Significant accrual of soil organic carbon through long-term rice cultivation in paddy fields in China.

Paddy fields serve as significant reservoirs of soil organic carbon (SOC) and their potential for terrestrial carbon (C) sequestration is closely associated with changes in SOC pools. However, there has been a dearth of comprehensive studies quantifying changes in SOC pools following extended periods of rice cultivation across a broad geographical scale. Using 104 rice paddy sampling sites that have been in continuous cultivation since the 1980s across China, we studied the changes in topsoil (0-20 cm) labile organic C (LOC I), semi-labile organic C (LOC II), recalcitrant organic C (ROC), and total SOC. We found a substantial increase in both the content (48%) and density (39%) of total SOC within China's paddy fields between the 1980s to the 2010s. Intriguingly, the rate of increase in content and density of ROC exceeded that of LOC (I and II). Using a structural equation model, we revealed that changes in the content and density of total SOC were mainly driven by corresponding shifts in ROC, which are influenced both directly and indirectly by climatic and soil physicochemical factors; in particular temperature, precipitation, phosphorous (P) and clay content. We also showed that the δ13 CLOC were greater than δ13 CROC , independent of the rice cropping region, and that there was a significant positive correlation between δ13 CSOC and δ13 Cstraw . The δ13 CLOC and δ13 CSOC showed significantly negative correlation with soil total Si, suggesting that soil Si plays a part in the allocation of C into different SOC pools, and its turnover or stabilization. Our study underscores that the global C sequestration of the paddy fields mainly stems from the substantial increase in ROC pool.

Effects of Cu(II)-DOM complexation on DOM degradation: Insights from spectroscopic evidence.

The fate of dissolved organic matter (DOM) is primarily governed by its sources, degradation, and transformation processes within the environment. However, the influence of metal-DOM complexation on DOM degradation remains ambiguous. In this study, controlled laboratory experiments were conducted using Cu(II) and natural water from the Duliujian River and the Beidagang Wetland to examine the effects of metal-DOM binding on the degradation pathway of DOM. Our results showed that Cu(II)-DOM complexation affected the distribution of DOM molecular weight with elevated Mw after complexed with Cu(II). Nevertheless, the concentration of DOM decreased over the incubation period due to degradation. In the absence of Cu(II) binding, both wetland and river DOM followed similar degradation pathways, transforming from high to low molecular weight with changes predominantly in the 1-10 kDa size-fraction during DOM degradation. In contrast, in the presence of Cu(II) and thus Cu(II)-DOM binding, the degradation of DOM was enhanced, resulting in higher kinetic rate constants for both wetland and river DOM. The results of differential spectra further confirmed the degradation of DOM with a decrease in bulk spectroscopic properties and an increase in the degree of DOM-Cu(II) complexation. These findings imply a mutually reinforcing relationship between metal-DOM complexation and the degradation of DOM in aquatic environments, providing new insights into the biogeochemical behavior and environmental fate of DOM.

Distinct variations in fluorescent DOM components along a trophic gradient in the lower Fox River-Green Bay as characterized using one-sample PARAFAC approach.

Variations in molecular weight distributions of dissolved organic matter (DOM) and PARAFAC-derived fluorescent components were investigated along a transect in the seasonally hypereutrophic lower Fox River-Green Bay using the one-sample PARAFAC approach coupling flow field-flow fractionation for size-separation with fluorescence excitation-emission matrix (EEM) and PARAFAC analysis. Concentrations of dissolved organic carbon and nitrogen, chromophoric-DOM, specific UV absorbance at 254 nm, and humification index all decreased monotonically from river to open bay, showing a strong river-dominated DOM source and a dynamic change in DOM quality along the river-lake transect. The relative abundance of colloidal DOM (>1 kDa) derived from ultrafiltration exhibited minimal variation, averaging 71 ± 4 % of the bulk DOM, across the entire estuarine transect although the colloidal concentration decreased in general. Using the one-sample EEM-PARAFAC approach, the identified major fluorescent components were distinct between stations along the river-estuary-open bay continuum, with four components in river/upper-estuary but three components in open bay waters. Among the four common fluorescent components (C475, C410, C320 and C290), the most abundant and refractory humic-like component, C475, behaved conservatively and its relative abundance (%ΣFmax) remained fairly constant (50 ± 4 %) along the transect, while the semi-labile humic-like component, C410, consistently decreased from river to estuary and eventually vanished in open Green Bay. In contrast, the two autochthonous protein-like components (C320 and C290) increased from river to open bay along the trophic gradient. The new results presented here provide an improved understanding of the diverse and fluctuating characteristics in DOM composition, lability, and estuarine mixing behavior across the river-lake interface and demonstrate the efficacy of the one-sample PARAFAC approach.

