Effects of switching redox conditions on sediment phosphorus immobilization by calcium/aluminum composite capping: Performance, ecological safety and mechanisms.

There many materials were used in lake restoration to immobilize phosphorus (P) and reduce the effect of eutrophication. Among them, calcium/aluminum composite (CAC) showed a good capacity of P adsorption. However, a comprehensive of its performance, ecological safety, and the mechanism of P passivation in the aluminum-bound P (Al -P) dominated sediments under varying redox conditions remains incomplete. In the current study, both unwashed CAC (UCAC) and washed CAC (WCAC) showed good P adsorption properties, and the greatest maximum capacity for P adsorption (Qmax) reached 206.8 mg/g at pH 8.5 for UCAC. The SRP and TP in the overlying water of the uncapped sediments showed a decrease-increase-decrease trend in a sequence of transition from aerobic to anaerobic to re-aerobic stages. In contrast, the SRP and TP of the two CACs-capped sediments were maintained low. Phosphorus forms in the uncapped sediment also underwent significant changes during continuous variation of dissolved oxygen (DO) levels. In particular, the decrease in iron-bound P (Fe-P) and Al-P was significantly promoted in the anaerobic phase, and the released P was reabsorbed to form mainly Fe-P in the re-aerobic phase. The CACs-capping promoted the transformation of Fe-P to residual P (Res-P), forming a thick static layer in the surface sediment, thus significantly inhibiting sediment P release. Moreover, the CACs-capping did not induce the Al3+ leaching and significant changes of the microbial community in sediments, and their performances of P immobilization could keep stable to resist the redox variation, which promised to be a good choice for P passivation in eutrophic lake sediments dominated by Al/Fe-P. These findings also confirmed that the risk of P release from Al/Fe-P (mainly Al-P)-dominated sediments was strongly influenced by continuously changing redox conditions, and was probably enhanced by the formation of Fe-P from the resorption of the released P.

Sediment phosphorus immobilization with the addition of calcium/aluminum and lanthanum/calcium/aluminum composite materials under wide ranges of pH and redox conditions.

Aquatic environment factors often influence and regulate the direction of phosphorus (P) flow at the sediment-water interface (SWI). High pH and low DO, common in eutrophic lakes, would induce large releases of P from sediment, and thus cause the negative effect on the efficiency of some P-passivators. Hence, the development of P passivators that could function over a wide range of pH condition and redox state in the overlaying water with reduced undesirable side effects is critical for the eutrophic lake remediation. In the present study, a calcium (Ca)/aluminum (Al) composite (CA) and a lanthanum (La)/Ca/Al composite (LCA) were prepared for P immobilization in lake sediments, using calcium and lanthanum coprecipitated with aluminum. CA and LCA were shown to have good P sorption performance at pH 4-11, particularly at pH 8-11. Furthermore, CA and LCA have an ability to correct the pH of water that deviates from neutral. The maximum P adsorption (Qmax) of sediment amended by 4 % CA and 4 % LCA increased by 83 % and 103 %, and their equilibrium P concentration (EPC0) decreased by 76 % and 88 %, respectively. Under various pH and DO conditions, the P concentration in overlying water was significantly decreased by CA and LCA amendment, and their addition could effectively counteract the P release from sediments induced by high pH and low DO. The mechanisms of P immobilization in amended sediments under various pH and DO levels are primarily the conversion of reactive P to stable P. The P immobilization performance of CA and LCA could cope with a wide range of pH and redox conditions in eutrophic lakes, and they would help to correct extreme pH values, thus they are expected to be a new generation of commercial P-passivators.

Growth, ROS accumulation site, and photosynthesis inhibition mechanism of Chlorella vulgaris by triclosan.

Although the addition of triclosan (TCS) in consumer products has been strictly restricted, its continuous applications in hospitals and other medical facilities and its numerous residues still pose a potential risk to aquatic organisms and aquatic ecosystems. In this study, we investigated the growth, biochemical alterations, and physiological responses of Chlorella vulgaris exposed to different concentrations of TCS. The potential toxicity mechanisms associated with excessive production of reactive oxygen species (ROS) and disruption of photosynthetic system II (PSII) were also analyzed. The results indicated that the growth, cellular ultrastructure, and physiology of C. vulgaris were severely affected by TCS in a dose-effect dependent manner. TCS inhibited the growth of C. vulgaris, leading to mitochondria enlargement, the disordering of the arrangement of thylakoids, cell wall rupture, organelles loss, and the cytoplasm lysis. TCS induced severe oxidative damage characterized by ROS accumulation, elevated malondialdehyde (MDA), and up-regulation of antioxidant enzyme activities. Moreover, in TCS-induced algal cells, the main sites of ROS accumulation were chloroplasts, mitochondria, and cell membranes, with ROS accumulating most in the mitochondria. In addition, TCS caused damage to the reaction center (RC inactivation), donor side (OEC damage), and accepted side (electron transport from QA to QB) of PSII in C. vulgaris, leading to inhibition of photosynthetic activity. These results could provide novel insights into the mechanisms of TCS-induced ROS accumulation and photosynthetic inhibition in C. vulgaris, which would contribute to a deep understanding of TCS toxicity on algae.

