Recommendations and good practices for dissolved organic carbon (DOC) analyses at low concentrations.

Numerous protocols for dissolved organic carbon (DOC) measurements on natural water are used in the literature. An ISO protocol for the determination of DOC exists since 2018, but it is certified for DOC values ≥ 1 mg L-1, while many publications report DOC values much lower. In addition, this ISO protocol does not include indications on vials cleaning, filtering material, and type of caps and septa to be used. The purpose of this study was to evaluate protocols for measurements of low DOC concentrations (≤ 1 mg L-1). The effect of the sample container, type of septum, filtration material, nature of acid used for storage, and matrix effects on DOC concentration were evaluated.•The use of glass vials decontaminated at 450 °C or 500 °C for at least 1 h, 0.45 µm hydrophilic polytetrafluoroethylene (PTFE) membranes previously rinsed with 20 mL ultra-pure water and HCl acidification gives the lowest DOC contamination,•Sulfides (ΣH2S), sodium (Na+) or calcium (Ca2+) do not induce high matrix effect for the analysis (≤ 10%),•At low DOC concentrations (≤ 1 mg L-1), the use of pierced PTFE septa with acidified samples induce slight DOC contamination after storage at 4 °C, and dramatic contamination after storage at -18 °C.

Impact of a megacity on the water quality of a tropical estuary assessed by a combination of chemical analysis and in-vitro bioassays.

Tropical estuaries are threatened by rapid urbanization, which leads to the spread of thousands of micropollutants and poses an environmental risk to such sensitive aqueous ecosystems. In the present study, a combination of chemical and bioanalytical water characterization was applied to investigate the impact of Ho Chi Minh megacity (HCMC, 9.2 million inhabitants in 2021) on the Saigon River and its estuary and provide a comprehensive water quality assessment. Water samples were collected along a 140-km stretch integrating the river-estuary continuum from upstream HCMC down to the estuary mouth in the East Sea. Additional water samples were collected at the mouth of the four main canals of the city center. Chemical analysis was performed targeting up to 217 micropollutants (pharmaceuticals, plasticizers, PFASs, flame retardants, hormones, pesticides). Bioanalysis was performed using six in-vitro bioassays for hormone receptor-mediated effects, xenobiotic metabolism pathways and oxidative stress response, respectively, all accompanied by cytotoxicity measurement. A total of 120 micropollutants were detected and displayed high variability along the river continuum with total concentration ranging from 0.25 to 78 µg L-1. Among them, 59 micropollutants were ubiquitous (detection frequency ≥ 80 %). An attenuation was observed in concentration and effect profiles towards the estuary. The urban canals were identified as major sources of micropollutants and bioactivity to the river, and one canal (Ben Nghé) exceeded the effect-based trigger values derived for estrogenicity and xenobiotic metabolism. Iceberg modelling apportioned the contribution of the quantified and the unknown chemicals to the measured effects. Diuron, metolachlor, chlorpyrifos, daidzein, genistein, climbazole, mebendazole and telmisartan were identified as main risk drivers of the oxidative stress response and xenobiotic metabolism pathway activation. Our study reinforced the need for improved wastewater management and deeper evaluations of the occurrence and fate of micropollutants in urbanized tropical estuarine environments.

Does eutrophication enhance greenhouse gas emissions in urbanized tropical estuaries?

Estuaries are considered as important sources of the global emission of greenhouse gases (GHGs). Urbanized estuaries often experience eutrophication under strong anthropogenic activities. Eutrophication can enhance phytoplankton abundance, leading to carbon dioxide (CO2) consumption in the water column. Only a few studies have evaluated the relationship between GHGs and eutrophication in estuaries. In this study, we assessed the concentrations and fluxes of CO2, methane (CH4) and nitrous oxide (N2O) in combination with a suite of biogeochemical variables in four sampling campaigns over two years in a highly urbanized tropical estuary in Southeast Asia (the Saigon River Estuary, Vietnam). The impact of eutrophication on GHGs was evaluated through several statistical methods and interpreted by biological processes. The average concentrations of CO2, CH4 and N2O at the Saigon River in 2019-2020 were 3174 ± 1725 µgC-CO2 L-1, 5.9 ± 16.8 µgC-CH4 L-1 and 3.0 ± 4.8 µgN-N2O L-1, respectively. Their concentrations were 13-18 times, 52-332 times, and 9-37 times higher than the global mean concentrations of GHGs, respectively. While CO2 concentration had no clear seasonal pattern, N2O and CH4 concentrations significantly differed between the dry and the rainy seasons. The increase in eutrophication status along the dense urban area was linearly correlated with the increase in GHGs concentrations. The presence of both nitrification and denitrification resulted in elevated N2O concentrations in this urban area of the estuary. The high concentration of CO2 was contributed by the high concentration of organic carbon and mineralization process. GHGs fluxes at the Saigon River Estuary were comparable to other urbanized estuaries regardless of climatic condition. Control of eutrophication in urbanized estuaries through the implantation of efficient wastewater treatment facilities will be an effective solution in mitigating the global warming potential caused by estuarine emissions.