Microplastics in aquatic environments: A comprehensive review of toxicity, removal, and remediation strategies.

The occurrence of microplastics (MPs) in aquatic environments has been a global concern because they are toxic and persistent and may serve as a vector for many legacies and emerging pollutants. MPs are discharged to aquatic environments from different sources, especially from wastewater plants (WWPs), causing severe impacts on aquatic organisms. This study mainly aims to review the Toxicity of MPs along with plastic additives in aquatic organisms at various trophic compartments and available remediation methods/strategies for MPs in aquatic environments. Occurrences of oxidative stress, neurotoxicity, and alterations in enzyme activity, growth, and feeding performance were identical in fish due to MPs toxicity. On the other hand, growth inhibition and ROS formation were observed in most of the microalgae species. In zooplankton, potential impacts were acceleration of premature molting, growth retardation, mortality increase, feeding behaviour, lipid accumulation, and decreased reproduction activity. MPs togather with additive contaminants could also exert some toxicological impacts on polychaete, including neurotoxicity, destabilization of the cytoskeleton, reduced feeding rate, growth, survivability and burrowing ability, weight loss, and high rate of mRNA transcription. Among different chemical and biological treatments for MPs, high removal rates have been reported for coagulation and filtration (>86.5 %), electrocoagulation (>90 %), advanced oxidation process (AOPs) (30 % to 95 %), primary sedimentation/Grit chamber (16.5 % to 58.84 %), adsorption removal technique (>95 %), magnetic filtration (78 % to 93 %), oil film extraction (>95 %), and density separation (95 % to 100 %). However, desirable extraction methods are required for large-scale research in MPs removal from aquatic environments.

Comparisons in molecular weight distributions and size-dependent optical properties among model and reference natural dissolved organic matter.

Humic acid (HA) and reference natural organic matter (NOM) have been widely used in environmental assessment, biogeochemistry, and ecotoxicity studies. Nevertheless, similarities and differences among the commonly used model/reference NOMs and bulk dissolved organic matter (DOM) have rarely been systematically evaluated. In this study, HA, SNOM (Suwannee River NOM) and MNOM (Mississippi River NOM), both from International Humic Substances Society, and freshly collected unfractionated NOM (FNOM) were concurrently characterized to evaluate their heterogeneous nature and size-dependent chemical properties. We found that molecular weight distributions, PARAFAC-derived fluorescent components, and size-dependent optical properties are NOM-specific and highly variable with pH. The < 1 kDa DOM abundance followed the order of HA < SNOM < MNOM < FNOM. In addition, FNOM was more hydrophilic and contained more protein-like and autochthonous components with a higher UV-absorbance ratio index (URI) and biological fluorescence index, whereas HA and SNOM contained more allochthonous, humic-like components with a higher aromaticity and lower URI. Significant differences in molecular composition and size spectra between FNOM and model/reference NOMs suggest that environmental role of NOMs should be evaluated at the levels of molecular weight and functionalities under the same experimental conditions and that HA and SNOM may not represent bulk NOM in the environment. This study provides new information about similarities and differences in DOM size-spectra and chemical properties between reference NOMs and in-situ NOM and highlights the need to better understand the heterogenous roles of NOMs in regulating the toxicity/bioavailability and environmental fate of pollutants in aquatic environments.

Role of molecular weight-dependent spectral properties in regulating Cu(II) binding by dissolved organic matter from different sources.

