Heavy metal pollution in the mariculture areas is of considerable attention due to its potential ecological effects and public concern for seafood safety. A better understanding of the current contamination status and historical trend of heavy metals in the ecosystems of mariculture areas has an important implication for the sustainable development of marine ecosystems and for public health concerns. To assess the impact of human activities on heavy metal pollution in the mariculture area, seven metals (Cu, Pb, Zn, Cd, Hg, As, and Cr) and the environmental parameters were seasonally investigated in the surface seawater and sediments in Qinzhou Bay, a typical mariculture bay in South China. Seasonal variations in the concentration of heavy metals were found in both seawater and sediment, which are mainly influenced by seasonal hydrological change, biological activity, and human influence. The concentration of heavy metals in the seawater was at a relatively higher level than that of other mariculture areas in China, while a lower level was found in the sediment. The concentration of Cu increased in both seawater and sediment for the past decades (by nearly 2 times), which is mainly influenced by the mariculture and shipping activities. The concentration of Hg decreased significantly in the seawater for the past 40 years (decreased by 13 times) due to the decrease in production and usage of Hg. However, the concentrations of Pb, Zn, and Cd in seawater showed an increasing trend in the mariculture bay, while the concentrations of Pb, Zn, As, and Cr decreased in the sediment over the past decades. The decrease in pH value (decreasing by 4.7% for the past 20 years) was responsible for the different trend of those metals between seawater and sediment because the decrease in pH could re-release metals from sediments into the water column. Hg and As are the main ecological risk factors in the mariculture bay. This study suggests that environmental changes, such as ocean acidification, affect the distribution of metals in seawater and sediments, which we should be more vigilant and concerned about under the global climate change.

Eutrophication, mainly caused by the oversupply of inorganic nitrogen and phosphate, has increased and become a serious environmental problem in the coastal bays of Beibu Gulf, a newly developing industry and port in South China. However, the sources of nitrate are poorly understood in the gulf. In this study, nitrate dual isotopes (δ15N-NO3- and δ18O-NO3-) and ammonium isotopes (δ15N-NH4+) were measured during the rainy season to identify the nitrate sources and elucidate their biogeochemical processes in Xi Bay, a semi-enclosed bay that is strongly affected by human activities in the Beibu Gulf. The results showed that a high dissolved inorganic nitrogen (DIN, 10.24-99.09 µmol L-1) was observed in Xi Bay, particularly in the bay mouth. The concentrations of DIN in the bay were 1.5 times higher than that in Qinzhou Bay and 1.7 times than that in Tieshangang Bay, which mainly influenced by the intensive human activities (i.e., industrial and port activities). In addition, lower values of δ15N-NO3- and δ18O-NO3- and higher values of δ15N-NH4+ were observed in the upper bay, suggesting that microbial nitrification occurs in the upper bay, which was the dominant nitrate source in the upper bay (39%). In addition to nitrification, external sources, including sewage and manure (33%), soil N (15%) and fertilizer (11%), contributed to the higher nutrients in the upper bay. In the lower bay, severe nitrogen pollution led to a weaker impact of biological processes on isotopic fractionation, although a high Chl a level (average of 7.47 µg L-1) was found in this region. The heavy nitrate pollution in the lower bay mainly originated from sewage and manure (54%), followed by soil N (26%) and fertilizer (17%). The contribution of the nitrate source from atmospheric deposition was relatively low in the bay (<3%). This study suggests that biogeochemical processes have little impact on nitrate dual isotopes under heavy nitrogen pollution, and isotopes are an ideal proxy for tracing nitrogen sources.

Both dissolved and particulate organic matters (DOM and POM) provide a reduced carbon pool of considerable size in coastal ecosystems, and the two are closely linked. Currently, however, the integrated study of DOM and POM remains limited, precluding a more in-depth understanding of their interaction in coastal regions. In April 2021, 13 surface water samples were collected from Qinzhou Bay, in the northern Beibu Gulf. The DOM samples were characterized using dissolved organic carbon (DOC) analysis and UV-visible and fluorescence spectroscopy techniques. We determined the POM for the particulate organic carbon and nitrogen (POC and PN) and also isotopic composition (δ13C and δ15N). The weak to negligible relationships found between the DOC, colored and fluorescent DOM, salinity, and chlorophyll a together suggested that DOM’s distribution in Qinzhou Bay is concurrently shaped by various processes, namely, hydrological and in situ biological processes. A high C/N ratio of ~17, high POC/chlorophyll a ratio (253 ± 112), and depleted δ13C (−25.7 ± 1.6‰) confirmed that POM is highly degraded and originates mainly from allochthonous input, to which the terrigenous organic matter and freshwater phytoplankton each contributes 35%. The total organic carbon (TOC = DOC + POC) was positively correlated with the humic-like peak M, revealing the transformation of labile DOM and POM into recalcitrant DOM components. The in situ production efficiency of peak M in surface waters of Qinzhou Bay is one order of magnitude greater than that in inland waters or open oceans, indicating that not only temperature but also the activity of substrate is a key factor controlling the in situ production of recalcitrant DOM in Qinzhou Bay. High levels of TOC and humic-like fluorescent DOM suggest the mass coexistence of organic matter differing in its reactivity, highlighting the large potential for photochemical as well as microbial degradation in the future.