Physiological and morphological response of Aphanizomenon flos-aquae to watermelon (Citrullus lanatus) peel aqueous extract.

Natural algaecides are more likely to be specific and biodegradable, and may offer an environmentally friendly method for control of cyanobacterial blooms. We explored, for the first time, the potential for watermelon peel aqueous extract (WMPAE) to control the growth of the harmful blue-green alga Aphanizomenon flos-aquae. The growth inhibition and several physiological parameters of A. flos-aquae, in response to WMPAE, were analyzed. Results showed that WMPAE significantly inhibited the growth of A. flos-aquae in a concentration-dependent way. The highest inhibition reached 94 % after 3 days' treatment with 6 g L-1 of WMPAE and a significant effect was obtained with lower doses and shorter times as well. The cell viability decreased quickly, cell shape changed, and intracellular structural damage occurred. At the same time, the antioxidant enzymes (superoxide dismutase SOD, catalase CAT and peroxidase POD) and malondialdehyde (MDA) levels all increased significantly, indicating that WMPAE between 2-6 g L-1 induced severe oxidative stress and damage to A. flos-aquae. Moreover, production of the four pigments chlorophyll a (Chl a), carotenoids, phycocyanin (PC), and allophycocyanin (APC) were all stimulated, though photosynthesis of A. flos-aquae was clearly inhibited. The maximum quantum yield of photosystem II (Fv/Fm) and the effective quantum yield of photosystem II ( Fv'/Fm') declined sharply, suggesting the decreased photosystem capacity of A. flos-aquae to convert light energy into chemical energy. In addition, non-photochemical quenching (NPQ) of A. flos-aquae increased after a very short time exposure to WMPAE, and decreased significantly with prolonged exposure time, which indicated the failure of photo protection mechanisms. These results suggest that the loss of cell viability, and increases in oxidative stress, and damage to intracellular structure and photosynthetic systems might be the mechanisms for the inhibitory effects. Our results suggested that WMPAE could be a novel and effective approach for controlling the growth of A. flos-aquae in aquatic environments.

Variations in CH4 and CO2 productions and emissions driven by pollution sources in municipal sewers: An assessment of the role of dissolved organic matter components and microbiota.

Variations in methane (CH4) and carbon dioxide (CO2) emissions in municipal sewer driven by pollution sources are complex and multifaceted. It is important to investigate the role of dissolved organic matter (DOM) components and microbiota to better understand what and how those variations occurred. For this purpose, this study provides a systematic assessment based on short-term in-sewer conditioned cultivations, in conjunction with a field survey in four typical sewers in Shanghai Megacity. The results are as follows: (1) Sediment plays a main role in driving the sewer carbon emission behavior owing to its strong associations with the utilized substrates and predominant microbes that significantly promoted the gas fluxes (genera Bacteroidete_vadinHA17, Candidatus_competibacter, and Methanospirillum). (2) Aquatic DOM in overlying water is an indispensable factor in promoting total carbon emissions, yet the dominant microbes present there inversely correlated with gas fluxes (genera Methanothermobacter and Bacteroides). (3) The total fluxes of both CH4 and CO2 enhanced by pavement runoff were limited. Its high COD-CH4/CO2 conversion efficiencies can be ascribed to its dominant anthropogenic humic-like components and the emerged aquatic tyrosine-like components. (4) Domestic sewage can significantly enhance the total fluxes because of its high concentration of bioavailable DOM. However, these substrates, which were more suitable for supporting microbial growth, as well as the substrate competition caused by sulfate reduction and the nitrogen cycle (revealed by the dominant functional microbes genera Acinetobacter, Pseudomonas, Dechloromona, and Candidatus_competibacter and their correlations with indicators), seemed to be responsible for the low COD-CH4/CO2 conversion efficiencies of domestic sewage. (5) A field survey indicated the distinct features of carbon emissions of sewer sewage discharged from different catchments. An extreme hydraulic condition in a sewer in the absence of influent showed unexpectedly high levels of CO2, while a small amount of CH4 emissions.

