical Daya Bay, China.

The bacterial community plays an important role in biogeochemical cycles in marine sediment. However, little is known about the vertical profiles and co-occurrence patterns of bacterial community in sediment cores from the marine environment. In this study, five sediment cores were taken from a subtropical bay in China, heavily impacted by anthropogenic activities. The bacterial composition in sediment cores was investigated by using high-throughput sequencing of the 16S rRNA gene. A principal coordinates analysis and an adonis analysis of the operational taxonomic unit (OTU) compositions showed that spatial variation, rather than vertical variation, determined the bacterial structure in sediment cores. The bacterial complexity varied greatly across the five sediment cores, and the rare taxa played an important role in supporting the stability of the bacterial network. This study revealed that sediment properties and anthropogenic activities may induce a shift in the bacterial composition in sediment cores of a subtropical bay.

Coastal sediment heavy metal(loid) pollution under multifaceted anthropogenic stress: Insights based on geochemical baselines and source-related risks.

Contamination and risk assessments generally ignore the potential bias in results caused by the variation of background values at different spatial scales due to the spatial heterogeneity of sediments. This study aims to perform quantitative source-ecological risk assessment via establishing geochemical baselines values (GBVs) of heavy metal(loid)s (HMs) in Daya Bay, China. Cumulative frequency distribution (CFD) curves determined the GBVs of 12.44 (Cu), 30.88 (Pb), 69.89 (Zn), 0.06 (Cd), 47.85 (Cr), 6.80 (As), and 0.056 mg kg-1 (Hg), which were comparable to the background values of Guangdong Province surface soils, and implied a potential terrestrial origin of the coastal sediments. Principal component analysis (PCA) and positive matrix factorization (PMF) identified three sources (F1: natural processes; F2: anthropogenic impacts; F3: specific sources) with contributions of 51.7%, 29.2%, and 19.1%, respectively. The source-specific risk assessment revealed an ecological risk contribution potential of 73.8% for the mixed anthropogenic sources (F2 + F3) and only 26.2% for natural processes. Cd and Hg were the priority management of metallic elements, occupying 63.5% and 72.5% of the contribution weights of F2 and F3, respectively, which showed multi-level pollution potentials and ecological risk levels. The spatial distribution patterns demonstrated the hotspot features of HM pollution, and priority concerns should be given to the management of marine traffic and industrial point source pollution in Daya Bay. The results of the study provide a scientific approach and perspective for pollution treatment and risk management in the coastal environment.

Impact of long-term operation of nuclear power plants on the marine ecosystem of Daya Bay.

Based on the monitoring data of Daya Bay in 2011-2017, the impact of long-term operation of nuclear power plants (NPPs) on the marine ecosystem was accessed. 137Cs and 90Sr in seawater and sediment of Daya Bay decreased with time. The environmental half-lives of 137Cs and 90Sr in seawater, 137Cs in sediment were 7.1 a, 11.7 a and 13.9 a, respectively. The total dose rates of the marine organisms ranged from 230.5 to 853.9 nGy/h, lower than the ERICA screening benchmark (10 µGy/h). 210Po, 226Ra and 232Th were the main dose contributors. 137Cs and 90Sr contributed to ~0.01 %-~0.06 % of the total radiation. 137Cs contributed to <0.6 ‰ of the committed effective dose for humans. There were almost no radiation effects on the marine ecosystem of Daya Bay from NPPs before 2017. In the future, there will be no radiation risk for the long-term discharge of low-level radioactive waste to Daya Bay.

Nonmetric multidimensional scaling and probabilistic ecological risk assessment of trace metals in surface sediments of Daya Bay (China) using diffusive gradients in thin films.