Phytoplankton characterization in a tropical tidal river impacted by a megacity: the case of the Saigon River (Southern Vietnam).

The spatiotemporal variation of phytoplankton and their relationship with environmental variables were analyzed in the Saigon River-a tropical river in Southern Vietnam. Two longitudinal profiles were conducted during dry and rainy season at 18 sampling sites covering more than 60 km long in the river. Besides, a bi-weekly monitoring conducted in the upstream, urban area (Ho Chi Minh City-HCMC), and downstream of Saigon River was organized from December 2016 to November 2017. The major phytoplankton were diatoms (e.g., Cyclotella cf. meneghiniana, Leptocylindrus danicus, Aulacoseira granulata), cyanobacteria (Microcystis spp., Raphidiopsis raciborskii, Pseudanabaena sp.), and euglenoids (Trachelomonas volvocina). Commonly freshwater phytoplankton species and sometimes brackish water species were dominant during the monitoring. Phytoplankton abundances in dry season were much higher than in rainy season (>100 times) which was explained by a shorter riverine water residence time and higher flushing capacity during the dry season. There was a clear separation of phytoplankton abundance between the urban area and the remaining area of Saigon River because of polluted urban emissions of HCMC. Redundancy analysis shows that the environmental variables (TOC, nitrogen, pH, salinity, Mo, Mn) were the driving factors related to the dominance of L. danicus and Cyclotella cf. meneghiniana in the upstream river and urban section of Saigon River. The dominance of cyanobacterium Microcystis spp. in the downstream of Saigon River was related to higher salinity, Mg, Cu concentrations, and lower concentrations of nutrients, Mn, Co, and Mo. The dominance of potentially toxic cyanobacteria in Saigon River possesses health risk to local residents especially upon the increasing temperature context and nutrient loading into the river in the next decades.

Sedimentological and geochemical data in bed sediments from a tropical river-estuary system impacted by a developing megacity, Ho Chi Minh City - Vietnam.

Sedimentological and geochemical data were obtained for bed sediments from a tropical estuary environment in Vietnam in October 2014, January 2016, and November 2016. The data include grain-size distribution, percentage of clay, silt and sand, percentage of organic matter, concentration of total particulate phosphorus (TPP), concentration of particulate inorganic phosphorus (PIP), concentration of particulate organic phosphorus (POP), percentage of total nitrogen (TN), percentage of total carbon (TC), trace metals concentrations (V, Cr, Co, Ni, Cu, Zn, As, Mo, Cd, Pb) and major elements (Al, Fe, Mn). Geochemical indexes (Enrichment factor EF and Geo-accumulation Index I-geo) and sediment quality guideline (mean Effect Range Median quotients) were calculated.

Nutrient dynamics and eutrophication assessment in the tropical river system of Saigon - Dongnai (southern Vietnam).

