Estuarine hydrodynamic processes driving the molecular changes of terrestrial dissolved organic nitrogen: From mixing to biological modification.

Estuaries receive substantial amounts of terrestrial dissolved organic nitrogen (tDON), which will be transported from the freshwater to the oceanic terminus through vigorous exchange processes. However, the intricate migration and transformation dynamics of tDON during this transportation, particularly at a molecular level, remain constrained. To address this knowledge gap, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used for the analysis of DON molecular composition in the Pearl River Estuary (PRE), a river-dominated estuarine system influenced by intensified anthropogenic activities in southern China. The results showed a pronounced spatial-temporal variation in DON concentration in the study area. At the molecular level, tDON exhibited reduced unsaturation and aromaticity, coupled with an elevated abundance of DON compounds containing one­nitrogen atom (1 N-DON, 53.17 %) and compounds containing carbon, hydrogen, oxygen, nitrogen, and sulfur (CHONS) (27.46 %). It was evident that lignin was depleted while more oxygenated tannin compounds were generated in the freshwater-seawater mixing zone. This transformation is attributed to heightened biological activities, likely influenced by the priming effect of terrestrial nutrient inputs. In summer, the prevailing plume combined with biological activities in the strong mixing area and outer estuary increased the abundance of 3 N-DON molecules and a concurrent rise in the abundance of DON compounds containing only carbon, hydrogen, oxygen, and nitrogen (CHON), DON compounds containing carbon, hydrogen, oxygen, nitrogen, sulfur, and phosphorus (CHONSP), and CHONS. This trend also underscores the expanding role of marine plankton and microbes in the utilization of DON compounds containing carbon, hydrogen, oxygen, nitrogen, and phosphorus (CHONP). These findings provide details of tDON transformation processes at the molecular level in a river-dominated estuary and underline the estuarine hydrodynamics involved in transporting and altering DON within the estuary.

The combined effects of lanthanum-modified bentonite and Vallisneria spiralis on phosphorus, dissolved organic matter, and heavy metal(loid)s.

The use of lanthanum-modified bentonite (LMB) combined with Vallisneria spiralis (V∙s) (LMB + V∙s) is a common method for controlling internal phosphorus (P) release from sediments. However, the behaviors of iron (Fe) and manganese (Mn) under LMB + V∙s treatments, as well as the associated coupling effect on P, dissolved organic matter (DOM), and heavy metal(loid)s (HMs), require further investigations. Therefore, we used in this study a microelectrode system and high-resolution dialysis technology (HR-Peeper) to study the combined effects of LMB and V∙s on P, DOM, and HMs through a 66-day incubation experiment. The LMB + V∙s treatment increased the sediment DO concentration, promoting in-situ formations of Fe (III)/Mn (IV) oxyhydroxides, which, in turn, adsorbed P, soluble tungsten (W), DOM, and HMs. The increase in the concentrations of HCl-P, amorphous and poorly crystalline (oxyhydr) oxides-bound W, and oxidizable HMs forms demonstrated the capacity of the LMB + V∙s treatment to transform mobile P, W, and other HMs forms into more stable forms. The significant positive correlations between SRP, soluble W, UV254, and soluble Fe (II)/Mn, and the increased concentrations of the oxidizable HMs forms suggested the crucial role of the Fe/Mn redox in controlling the release of SRP, DOM, and HMs from sediments. The LMB + V∙s treatment resulted in SRP, W, and DOM removal rates of 74.49, 78.58, and 54.78 %, which were higher than those observed in the control group (without LMB and V∙s applications). On the other hand, the single and combined uses of LMB and V·s influenced the relative abundances of the sediment microbial communities without exhibiting effects on microbial diversity. This study demonstrated the key role of combined LMB and V∙s applications in controlling the release of P, W, DOM, and HMs in eutrophic lakes.

Riverine fluxes of different species of phosphorus in the Pearl River estuary.

