Assessment of occurrence, partitioning and ecological risk for 144 steroid hormones in Taihu Lake using UPLC-MS/MS with machine learning model.

Steroid hormones (SHs) have attracted mounting attention due to their endocrine-disrupting effects on humans and aquatic organisms. However, the lack of analytical methods and toxicity data for a large number of SHs has limited the effective management of SH contamination in the water-sediment systems. In this study, we developed a highly sensitive analytical method for the simultaneous quantification of 144 SHs to investigate their occurrence, spatial distribution and partitioning in the water and sediment in Taihu Lake. The results showed that the total concentrations of SHs in water and sediment were 366.88-998.23 ng/L (mean: 612.84 ng/L) and 17.46-150.20 ng/g (mean: 63.41 ng/g), respectively. The spatial distribution of SHs in Taihu Lake might be simultaneously influenced by the pollution sources, lake hydrodynamics, and sediment properties. The sediment-water partitioning result implied that 28 SHs were in dynamic equilibrium at the water-water interface. In addition, 22 and 12 SHs tended to spread to water and settle into sediment, respectively. To assess the ecological risk of all SHs, a robust random forest model (R2 = 0.801) was developed to predict the acute toxicity of SHs for which toxicity data were not available from publications. Risk assessment showed that SHs posed a high ecological risk throughout Taihu Lake, with the highest risk in the northwestern areas. Estrone, 17ß-estradiol and 17α-ethynylestradiol were the dominant risk contributors and were therefore recommended as the priority SHs in Taihu Lake. This work provided a valuable dataset for Taihu Lake, which would help to provide guidance and suggestions for future studies and be useful for the government to develop the mitigation and management measures.

Characteristics of the presence and migration patterns of DOM between ice and water in the cold and arid Daihai Lake.

Seasonal ice cover plays a crucial role in shaping the physical characteristics of lakes in cold and arid regions. Moreover, the ice significantly affects the level and quality of dissolved organic matter (DOM) in the water column. We utilized spectroscopy and mass spectrometry to analyze the molecular composition and distribution of DOM in ice cores and under-ice water in Daihai Lake. We identified the main environmental factors affecting DOM migration through structural equation modelling (SEM). The freezing process created a repulsive effect on DOM, with water samples demonstrating a greater DOM content than ice. The dominant part of the DOM in the ice cores was mainly comprised of protein-like materials (71.45 %), whereas water consisted of humus-like materials (54.81 %). The average molecular weight of the ice cover DOM (m/z = 396.77) was smaller than in the under-ice water (m/z = 405.42). While low-molecular and low-aromatic protein-like material tended to be trapped in the ice layer during ice formation, large-molecular and highly aromatic humic substances were more easily expelled into the water. Interestingly, condensed aromatic hydrocarbons were found to occur less frequently in the ice phase (11 %) compared to the aqueous phase (13 %). Both the lipid and protein/aliphatic compound structures exhibited slightly higher ratios in the ice (6 % and 8 %, respectively) than in water (1 % and 5 %, respectively). SEM between the ice cover environment and DOM indicated that the ice can influence the distribution pattern of DOM through the regulation of internal solute factors and other chemicals. The nature of the DOM and the rate of ice growth also play critical roles in determining the distribution mechanism of DOM for ice and water. The pollutant distribution characteristics and migration patterns between ice and water are essential for comprehending environmental water pollution and promoting pollution management and protection measures in cold region lakes.

Spatiotemporal distributions and ecological risk of polycyclic aromatic hydrocarbons in the surface seawater of Laizhou Bay, China.

The spatial-temporal distribution, source, and potential ecological risk of polycyclic aromatic hydrocarbons (PAHs) in surface seawater from Laizhou Bay were investigated. The total PAH (ΣPAH) concentrations ranged from 277 to 4393 ng/L with an average of 1178 ng/L, thereby suggesting a relatively moderate to high PAH exposure level in Laizhou Bay in comparison to other bays in the world. The composition patterns and source apportionment results revealed that the coal, biomass burning, diesel emissions, and petroleum combustion as well as the combination of these processes were the dominant sources of PAHs in the surface water, which were closely associated with sail process and sewage effluents. The ecological risk assessment indicated that benzo(a)pyrene (BaP), phenanthrene (Phe), luoranthene (Flua), and naphthalene (Nap) would exist ecological risks in most of surface seawater sites, but the probabilistic risk assessment (PRA) results showed that the current level of risk is not as severe as the risk quotient (RQ) results revealed.