This research is one main objective to assess combined toxicity of trace metal mixtures in aquatic biota in coastal sediments. Coastal sediments around the world are a major reservoir of trace metals from industrial wastewater discharge. Our case study site, Daya Bay in southern China, was selected because it has been under severe man-made impacts. Diffusive gradients in thin films (DGT) technique has proven to be a good method for measuring the bioavailability of trace metals. The bioavailability and distribution of trace metals in surface sediments were investigated along with their possible biological risks. The average bioavailable (DGT-labile) concentrations (µg/L) were 0.44 (V), 0.51 (Cr), 52.49 (Mn), 0.10 (Co), 1.36 (Ni), 0.74 (Cu), 14.53 (Zn), 0.97 (As), 0.14 (Se), 6.73 (Mo), 0.17 (Cd), 0.27 (Sb), 0.10 (W), and 1.32 (Pb). Nonmetric multidimensional scaling (NMS) is a robust multivariate ordination method that makes no assumptions about the distribution of the underlying data. NMS was used to explore that DGT-labile concentrations of trace metals were influenced by sediment properties. NMS results indicated that most DGT- labile trace metals influenced by sediment properties. Risk assessment of single trace metal toxicity revealed that risk quotient (RQ) values for Mn, Cu, Zn and Pb significantly exceeded 1, demonstrating that the toxic effects of these trace metals should be not ignored. The probabilistic ecological risk assessment for integral toxicity of one mixture of 14 trace metals revealed that Daya Bay surface sediments had a low probability (9.04 %) of adverse effects on aquatic biota.

Diversity and distribution of culturable fouling bacteria in typical mariculture zones in Daya Bay, South China.

The diversity and distribution of culturable fouling bacteria in shellfish, fish and non-mariculture zones in Daya Bay were investigated by using a traditional culture-dependent approach combined with an analysis of bacterial 16S rRNA gene sequences. A total of 129 isolates of fouling bacteria belonging to 37 species in 25 genera were collected and identified, which indicated that the three different mariculture zones harbored abundant and diverse fouling bacterial community. At the genus level, Pseudomonas, Arcobacter and Curtobacterium dominated the fouling bacterial community. Moreover, approximately 46% of the 37 representative isolates could form biofilms. After comparing the diversity and distribution of the biofilm-forming bacteria in three different mariculture zones, it was concluded that the ratios of biofilm-forming bacteria in shellfish (68.4%) and fish (63.4%) in mariculture zones were much greater than those in non-mariculture (42.0%) zone. These results provide important information, for the first time, regarding the fouling bacterial community in typical mariculture zones in South China, which will establish a foundation to develop strategies for biofilm control and disease defense.

Anthropogenic impacts on the temporal variation of heavy metals in Daya Bay (South China).

A detailed study of a sediment core from Daya Bay (South China) has revealed three stages of heavy metal deposition over the past century. Prior to the 1980s, heavy metal concentrations were low with limited influence by human activities. From the 1980s to 2000, metal pollution intensified, and anthropogenic activities, such as oil and petrochemical industries, and fuel combustion, had the greatest direct influence on Hg, Ni, Pb, and Zn concentrations, whereas atmospheric deposition and mariculture were also contributors to the continued increase in Cr, Cu, Pb, Zn, and Ni. Since the year 2000, heavy metal concentration has declined and stabilized. It is noteworthy that anthropogenic input of Cu and Pb is ongoing and may result in a moderate pollution risk. Both modified pollution index (MPI) and modified ecological risk (MRI) consistently indicate that the ecological risk in terms of heavy metals in Daya Bay has remained moderate over the past 70 years.

Sources, burial flux and mass inventory of black carbon in surface sediments of the Daya Bay, a typical mariculture bay of China.

The contents of chemothermal oxidation (CTO)-derived black carbon (BC) and organic carbon (OC) and their stable isotopes (δ13CBC and δ13COC), including major elemental oxides, and grain sizes were measured to constrain the sources, burial flux, and mass inventory of BC in surface sediments of the Daya Bay. Surface sediments were mainly clayey silt (>90%) and contained 0.28-1.18% OC and 0.05-0.18% BC. Fossil fuel emission and physical erosion contributed to the sedimentary BC sources. High BC/OC ratio (6-30%), burial flux (154.88-922.67 µg cm-2 y-1), and mass inventory (22-34 Gg y-1) of BC in the upper 5 cm of surface sediments indicated that the Daya Bay is a significant sink of BC. The high accumulation of BC in sediments is attributed to a strong affinity to fine-grained sediments due to the enrichment of muddy biodeposits excrements from the cultured species in the bay.

Assessment and Implication of PAHs and Compound-Specific δ13C Compositions in a Dated Marine Sediment Core from Daya Bay, China.