Phosphorus is the most limiting nutrient in coastal waters of China, particularly in the Pearl River (PR) estuary. Rivers have different P forms including dissolved inorganic phosphorus (DIP), dissolved organic phosphorus (DOP), particulate inorganic phosphorus (PIP), and particulate organic phosphorus (POP). Their input to coastal seas has been overlooked. We hypothesize that DIP is a small fraction of total phosphorus (TP). We investigated these P forms and estimated their fluxes in PR eight outlets during 2015-2019. DIP on average is only a 30.90 % fraction of TP with PIP, POP and DOP accounting for 22.43, 31.56 and 15.37 %, respectively. The average annual fluxes of TP, DIP, DOP, PIP and POP were 12.58×, 3.34×, 1.68×, 3.19× and 4.26 × 106 mol/month, respectively, which are regulated by runoff and suspended particulate matter (SPM). The finding reveals the importance of other P forms for phytoplankton in the Pearl River estuary and their bio-availability deserves further study.

Ecosystem-scale insights into the dynamics of dissolved organic matter in an Asia's largest brackish water lagoon: Sources, fluxes, and biogeochemical significance.

A twenty-four month long observational study conducted in an Asia's largest brackish water ecosystem, Chilika Lagoon, India, aimed to unravel dissolved organic matter (DOM) dynamics in this tropical brackish water ecosystem. The study assessed the interplay between allochthonous and autochthonous DOM sources during lean and active flow periods based on regional rainfall. Dissolved organic carbon (DOC), nitrogen (DON), and phosphorus (DOP) fluxes were analyzed, considering catchment runoff, phytoplankton production, benthic-pelagic interactions, and sea-lagoon exchanges as contributors. Contrary to conventional thinking, the study found autochthonous processes to be more significant than conservative mixing in shaping DOM dynamics. It introduced a novel conceptual model illustrating the multifaceted origins of DOM, encompassing catchment runoff, phytoplankton, benthic-pelagic interactions, bacterial activity, and sea-lagoon exchanges. These findings underscore the importance of holistic management strategies for Chilika Lagoon to preserve its ecological health, given its vital role in global carbon cycling, fisheries, and aquaculture.

Tradeoffs between pH, dissolved organic carbon, and mineral ions regulate cadmium uptake by Solanum hyperaccumulators in calcareous soil.

Soil solution pH and dissolved organic carbon (DOC) influence cadmium (Cd) uptake by hyperaccumulators but their tradeoff in calcareous soils is unclear. This study investigated the mechanisms of Solanum nigrum L. and Solanum alatum Moench in calcareous soil using a combination of concentration gradient experiments (0.6-100 mg Cd kg-1) and soil solution composition analysis. The results showed that the soil solution pH of S. nigrum remained stable despite Cd stress. On average, the soil solution pH of S. alatum was 0.23 units higher than that of S. nigrum, although pH decreased significantly under high Cd stress. In addition, the concentrations of potassium (K) and calcium (Ca) in the soil solution of S. nigrum increased and decreased under low and high levels of Cd stress, respectively. In S. alatum, the K and Ca concentrations in the soil solution generally increased with increasing Cd stress levels. Moreover, the level of DOC in the soil solution of both plants was higher under Cd stress compared to the control, and a gradually increasing trend with Cd stress level was observed in S. alatum. Consequently, the bioconcentration factors of the roots (2.62-19.35) and shoots (1.20-9.59) of both plants were >1, while the translocation factors were <1, showing an obstacle of Solanum hyperaccumulators in transferring Cd into their aboveground parts. Redundancy analysis revealed that the Cd concentration in S. nigrum roots was significantly negatively correlated with the soil solutions of K and Ca. In contrast, Cd concentrations in S. alatum roots and shoots were significantly positively correlated with soil solution DOC, K, and Ca but negatively correlated with pH. Our results suggest that calcareous soil neutralizes the acidity of released protons but does not affect cation exchange, inhibiting DOC in assisting the translocation of Cd within plants.

Emerging investigator series: impacts of land use on dissolved organic matter quality in agricultural watersheds: a molecular perspective.