The complexation of metals with dissolved organic matter (DOM) under different compositions and molecular weights (MWs) will result in different environmental fate and toxicity, but the specific role and impact of DOM MWs remain less well understood. This study explored the metal binding characteristics by DOM with different MWs from different sources, including sea, river, and wetland waters. The results of fluorescence characterization showed that the >1 kDa high-molecular-weight (HMW)-DOM were mainly from terrestrial sources while the low-molecular-weight (LMW)-DOM fractions were mostly from microbial sources. Based on UV-Vis spectroscopic characterization, the LMW-DOM contained more unsaturated bonds than its HMW counterpart, and the substituents are generally dominated by polar functional groups. Summer DOM had more unsaturated bonds and a higher metal binding capacity than winter DOM. Furthermore, DOM with different MWs had significantly different Cu binding properties. In addition, Cu binding with microbially derived LMW-DOM mainly caused the change in the peak at 280 nm, while binding with terrigenous HMW-DOM resulted in the change of the 210 nm peak. Compared with the HMW-DOM, most of the LMW-DOM had stronger Cu-binding ability. Correlation analysis indicates that metal binding ability of DOM mainly depends on its concentration, number of unsaturated bonds and benzene rings, and types of substituents during interactions. This work provides an improved understanding of the metal-DOM binding mechanism, the role of composition- and MW-dependent DOM from different sources, and thus the transformation and environmental/ecological role of metals in aquatic systems.

Specific PhytOC fractions in rice straw and consequent implications for potential of phytolith carbon sequestration in global paddy fields.

Phytoliths are silica biomineralization products within plants and have been considered as a promising material to sequester carbon (C). However, there is considerable uncertainty and controversy regarding the C content in phytoliths due to the lack of detailed information on variation of C under different extraction procedures. Herein, we established a series of batch digestion experimental procedures coupled with analyses of phytoliths using Scanning Electron Microscopy and Energy-Dispersive X-ray Spectroscopy to divide phytoliths into three fractions. We then reported an approach for standardizing across hundreds of values found in the literature. Combining this standardized approach with C contents in phytoliths extracted from different digestion degrees, we revaluated the potential production rates of phytolith-occluded carbon (PhytOC) input globally in rice paddy fields. The results showed that the C content in recovered phytoliths exhibited a significantly fitting exponential relationship (p < 0.01) with digestion degrees and decreased from 30 to 75 g kg-1 under moderate digestion to <5 g kg-1 under over digestion. On a global scale, the production of total PhytOC in the world paddy fields reached up to (2.71 ± 0.85) × 106 t year-1. Therein, the contribution of sub-stable PhytOC fraction, stable PhytOC fraction, and recalcitrant PhytOC fraction was 63 %, 28 %, and 9 %, respectively. Our results imply that the estimation of phytolith C sequestration potential across the global paddy fields is associated with specific PhytOC fractions. Therefore, further determining the storage time limits of these specific PhytOC fractions after returning to soil will be vital for predicting terrestrial biogeochemical C sequestration potentials of phytoliths.

Storage, patterns and influencing factors for soil organic carbon in coastal wetlands of China.

Soil organic carbon (SOC) in coastal wetlands, also known as "blue C," is an essential component of the global C cycles. To gain a detailed insight into blue C storage and controlling factors, we studied 142 sites across ca. 5000 km of coastal wetlands, covering temperate, subtropical, and tropical climates in China. The wetlands represented six vegetation types (Phragmites australis, mixed of P. australis and Suaeda, single Suaeda, Spartina alterniflora, mangrove [Kandelia obovata and Avicennia marina], tidal flat) and three vegetation types invaded by S. alterniflora (P. australis, K. obovata, A. marina). Our results revealed large spatial heterogeneity in SOC density of the top 1-m ranging 40-200 Mg C ha-1 , with higher values in mid-latitude regions (25-30° N) compared with those in both low- (20°N) and high-latitude (38-40°N) regions. Vegetation type influenced SOC density, with P. australis and S. alterniflora having the largest SOC density, followed by mangrove, mixed P. australis and Suaeda, single Suaeda and tidal flat. SOC density increased by 6.25 Mg ha-1 following S. alterniflora invasion into P. australis community but decreased by 28.56 and 8.17 Mg ha-1 following invasion into K. obovata and A. marina communities. Based on field measurements and published literature, we calculated a total inventory of 57 × 106 Mg C in the top 1-m soil across China's coastal wetlands. Edaphic variables controlled SOC content, with soil chemical properties explaining the largest variance in SOC content. Climate did not control SOC content but had a strong interactive effect with edaphic variables. Plant biomass and quality traits were a minor contributor in regulating SOC content, highlighting the importance of quantity and quality of OC inputs and the balance between production and degradation within the coastal wetlands. These findings provide new insights into blue C stabilization mechanisms and sequestration capacity in coastal wetlands.

