Comparison between granular pillared, organo- and inorgano-organo-bentonites for hydrocarbon and metal ion adsorption

Granular reactive materials have higher permeability and are therefore desirable for in situ groundwater pollution control. Three granular bentonites were prepared: an Al-pillared bentonite (PBg), an organo-bentonite (OBg) using a quaternary ammonium cation (QAC), and an inorgano-organo-bentonite (IOBg), using both the pillaring agent and the QAC. Powdered IOB (IOBp) was also prepared to test the effect of particle size. The modified bentonites were characterised with X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA) and uniaxial compression tests. The d-spacing increased only with QAC intercalation. The Young's modulus of IOBg was twice as high as OBg. Batch adsorption tests were performed with aqueous multimetal solutions of Pb2+, Cu2+, Cd2+, Zn2+ and Ni2+ ions, with liquid dodecane and with aqueous dodecane solutions. Metal adsorption fit the Langmuir isotherm. Adsorption occurred within 30min for PBg, while the granular organo-bentonite needed at least 12h to reach equilibrium. IOBp had the maximum adsorption capacity at higher metal concentration and lower adsorbent content (Cu2+: 2.2, Ni2+: 1.7, Zn2+: 1.4, Cd2+: 0.9 and Pb2+: 0.7 all in mmolg-1). The dual pillaring of the QAC and Al hydroxide increased the adsorption. The adsorption of liquid dodecane was in the order IOBg>OBg>PBg (3.2>2.7>1.7mmolg-1). Therefore IOBg has potential for the removal of toxic compounds found in soil, groundwater, storm water and wastewater. © 2012 Elsevier B.V.

Diversity and abundance of ammonia-oxidizing bacteria in eutrophic and oligotrophic basins of a shallow Chinese lake (Lake Donghu)

Classical cultivation and molecular methods based on the ammonia monooxygenase gene (amoA) were used to study the abundance and diversity of beta-proteobacterial ammonia-oxidizing bacteria (AOB) in lake sediments. The eutrophic and oligotrophic basins of a Chinese shallow lake (Lake Donghu), in terms of ammonium (NH4+) concentrations, were sampled. The AOB number was significantly lower in the oligotrophic basin, but significantly higher in the eutrophic basin. In addition, using restriction fragment length polymorphism targeting the amoA, ten restriction patterns including six unique ones were found in the eutrophic basin, while five patterns were observed in the oligotrophic basin with only one unique restriction group. Phylogenetic analysis for AOB revealed that Nitrosomonas oligotropha- and Nitrosomonas ureae-related AOB and Nitrosospira-affiliated AOB were ubiquitous; the former dominated in the eutrophic basin (87.2%), while the latter dominated in the oligotrophic basin (65.5%). Furthermore, Nitrosomonas communis-related AOB was only detected in the eutrophic basin, at a small proportion (3.2%). These results indicate significant selection and adaptation of sediment AOB in lakes with differing trophic status. (C) 2009 Elsevier Masson SAS. All rights reserved.

Carbon and nitrogen metabolism of an eutrophication tolerative macrophyte, Potamogeton crispus, under NH4+ stress and low light availability

Submersed macrophytes in eutrophic lakes often experience high NH4+ concentration and low light availability in the water column. This study found that an NH4+-N concentration of 1 mgL(-1) in the water column apparently caused physiological stress on the macrophyte Potamogeton crispus; L The plants accumulated free amino acids (FAA) and lost soluble carbohydrates (SC) under NH4+ stress. These stressful effects of NH4+ were exacerbated under low light availability. Shading significantly increased NH4+ and FAA contents and dramatically decreased SC and starch contents in the plant shoots. At an NH4+-N concentration of 1 mg L-1 in the water column, neither growth inhibition nor NH4+ accumulation was observed in the plant tissues of P. crispus under normal light availability. The results showed that 1 mg L-1 NH4+-N in the water column was not toxic to P. crispus in a short term. To avoid NH4+ toxicity. active NH4+ transportation out of the cell may cost energy and thus result in a decline of carbohydrate. When NH4+ inescapably accumulates in the plant cell, i.e. under NH4+ Stress and shading, NH4+ is scavenged by FAA synthesis. (c) 2009 Published by Elsevier B.V.