In aquatic systems, dissolved organic matter (DOM) has important ecological and biogeochemical functions, where the molecular composition of DOM has larger-scale implications for climate change and global carbon cycles. However, there is limited information about the relationships between landscape characteristics and human disturbance that influence the molecular composition of DOM changes in watersheds. In this study, we collected water samples from 22 sites across a gradient of topographically characterized agricultural land coverage and community infrastructure development in the Kawartha region in Ontario, Canada. We employed a combination of Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and absorbance spectroscopy to investigate changes in the molecular composition of DOM with increasing agricultural and community development disturbance on the optical and molecular characteristics of DOM. We found that dissolved organic carbon (DOC) concentrations in disturbed (>75%) watersheds ranged from 3.67-32.8 mg L-1 and were significantly higher than in watersheds with more abundant forest coverage (3.78-9.13 mg L-1). In addition, watersheds with higher phosphorus concentrations had more negative nominal oxygenation state of carbon (NOSC) values, suggesting biologically processed DOM correlating with increased phosphorus levels in aquatic systems. To relate the molecular properties of DOM to landscape metrics, we used Spearman's correlation analysis to reveal that agriculturally impacted and community developments enhanced the molecular signature of unsaturated hydrocarbon. In addition, we identified 65 dissolved organic phosphorus (DOP) molecules that significantly increased in abundance with disturbance, likely due to microbial mineralization of existing DOM with the addition of phosphorus to form larger, biologically inaccessible molecules. The overall recalcitrance of the identified molecules can serve as molecular signatures when evaluating the level of disturbance of a watershed.

Differential Adsorption of Dissolved Organic Matter and Phosphorus on Clay Mineral in Water-Sediment System.

Lake sediments connection to the biogeochemical cycling of phosphorus (P) and carbon (C) influences streamwater quality. However, it is unclear whether and how the type of sediment controls P and C cycling in water. Here, the adsorption behavior of montmorillonite (Mt) with different interlayer cations (Na+, Ca2+, or Fe3+) on dissolved organic matter (DOM) and P was investigated to understand the role of Mt in regulating the organic carbon-to-phosphate (OC/P) ratio within freshwater systems. The adsorption capacity of Fe-Mt for P was 3.2-fold higher than that of Ca-Mt, while it was 1/3 lower for DOM. This dissimilarity in adsorption led to an increased OC/P in Fe-Mt-dominated water and a decreased OC/P in Ca-Mt-dominated water. Moreover, an in situ atomic force microscope and high-resolution mass spectrometry revealed molecular fractionation mechanisms and adsorptive processes. It was observed that DOM inhibited the nucleation and crystallization processes of P on the Mt surface, and P affected the binding energy of DOM on Mt through competitive adsorption, thereby governing the interfacial P/DOM dynamics on Mt substrates at a molecular level. These findings have important implications for water quality management, by highlighting the role of clay minerals as nutrient sinks and providing new strategies for controlling P and C dynamics in freshwater systems.

Combining lanthanum-modified bentonite and calcium peroxide to enhance phosphorus removal from lake sediments.

Lanthanum-modified bentonite (LMB) and calcium peroxide (CP) are known for their effective removal phosphorus (P) capacities. The present study aims to investigate the effects of the combined use of LMB and CP（LMB + CP）on the sediment P, dissolved organic matter (DOM) and iron (Fe) concentrations through a 90-day incubation experiment. The combined treatment showed strong removal effects on sediment P and DOM. Indeed, the SRP and DOM concentrations in the 0-10 cm sediment layer decreased following the combined application of LMB and CP by 40.67 and 28.95%, respectively, compared to those of the control group (CK). In contrast, the HCl-P in the 0-5 cm sediment layer increased following the combined treatment by 13.28%. In addition, compared with the single application of LMB, the LMB + CP treatment significantly reduced the soluble Fe (Ⅱ) in the sediment pore water and promoted the oxidation of Fe. Therefore, LMB + CP can enhance the removal of internal P from sediments. The DOM removal and Fe oxidation in sediment pore waters are beneficial for enhancing the adsorption of P by LMB. On the other hand, the single and combined applications of LMB and CP increased the richness of the sediment microbial communities while exhibiting slight effects on their diversity. According to the results of this study, the combined use of LMB and oxidizing materials represents a novel method for treating lakes with high internal phosphorus and DOM loads in sediments.

Diatom-dinoflagellate succession in the Bohai Sea: The role of N/P ratios and dissolved organic nitrogen components.