Comparative physiological tolerance of unicellular and colonial Microcystis aeruginosa to extract from Acorus calamus rhizome.

Microcystis blooms and their associated microcystins pose a significant health risk to humans. Microcystis normally occurs as colonies in eutrophic water bodies, and its physiological tolerance to algaecides is dissimilar to that of unicellular forms. However, the differences of physiological response to algaecides between unicellular and colonial Microcystis have been poorly explored. The current study investigated the effects of hexane extract of Acorus calamus rhizome (HEACR) on the physiological and photosynthetic mechanisms of unicellular and colonial M. aeruginosa in the laboratory. We analyzed the cell density, reactive oxygen species (ROS) level, malonaldehyde (MDA) content, photosynthetic pigments, capsular polysaccharide (CPS), and photosystem (PS II) parameters of the two morphological forms of Microcystis. Our results show that HEACR suppresses the growth of both unicellular and colonial M. aeruginosa, increases the intracellular ROS level and cause lipid peroxidation, as well as exerting a detrimental effect on chlorophyll a (chl a) content and photosynthetic efficiency. Almost 100% inhibition was observed for unicellular and colonial M. aeruginosa after 3 d exposure to 50 and 100 mg L-1 HEACR, respectively. The ROS level increase, MDA accumulation, the chl a decrease and carotenoid increase in unicellular M. aeruginosa were all more obvious than that in colonial cells. The fall in photosynthetic efficiency of unicellular M. aeruginosa were also more significant than that of colonial cells. After 3d exposure, the maximum quantum yield of PS II photochemistry (Fv/Fm), effective quantum yield of PS II photochemistry (Fv'/Fm') and effective quantum yield of photochemical energy conversion in PS II (YII) of unicellular M. aeruginosa was almost totally inhibited by 20 mg L-1 HEACR, while the Fv/Fm, Fv'/Fm' and YII of colonial M. aeruginosa decreased by 43%, 26% and 66% for 100 mg L-1 of HEACR, respectively. Comparing the two morphological forms of Microcystis, colonies show a greater increase in CPS level to more effectively resist the stress of HEACR and to mitigate ROS generation thereby better defending against oxidative damage. Furthermore, colonial M. aeruginosa shows better photoprotection ability than the unicellular form when exposed to HEACR. The colonies also sustain their maximum electron transport rate, increase their tolerance to strong light, and maintain a higher ability to disperse excess energy. These results demonstrated that HEACR can significantly interfere with the growth and physiological processes of both unicellular and colonial M. aeruginosa, but that colonial M. aeruginosa has a greater ability to adjust physiological tolerance to resist the stresses of HEACR.

Reduction of clog matter in constructed wetlands by metabolism of Eisenia foetida: Process and modeling.

Introducing of earthworms to constructed wetlands (CWs) has been considered as a new approach to solve the clogging problems in the long-established systems. Despite its potential advantage, the correlational researches are still in the stage of preliminary observation and speculation. This paper presents a comprehensive and in-depth research about the positive effects of earthworms (Eisenia foetida) on clog matter (CM) reduction through different pathways, including in vivo metabolism and uptake, conversion, transport, and promotion of microorganism quantities. The results showed that the metabolism and uptake by Eisenia foetida could effectively reduce the CM content at an average removal rate of 0.155 mg g-1 d-1, which was obviously higher than the rate of CM decomposition by microorganisms alone. Through the metabolism of earthworms, the amounts of proteins and polysaccharides in CM were decreased, while the amounts of humin and nucleic acids were increased. Simultaneously, the viscosity of CM was reduced by 0.0082 mPa s g-1 d-1, and the quantity of microorganisms was increased by 0.0109 mg g-1 d-1, which finally made the treated CM can be easily washed away and decomposed. Furthermore, earthworms could reduce the CM content in the clogging layer by transporting the metabolic products out. A regression model was further performed for describing the interaction between earthworm and CM. The simulated value of porosity fitted well with the measured one, suggesting that the earthworms can increase the substrate porosity at a rate of 0.33 mL g-1 d-1. This study quantitively depicted the mechanisms of earthworms on the decrement of CM content in CWs, which is of great benefit for the engineering management of constructed wetlands in the future. We also proposed that the density of introduced earthworms should exceed a certain threshold for effectively increasing the substrate porosity and solving the clogging problems.

Mercury in dated sediment cores from coastal ponds of St Thomas, USVI.