Trends of Superoxide Dismutase and Soluble Protein of Aquatic Plants in Lakes of Different Trophic Levels in the Middle and Lower Reaches of the Yangtze River, China

A limnological study was carried out to determine the responses of superoxide dismutase (SOD) activities and soluble protein (SP) contents of 11 common aquatic plants to eutrophication stress. Field investigation in 12 lakes in the middle and lower reaches of the Yangtze River was carried out from March to September 2004. Our results indicated that non-submersed (emergent and floating-leafed) plants and submersed plants showed different responses to eutrophication stress. Both SOD activities of the non-submersed and submersed plants were negatively correlated with their SP contents (P < 0.000 1). SP contents of non-submersed plants were significantly correlated with all nitrogen variables in the water (P < 0.05), whereas SP contents of submersed plants were only significantly correlated with carbon variables as well as ammonium and Secchi depth (SD) in water (P < 0.05). Only SOD activities of submersed plants were decreased with decline of SD in water (P < 0.001). Our results indicate that the decline of SOD activities of submersed plants were mainly caused by light limitation, this showed a coincidence with the decline of macrophytes in eutrophic lakes, which might imply that the antioxidant system of the submersed plants were impaired under eutrophication stress.

Physiological Stress of High NH (4) (+) Concentration in Water Column on the Submersed Macrophyte Vallisneria Natans L.

The submersed macrophyte, Vallisneria natans L., was cultured in laboratory with NH (4) (+) -enriched tap water (1 mg L-1 NH4-N) for 2 months and the stressful effects of high ammonium (NH (4) (+) ) concentrations in the water column on this species was evaluated. The plant growth was severely inhibited by the NH (4) (+) supplement in the water column. The plant carbon and nitrogen metabolisms were disturbed by the NH (4) (+) supplement as indicated by the accumulation of free amino acids and the depletion of soluble carbohydrates in the plant tissues. The results suggested that high NH (4) (+) concentrations in the water column may hamper the restoration of submersed vegetation in eutrophic lakes.

Nitrogen dynamics in large shallow eutrophic Lake Chaohu, China

Temporal and spatial dynamics of nitrogen in lake and interstitial water were studied monthly in a large shallow, eutrophic lake in subtropical China from October 2002 to September 2003. The distribution of nitrogen was consistent with the idea that high nitrogen concentrations in the western part of the lake resulted from high levels of the nutrients from the surrounding cities through sewage-drainage systems. Nitrate was the predominant form of nitrogen in the overlying water, while ammonium was predominant in the interstitial water, indicating that strong oxidative nutrient regeneration occurred near the sediment-water interface. Nitrate could be an important dissolved inorganic matter source for phytoplankton, which in turn influenced the seasonal variations of nitrate concentrations in lake water. Significant positive correlation between ammonium fluxes and water temperature was observed and could probably be attributed to the intensified ammonification and nitrate reduction with increased temperature. Positive correlation between ammonium fluxes and algae biomass and Chl a concentrations may indicate that phytoplankton was an important factor driving ammonium fluxes in our study lake, and vice versa that higher fluxes of ammonium supported a higher biomass of the phytoplankton.

Controlling factors of spring-summer phytoplankton succession in Lake Taihu (Meiliang Bay, China)

The spring-summer successions of phytoplankton and crustacean zooplankton were examined weekly in Meiliang Bay of the subtropical Lake Taihu in 2004 and 2005. During the study period, the ecosystem of Meiliang Bay was characterized by (i) clearly declined nitrogen compounds (nitrate, TN, and ammonium) and slowly increased phosphorus compounds (TP and SRP), (ii) increased total phytoplankton density and rapid replacement of chlorophyta (mainly Ulothrix) by cyanobacteria (mainly Microcystis), and (iii) rapid replacement of large-sized crustaceans (Daphnia and Moina) by small-sized ones (Bosmina, Limnoithona, and Ceriodaphnia). Results from the CCA and correlation analysis indicate that the spring-summer phytoplankton succession was primarily controlled by abiotic factors. Cyanobacteria were mainly promoted by increased temperature and decreased concentrations of nitrogen compounds. The pure contribution of crustacean was low for the variation of phytoplankton suggesting a weak top-down control by crustacean zooplankton in the subtropical Lake Taihu.

Field studies on the environmental factors in controlling microcystin production in the subtropical shallow lakes of the Yangtze River

Microcystin (MC) problem made more and more care about in China, intercellular MC (Int-MC) and cellular MC (Cel-MC) were important contents to reflect the producing-MC ability by cyanobacteria and by lakes. To study the correlations between Int-MC, Cel-MC concentration and biological and environmental factors, eight cyanobacterial blooming lakes were studied in the middle and lower reaches of the Yangtze River. Microcystin-RR (MC-RR) and Microcystin-LR (MC-LR) were the primary toxin variants in our data. From the linear correlations between MC and environmental factors, cellular-YR had significant correlation with most of chemical factors except total nitrogen (TN) and the ratio of total nitrogen and total phosphorus (TN/TP), most intracellular MC analogues had significant correlations with total dissolved nitrogen (TDN), ammonium (NH4+), nitrite (NO2-), TP, total dissolved phosphorus (TDP), Microcystis. From the canonal correspondence analysis, Int-MC concentrations were closely related with the chemical and biological factors, such as TP, total organic carbon (TOC), chlorophyll a (Chl a), Microcystis biomass, et al. While Cel-MC contents, especially Cel-RR and Cel-LR, were closely related with light environmental in the lakes such as water depth and transparence.