Dissolved organic nitrogen (DON) is a pivotal component of total dissolved nitrogen pools, serving as a crucial nitrogen source for phytoplankton. This study investigated the impact of nitrogen-to-phosphorus (N/P) ratios and different DON components (hydrophilic vs hydrophobic DON) on diatom-dinoflagellate succession through field culture experiments. Results showed that dinoflagellates have a competitive advantage under high N/P ratios and phosphorus limitation, regardless of DON or DIN treatments. Hydrophilic DON exhibits greater bioavailability than hydrophobic DON (40.6% vs. 21.7 %), resulting in increased algal biomass and diatoms dominance in the community. Additionally, DON was categorized into labile and refractory components (LDON and RDON) based on bioavailability. LDON primarily consists of protein-like components that can be readily consumed by algae, whereas RDON is primarily composed of humic-like components that are less accessible to algae. Diatoms and dinoflagellates exhibited differential responses to LDON and RDON, with diatoms thriving in high LDON environments, while dinoflagellates gained a competitive advantage when RDON was the predominant nitrogen source. Furthermore, a significant negative correlation was observed between bioavailable nitrogen concentration (BAN: DIN + LDON) and the ratio of dinoflagellates to diatoms (p<0.05). In conclusion, our study highlights the role of LDON in promoting diatom dominance, whereas environments dominated by RDON foster dinoflagellate success. These findings enhance our comprehension of diatom-dinoflagellate succession dynamics.

Effects and mechanisms of glyphosate as phosphorus nutrient on element stoichiometry and metabolism in the diatom Phaeodactylum tricornutum.

The ability to utilize dissolved organic phosphorus (DOP) gives phytoplankton competitive advantages in P-limited environments. Our previous research indicates that the diatom Phaeodactylum tricornutum could grow on glyphosate, a DOP with carbon-phosphorus (C-P) bond and an herbicide, as sole P source. However, direct evidence and mechanism of glyphosate utilization are still lacking. In this study, using physiological and isotopic analysis, combined with transcriptomic profiling, we demonstrated the uptake of glyphosate by P. tricornutum and revealed the candidate responsible genes. Our data showed a low efficiency of glyphosate utilization by P. tricornutum, suggesting that glyphosate utilization costs energy and that the alga possessed an herbicide-resistant type of 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase. Compared to the P-limited cultures, the glyphosate-grown P. tricornutum cells up-regulated genes involved in DNA replication, cell growth, transcription, translation, carbon metabolism, and many genes encoding antioxidants. Additionally, cellular C and silicon (Si) increased remarkably while cellular nitrogen (N) declined in the glyphosate-grown P. tricornutum, leading to higher Si:C and Si:N ratios, which corresponded to the up-regulation of genes involved in the C metabolism and Si uptake and the down-regulation of those encoding N uptake. This has the potential to enhance C and Si export to the deep sea when P is limited but phosphonate is available. In sum, our study documented how P. tricornutum could utilize the herbicide glyphosate as P nutrient and how glyphosate utilization may affect the element content and stoichiometry in this diatom, which have important ecological implications in the future ocean.IMPORTANCEGlyphosate is the most widely used herbicide in the world and could be utilized as phosphorus (P) source by some bacteria. Our study first revealed that glyphosate could be transported into Phaeodactylum tricornutum cells for utilization and identified putative genes responsible for glyphosate uptake. This uncovers an alternative strategy of phytoplankton to cope with P deficiency considering phosphonate accounts for about 25% of the total dissolved organic phosphorus (DOP) in the ocean. Additionally, accumulation of carbon (C) and silicon (Si), as well as elevation of Si:C ratio in P. tricornutum cells when grown on glyphosate indicates glyphosate as the source of P nutrient has the potential to result in more C and Si export into the deep ocean. This, along with the differential ability to utilize glyphosate among different species, glyphosate supply in dissolved inorganic phosphorus (DIP)-depleted ecosystems may cause changes in phytoplankton community structure. These insights have implications in evaluating the effects of human activities (use of Roundup) and climate change (potentially reducing DIP supply in sunlit layer) on phytoplankton in the future ocean.

Dissolved organic phosphorus promotes Cyclotella growth and adaptability in eutrophic tropical estuaries.