Occurrence of microplastics in commercial marine dried fish in Asian countries.

The major risk of microplastics in marine environments is the bioaccumulation in marine organisms. Plastic ingestion by marine organisms has been investigated and recently more attention has been given to microplastics in seafood. However, it is seldom reported the occurrence of microplastics in marine commercial dried fish products available for human consumption. Here, we report the occurrence of microplastics in 14different marine dried fish products from seven Asian countries. Microplastics were observed in most dried fish, with fibers representing ~80% of the total-microplastics. The major plastic polymers, identified using Micro-Raman spectroscopy, included polyethylene (35%), polyethylene terephthalate (26%), polystyrene (18%), polyvinyl chloride (12%), and polypropylene (9%). The highest count, in either per individual (1.92 ± 0.12) or per gram of dried fish (0.56 ± 0.03), were found in Etrumeus micropus from Japan. Marine dried fish, which are typically eaten whole, may contribute to the ingestion of microplastics by humans, posing potential health risks especially in Asian countries. Further studies are needed to identify the occurrence of smaller sized microplastics and nanoplastics and their potential health impacts.

Differences in the spectroscopic characteristics of wetland dissolved organic matter binding with Fe3+, Cu2+, Cd2+, Cr3+ and Zn2.

Understanding of the binding characteristics of wetland dissolved organic matter (DOM) and different metals is important for the quantitative assessment of the environmental behavior of metals in wetlands. In this study, different types of spectroscopy including ultraviolet-visible absorption, Fourier transform infrared, and fluorescence spectroscopy was used to investigate the binding characteristics of Fe3+, Cu2+, Cr3+, Cd2+, and Zn2+ with DOM from wetland water. Differential absorption spectra identified binding sites for these five metals in this wetland DOM at 210 nm, 280 nm, 335 nm, and > 400 nm regions. The low binding capacity of DOM in this wetland with Cd and Zn indicated that the toxicity and environmental effects of these metals in this wetland warrant further study. The calculated △EEM combined with fluorescence regional integration (FRI) analysis clearly revealed that Fe and Cu preferred to bind with humic-like DOM while Cd and Zn preferred to bind with protein-like DOM in this wetland. △EEM successfully demonstrated the characteristics of DOM complexing with different metals and could be a compelling tool in evaluating metal-DOM interactions. In addition, 2D-FTIR-COS identified the binding sites and the dynamic processes of binding at the functional group level. Metals preferentially bind with the CO, CO functional group, and then binds to the OH functional group. This study revealed that different DOM components will facilitate the migration of different metals in the environment and provided new slights into an improved understanding of migration and transformation of metals in aquatic environments.

Synchronous evaporation and aquatic primary production in tropical river networks.

Rivers play an important role in global water and carbon cycling, but there are still large uncertainties concerning evaporation and aquatic photosynthesis. Here we combined measurements of water chemistry, isotopic compositions (i.e., δDw, δ18Ow, δ13CDIC and ▵14CDIC) and geographic characteristics (i.e., river width) to elucidate in-stream hydrological and biogeochemical processes across rivers in Hainan Island, China. The results showed that dissolved inorganic carbon (DIC) in river waters was largely of modern origin, with about 95% from contemporary biogenic sources based on an isotopic mass balance of ▵14CDIC. Significant evaporation and aquatic primary production co-occurred in these tropical rivers with large amounts of water and DIC being rapidly turned over in the water column, altering the water cycle and the carbon balance. High rates of evaporation and aquatic primary production were observed in the headwater segments, with narrow river width but broad available reactive surface area at the air-water interface. The asymmetric aquatic photosynthesis at different river segments caused the spatial heterogeneities of dissolved solutes. The results suggest that the available reactive area at the water-air interface is responsible for synchronous water loss and dissolved carbon evolution in flat tropical rivers. This study provides evidence that intense evaporation and aquatic photosynthesis mainly occurred in headwater segments, which has implications for understanding global carbon cycling.