We collected seven cores from five coastal ponds in St Thomas, USVI, dated them via 210Pb, and measured their Hg profiles. Levels ranged from 20 to 100ngg-1 and always increased upward to the surface or a shallow mixed zone. Taking into account differences in sediment accumulation rates and the presence or absence of a mixed zone, all sites revealed similar deposition histories. Mercury levels were at low, possibly pristine, values until the early to mid-20th century. Then they then doubled or quadrupled steadily until about 1990, after which Hg became relatively constant. We conclude that Hg in the sediments of these ponds came from long range deposition directly to the ponds and to their watersheds. Constant levels in recent years may be caused by transfer from watersheds, a pathway that is delayed compared to direct deposition from the atmosphere.

Laboratory Investigation of Mineralization of Refractory Nitrogen from Sewage Treatment Plants.

Laboratory studies were conducted and modeled to evaluate whether refractory organic nitrogen in tertiary-treated wastewater effluent could become bioavailable by conversion to mineral forms. Multiday incubations of effluent collected from the Branford and New Haven, Connecticut, waste water treatment plants (WWTP) revealed low but steady conversion of organic nitrogen to nitrate (NO3-). In Branford, the principal form of organic nitrogen was dissolved, and in New Haven it was particulate. Modeling suggested that in both the cases conversion to NO3- from organic forms occurred at several per cent per day, and appeared to happen via the intermediary NH4+. The results suggest that organic nitrogen may be an important source of bioavailable N, contributing to the problem of hypoxia in Long Island Sound and other estuaries.

An integrated system dynamics model developed for managing lake water quality at the watershed scale.

A reliable system simulation to relate socioeconomic development with water environment and to comprehensively represent a watershed's dynamic features is important. In this study, after identifying lake watershed system processes, we developed a system dynamics modeling framework for managing lake water quality at the watershed scale. Two reinforcing loops (Development and Investment Promotion) and three balancing loops (Pollution, Resource Consumption, and Pollution Control) were constituted. Based on this work, we constructed Stock and Flow Diagrams that embedded a pollutant load model and a lake water quality model into a socioeconomic system dynamics model. The Dianchi Lake in Yunnan Province, China, which is the sixth largest and among the most severely polluted freshwater lakes in China, was employed as a case study to demonstrate the applicability of the model. Water quality parameters considered in the model included chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP). The business-as-usual (BAU) scenario and three alternative management scenarios on spatial adjustment of industries and population (S1), wastewater treatment capacity construction (S2), and structural adjustment of agriculture (S3), were simulated to assess the effectiveness of certain policies in improving water quality. Results showed that S2 is most effective scenario, and the COD, TN, and TP concentrations in Caohai in 2030 are 52.5, 10.9, and 0.8 mg/L, while those in Waihai are 9.6, 1.2, and 0.08 mg/L, with sustained development in the watershed. Thus, the model can help support the decision making required in development and environmental protection strategies.

Current and historic mercury deposition to New Haven Harbor (CT, USA): implications for industrial coastal environments.

This study quantifies historic and current mercury contamination in New Haven Harbor (New Haven, Connecticut, USA) through the analysis of sediment cores. The mercury concentration measured in surface sediment ranged from 320 to 1640 microg kg(-1) with an average of 530 microg kg(-1). The harbor is relatively small in area (6.6 km(2)) but displays a large range in concentrations, illustrating the important methodological issue that a large number of samples may be necessary to capture the variability in even a small area. Depth profiles of mercury reflect sedimentation over a range of 20 to 200 years and indicate a complex history of contamination. Mercury depth profiles were compared with lead, copper, cadmium, and silver concentrations and the metals generally covary. This trend indicates that the sources of mercury and heavy metals are linked and that regionally specific sources dominate the historic input of metals rather than large-scale atmospheric deposition patterns. Results also show there are large differences in absolute concentrations of metals among sites in the harbor. Differences in the abundance of Fe-rich, fine-grained sediment likely control the level of metals in various parts of the harbor. Proximity to current sources and the long, diverse industrial history of the harbor also influence the distribution pattern. All of the cores can be modeled as mixing between pre-industrial sediments and either one or two pollution endmembers. This study demonstrates the importance of riverine sources in the mass balance of mercury delivered to coastal areas and of watershed management to preserve coastal ecosystems.

Volatile organic sulfur compounds in a stratified lake.