Dissolved organic phosphorus (DOP) is an important nutrient for phytoplankton growth in oligotrophic oceans. However, little is known about the impact of DOP on phytoplankton growth in eutrophic waters. In the present study, we conducted field monitoring as well as in situ and laboratory experiments in the Pearl River estuary (PRE). Field observations showed an increase in the nitrogen-to-phosphorus ratio and DOP in recent years in the PRE. The phytoplankton community was dominated by nanophytoplankton Cyclotella in the upper and middle estuary, with high concentrations of DOP and light limitation during the ebb stage of the spring to neap tide in summer. The relative abundance of Cyclotella in natural waters was higher after enrichment with estuarine water with a background of 0.40-0.46 µM DOP, even when dissolved inorganic phosphorus was sufficient (0.55-0.76 µM). In addition, the relative abundance of Cyclotella in natural waters was higher after enrichment with phosphoesters. Laboratory culture results also confirmed that phosphoesters can enhance the growth rate of Cyclotella cryptica. Our study highlights that Cyclotella can become the dominant species in estuaries with increased levels of phosphoesters and low and fluctuating light adaptability and under the joint effect of dynamic processes such as upwelling and tides. Our results provide new insights into the role of Cyclotella in biogeochemical cycles affected by DOP utilization and potential applications in relieving the hypoxia of tropical eutrophic estuaries.IMPORTANCEThis study provides evidence that Cyclotella can become the dominant species in estuaries with increased levels of phosphoesters and low and fluctuating light adaptability and under the joint effect of dynamic processes such as upwelling and tides. Our study provides new insights into the role of Cyclotella in biogeochemical cycles affected by dissolved organic phosphorus utilization, especially affected by anthropogenic inputs and climate change. Potential applications include relieving the hypoxia of tropical eutrophic estuaries.

[Spatial Distribution of Aerobic Bacteria, Sources and Risks of Nitrogen and Phosphorus in Taihu Lake Sediments].

The release of nitrogen and phosphorus from sediments into lake water will exacerbate the eutrophication of lakes and endanger ecological safety and human health. Microorganisms are indispensable in nitrogen and phosphorus conversion, and accurate analysis of the distribution characteristics and sources of nitrogen and phosphorus in sediments as well as their relationship with microorganisms is an important prerequisite for lake eutrophication control. Taking Taihu Lake as the study area, 30 surface sediment samples were collected, and the grain size, pH, organic matter (OM), dissolved organic carbon (DOC), total phosphorus (TP), total nitrogen (TN), nitrate nitrogen (NO3--N), and dissolved organic nitrogen (DON) along with some other index contents were measured and analyzed; accordingly, spatial distribution characteristics were analyzed. While using nutrient agar (NA), the number of aerobic bacteria (AB) was determined by plate counting in the medium. Combined with principal component analysis (PCA) and Pearson correlation analysis, the spatial distribution characteristics and sources of sediments and AB in Taihu Lake were explored. The characteristics of sediment pollution in Taihu Lake were studied using the comprehensive pollution index and the organic pollution index methods. The results revealed that the average sediment indicators of the surface layer of Taihu Lake were as follows:AB was 9.25×104 CFU·g-1, average particle size (MZ) was 17.59 µm, pH was 7.62, ω(OM) was 15.05 g·kg-1, ω(DOC) was 71.60 mg·kg-1, ω(TP) was 598.13 mg·kg-1, ω(TN) was 1113.92 mg·kg-1, ω(NO3--N) was 3.22 mg·kg-1, and ω(DON) was 22.60 mg·kg-1. The comprehensive pollution index (FF) showed that 13% of the Taihu Lake was moderately polluted, while 87% was heavily polluted. Excluding the area in the center of the lake, the southern lake area, and some lakes in the western part of the East Taihu Lake, TN in the rest of the area was moderately and severely polluted. In addition to the heavy pollution of Zhushan Bay, the TP in Taihu Lake was generally at light and moderate pollution. The organic pollution index (OI) showed that the organic pollution of the sediments of Taihu Lake was relatively light, majorly caused by organic nitrogen (ON) pollution. DOC, DON, TN, and OM in Taihu Lake were primarily derived from the influence of aquatic plants, and TP And AB were primarily derived from the influence of the external input of rivers. This research will provide theoretical support for lake eutrophication treatment and also provide new ideas for further analysis of AB to remove nitrogen and phosphorus pollution from sediments.

