Salinity, mineralogy, porosity, and hydrodynamics as drivers of carbon burial in urban mangroves from a megacity.

Mangrove ecosystems are an important blue carbon store but exhibit considerable variation in soil carbon stocks globally. Unravelling the conditions controlling carbon stock is critical for assessing current and future carbon budgets. Mangrove soil biogeochemical cycles can strongly influence carbon storage capacities. We thus investigated carbon sequestration and the environmental parameters shaping variability in biogeochemical cycling and carbon storage in sediment samples from four mangrove sites along an estuarine-to-marine gradient in Hong Kong, a megacity. Our results showed that organic matter in Hong Kong mangroves is sourced principally from autochthonous mangrove plants. Total nitrogen was higher in the freshwater-influenced sites and supplied from different sources. Marine-influenced sites had larger sulfur fractionations, reflecting higher marine-sourced sulfate concentrations and indicating a relatively open sulfate system. We estimated an average organic carbon stock of 115 ± 8 Mg C ha-1 in the upper 100 cm soil layer placing Hong Kong mangroves at the lower end of the global spectrum of the soil carbon stock. Carbon accumulation was found to be driven by a combination of higher total organic matter inputs, soil fluxes, and porosity. Notably, despite having the highest mass-specific soil organic carbon contents, Mai Po had the lowest integrated soil organic carbon storage (77 ± 3 Mg C ha-1). This was primarily due to lower sediment density and higher tidal pumping leading to a decrease in carbon retention. Total organic matter input, sediment characteristics, and hydrodynamics were the main factors influencing soil organic carbon storage. Overall, our results suggest that (1) while multiple parameters can enhance soil organic carbon content and increase carbon storage capacities, (2) hydrodynamics and sediment characteristics can increase the potential for leakage of carbon, and (3) high carbon content does not always equal high carbon sequestration and stock.

Coral carbonate-bound isotopes reveal monsoonal influence on nitrogen sources in Southeastern China's Greater Bay Area from the mid-Holocene until the Anthropocene.

Most anthropogenic nitrogen (N) reaches coastal waters via rivers carrying increasing loads of sewage, fertilizer, and sediments. To understand anthropogenic N impacts, we need to understand historical N-dynamics before human influence. Stable isotope ratios of N preserved in carbonates are one way to create temporal N records. However, records that span periods of human occupation are scarce, limiting our ability to contextualize modern N dynamics. Here, we produce a fossil-bound N-record using coral subfossils, spanning 6700 years in China's Greater Bay Area (GBA). We found that during the mid-to-late Holocene, the GBA's coastal N was dominated by fluvial sources. The weakening of the Asia monsoon throughout the late-Holocene decreased river outflow, leading to a relative increase of marine nitrate. This source shift from riverine-to-ocean dominance was overprinted by anthropogenic N. During the late 1980s to early 1990s, human development and associated effluent inundated the coastal system, contributing to the decline of coral communities.

Elucidating sources of atmospheric NOX pollution in a heavily urbanized environment using multiple stable isotopes.

Atmospheric deposition of nitrogen (N) from rain and aerosols can be a significant non-point source - particularly in urbanized coastal areas and contribute to coastal eutrophication and hypoxia. Here, we present geochemical and isotopic data from surface waters coupled with an 18-month time series of geochemical and isotopic data measured on wet and dry deposition over Hong Kong from June 2018. Dual stable isotopes of nitrate (δ15N-NO3- and δ18O-NO3-) of rain and total suspended particulates (TSP) were analyzed to trace the sources and understand seasonal pattern of atmospheric nitrate. The δ15N of TSP, δ15N-NO3 in rain and TSP ranged from +0.94 to +17.6‰, -4.1 to +3.0‰ and -1.3 to +9.0‰ respectively. δ15N varied seasonally with higher values in winter and lower values in summer. This variation can be explained by a change in the sources of atmospheric NOx driven by the East Asian Monsoon. It was found that most NOx comes from coal burning in winter and a mix of vehicle emissions, fossil fuel combustion and lightning in summer. Moreover, the estimated dry and wet deposition of nitrate and ammonium in Hong Kong is around 18 kg N ha-1 annually, which is of the same order of magnitude as N released by sewage effluents and groundwater. This implies that atmospheric N deposition over the N-limited waters of the eastern side of Hong Kong could contribute significantly to the N budget. Therefore, atmospheric N deposition may alter the local N marine cycling, thus monitoring its impact is crucial for water quality in Southern China.

Investigating the link between Pearl River-induced eutrophication and hypoxia in Hong Kong shallow coastal waters.