Global scale identification of catchments phosphorus source shifts with urbanization: A phosphate oxygen isotope and Bayesian mixing model approach.

Different scenarios of urban expansion can influence the dynamic characteristics of catchments in terms of phosphorus (P). It is important to identify the changes in P sources that occur during the process of urbanization to develop targeted policies for managing P in catchments. However, there is a knowledge gap in quantifying the variations of potential P sources associated with urbanization. By combining phosphate oxygen isotopes from global catchments with a Bayesian model and the urbanization process, we demonstrate that the characteristics of potential P sources (such as fertilizers, urban wastewater, faeces, and bedrock) change as urban areas expand. Our results indicate that using phosphate oxygen isotopes in conjunction with a Bayesian model provides direct evidence of the proportions of potential P sources. We classify catchment P loadings into three stages based on shifts in potential P sources during urban expansion. During the initial stage of urbanization (urban areas < 1.5 %), urban domestic and industrial wastewater are the main contributors to P loadings in catchments. In the mid-term acceleration stage (1.5 % ≤ urban areas < 3.5 %), efforts to improve wastewater treatment significantly reduce wastewater P input, but the increase in fertilizer P input offsets this reduction in sewage-derived P. In the high-level urbanization stage (urban areas ≥ 3.5 %), the proportions of the four potential P sources tend to stabilize. Remote areas bear the burden of excessive P loadings to meet the growing food demand and improved diets resulting from the increasing urban population. Our findings support the development of strategies for water quality management that better consider the driving forces of urbanization on catchment P loadings.

Source partitioning using phosphate oxygen isotopes and multiple models in a large catchment.

Excessive phosphorus (P) loadings cause major pollution concerns in large catchments. Quantifying the point and nonpoint P sources of large catchments is essential for catchment P management. Although phosphate oxygen isotopes (δ18O(PO4)) can reveal P sources and P cycling in catchments, quantifying multiple P sources in a whole catchment should be a research focus. Therefore, this study aimed to quantitatively identify the proportions of multiple potential end members in a typical large catchment (the Yangtze River Catchment) by combining the phosphate oxygen isotopes, land use type, mixed end-element model, and a Bayesian model. The δ18O(PO4) values of river water varied spatially from 4.9‰ to18.3‰ in the wet season and 6.0‰ to 20.9‰ in the dry season. Minor seasonal differences but obvious spatial changes in δ18O(PO4) values could illustrate how human activity changed the functioning of the system. The results of isotopic mass balance and the Bayesian model confirmed that controlling agricultural P from fertilizers was the key to achieving P emission reduction goals by reducing P inputs. Additionally, the effective rural domestic sewage treatment, development of composting technology, and resource utilization of phosphogypsum waste could also contribute to catchment P control. P sources in catchment ecosystems can be assessed by coupling an isotope approach and multiple-models.

The pollution of microplastics in sediments of the Yangtze River Basin: Occurrence, distribution characteristics, and basin-scale multilevel ecological risk assessment.

Microplastics (MPs) pollution in the Yangtze River Basin (YRB) of China has grown to be a serious issue, yet there is a lack of understanding of the environmental risks of MPs in the sediment of the entire basin. This work revealed the spatial distribution characteristics of MPs in YRB sediments, and it methodically assessed the ecological risks of MPs by taking into consideration their abundance, toxic effects, and polymer types. The results showed a high heterogeneity in the abundance of MPs in YRB sediments, with an average of 611 particles/kg dry weight (DW) sediment. Small-sized MPs (<1 mm), fibrous, transparent-colored and polypropylene (PP) accounted for the majority with 71.6%, 68%, 37% and 30.8%, respectively. Correlation analysis indicated significant influences of human activities such as population, industrial structure, and urban wastewater discharge on the abundance and morphological types of MPs in sediments. Based on chronic toxicity data exposed to sediments, a predicted no-effect concentration (PNEC) of 539 particles/kg DW was calculated using the species susceptibility distribution (SSD). Multiple deterministic risk assessment indices indicated that MPs in YRB sediments exhibited primarily low pollution load levels, moderate-to-low potential ecological risk levels, and high levels of polymer pollution. However, probabilistic risk assessment revealed an overall low risk of MPs in YRB sediments. Monte Carlo simulation results demonstrated that polyvinyl chloride (PVC) and polycarbonate (PC) made a great contribution to ecological risk and should be considered as priority control pollutants in MPs. In addition, various assessments showed that the ecological risk of MPs in river sediments was higher than that in lake reservoir sediments. This is the first study to comprehensively assess the ecological risk of MPs in sediments of the YRB, which improves the understanding of the basin-wide occurrence characteristics and environmental risks of MPs in freshwater systems.