Partitioning and transformation of organic and inorganic phosphorus among dissolved, colloidal and particulate phases in a hypereutrophic freshwater estuary.

Phosphorus (P) loadings to the Great Lakes have been regulated for decades, but re-eutrophication and seasonal hypoxia have recently been increasingly reported. It is of paramount importance to better understand the fate, transformation, and biogeochemical cycling processes of different P species across the river-lake interface. We report here results on chemical speciation of P in the seasonally hypoxic Fox River-Green Bay system and variations in sources and partitioning of P species along the aquatic continuum. During midsummer when productivity is generally high, phosphate and dissolved organic P (DOP) were the major species in river water while particulate-organic-P predominated in open bay waters, showing a dynamic change in the chemical speciation of P along the river-bay transect with active transformations between inorganic and organic P and between colloidal and particulate phases. Colloidal organic P (COP, >1 kDa) comprised 33‒65% of the bulk DOP, while colloidal inorganic P was generally insignificant and undetectable especially in open bay water. Sources of COP changed from mainly allochthonous in the Fox River, having mostly smaller sized colloids (1-3 kDa) and a lower organic carbon to phosphorus (C/P) ratio, to predominantly autochthonous in open bay waters with larger sized colloids (>10 kDa) and a higher organic C/P ratio. The observed high apparent distribution coefficients (Kd) of P between dissolved and particulate phases and high-abundant autochthonous colloidal and particulate organic P in the hypereutrophic environment suggest that, in addition to phosphate, colloidal/particulate organic P may play a critical role in the biogeochemical cycling of P and the development of seasonal hypoxia.

Spartina alterniflora invasion controls organic carbon stocks in coastal marsh and mangrove soils across tropics and subtropics.

Coastal wetlands are among the most productive ecosystems and store large amounts of organic carbon (C)-the so termed "blue carbon." However, wetlands in the tropics and subtropics have been invaded by smooth cordgrass (Spartina alterniflora) affecting storage of blue C. To understand how S. alterniflora affects soil organic carbon (SOC) stocks, sources, stability, and their spatial distribution, we sampled soils along a 2500 km coastal transect encompassing tropical to subtropical climate zones. This included 216 samplings within three coastal wetland types: a marsh (Phragmites australis) and two mangroves (Kandelia candel and Avicennia marina). Using δ13 C, C:nitrogen (N) ratios, and lignin biomarker composition, we traced changes in the sources, stability, and storage of SOC in response to S. alterniflora invasion. The contribution of S. alterniflora-derived C up to 40 cm accounts for 5.6%, 23%, and 12% in the P. australis, K. candel, and A. marina communities, respectively, with a corresponding change in SOC storage of +3.5, -14, and -3.9 t C ha-1 . SOC storage did not follow the trend in aboveground biomass from the native to invasive species, or with vegetation types and invasion duration (7-15 years). SOC storage decreased with increasing mean annual precipitation (1000-1900 mm) and temperature (15.3-23.4℃). Edaphic variables in P. australis marshes remained stable after S. alterniflora invasion, and hence, their effects on SOC content were absent. In mangrove wetlands, however, electrical conductivity, total N and phosphorus, pH, and active silicon were the main factors controlling SOC stocks. Mangrove wetlands were most strongly impacted by S. alterniflora invasion and efforts are needed to focus on restoring native vegetation. By understanding the mechanisms and consequences of invasion by S. alterniflora, changes in blue C sequestration can be predicted to optimize storage can be developed.

Distribution, sources, and decomposition of soil organic matter along a salinity gradient in estuarine wetlands characterized by C:N ratio, δ13 C-δ15 N, and lignin biomarker.