Spatiotemporal evolution of dissolved organic matter (DOM) and its response to environmental factors and human activities.

The South-to-North Water Diversion East Project (SNWDP-E) is an effective way to realize the optimal allocation of water resources in China. The North Dasha River (NDR) is the reverse recharge section that receives water from the Yufu River to the Wohushan Reservoir transfer project line in the SNWDP. However, the dissolved organic matter (DOM) evolution mechanism of seasonal water transfer projects on tributary waters has not been fully elucidated. In this paper, the NDR is the main object, and the changes in the composition and distribution of spectral characteristics during the winter water transfer period (WT) as well as during the summer non-water transfer period (NWT) are investigated by parallel factor analysis (PARAFAC). The results showed that the water connectivity caused by water transfer reduces the environmental heterogeneity of waters in the basin, as evidenced by the ammonia nitrogen (NH4+-N) and total phosphorus (TP) in the water body were significantly lower (p<0.05, p<0.01) during the water transfer period than the non-water transfer period. In addition, the fluorescence intensity of DOM was significantly lower in the WT than the NWT (p<0.05) and was mainly composed of humic substances generated from endogenous sources with high stability. While the NWT was disturbed by anthropogenic activities leading to significant differences in DOM composition in different functional areas. Based on the redundancy analysis (RDA) and multiple regression analysis, it was found that the evolution of the protein-like components is dominated by chemical oxygen demand (COD) and NH4+-N factors during the WT. While the NWT is mainly dominated by total nitrogen (TN) and TP factors for the evolution of the humic-like components. This study helps to elucidate the impact of water transfer projects on the trunk basin and contribute to the regulation and management of inter-basin water transfer projects.

Recognizing the variation of DNA-P during and after the algal bloom in lake Hulun.

Eutrophication has spread from shallow lakes in temperature zones to lakes in cold regions as a result of a continuous warm climate and human activities. Little proof for the importance of dissolved organic phosphorus (DOP) in contributing to phosphorus cycling and algae growth has been generated for aquatic ecosystems, particularly in cold eutrophic lakes. In this study, a comprehensive in situ study was conducted in overlying water, suspended particulate matter, and sediment during and after algal bloom (in July and September, respectively) in Lake Hulun. Multiple methods of 31P NMR, enzymatic hydrolysis, and UV-visible technologies were combined to detect phosphorus occurrence, bioavailability, and molecular structure from a novel angle. The 31P NMR analysis results showed that DNA-P is mainly stored in the dissolved phase and has not been detected in suspended particulate matter or sediment. Enzymatic hydrolysis was used to determine the bioavailability of DOP, which revealed that in July and September, respectively, 85% and 79% of DOP were hydrolyzable. UV-visible analysis represented that the degree of humification and molecular weight of DOP were high during the algal bloom, but these values considerably dropped following the algal bloom. The large amount of DNA-P present in the overlying water is the main reason for the high degree of humification and high molecular weight of the water body. Besides, Lake Hulun's DNA-P remains highly bioavailable during algal blooms, despite its high degree of humification and molecular weight. These findings can serve as a theoretical basis for understanding the migration and transformation of DOP, as well as the persistence of algal blooms in eutrophic lakes located in cold regions.

Understanding the role of land use for urban stormwater management in coastal waterways.