Distribution, abundance, and risks posed by microplastics in surface waters of the Yangtze River Basin, China.

Microplastic (MP) pollution in the Yangtze River Basin, China, has become an environmental issue of great concern. However, most studies on MPs have focused on a part of the Yangtze River Basin, and still lack knowledge on the risk of MPs exposure in surface waters of the whole basin. This study overviews the differences in abundance and spatial distribution of MPs in surface waters basin-wide and comprehensively assesses the ecological risk of MPs exposure in surface waters of the Yangtze River Basin by considering the abundance and toxicity effects. The results showed that the MP abundance at the collected sampling sites ranged from 0 to 44,080 particles/m3, with a mean of 3441 particles/m3. MPs were unevenly distributed throughout the basin, with hotspots such as Three Gorges Reservoir, Yangtze River estuary, and some urban lakes showing relatively higher abundance than the surroundings. Based on the available toxicity data, chronic and acute predicted no-effect concentrations (PNECs) of 12.3 particles/L and 21 particles/L were derived for freshwater MPs exposure using constructed species sensitivity distributions (SSDs). The hazard quotient (HQ) method was used to compare the environmental exposure concentrations of MPs with PNECs, and the results showed that 71.8% of the sampling sites in the Yangtze River Basin had moderate chronic ecological risk, while 43% of the sampling sites had moderate acute ecological risk. Overall, the ecological risk of MPs in lake and reservoir water was higher than that in river water. Joint probability curves (JPCs) showed that the overall risk probability of MPs in the surface water of the Yangtze River Basin was lower than that of other basins in China and other countries. This research provides valuable information for the ecological risk assessment of MPs at the watershed scale.

Multiple Risk Assessment of Heavy Metals in Surface Water and Sediment in Taihu Lake, China.

Taihu Lake is the third-largest freshwater lake in eastern China. The contamination of heavy metals (HMs) in Taihu Lake resulting from rapid economic development and population growth has raised significant concerns in recent years. In this study, the contents and spatial distributions of eight typical HMs (Hg, Cr(VI), As, Cd, Cu, Ni, Pb, and Zn) in the fresh surface water and sediments from Taihu Lake were investigated. The potential ecological and health risks posed by HMs were evaluated using multiple assessment methods. Risk quotients were used to assess the ecological risks of HMs, and chronic risk quotients of Cu, Ni, and Pb (>1.0) were found in the surface water of Taihu Lake. According to the geo-accumulation index (Igeo) and pollution load index (PLI) values, the lake sediments exhibited moderate risks of Cd and Hg. In general, the sediments were moderately contaminated by HMs based on the average risk index (RI < 300). Spatially, a high ecological risk posed by the HMs existed in the sediments of northern Taihu Lake (RI > 300), while the sediments in the southwestern and eastern regions had moderate risk levels. The non-carcinogenic risk levels of Hg, Cd, Cu, and Zn were acceptable based on the exposure characteristics of residents living around Taihu Lake. The carcinogenic risk levels of Cr(VI), As, Pb, and Ni through drinking water were acceptable. However, the ingestion of Cr(VI), As, and Ni through drinking water and fish consumption may pose certain health risks. Therefore, the levels of toxic metals, in particular, Cr(VI), As, and Ni, in edible organisms should be monitored periodically and controlled to alleviate the potential carcinogenic risks through food ingestion. Our work provides valuable information concerning the ecological risk distribution of HMs in Taihu Lake, which is essential for protecting the safety of aquatic organisms and human health and minimizing HM pollution in the lake.

Pollution levels and risk assessment of thallium in Chinese surface water and sediments.