Despite increasing recognition of the critical role of coastal wetlands in mitigating climate change, sea-level rise, and salinity increase, soil organic carbon (SOC) sequestration mechanisms in estuarine wetlands remain poorly understood. Here, we present new results on the source, decomposition, and storage of SOC in estuarine wetlands with four vegetation types, including single Phragmites australis (P, habitat I), a mixture of P. australis and Suaeda salsa (P + S, habitat II), single S. salsa (S, habitat III), and tidal flat (TF, habitat IV) across a salinity gradient. Values of δ13 C increased with depth in aerobic soil layers (0-40 cm) but slightly decreased in anaerobic soil layers (40-100 cm). The δ15 N was significantly enriched in soil organic matter at all depths than in the living plant tissues, indicating a preferential decomposition of 14 N-enriched organic components. Thus, the kinetic isotope fractionation during microbial degradation and the preferential substrate utilization are the dominant mechanisms in regulating isotopic compositions in aerobic and anaerobic conditions, respectively. Stable isotopic (δ13 C and δ15 N), elemental (C and N), and lignin composition (inherited (Ad/Al)s and C/V) were not completely consistent in reflecting the differences in SOC decomposition or accumulation among four vegetation types, possibly due to differences in litter inputs, root distributions, substrate quality, water-table level, salinity, and microbial community composition/activity. Organic C contents and storage decreased from upstream to downstream, likely due to primarily changes in autochthonous sources (e.g., decreased onsite plant biomass input) and allochthonous materials (e.g., decreased fluvially transported upland river inputs, and increased tidally induced marine algae and phytoplankton). Our results revealed that multiple indicators are essential to unravel the degree of SOC decomposition and accumulation, and a combination of C:N ratios, δ13 C, δ15 N, and lignin biomarker provides a robust approach to decipher the decomposition and source of sedimentary organic matter along the river-estuary-ocean continuum.

Variations in Colloidal DOM Composition with Molecular Weight within Individual Water Samples as Characterized by Flow Field-Flow Fractionation and EEM-PARAFAC Analysis.

Fluorescence excitation emission matrices (EEM) and parallel factor (PARAFAC) analysis have been widely used in the characterization of dissolved organic matter (DOM) in the aquatic continuum. However, large sample sets are typically needed for establishing a meaningful EEM-PARAFAC model. Applications of the EEM-PARAFAC technique to individual samples require new approaches. Here, flow field-flow fractionation (FlFFF) combined with offline EEM measurements and PARAFAC analysis was used to elucidate the dynamic changes in DOM composition/optical properties with molecular weight within individual samples. FlFFF-derived size spectra of ultrafiltration-isolated colloidal DOM show that peak-C related fluorophores (Ex/Em= 350/450 nm) are present mostly in the 1-3 kDa size range, while peak-T associated fluorophores (Ex/Em = 275/340 nm) have a bimodal distribution with peaks in both the 1-3 kDa and the >100 kDa size fractions. The integrated EEM spectra from FlFFF size-fractionated subsamples closely resembled the bulk EEM spectra, attesting to the convincing comparability between bulk and FlFFF size-fractionated EEMs. The PARAFAC-derived DOM components are distinctive among individual samples with the predominant components being humic-like in river water, but protein-like in a highly eutrophic lagoon sample. This compelling new approach combining FlFFF and EEM-PARAFAC can be used to decipher the dynamic changes in size spectra and composition of individual DOM samples from sources to sinks or across the redox/hydrological/trophic interfaces.

Mitigative effects of natural and model dissolved organic matter with different functionalities on the toxicity of methylmercury in embryonic zebrafish.

Dissolved organic matter (DOM) occurs ubiquitously in aquatic environments and plays an intrinsic role in altering the chemical speciation and toxicity of methylmercury (MeHg). However, interactions between MeHg and natural DOM remain poorly understood, especially at the functional group level. We report here the mitigative effects of three natural organic matter (NOM) and five model-DOM under different concentrations (0, 1, 3, 10, 30 and 100 mg-C/L) on the toxicity of MeHg in embryonic zebrafish (<4 h post-fertilization, hpf). NOM are those from the Mississippi River, Yukon River, and Suwannee River, while model-DOM include those containing thiosalicylic acid, L-glutathione, dextran, alginic acid, and humic acid. We selected a MeHg concentration (100 n-mol/L) that reduces the survival rate of embryos at 24 hpf by 18% and increases malformations at 72 and 96 hpf. In the presence of DOM, however, the malformation rates induced by MeHg can be mitigated to a different extent depending on DOM concentrations, specific functional groups, and/or specific components. Model DOM with aromatic thiols was the most effective at mitigating the effects of MeHg, followed by L-glutathione, carbohydrates, and humic acid. NOM also mitigated the toxicity of MeHg dependent on their composition and/or effective DOM components as characterized by fluorescence excitation-emission matrix techniques. Specifically, humic-like DOM components are more effective in reducing the MeHg toxicity in the embryonic zebrafish compared to protein-like components. Further studies are needed to elucidate the interactions between DOM and MeHg and the mitigative mechanisms at the molecular level.