A holistic understanding of the quality and quantity of stormwater in the context of catchment land use plays a crucial role in stormwater management. This study investigated the quality and quantity of stormwater from forested, residential, industrial, and mixed land use areas. Water samples were collected from seven sites over two years at different stages of the runoff hydrograph using fixed sampling stations. Analysis of physicochemical and hydrological variables showed different patterns across the four land use types at various flow conditions highlighting the complex nature of stormwater quality influenced by catchment and rainfall characteristics. Mean concentrations of dissolved organic and oxidised nitrogen (DON and NOx-N) and dissolved organic and filterable reactive phosphorus (DOP and FRP) in stormwater from industrial, mixed-use and residential catchment types were statistically different from stormwater originating from a forested catchment. On average, residential, mixed-use and industrial catchments transported over 50 times more NOx-N to the receiving waters compared to forested catchments. Under high flow conditions, total phosphorus, FRP and total suspended solids (TSS) were mobilised, indicating that phosphorous export is directly related to sediment export regardless of the land use. The study outcomes contribute to the formulation of more effective stormwater management strategies to deal with the drivers of nutrients and TSS inputs resulting from modified land use types to minimise the urbanisation impacts on aquatic biota. In particular, the elevated dissolved nitrogen fractions from all the catchment types other than the forested catchment is a concern for receiving waters, as these can potentially impair water quality and impact the ecosystem health of downstream water bodies such as Intermittently Closed and Open Lakes or Lagoons (ICOLL). The stochastic nature of hydrology and corresponding nutrient loads should be prioritised in stormwater management action plans. However, as space limitations hinder the expansion of vegetation cover and retrofitting stormwater management devices, a paradigm shift in stormwater management is required to achieve the desired outcomes. The study outcomes further indicate that a one-size-fits-all approach to stormwater management may not deliver the desired outcomes, and a suite of tailor-made approaches targeting various flow conditions and catchment surface types is needed.

Effects of reservoir construction on optical and molecular characteristics of dissolved organic matter in a typical P-contaminated river.

The source and composition characteristics of dissolved organic matter (DOM) are crucial to identify and evaluate the sources of pollution in the watershed. The construction of reservoirs changes the hydrological condition and pollutant fate of the river. However, the effects of reservoirs' construction on DOM in the watershed and the underlying mechanisms are still unclear. This study aims to examine and compare the characteristics of DOM in reservoirs and streams in the Huangbai River, a typical reservoir-affected and P-contaminated river within the Yangtze River catchment. The results showed that DOM in reservoirs was characterized by more contribution from autochthonous source, under the influence of reservoirs' construction; while, DOM in rivers was mainly originated from terrestrial input. Reservoirs had more lipid-like and protein-like compounds, while rivers contained more oxy-aromatic-like compounds. The percentage of CHOP molecules in reservoirs was significantly higher than that in rivers. The underlying mechanism is that more suitable conditions were created for plankton to grow after constructing reservoirs, which converted inorganic orthophosphate into organic phosphorus, and over time, organic phosphorus was gradually enriched in reservoirs, which exacerbated the risk of eutrophication in the reservoir water body. This study can provide theoretical support for monitoring and evaluation of water quality in reservoir-affected rivers.

Photochemical mobilization of dissolved hydrocarbon oxidation products from petroleum contaminated soil into a shallow aquifer activate human nuclear receptors.

Elevated non-volatile dissolved organic carbon (NVDOC) concentrations in groundwater (GW) monitoring wells under oil-contaminated hydrophobic soils originating from a pipeline rupture at the National Crude Oil Spill & Natural Attenuation Research Site near Bemidji, MN are documented. We hypothesized the elevated NVDOC is comprised of water-soluble photooxidation products transported from the surface to the aquifer. We use field and laboratory samples in combination with complementary analytical methods to test this hypothesis and determine the biological response to these products. Observations from optical spectroscopy and ultrahigh-resolution mass spectrometry reveal a significant correlation between the chemical composition of NVDOC leached from photochemically weathered soils and GW monitoring wells with high NVDOC concentrations measured in the aquifer beneath the contaminated soil. Conversely, the chemical composition from the uncontaminated soil photoleachate matches the NVDOC observed in the uncontaminated wells. Contaminated GW and photodissolution leachates from contaminated soil activated biological targets indicative of xenobiotic metabolism and exhibited potential for adverse effects. Newly formed hydrocarbon oxidation products (HOPs) from fresh oil could be distinguished from those downgradient. This study illustrates another pathway for dissolved HOPs to infiltrate GW and potentially affect human health and the environment.

Atomic-Level Structural Differences between Fe(III) Coprecipitates Generated by the Addition of Fe(III) Coagulants and by the Oxidation of Fe(II) Coagulants Determine Their Coagulation Behavior in Phosphate and DOM Removal.