Saigon-Dongnai Rivers in Southern Vietnam is a complex lowland hydrological network of tributaries that is strongly influenced by the tidal cycles. The increasing economic, industrial and domestic developments in and around Ho Chi Minh City (HCMC) have led to serious impacts on water quality due to lack of appropriate wastewaters treatment. Drinking water production is impacted and the large aquaculture production areas may also be affected. We analyzed spatial and seasonal variability of nutrient concentrations (Phosphorus, Nitrogen and Silica) and eutrophication indicators (Organic Carbon, Chlorophyll-a and Dissolved Oxygen) based on bi-monthly monitoring during two hydrological cycles (July 2015-December 2017). Four monitoring sites were selected to assess the impact of HCMC: two upstream stations on the Saigon River and Dongnai River branches to provide the reference water quality status before reaching the urbanized area of HCMC; one monitoring station in the city center to highlight Saigon River water quality within the heart of the megacity; the fourth station downstream of the confluence to evaluate the impact of HCMC on the estuarine waters. This study points to excess nutrients in HCMC's water body with concentrations of NH4+ and PO43- averaging to 0.7 ±â€¯0.6 mgN L-1 and 0.07 ±â€¯0.06 mgP L-1, respectively in mean over the monitored period and rising up to 3 mgN L-1 and 0.2 mgP L-1, in extreme conditions. During the dry season, we evidenced that untreated domestic discharges leads to degradation of the Saigon River's water quality with extreme values of algal biomass (up 150 µChl-a L-1) and hypoxic conditions occurring episodically (DO < 2 mg L-1) in the heart of the megacity. Until now, eutrophication in the urban center has had no clear effect downstream because eutrophic water mass from the Saigon River is efficiently mixed with the Dongnai River and sea water masses during the successive semi-diurnal tidal cycles.

Atmospheric nitrate export in streams along a montane to urban gradient.

Nitrogen (N) emissions associated with urbanization exacerbate the atmospheric N influx to remote ecosystems - like mountains -, leading to well-documented detrimental effects on ecosystems (e.g., soil acidification, pollution of freshwaters). Here, the importance and fate of N deposition in a watershed was evaluated along a montane to urban gradient, using a multi-isotopic tracers approach (Δ17O, δ15N, δ18O of nitrate, δ2H and δ18O of water). In this setting, the montane streams had higher proportions of atmospheric nitrate compared to urban streams, and exported more atmospheric nitrate on a yearly basis (0.35 vs 0.10 kg-Nha-1yr-1). In urban areas, nitrate exports were driven by groundwater, whereas in the catchment head nitrate exports were dominated by surface runoff. The main sources of nitrate to the montane streams were microbial nitrification and atmospheric deposition, whereas microbial nitrification and sewage leakage contributed most to urban streams. Based on the measurement of δ15N and δ18O-NO3-, biological processes such as denitrification or N assimilation were not predominant in any streams in this study. The observed low δ15N and δ18O range of terrestrial nitrate (i.e., nitrate not coming from atmospheric deposition) in surface water compared to literature suggests that atmospheric deposition may be underestimated as a direct source of N.

How can water quality be improved when the urban waste water directive has been fulfilled? A case study of the Lot river (France).

The Lot river, a major tributary of the downstream Garonne river, the largest river on the Northern side of the Pyrenees Mountains, was intensively studied in the 1970s. A pioneering program called "Lot Rivière Claire" provided a diagnosis of water quality at the scale of the whole watershed and proposed an ambitious program to manage nutrient pollution and eutrophication largely caused by urban wastewater releases. Later on, the implementation of European directives from 1991 to 2000 resulted in the nearly complete treatment of point sources of pollution in spite of a doubling of the basin's population. At the outlet of the Lot river, ammonium and phosphate contamination which respectively peaked to 1 mg N-NH4 L-1 and 0.3 mg P-PO4 L-1 in the 1980s returned to much lower levels in recent years (0.06 mg N-NH4 L-1 and 0.02 mg P-PO4 L-1), a reduction by a factor 15. However, during this time, nitrate contamination has regularly increased since the 1980s, from 0.5 to 1.2 mg N-NO3 L-1 in average, owing to the intensification of agriculture and livestock farming. Application of the Riverstrahler model allowed us to simulate the water quality of the Lot drainage network for the 2002-2014 period. We showed that, with respect to algal requirements, phosphorus and silica are well balanced, but nitrogen remains largely in excess over phosphorus and silica. This imbalance can be problematic for the ecological status of the water bodies. Using the model, for simulating various scenarios of watershed management, we showed that improvement of urban wastewater treatment would not result in any significant change in the river's water quality. Even though arable land occupies a rather limited fraction of the watershed area, only the adoption of better farming practices or more radical changes in the agro-food system could reverse the trend of increasing nitrate contamination.

Impact of anthropogenic activities on water quality and plankton communities in the Day River (Red River Delta, Vietnam).