Role of organic components in regulating denitrification in the coastal water of Daya Bay, southern China.

Both dissolved and particulate organic materials have been proposed to be important factors in regulating heterotrophic denitrification in various aquatic environments. However, the specific pathways and mechanisms remain elusive. In this study, water column samples were collected from Daya Bay, southern China, to examine the relationships between potential denitrification and different organic components in the water column. Bulk dissolved organic carbon (DOC) was categorized into three major components including terrigenous fluorescent (tFDOC), autochthonous fluorescent (bFDOC) and non-fluorescent (nFDOC) fractions, while the bulk particulate organic carbon (POC) was divided into terrigenous (tPOC) and autochthonous (bPOC) fractions based on an isotope mixing model. Potential denitrification derived from in situ incubation experiments under anoxic conditions was evident (ranging from 6 to 107 nmol N2 per L per h) and varied markedly among stations. When normalized to nitrate concentration, the denitrification rate (NDR) followed a positive trend with either the concentration or proportion of tFDOC, and a negative trend with the proportion of nFDOC, suggesting tFDOC was potentially favorable while nFDOC was unfavorable for denitrifying degradation. In comparison, the NDR showed a significant positive correlation with the proportion of bPOC in the bulk POC (p = 0.01), with a predictive power of >70%, indicating that the composition of POC has a substantial impact on potential denitrification. Furthermore, if both bPOC and suspended particulate matter (SPM) were considered as variables concurrently, the variability of NDR can be better predicted with a predictive power as high as 80%. Therefore, denitrifiers may preferentially utilize fresher and labile autochthonous POC instead of DOC especially in coastal waters where particles/colloids are abundant. Our results thus provide new insights for a better understanding of denitrification mechanisms in water columns and the importance of both suspended particles and POC components in regulating denitrification, especially in turbid and productive coastal environments.

Dynamic molecular size transformation of aquatic colloidal organic matter as a function of pH and cations.

Knowledge of the dynamic changes in molecular size of natural colloidal organic matter (COM) along the aquatic continuum is of vital importance for a better understanding of the environmental fate and ecological role of dissolved organic matter and associated contaminants in aquatic systems. We report here the pH- and cation-dependent size variations of COMs with different sources (river and lake) quantified using flow field-flow fractionation (FIFFF), fluorescence spectroscopy and parallel factor analysis (PARAFAC), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and zeta potential analysis. Increasing pH caused a decline in molecular sizes and an obvious size transformation from the >10 kDa to 5-10 kDa and further to 1-5 kDa size fraction, whereas the opposite trend was observed for increasing cation (e.g., Ca2+ and Cu2+) abundance. Compared with lakewater COM, the riverwater COM exhibited a greater pH-dependent dispersion but less extent in cation-induced aggregation, demonstrating that the dispersion and aggregation dynamics were highly dependent on COM source and solution chemistry (e.g., pH and cations). Based on ATR-FTIR analysis, the extensive dissolution of C=O and C-O functional groups resulted in a greater pH-dependent dispersion for river COM. Fluorescence titration revealed that, despite their similar cation-induced aggregation behavior, the binding constants of all the PARAFAC-derived components for Cu2+ were 1-2 orders of magnitude higher than those for Ca2+ (logKM: 4.54-5.45 vs. 3.35-3.70), indicating a heterogeneous nature in cation-DOM interactions. The greater extent of decline in zeta potential for lake COM suggested a Ca-induced charge neutralization and aggregation mechanism. However, for Cu-induced aggregation, chemical complexation was the predominant pathway for the river COM, with higher binding constants, while charge neutralization and chemical complexation co-induced the aggregation of lake COM. Thus, natural COMs may have different environmental behavior along the aquatic continuum and further affect the fate and transport of contaminants in aquatic environments.