In situ Fe(III) coprecipitation from Fe2+ oxidation is a widespread phenomenon in natural environments and water treatment processes. Studies have shown the superiority of in situ Fe(III) (formed by in situ oxidation of a Fe(II) coagulant) over ex situ Fe(III) (using a Fe(III) coagulant directly) in coagulation, but the reasons remain unclear due to the uncertain nature of amorphous structures. Here, we utilized an in situ Fe(III) coagulation process, oxidizing the Fe(II) coagulant by potassium permanganate (KMnO4), to treat phosphate-containing surface water and analyzed differences between in situ and ex situ Fe(III) coagulation in phosphate removal, dissolved organic matter (DOM) removal, and floc growth. Compared to ex situ Fe(III), flocs formed by the natural oxidizing Fe2+ coagulant exhibited more effective phosphate removal. Furthermore, in situ Fe(III) formed through accelerated oxidation by KMnO4 demonstrated improved flocculation behavior and enhanced removal of specific types of DOM by forming a more stable structure while still maintaining effective phosphate removal. Fe K-edge extended X-ray absorption fine structure spectra (EXAFS) of the flocs explained their differences. A short-range ordered strengite-like structure (corner-linked PO4 tetrahedra to FeO6 octahedra) was the key to more effective phosphorus removal of in situ Fe(III) than ex situ Fe(III) and was well preserved when KMnO4 accelerated in situ Fe(III) formation. Conversely, KMnO4 significantly inhibited the edge and corner coordination between FeO6 octahedra and altered the floc-chain-forming behavior by accelerating hydrolysis, resulting in a more dispersed monomeric structure than ex situ Fe(III). This research provides an explanation for the superiority of in situ Fe(III) in phosphorus removal and highlights the importance of atomic-level structural differences between ex situ and in situ Fe(III) coprecipitates in water treatment.

Cyanobacterial blooms increase the release of vanadium through iron reduction and dissolved organic matter complexation in the sediment of eutrophic lakes.

Vanadium (V), a hazardous environmental contaminant, can be highly toxic to aquatic or even human life. Nonetheless, knowledge of its redox geochemistry and mobility in sediments, especially those of eutrophic lakes, remains limited. In this study, we combined in situ high-resolution sampling and laboratory simulation experiments for monitoring soluble and labile V to reveal the mobilization mechanism of V in the sediment of Lake Taihu. The results showed that the concentration of soluble V (1.18-5.22 µg L-1) exceeded the long-term ecotoxicology limitation proposed by the government of the Netherlands. The highest value appeared in summer (July to September), with an average concentration of 3.87 µg L-1, which exceeded the short-term exposure limit. The remobilization of V in summer was caused by the combined effect of the reduction of Fe(hydr)oxides and dissolved organic matter (DOM) complexation, which accelerated the release of associated Fe-bound V and increased the solubility of DOM-V. Additionally, V showed high mobility in winter, owing to the species of V(Ⅲ)/V(Ⅳ) being oxidized to V(Ⅴ) with higher solubility. It is noteworthy that the elevated remobilization of V in sediments increases the risk of V release from sediments, which poses the threat of water V pollution in Lake Taihu.

Effect of passively aerated biological pretreatment on different biomasses with diverse lignocellulosic fiber profiles.

Passively aerated biological pretreatment was applied to four different lignocellulosic biomasses with varying fiber content profiles: sugar beet pulp (SBP), brewery bagasse (BB), rice husk (RH), and orange peel (OP). In order to analyze the organic matter solubilization yield at 24 and 48 h, different percentages of activated sewage sludge (2.5-10%) were utilized as inoculum. The OP achieved the best organic matter solubilization yield in terms of soluble chemical oxygen demand (sCOD) and dissolved organic carbon (DOC) at 2.5% inoculation and 24 h: 58.6% and 20%, respectively, since some total reducing sugars (TRS) consumption was identified after 24 h. On the contrary, the worst organic matter solubilization yield was obtained with RH, the substrate with the highest lignin content among the tested, with percentages of 3.6% and 0.7% in terms of sCOD and DOC respectively. In fact, it could be considered that this pretreatment was not successful with RH. The optimum inoculation proportion was 7.5% (v/v) except for the OP (2.5% (v/v)). Finally, due to the counterproductive organic matter consumption at longer pretreatment durations, the optimal time for BB, SBP, and OP was 24 h.