We present geochemical analysis of 75 surface water samples collected in 2016 in Hong Kong coastal waters. We found that nitrogen distribution around Hong Kong can be characterized by two regimes driven by the influence of the Pearl River: 1) a regime where nitrate is the dominant species of nitrogen, associated with lower salinity and more faecal coliform and 2) a regime where dissolved organic nitrogen is dominant, associated with higher salinity and fewer faecal coliform. While the impact of the Pearl River on Hong Kong coastal waters is well characterized, we used the sharp contrast between the nitrogen regimes to produce new evidence about the role of the Pearl River on the generation of local hypoxia in Hong Kong. The impact of nitrate originating from the Pearl River on the generation of hypoxia in Hong Kong might be less important than previously thought, as no sign of eutrophication was found within the zones dominated by dissolved organic nitrogen and an historical decoupling of surface processes and bottom water oxygenation was observed. Moreover, we measured elevated ammonium levels and rapid cycling of ammonium and dissolved organic nitrogen in Victoria Harbour suggesting local sources, such as wastewater, might be rapidly oxidized and thus play an important role in the consumption of oxygen locally. A first-order calculation highlighted the potential for wastewater to drive the observed seasonal decline in oxygen. Taken together, these evidences suggest that eutrophication might not be the primary driver in the generation of seasonal hypoxia and that oxidation of ammonium released locally might play a bigger role than initially thought.

Quantifying the Impact of Anthropogenic Atmospheric Nitrogen Deposition on the Generation of Hypoxia under Future Emission Scenarios in Chinese Coastal Waters.

Atmospheric deposition is an important source of nitrogen to coastal waters. In nitrogen-limited waters, the atmosphere can contribute significantly to eutrophication and hypoxia. This is especially true in China, where nitrogen emissions have increased dramatically and are projected to further increase in the future. Here, we modeled the potential future impact of change in atmospheric nitrogen deposition on hypoxia in Chinese coastal seas. We used changes in nitrogen deposition under two IPCC scenarios that included emission regulation and climate change (representative concentration pathway (RCP) 4.5 and 8.5) to evaluate the impacts of such deposition on hypoxia in the 2030s and 2100s. We found that by 2030 the extent of hypoxic areas would increase up to 5% in China seas under RCP 8.5 due to the projected increase in nitrogen deposition. However, the hypoxia extent was projected to decrease by up to 9% by 2100 once emission regulations included in RCP 4.5 and 8.5 are implemented. The South China Sea was found to be the most sensitive region to changes in nitrogen loads, which indicates that more effort in emissions control is needed to avoid expansion of the hypoxic zones in that specific region.

Nitrogen sources and cycling revealed by dual isotopes of nitrate in a complex urbanized environment.

Elevated nutrient inputs have led to increased eutrophication in coastal marine ecosystems worldwide. An understanding of the relative contribution of different nutrient sources is imperative for effective water quality management. Stable isotope values of nitrate (δ15NNO3-, δ18ONO3-) can complement conventional water quality monitoring programs to help differentiate natural sources of NO3- from anthropogenic inputs and estimate the processes involved in N cycling within an ecosystem. We measured nutrient concentrations, δ15NNO3-, and δ18ONO3- in 76 locations along a salinity gradient from the lower end of the Pearl River Estuary, one of China's largest rivers discharging into the South China Sea, towards the open ocean. NO3- concentrations decreased with increasing salinity, indicative of conservative mixing of eutrophic freshwater and oligotrophic seawater. However, our data did not follow conservative mixing patterns. At salinities <20 psu, samples exhibited decreasing NO3-concentrations with almost unchanged NO3- isotope values, indicating simple dilution. At salinities >20 psu, NO3- concentrations decreased, while dual NO3- isotopes increased, suggesting mixing and/or other transformation processes. Our analysis yielded mean estimates for isotope enrichment factors (15ε = -2.02‰ and 18ε = -3.37‰), Δ(15,18) = -5.5‰ and δ15NNO3- - δ15NNO2- = 12.3‰. After consideration of potential alternative sources (sewage, atmospheric deposition and groundwater) we concluded that there are three plausible interpretations for deviations from conservative mixing behaviour (1) NO3- uptake by assimilation (2) in situ NO3- production (from fixation-derived nitrogen and nitrification of sewage-derived effluents) and (3) input of groundwater nitrate carrying a denitrification signal. Through this study, we propose a simple workflow that incorporates a synthesis of numerous isotope-based studies to constrain sources and behaviour of NO3- in urbanized marine environments.

Variations in nitrate isotope composition of wastewater effluents by treatment type in Hong Kong.

Stable isotopes (δ(15)N, δ(18)O) can serve as tracers for sources of nitrogen in the receiving environment. Hong Kong discharges ~3×10(6)m(3)d(-1) of treated wastewater into the ocean from 68 facilities implementing preliminary to tertiary treatment. We sampled treated sewage from 18 plants across 5 treatment types and examined receiving seawater from northeast Hong Kong. We analyzed nitrate and nitrite (NO3(-)+NO2(-), hereafter NOx) ammonium (NH4(+)), phosphate (PO4(+)) concentrations and δ(15)NNOx, δ(18)ONOx. Sewage effluents contained high mean nutrient concentrations (NO3(-)=260µmolL(-1), NH4(+)=1400µmolL(-1), PO4(+)=50µmolL(-1)) with some indication of nitrogen removal in advanced treatment types. Mean δ(15)NNOx of sewage effluents from all plants and treatment types (12‰) was higher than natural sources and varied spatially and seasonally. There was no overall effect of sewage treatment type on δ(15)NNOx. A mass balance model indicated that sewage (>68%) remains a dominant source of nitrate pollution in seawater in Tolo Harbor.