The role of NH4+ toxicity in the decline of the submersed macrophyte Vallisneria natans in lakes of the Yangtze River basin, China

Experimental and field studies were conducted to evaluate the effects of NH4+ enrichment on growth and distribution of the submersed macrophyte, Vallisneria natans L, in lakes of the Yangtze River in China, based on the balance between free amino acids (FAA) and soluble carbohydrates (SC) in the plant tissue. Increase of NH4+ rather than NO3- concentrations in the water column caused FAA accumulation and SC depletion of the plant. The plant showed a unimodal pattern of biomass distribution along both FAA/SC ratios and external NH4+ concentrations, indicating that a moderate NH4-N concentration (< 0.3 mg L-1) benefited the plant, whereas the high NH4-N concentration (> 0.56 mg L-1) eliminated the plant completely. Therefore, 0.56 mg NH4-N mg L-1 in the water column was taken as the upper limit for V. natans in lakes of the Yangtze River basin. The mesocosm experiment showed that at a high external NH4-N (0.81 mg L-1), V. natans failed to propagate with a loss of half SC content (5 mg g(-1) DW) in the rhizomes, indicating that the consumption of carbohydrates for detoxification of excess NH4+ into non-toxic FAA significantly diminished carbohydrate supply to the rhizomes. This might consequently inhibit the vegetative reproduction of the plant, and also might be an important cause for the decline and disappearance of the plant with eutrophication. The present study for the first time reports substantial ecophysiological evidences for NH4+ stress to submersed macrophytes, and indicates that NH4+ toxicity arising from eutrophication probably plays a key role in the deterioration of submersed macrophytes like V. natans.

Studies on temporal and spatial variations of phytoplankton in Lake Chaohu

Temporal and spatial variations of the phytoplankton assemblage in Lake Chaohu, a large shallow eutrophic lake in China, were studied from September 2002 to August 2003. A total of 191 phytoplankton species was identified, among which Chlorophytes (101) ranked the first, followed by Cyanophytes (46) and Bacillariophytes (28). On average over the entire lake, the maximum total algal biomass appeared in June (19.70 mg/L) with a minimum (5.05 mg/ L) in November. In terms of annual mean biomass, cyanobacteria contributed 45.43% to total algal biomass, followed by Chlorophytes (27.14%), and Bacillariophytes (20.6%). When nitrate (NO3-N) and ammonium (NH4-N) concentrations dropped in spring, fixing-nitrogen cyanobacterium (Anabaena) developed quickly and ranked the first in terms of biomass in summer. It is likely that dominance of zooplanktivorous fish and small crustacean zooplankton favored the development of the inedible filamentous or colony forming cyanobacteria. The persistent dominance of cyanobacteria throughout all seasons may indicate a new tendency of the response of phytoplankton to eutrophication in Lake Chaohu.

Changes in the patterns of inorganic nitrogen and TN/TP ratio and the associated mechanism of biological regulation in the shallow lakes of the middle and lower reaches of the Yangtze River

The changes of NH3-N, NO3-N, NO2-N and TN/TP were studied during growth and non-growth season in 33 subtropical shallow lakes in the middle and lower reaches of the Yangtze River. There were significant positive correlations among all nutrient concentrations, and the correlations were better in growth season than in non-growth season. When TP > 0.1 mgL(-1), NH3-N increased sharply in non-growth season with increasing TP, and NO3-N increased in growth season but decreased in non-growth season with TP. These might be attributed to lower dissolved oxygen and low temperature in non-growth season of the hypereutrophic lakes, since nitrification is more sensitive to dissolved oxygen and temperature than anti nitrification. When 0.1 mgL(-1)> TP > 0.035 mgL(-1), TN and all kinds of inorganic nitrogen were lower in growth season than in non-growth season, and phytoplankton might be the vital regulating factor. When TP < 0.035 mgL(-1), inorganic nitrogen concentrations were relatively low and NH3-N, NO2-N had significant correlations with phytoplankton, indicating that NH3-N and NO2-N might be limiting factors to phytoplankton. In addition, TN/TP went down with decline in TIP concentration, and TN and inorganic nitrogen concentrations were obviously lower in growth season than in non-growth season, suggesting that decreasing nitrogen (especially NH3-N and NO3-N) was an important reason for the decreasing TN/TP in growth season. The ranges of TN/TP were closely related to trophic level in both growth and non-growth seasons, and it is apparent that in the eutrophic and hypertrophic state the TN/TP ratio was obviously lower in growth season than in non-growth season. The changes of the TN/TP ratio were closely correlated with trophic levels, and both declines of TN in the water column and TP release from the sediment were important factors for the decline of the TN/TP ratio in growth season.