Thallium (Tl) is one of the most toxic metals and can cause chronic and acute damage to humans. Due to occurrences of incidents involving Tl pollution in China, its potential environmental impacts are receiving increased attention. However, there is still limited information on Tl concentrations in the environment and their risks to human health and wildlife. This paper provides an overview of the contamination of surface water and sediments by Tl across China and assesses the potential risks using several methods. The acute and chronic aquatic life criteria for Tl were determined to be 13.25 and 1.65 µg/L, respectively. The acute and chronic risk quotients (RQs) of Tl in surface water near mining areas were 0.01-41.51 and 0.20-666.67, respectively, indicating medium to high ecological risks to aquatic organisms. Tl in sediments of Pearl and Gaofeng rivers pose a high risk based on the higher geo-accumulation index (Igeo) and potential ecological risk index (EI) values. Exposure parameters for the Chinese population were used to derive health criteria and assess non-carcinogenic risk posed by Tl in centralized drinking water sources. Tl criteria for protection of human health were calculated to be 0.18 µg/L for water+organisms and 0.30 µg/L for organisms only. The non-carcinogenic risk posed by Tl was acceptable. The human health criteria of Tl for children were the lowest among all age groups. The risks posed by Tl to health of children are greater than those for adults. Therefore, emphasis should be placed on protecting children from exposure to Tl. For the Chinese population, the drinking water guidance value to ensure protection of human health was determined to be 0.44 µg/L. The availability of multiple Tl guidance values for designated water uses will improve the environmental regulation and surveillance of Tl pollution in China and other countries.

Development of regional water quality criteria of lead for protecting aquatic organism in Taihu Lake, China.

Lead is a widely distributed priority controlled heavy metals in aquatic system, its toxicity to aquatic organisms affected by water quality parameters. This study investigated the acute toxicity of lead (Pb) to the aquatic organisms in Taihu Lake under various water hardness, corresponding regional water quality criteria were derived. The acute toxicity experimental results revealed that the toxicity of Pb to aquatic organisms increased with water hardness. The Pb toxicity has a highest toxicity at water hardness 50 mg/L (expressed as CaCO3), especially for Palaemon modestus where the 96 h LC50 value was 0.024 mg/L. The hazardous concentration for 5% of biological species (HC5) values were determined via species sensitivity distribution (SSD) method as 94.0 µg/L, 222.3 µg/L and 375.8 µg/L for Pb at water hardness 50, 150, and 250 mg/L, respectively. The assessment factor (AF) value was set at 2, followed by the current SSD framework where European commission recommend a fixed AF of 5-1. Thus, the predicted no effect concentration (PNEC) values was 47.0 µg/L, 111.2 µg/Land 187.9 µg/L at water hardness 50, 150, and 250 mg/L, respectively. Meanwhile, the short-term water quality criteria of Pb for Taihu lake aquatic organisms were derived as 111.2 µg/L at water hardness 150 mg CaCO3/L. The long-term water quality criteria were derived as 4.3 µg/L by using acute/chronic ratio 51.29. When the derived value was used for Taihu Lake, 2.7% of the sampling sites in Taihu Lake was exceeded this criterion. The results of this study can provide technical methods and basic information for deriving Pb regional water quality criteria for protecting native aquatic organisms, in China.

Derivation of water quality criteria of zinc to protect aquatic life in Taihu Lake and the associated risk assessment.

Zinc is a widely distributed environmental pollutants and has been listed as priority heavy metal pollutant in China. Similar as other heavy metals, toxicity of zinc to aquatic organisms affects by environmental factors such as water hardness. It is necessary to develop regional water quality criteria (WQC) to protect native aquatic life against zinc due to the diversity of aquatic organisms' variability across different water systems, as a concretization and supplement for national zinc WQC. This study derived WQC for zinc by species sensitivity distribution (SSD) curve method. The zinc toxicity data of the aquatic organisms in Taihu Lake used in SSD curve was collected based on published toxicity data for zinc with hardness values and supplemented with acute toxicity tests conducted in this study. Six aquatic organism natives to Taihu Lake were selected to conduct zinc acute toxicity test in a range of hardness conditions. The relationship between water hardness and zinc toxicity was constructed. The criterion maximum concentration (CMC) and criterion continuous concentration (CCC) for zinc in Taihu Lake were then derived, which considered the water quality and taxonomic groups in Taihu Lake. The CMC and CCC were 100.69 µg/L and 30.79 µg/L, respectively. The environmental risk of zinc to Taihu Lake are acceptable, at moderate to low levels. This study has provided a basis for regional water quality criterion derivation and risk assessment in China.