Three volatile organic sulfur compounds (VOSCs), dimethyl sulfide (DMS), carbon disulfide (CS(2)), and dimethyl disulfide (DMDS), were detected in the stratified water column of a lake (Linsley Pond) in Connecticut. The compounds DMS and DMDS appeared in both the oxic and the anoxic portions of the water column, CS(2) was primarily found in anoxic hypolimnion. Algal metabolism and/or bacterial degradation of sulfur-containing amino acids or other organic materials are potential sources of VOSCs in the oxic lake water. Reactions of hydrogen sulfide with organic compounds and microbial degradation of organic matter may be responsible for the production of VOSCs in the anoxic lake water. The vertical distribution patterns of these three VOSCs varied from month to month in the summer, but the daily profiles obtained in one 5-day period in the summer displayed consistency. No clear diurnal pattern for any of the three VOSCs was observed. Based on observation that these VOSCs were not present in surface and near surface waters of Linsley Pond, freshwater inputs of reduced sulfur compounds to the atmosphere may be insignificant.

Temporal variability in physical speciation of metals during a winter rain-on-snow event.

Particulate matter in urban rivers transports a significant fraction of pollutants, changes rapidly during storm events, and is difficult to characterize. In this study, the physical speciation of trace metals and organic C in an urban river and upstream headwaters site in Torrington, CT, were measured during a winter rain-on-snow event. In addition, a selective fractionation scheme, using membrane and tangential-flow ultrafiltration methods to separate suspended particulate matter into sand, silt, clay, and colloid fractions, was evaluated based on the appropriateness of the chosen size categories. During peak runoff at the urban river site, total-recoverable concentrations of the metals Cu and Pb increased 6- and 13-fold to 16.9 and 9.5 microg L(-1), respectively, compared with baseflow concentrations. Concentrations of Cu and Pb reached only 0.9 and 0.86 microg L(-1) at the headwaters site. For the measured storm event, the majority of metals were transported by the urban river in association with coarse silt (20-80 microm particle diam.) during peak runoff. During peak runoff at the urban site, organic C associated with the large colloid fraction (0.1-1.0 microm) increased from 5% (at baseflow) to 54% of the total C in transport, whereas dissolved organic C and that associated with smaller colloids decreased from 91.5% (at baseflow) to 41% of the total. Other elements that were monitored as part of the study were Na, K, Ca, Mg, Fe, Mn, Al, Cd, Cl-, NO3(-), and SO4(2-). The chosen fractionation scheme was useful to characterize pollutant transport during this event, but further testing should be undertaken to determine the most appropriate size range categories, and to ensure that the sizes measured are comparable to those used in other studies.

Investigation of conventional membrane and tangential flow ultrafiltration artifacts and their application to the characterization of freshwater colloids.

Artifacts associated with the fractionation of colloids in a freshwater sample were investigated for conventional membrane filtration (0.45 microm cutoff), and two tangential flow ultrafiltration cartridges (0.1 microm cutoff and 3000 MW cutoff). Membrane clogging during conventional filtration removed some colloids smaller than 0.1 microm in diameter, much smaller than the nominal size of the filter. For certain constituents (e.g., Fe), filter clogging had a significant effect on filtrate concentrations, while artifacts associated with tangential flow ultrafiltration using a 0.1 microm cutoff were minimal. Artifacts occurred during tangential flow ultrafiltration with a 3000 MW cutoff, but did not deviate from predicted changes in concentration based on a standard permeation model. Comparison of filtrate concentrations for membrane filtration (at 1.0 and 0.45 microm) and tangential flow ultrafiltration (at 0.1 microm) for a large number of samples from Connecticut rivers shows that significant and consistent differences exist between their separation characteristics. Results for organic carbon, Fe, Mn, Al, Cu, and Pb demonstrate the magnitude of the effects of the fractionation technique on filtrate element concentration, show variability by element and flow condition, and highlight the importance of larger colloids to freshwater metal speciation. One implication of the research is that tangential flow ultrafiltration with large size cutoff membranes (e.g., approximately 0.1 microm) may be superior to conventional filtration with filters in the same size discrimination range, and potentially more appropriate for the fractionation of natural water samples.

Unsuitability of Cr(II) reduction for the measurement of sulfides in oxic water samples.

After developing a highly sensitive method for detecting acid-volatile sulfides (AVS) in oxic freshwaters, we hoped to apply that method to measuring a different class of dissolved reduced sulfur compounds, chromium-labile sulfides (CLS). A popular method for measuring this pool of sulfides in sediments relies on reduction dissolution of metal sulfides by Cr(II) and has been employed by researchers for over 15 years. Here, we demonstrate that this method is inappropriate for measuring CLS in oxic freshwaters in which sulfate concentrations are large relative to the dissolved metal sulfides. We observe the reduction of sulfate by Cr(II), and this presents a significant interference.