Effects of nitrogen forms on the production of cyanobacterial toxin microcystin-LR by an isolated Microcystis aeruginosa

A cyanobacterial strain, which produced high content of microcystin-LR (MC-LR) but no rnicrocystin-RR (MC-RR), was isolated from the hypertrophic Dianchi Lake in China and identified as Microcystis aeruginosa DC-1. Effects of nitrogen containing chemicals and trace elements on the growth and the production of MC-LR by this strain were Studied. In the presence of bicine, compared with urea and ammonium, nitrate greatly promoted the growth and the production of MC-LR. However, leucine and arginine, which were the constitutional components in the molecular structure of MC-LR or RR, inhibited the production of MC-LR. Iron and silicon up to 10mg/L had little effects on the growth of M. aeruginosa DC-1, but the production of MC-LR was apparently enhanced. Under all conditions studied here, only MC-LR but no RR was detected within the cells of M. aeruginosa DC-1. Thus, chemical forms of nitrogen, rather than the usually concerned the total nitrogen, Lind trace elements played important roles in the production of MC toxins during cyanobacterial blooms.

Budgets and dynamics of nitrogen and phosphorus in a shallow, hypereutrophic lake in China

Budgets and dynamics of nitrogen and phosphorus in Lake Donghu were investigated from Oct. 1997 to Sept. 1999. The water residence time was estimated to be 89 days in 1997-1998 and 124 days in 1998-1999. The total external loadings were 53 g N m(-2) yr(-1) and 3.2 g P m(-2) yr(-1) in 1997-1998, and 42 g N m(-2) yr(-1) and 3.1 g P m(-2) yr(-1) in 1998-1999. On average, about 80% of nitrogen and phosphorus input was from sewage outlets, while the rest was from land runoff and precipitation. Ammonium ion was the most abundant form of inorganic nitrogen in the sewage. The nutrient output was mainly through water outflow and fish catch. The percentages of nutrients in fish were estimated to be 7.8%-11.2% for nitrogen and 47.6%- 49.6% for phosphorus. Lake Donghu has a very high nutrient retention (63% for nitrogen and 79% for phosphorus) mainly due to its closure and long water residence time. Sedimentation is an important nutrient retention mechanism in this lake. Using mass balance method, we estimated that denitrification of Lake Donghu involves about 50% of the retained nitrogen. Lake Donghu is rich in inorganic nitrogen and phosphorus and showed great seasonal variation.

KINETICS OF SIZE-FRACTIONATED AND DISSOLVED ALKALINE-PHOSPHATASE IN A FARM POND

Nutrient addition bioassays were conducted in 10 L carboys with water from a eutrophic farm pond. The four bioassay treatments each conducted in triplicate were control (no nutrients added), +N (160 mu mol L(-1) NH4Cl), +P (10 mu mol L(-1) KH2PO4), and N+P (160 mu mol L(-1) NH4Cl and 10 mu mol L(-1) KH2PO4). The size fractionated (0.2-0.8, 0.8-3, > 3 mu m) contents of the carboys were analyzed after 7 d for alkaline phosphatase activity (APA) and chlorophyll-a content. Chlorophyll data suggested P deficiency in ammonium and control mesocosms and no P deficiency with phosphate additions. Pond water also was collected in June, August, October, and March for measurement of APA. In water from the pond, the greatest V-max of APA usually was associated with microorganisms in the size classes between 0.8-3 mu m. In mesocosm experiments, the N+P treatment increased V-max of dissolved and particulate associated APA in the 0.2-0.8 mu m size range and in dissolved form. The V-max of APA in the largest size-fraction (> 3 mu m) increased markedly with P deficiency (+N treatment) and decreased in the P-enrichment treatment. The patterns of APA and chlorophyll associated with different size fractions often varied independently among different treatments and seasons and not always as a function of P deficiency, indicating the difficulty of attempting to normalize APA to phytoplankton biomass or chlorophyll. The Michaelis half saturation constant of APA in the pond water showed no strong trends with varied seasons or size fraction.

Electronic properties of sulfur passivated undoped-n(+) type GaAs surface studied by photoreflectance

Photoreflectance (PR) has been used to study surface electronic properties (electric field, Fermi level pinning, and density of surface states) of undoped-n(+) (UN+) GaAs treated in the solution of ammonium sulfide in isopropanol. Complex Fourier transformation (CFT) of PR spectra from passivated surface shows that the sulfur overlay on GaAs surface makes no contribution to Franz-Keldysh oscillations (FKOs). The barrier height measured by PR is derived from surface states directly, rather than the total barrier height, which includes the potentials derived from Ga-S and As-S dipole layers. Comparing with native oxidated surface, the passivation leads to 80 meV movement of surface Fermi level towards the conduction band minimum, and reduction by more than one order in density of surface states. (C) 2003 Elsevier Science B.V. All rights reserved.