PAHs in a sediment core covering ~120 years from Daya Bay in South China Sea were extracted using Soxhlet and high performance thin layer chromatography, and the compound-specific δ13C were analyzed using gas chromatography-combustion-isotopic ratio mass spectrometry. The concentrations of PAHs ranged from 99.3 to 676 ng g-1, with high molecular weight PAHs as a key component. PAHs' compound-specific δ13C ranged from -35.02‱ to -16.14‱. The patterns of 16 PAHs, molecular ratios, and compound specific δ13C compositions indicate important pyrolytic and petrogenic sources: PAHs derived predominantly from pyrogenic sources (including coal and wood incomplete combustion) before the 1960s, while after the 1960s, they derived predominantly from mixed pyrogenic and petrogenic sources (including automotive exhaust emissions, oil spills, and coal and wood incomplete combustion). Our results can provide important insights into organic pollution emissions influenced by human activities and the urbanization of Daya Bay.

Distribution, source and risk assessment of heavy metals in the seawater, sediments, and organisms of the Daya Bay, China.

Cu, Pb, Zn, Cd, Cr, Hg and As in seawater, sediment and organisms of the Daya Bay, Guangdong province, China were measured to acquire the comprehensive understanding on distribution, sources and risk assessment of heavy metals (HMs) in the marine ecosystem. The concentrations were relatively ideal, and the Pb was the major pollutant in the seawater and sediment. The contents of HMs were highest in spring; the concentrations near the sewage outlet and shore were noticeable. Submarine pipeline sewage, atmospheric deposition and runoff were the main sources of HMs in coastal waters. Studied HMs were preferentially retained by liquid phase; Cd, Cu and Zn were the most accumulated elements in the organisms from the surrounding environment. Cd in shellfish deserved particular attention, but the health risks including non-carcinogenic and carcinogenic risks of all elements were within acceptable limits. The potential health risks of Pb have been confirmed by molecular docking.

Diversity and abundance of diazotrophic communities of seagrass Halophila ovalis based on genomic and transcript level in Daya Bay, South China Sea.

Seagrass ecosystems are among the most productive marine ecosystems, and diazotrophic communities play a crucial role in sustaining the productivity and stability of such ecosystems by introducing fixed nitrogen. However, information concerning both total and active diazotrophic groups existing in different compartments of seagrass is lacking. This study comprehensively investigated the diversity, structure, and abundance of diazotrophic communities in different parts of the seagrass Halophila ovalis at the DNA and RNA level from clone libraries and real-time quantitative PCR. Our results indicated that nearly one-third of existing nitrogen-fixing bacteria were active, and their abundance might be controlled by nitrogen to phosphorus ratio (N:P). Deltaproteobacteria and Gammaproteobacteria were dominant groups among the total and active diazotrophic communities in all samples. These two groups accounted for 82.21% and 70.96% at the DNA and RNA levels, respectively. The genus Pseudomonas and sulfate-reducing bacteria (genera: Desulfosarcina, Desulfobulbus, Desulfocapsa, and Desulfopila) constituted the significant fraction of nitrogen-fixing bacteria in the seagrass ecosystem, playing an additional role in denitrification and sulfate reduction, respectively. Moreover, the abundance of the nitrogenase gene, nifH, was highest in seawater and lowest in rhizosphere sediments from all samples. This study highlighted the role of diazotropic communities in the subtropical seagrass ecosystem.

Effect of pyrene and phenanthrene in shaping bacterial communities in seagrass meadows sediments.

Polycyclic aromatic hydrocarbons (PAHs), originating from anthropogenic and natural sources, are highly concerned environmental pollutants. This study investigated the impact of two model PAHs (pyrene and phenanthrene) on bacterial community succession in the seagrass meadows sediment in a lab-scale microcosm. Halophila ovalis sediment slurry microcosms were established, one group was placed as a control, and the other two were treated with pyrene and phenanthrene. Bacterial community succession in response to respective PAHs was investigated by 16S rRNA amplicon sequencing. The results demonstrated that bacterial diversity decrease in each microcosm during the incubation process; however, the composition of bacterial communities in each microcosm was significantly different. Proteobacteria (37-89%), Firmicutes (9-41%), and Bacteroides (7-21%) were the predominant group at the phylum levels. Their abundance varies during the incubation process. Several previously reported hydrocarbon-degrading genera, such as Pseudomonas, Spinghobium, Sphingobacterium, Mycobacterium, Pseudoxanthomonas, Idiomarina, Stenotrophomonas, were detected in higher abundance in pyrene- and phenanthrene-treated microcosms. However, these genera were distinctly distributed in the pyrene and phenanthrene treatments, suggesting that certain bacterial groups favorably degrade different PAHs. Statistical analyses, such as ANOSIM and PERMANOVA, also revealed that significant differences existed among the treatments' bacterial consortia (P < 0.05). This work showed that polycyclic aromatic hydrocarbon significantly affects bacterial community succession, and different PAHs might influence the bacterial community succession differently.