Evaluation of toxicological responses and promising biomarkers of topmouth gudgeon (Pseudorasbora parva) exposed to fipronil at environmentally relevant levels.

Fipronil is an insecticide commonly used in agriculture. We report here on the sublethal and sub-chronic effects of fipronil on non-target topmouth gudgeon (Pseudorasbora parva) at environmentally relevant levels. The results showed that fipronil did not cause significant changes in brain acetylcholinesterase activities, glutathione S-transferase (GST) activities in the intestine, and GST, glutamic pyruvic transaminase (GPT), and glutamic oxaloacetic transaminase (GOT) activities in the liver tissues at environmentally relevant levels for 96-h exposure. In the further test for a 12-day exposure, dose-dependent responses of the serum GPT and GOT activities were observed in all treated groups with sublethal concentrations of fipronil. Furthermore, fipronil could reduce the liver mitochondrial membrane fluidity of P. parva, especially with high concentration of fipronil at high temperature. The results suggest that serum GPT and GOT in P. parva might be useful biomarkers for effects of fipronil exposure at environmentally relevant level, and reducing fluidity of liver mitochondrial membrane may be one toxic mechanism of fipronil.

Microplastics contamination in different trophic state lakes along the middle and lower reaches of Yangtze River Basin.

Microplastics can enter freshwater lakes through many sources. They can act as carriers to adsorb bacteria, virus, or pollutants (e.g., heavy metal and toxic organic compounds) that threaten human health through food chain. Microplastics can exist in surface water and sediments in freshwater lakes after they enter the lakes through discharge points. Wastewater discharge is the main cause of lake eutrophication and is the main emission source of microplastics. The correlation between lake trophic state and microplastic abundance has been rarely reported. This study investigated the microplastic contamination in surface water and sediments of 18 lakes along the middle and lower reaches of the Yangtze River Basin in the period of August-September 2018. The correlation between lake trophic state and microplastic abundance in surface water and sediments was investigated and discussed. The microplastic abundance in surface water was approximately two orders of magnitude lower than that in sediments in all 18 lakes. Hong Lake had the highest microplastic abundance in surface water sample, and Nantaizi Lake had the highest microplastic abundance in sediment sample. The dominant microplastic shape was fiber of 93.81% in surface water sample and 94.77% in sediment sample. Blue-colored microplastics were dominant in nearly all lakes in surface water sample (around 40%-60%) and sediment sample (around 60%-80%), followed by purple- and green-colored ones. The microplastics size <1 mm was dominant in surface water sample (around 40%-60%) and sediment sample (around 50%-80%). The dominant material was polypropylene in surface water sample (around 60%-80%) and sediment sample (around 40%-60%).

Occurrence and mass balance of sixty-two progestins in a municipal sewage treatment plant.

Progestins (PGs) are a group of steroid hormones known to have endocrine-disrupting effects. These compounds can enter the aquatic environment via the discharge of treated or untreated wastewater and the disposal of sludge from sewage treatment plants (STPs); thus, their removal in STPs are of great importance. The present study simultaneously investigated the occurrences and fates of 62 PGs in a municipal STP in Beijing, China. Progesterone (P) and its metabolites were found to be the predominant compounds, with total dissolved concentrations of 1866 ng/L in the influent. About 11 P metabolites were newly detected, accounting for 25-55% and 75-91% of the total concentrations in wastewater and sludge, respectively. For the other three groups of PGs derived from different parent compounds, P derivatives were first detected in the STP with the highest concentration in the wastewater and sludge, followed by 19-nortestosterone (NT) derivatives and 17α-hydroxyprogesterone (17α-OHP) derivatives. The removal efficiencies in the dissolved phase of wastewater were relatively high for P and its metabolites (95-99%) and P derivatives (91-99%). And the relative persistence of NT (68-99%) and 17α-OHP derivatives (79-99%) was observed during the wastewater treatment processes. Mass balance analysis showed that the lost mass proportions were as high as 41-99%, the mass fractions in sludge were in the range of 0-55%, and 0.24-25% of the initial mass loadings was present in the effluent. These results indicated that biodegradation was the major removal mechanism of PGs in the STP.