Dissolved organic matter binding with Pb(II) as characterized by differential spectra and 2D UV-FTIR heterospectral correlation analysis.

Dissolved organic matter (DOM) in aquatic environment significantly influences the behavior and fate of heavy metals via binding, complexation and thus changes the metal speciation; however detailed interfacial processes and mechanisms are still unclear. Here, differential absorbance and fluorescence spectra and two dimensional UV-FTIR heterospectral correlation analysis were applied to probe into the Pb(II)-DOM interaction at a wide range of pH and ionic strength (IS). The absorbance of DOM molecules under all conditions increased with metal addition, while the different extents of absorbance variations along the wavelength range in the differential zero-order and log-transformed absorbance spectra indicated the site heterogeneity within the DOM pool for metal binding. Spectral parameters, namely differential fluorescent components 1 and 2 (DFC1 and DFC2) and differential slopes of log-transformed absorbance in the range of wavelength 350-400 nm (DSlope350-400) were found to be highly correlated with the total amounts of DOM-bound Pb(II) predicted by the NICA-Donnan model, while the differential absorbance spectra at 235 nm (DA235) was related to the extent of Pb(II) bound by carboxylic groups. Thus, these parameters are an indicator or proxy for the in situ Pb(II)-DOM interaction extent. Aryl C-H gave the fastest response to Pb(II) binding at lower pH and IS (e.g., pH 4.7 and IS = 0.01 M), followed by carboxyl C=O and polysaccharide C-OH and then chromophoric groups at 265 nm (CDOM265). However, the CDOM265 bound to Pb(II) prior to aryl C-H and polysaccharide C-OH groups at higher pH and IS (6.0 and 0.1 M, respectively), showing that the binding sequences were highly dependent on solution chemistry. Differential spectra combined with two dimensional UV-FTIR heterospectral correlation analysis can be used as a promising approach to elucidate metal-DOM interaction processes, including site heterogeneity, binding sensitivity and sequence at the functional group level.

Exposure to ZnO nanoparticles alters neuronal and vascular development in zebrafish: Acute and transgenerational effects mitigated with dissolved organic matter.

Exposure to ZnO-nanoparticles (NPs) in embryonic zebrafish reduces hatching rates which can be mitigated with dissolved organic material (DOM). Although hatching rate can be a reliable indicator of toxicity and DOM mitigation potential, a fish that has been exposed to ZnO-NPs or any other toxicant may also exhibit other abnormal phenotypes not readily detected by the unaided eye. In this study, we moved beyond hatching rate analysis to investigate the consequences of ZnO-NPs exposure on the nervous and vascular systems in developing zebrafish. Zebrafish exposed to ZnO-NPs (1-100 ppm) exhibited an array of cellular phenotypes including: abnormal secondary motoneuron (SMN) axonal projections, abnormal dorsal root ganglion development and abnormal blood vessel development. Dissolved Zn (<10 kDa) exposure also caused abnormal SMN axonal projections, but to a lesser extent than ZnO-NPs. The ZnO-NPs-induced abnormal phenotypes were reversed in embryos concurrently exposed with various types of DOM. In these acute mitigation exposure experiments, humic acid and carbohydrate, along with natural organic matter obtained from the Suwannee River in Georgia and Milwaukee River in Wisconsin, were the best mitigators of ZnO-NPs-induced motoneuron toxicity at 96 h post fertilization. Further experiments were performed to determine if the ZnO-NPs-induced, abnormal axonal phenotypes and the DOM mitigated axonal phenotypes could persist across generations. Abnormal SMN axon phenotypes caused by ZnO-NPs-exposure were detected in F1 and F2 generations. These are fish that have not been directly exposed to ZnO-NPs. Fish mitigated with DOM during the acute exposure (F0 generation) had a reduction in abnormal motoneuron axon errors in larvae of subsequent generations. Therefore, ZnO-NPs exposure results in neurotoxicity in developing zebrafish which can persist from one generation to the next. Mitigation with DOM can reverse the abnormal phenotypes in an acute embryonic exposure context, as well as across generations, resulting in healthy fish.