Long-term changes of nutrients and biocenoses indicating the anthropogenic influences on ecosystem in Jiaozhou Bay and Daya Bay, China.

Long-term changes of nutrients, plankton and macrobenthos were studied to research the transformation of ecosystem in Jiaozhou Bay and Daya Bay in the past 30 years. Concentrations of dissolved inorganic nitrogen and phosphate increased with significant changes in nutrient compositions and ratios. Concentrations of Chl a slightly decreased in Jiaozhou Bay but increased in Daya Bay. Phytoplankton abundances increased and diatoms were dominant, however, dinoflagellate gradually had the competitive advantage under high N/P and N/Si in the two bays. Zooplankton biomass significantly increased in Jiaozhou Bay, but only increased slightly in Daya Bay over the past years. Polychaetes were dominant in macrobenthos in the bays, indicating their adaptation to the changing benthic environments. The long-time variations of biocenoses and nutrients reflected that the ecological environments have changed under the influence of anthropogenic activities in the two bays.

Influence of sedimentary organic matter sources on the distribution characteristics and preservation status of organic carbon, nitrogen, phosphorus, and biogenic silica in the Daya Bay, northern South China Sea.

Surface sediment samples were collected from Daya Bay in October 2018, and analyzed for total organic carbon (OC), total nitrogen (TN) and their stable isotopes (δ13C and δ15N), total phosphorus (TP), biogenic silica (BSi), sediment textures and specific surface area (SSA). The primary objective was to evaluate the influence of mariculture/aquaculture on the distribution characteristics of organic matter (OM), and preservation status of OC, TN, TP, and BSi in sediments. The average δ13C and δ15N values, and OC/TN ratios were -21.27‰, 6.74‰, and 8.90, respectively. Monte Carlo simulation results revealed that mariculture/aquaculture biodeposits accounted for >40% of the buried OM at sites where the breeding rafts and cages are located, whereas marine OM increased gradually to the open sea. Terrestrial OM was generally low accounting for 17% by average. The contents and distribution characteristics of biogenic elements were more influenced by mariculture/aquaculture and primary productivity than sediment textures. Lower OC/SSA (0.3-1.2 mg OC/m2), TN/SSA (~0.05-0.18 mg TN/m2), and TP/SSA (0.02-0.04 mg TP/m2) loadings indicated that increased sequestration of labile OM in a coastal bay could contribute to significant degradation of recalcitrant OM in sediments with significant loss of P relative to OC. Nitrogen contamination in surface sediments was due to increased injection of aquaculture biodeposits, and may pose a detrimental effect on the ecological sustainability of the bay. Higher BSi/SSA loadings (0.9-1.7 mg BSi/m2) revealed that BSi was more preserved, and that BSi-based proxy could be used for paleo-productivity studies. However, such preservation may induce adverse dissolved silicate limitation in a bay perturbed by eutrophication. Fine-grained sediments (clay and silt) accounted for >77% of the sediment texture types with higher SSA, and while controlling the contents of biogenic elements under given depositional conditions were not the main determining factors of OC, TN, TP, and BSi preservation.

Distribution and potential provenance of trace elements in a 120-year dated sediment core from west Daya Bay, northeastern South China Sea.

Eighteen trace elements were analyzed in a 120-year sediment core from Daya Bay. Burial flux history and potential provenance, the relationships among trace elements, and biogenic compositions were analyzed for determining the trend and extent of trace element accumulation and identifying corresponding anthropogenic effects. Additionally, the effects of anthropogenic activities on Daya Bay were reconstructed, and a baseline/background estimation was provided for Daya Bay. The burial fluxes of V, Cr, Cd, Cu, Zn, Mn, Fe, Co, Ni, Pb, Hg, Zn, Mo, Ag, As, Se, and Tl increased from 1960 to 2010, especially after the late 1980s. Our results are useful for understanding pollution and land-sea interactions along the coasts of the South China Sea, especially in the Guangdong-Hong Kong-Macao Greater Bay Area.