Spatial and Temporal Distributions of Short-, Medium-, and Long-Chain Chlorinated Paraffins in Sediment Cores from Nine Lakes in China.

The spatial and temporal distributions of short-, medium-, and long-chain chlorinated paraffins (SCCPs, MCCPs, and LCCPs) were studied in sediment cores and surface sediment from nine lakes in China. The highest total CP concentrations in surface sediment were found in the plateau lakes of southwest China, followed by lakes in the northeast, east, and remote northwest. The concentrations of three CP groups in cores showed an increasing trend from the 1970s to 2014, with the most rapid increase occurring from the late 2000s to 2014, consistent with the statistics on historical production of CPs in China. The three CP groups showed site-specific profiles in sediments from the nine lakes, and their percentages changed with sedimentary years. In sediment samples with dated year after 1980, MCCPs were dominant in sediment from Lakes Sihailongwan maar, Taihu, Erhai, and Chenghai, and LCCPs were predominant compounds in the other five lakes. The proportions of LCCPs rapidly increased after 1980, reflecting the increasing production and usage of LCCPs in China. The total burdens of ∑SCCPs, ∑MCCPs, and ∑LCCPs in sediment prior to 2006 were estimated to be 0.26-5100, 0.29-21000, and 0.07-4300 kg, respectively, which were 1.4-440-fold higher than those of ∑PBDEs.

Temporal variation in zooplankton and phytoplankton community species composition and the affecting factors in Lake Taihu-a large freshwater lake in China.

Monitoring diverse components of aquatic ecosystems is vital for elucidation of diversity dynamics and processes, which alter freshwater ecosystems, but such studies are seldom conducted. Phytoplankton and zooplankton are integral components which play indispensable parts in the structure and ecological service function of water bodies. However, few studies were made on how zooplankton and phytoplankton community may respond simultaneously to change of circumstance and their mutual relationship. Therefore, we researched synchronously the phytoplankton communities as well as zooplankton communities based on monthly monitoring data from September 2011 to August 2012 in heavily polluted areas and researched their responses to variation in environmental parameters and their mutual relationship. As indicated by Time-lag analysis (TLA), the long-term dynamics of phytoplankton and zooplankton were undergoing directional variations, what's more, there exists significant seasonal variations of phytoplankton and zooplankton communities as indicated by Non-Metric Multidimensional scaling (NMDS) methods. Also, Redundancy Analysis (RDA) demonstrated that environmental indicators together accounted for 25.6% and 50.1% variance of phytoplankton and zooplankton, respectively, indicating that environmental variations affected significantly on the temporal dynamics of phytoplankton as well as zooplankton communities. What's more, variance partioning suggested that the major environmental factors influencing variation structures of zooplankton communities were water temperature, concentration of nitrogen, revealing the dominating driving mechanism which shaped the communities of zooplankton. It was also found that there was significant synchronization between zooplankton biomass and phytoplankton biomass (expressed as Chl-a concentration), which suggested that zooplankton respond to changes in dynamic structure of phytoplankton community and can initiate a decrease in phytoplankton biomass through grazing in a few months.

Model for Predicting Toxicities of Metals and Metalloids in Coastal Marine Environments Worldwide.

Metals can pose hazards to marine species and can adversely affect structures and functions of communities of marine species. However, little is known about how structural properties of metal atoms combined with current geographical and climatic conditions affect their toxic potencies. A mathematical model, based on quantitative structure-activity relationships and species sensitivity distributions (QSAR-SSD) was developed by use of acute toxicities of six metals (Cd, Cr, Cu, Hg, Ni, and Zn) to eight marine species and accessory environmental conditions. The model was then used to predict toxicities of 31 metals and metalloids and then to investigate relationships between acute water quality criteria (WQC) and environmental conditions in coastal marine environments. The model was also used to predict WQC in the coastal areas of different countries. Given global climate change, the QSAR-SSD model allows development of WQC for metals that will be protective of marine ecosystems under various conditions related to changes in global climate. This approach could be of enormous benefit in delivering an evidence-based approach to support regulatory decision making in management of metal and metalloids in marine waters.

Cation-induced coagulation of aquatic plant-derived dissolved organic matter: Investigation by EEM-PARAFAC and FT-IR spectroscopy.