Planktons are a major component of food web structure in aquatic ecosystems. Their distribution and community structure are driven by the combination and interactions between physical, chemical, and biological factors within the environment. In the present study, water quality and the community structure of phytoplankton and zooplankton were monthly investigated from January to December 2015 at 11 sampling sites along the gradient course of the Day River (Red River Delta, northern Vietnam). The study demonstrated that the Day River was eutrophic with the average values of total phosphorus concentration 0.17 mg/L, total nitrogen concentration 1.98 mg/L, and Chl a 54 µg/L. Microscopic plankton analysis showed that phytoplankton comprised 87 species belonging to seven groups in which Chlorophyceae, Bacillariophyceae, and Cyanobacteria accounted for the most important constituents of the river's phytoplankton assemblage. A total 53 zooplankton species belonging to three main groups including Copepoda, Cladocera, and Rotatoria were identified. Plankton biomass values were greatest in rainy season (3002.10-3 cell/L for phytoplankton and 12.573 individuals/m3 for zooplankton). Using principal correspondence and Pearson correlation analyses, it was found that the Day River was divided into three main site groups based on water quality and characteristics of plankton community. Temperature and nutrients (total phosphorus and total nitrogen) are key factors regulating plankton abundance and distribution in the Day River.

Spatial variation and risk assessment of trace metals in water and sediment of the Mekong Delta.

The Mekong Delta, is home to 17 million inhabitants and faces numerous challenges relating to climate change, environmental degradation and water issues. In this study, we assess trace metals concentrations (Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Hg, Pb) in the water, suspended particulate matter and surface sediments of the Tien River, the Northern branch of the Mekong Delta, during both dry and rainy seasons. Metal concentrations in the dissolved and suspended particle phases remain in the low concentration range of the main Asian Tropical River. During transportation in the riverine part, we evidenced that V, Cr, Co, As and Pb are dominant in the particulate phase while Mo, Ni and Cu dominate in the dissolved fraction. In the salinity gradient, dissolved U, V, Mo exhibit conservative behaviour while Ni, Cu, As, Co and Cd showed additive behaviour suggesting desorption processes. In the surface sediment, metal concentrations are controlled by the particle-size, POC contents and Fe, Al and Mn - oxy(hydr)oxides. Calculated Enrichment Factor and Geoaccumulation Index evidenced As enrichment while the calculated mean effect range median quotients evidenced a low to medium ecotoxicological potential effects range in the surface sediments.

Baseline seasonal investigation of nutrients and trace metals in surface waters and sediments along the Saigon River basin impacted by the megacity of Ho Chi Minh (Vietnam).

The Saigon River, Southern Vietnam, crosses one of the most dynamic developing Megacity in Southeast Asia: Ho Chi Minh City (HCMC). The increased economic, industrial, and domestic developments may affect the environmental quality of water and halieutic resources. In this study, we evaluated the seasonal (dry and wet seasons) biogeochemical state of the Saigon River during two snapshot campaigns conducted along the river basin upstream from HCMC; the Saigon River was characterized by slightly acidic (pH 5.7-7.7) and oxygen-depleted water (dissolved oxygen (DO), 0.36-5.18 mg l-1). Nutrients (N-NH4 = 0.01-2.41, N-NO3 = 0.14-2.72, and P-PO4 = ~0-0.42 mg l-1), DOC (2.2-8.0 mg l-1), POC, and trace metal(oid) (As, Cd, Cr, Cu, Zn, and Hg) concentrations were low showing a good quality of the upstream river. In the urban center area, DO dropped to 0.03 mg l-1 accompanied with a rise of nutrient concentrations (e.g., N-NH4, up to 17.7 mg l-1) likely originating from wastewater discharges. Trace metal concentrations also rose sharply (e.g., Cr and Hg rose up to 10-fold higher) in both water and sediments but remained under the World Health Organization (WHO) and Vietnamese concentration guidelines. In the downstream estuarine area, the intrusion of marine waters diluted water flowing from HCMC, leading water quality to return close to the state observed upstream from HCMC. In general, levels of nutrient and metal contaminations along the Saigon River during both seasons appear moderate regarding to Vietnamese and WHO guidelines although the urban area is highlighted as the major contributor for metal(oid) emissions. Finally, we showed that apart from wastewater and industrial discharges that affect the river quality, metal(oid) partitioning between solid and solution is controlled by the change in water geochemistry along the continuum during both seasons, such as DO (e.g., for As and Cr) and pH (e.g., for Pb) which drives their sorption/dissolution dynamics.