Complexation and coagulation of plant-derived dissolved organic matter (DOM) by metal cations are important biogeochemical processes of organic matter in aquatic systems. Thus, coagulation and fractionation of DOM derived from aquatic plants by Ca(II), Al(III), and Fe(III) ions were investigated. Metal ion-induced removal of DOM was determined by analyzing dissolved organic carbon in supernatants after addition of these metal cations individually. After additions of metal ions, both dissolved and coagulated organic fractions were characterized by use of fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis and Fourier transform infrared (FT-IR) spectroscopy. Addition of Ca(II), Fe(III) or Al(III) resulted in net removal of aquatic plant-derived DOM. Efficiencies of removal of DOM by Fe(III) or Al(III) were greater than that by Ca(II). However, capacities to remove plant-derived DOM by the three metals were less than which had been previously reported for humic materials. Molecular and structural features of plant-derived DOM fractions in associations with metal cations were characterized by changes in fluorescent components and infrared absorption peaks. Both aromatic and carboxylic-like organic matters could be removed by Ca(II), Al(III) or Fe(III) ions. Whereas organic matters containing amides were preferentially removed by Ca(II), and phenolic materials were selectively removed by Fe(III) or Al(III). These observations indicated that plant-derived DOM might have a long-lasting effect on water quality and organisms due to its poor coagulation with metal cations in aquatic ecosystems. Plant-derived DOM is of different character than natural organic matter and it is not advisable to attempt removal through addition of metal salts during treatment of sewage.

Simulated bioavailability of phosphorus from aquatic macrophytes and phytoplankton by aqueous suspension and incubation with alkaline phosphatase.

Bioavailability of phosphorus (P) in biomass of aquatic macrophytes and phytoplankton and its possible relationship with eutrophication were explored by evaluation of forms and quantities of P in aqueous extracts of dried macrophytes. Specifically, effects of hydrolysis of organically-bound P by the enzyme alkaline phosphatase were studied by use of solution 31P-nuclear magnetic resonance (NMR) spectroscopy. Laboratory suspensions and incubations with enzymes were used to simulate natural releases of P from plant debris. Three aquatic macrophytes and three phytoplankters were collected from Tai Lake, China, for use in this simulation study. The trend of hydrolysis of organic P (Po) by alkaline phosphatase was similar for aquatic macrophytes and phytoplankton. Most monoester P (15.3% of total dissolved P) and pyrophosphate (1.8%) and polyphosphate (0.4%) and DNA (3.2%) were transformed into orthophosphate (14.3%). The major forms of monoester P were glycerophosphate (8.8%), nucleotide (2.5%), phytate (0.4%) and other monoesters P (3.6%). Proportions of Po including condensed P hydrolyzed in phytoplankton and aquatic macrophytes were different, with the percentage of 22.6% and 6.0%, respectively. Proportion of Po hydrolyzed in debris from phytoplankton was approximately four times greater than that of Po from aquatic macrophytes, and could be approximately twenty-five times greater than that of Po in sediments. Thus, release and hydrolysis of Po, derived from phytoplankton debris would be an important and fast way to provide bioavailable P to support cyanobacterial blooming in eutrophic lakes.

Predicting criteria continuous concentrations of metals or metalloids for protecting marine life by use of quantitative ion characteristic-activity relationships-species sensitivity distributions (QICAR-SSD).

Marine pollution by metals has been a major challenge for ecological systems; however, water quality criteria (WQC) for metals in saltwater is still lacking. Especially from a regulatory perspective, chronic effects of metals on marine organisms should receive more attention. A quantitative ion characteristic-activity relationships-species sensitivity distributions (QICAR-SSD) model, based on chronic toxicities for eight marine organisms, was established to predict the criteria continuous concentrations (CCCs) of 21 metals. The results showed that the chronic toxicities of various metals had good relationships with their physicochemical properties. Predicted CCCs of six metals (Hg2+, Cu2+, Pb2+, Cd2+, Ni2+ and Zn2+) were in accordance with the values recommended by the U.S. EPA, with prediction errors being less than an order of magnitude. The QICAR-SSD approach provides an alternative tool to empirical methods and can be useful for deriving scientifically defensible WQC for metals for marine organisms and conducting ecological risk assessments.