Differential Sensitivity of a Coccal Green Algal and a Cyanobacterial Species to Dissolved Natural Organic Matter (NOM) (8 pp)

Background

and Aim. In non-eutrophicated freshwaters, humic substances (HS) pose chemical stresses on aquatic organisms and, hence, separating sensitive from less sensitive or even tolerant species. One of the stresses, identified so far, is the reduction of photosynthetic oxygen production and reduction in growth in freshwater macrophytes and algae. In a previous paper, it has been shown that even closely related coccal green algae responded differently upon identical stress by HS, which is consistent with the hypothesis above. Due to their much simpler cellular ultrastructure, cyanobacteria are supposed to be more sensitive to HS exposure than eukaryote should be. One coccal green algal species (Desmodesmus communis) and one cyanobacterium (Chroococcus minutus) were exposed to four natural organic matter (NOM) isolates. One NOM has been isolated from a brown water lake (Schwarzer See) in Brandenburg State; three were obtained from a comprehensive Scandinavian NOM research project and originated from Norway (Birkenes), Finland (Hietajärvi), and Sweden (Svartberget).

Methods

Cultures of D. communis and C. minutus were obtained from the Culture Collection of Algae, Göttingen, and maintained in a common medium. The cultures were non-axenic. The algae and cyanobacteria were exposed under identical conditions to environmentally realistic NOM concentrations. Cell numbers were counted microscopically in Neugebauer cuvettes in triplicates. To avoid limitation by nutrient depletion, the experiments were terminated after 14 to 15 days. Until culture day 12, no growth limitation has been observed in the controls.

Results

All NOM isolates modulated the growth of the algae and cyanobacteria. During the early culture days, there was a slight growth promotion with the coccal green alga and to a much lesser degree with the cyanobacterium. Yet, the major effect were significant reductions in cell yield in both primary producer cultures. C. minutus was much more affected than D. communis. This applies particularly to the three tested Scandinavian NOM isolates, which were effective at concentrations even below 1 mg L-1 DOC.

Discussion

The growth promoting effect may be due to an increase in bioavailability of some trace nutrients in the presence of NOM, the release of some growth promoting substances by microbial or photochemical processing of the NOM, and/or a hormetic effect. The growth reducing effect can be explained as a herbicide-like mode of action that affects the photosystem II most prevalent by blocking the electron transport chain, absorption of electrons, or production of an internal oxidative stress after processing the bioconcentrated HS. Furthermore, it may be postulated that also photo-toxicity of these HS in the algal cells contributes to the overall toxicity; however, experimental evidence is lacking so far.

Conclusions

Upon exposure to HS, cyanobacteria appear to be much more sensitive than coccal green algae and respond in growth reduction. This high sensitivity of cyanobacteria to HS may explain phytoplankton patterns in the field. Eutrophic, humic-rich lakes do not support the cyanobacterial blooms characteristic of eutrophic, but humic-poor lakes. In the humic-rich systems, raphidophytes or, less frequent, specific coccal greens are more common. Obviously, cyanobacteria appear to be unable to make advantage of their accessory pigments (phycocyanin) to exploit the reddish light prevailing in humic-rich lakes.

Recommendation

. At present, no effective structure can be figured out which may be responsible for the adverse effect on the cyanobacterial species. It is reserved to future research whether or not HS may be applied more specifically (for instance, with elevated moieties of the effective structures) as a natural geochemical to combat cyanobacterial blooms.

     

Does quinone or phenol enrichment of humic substances alter the primary compound from a non-algicidal to an algicidal preparation?

Dissolved organic matter (DOM) has been shown to affect phytoplankton species directly. These interactions largely depend on the origin and molecular size of DOM and are different in prokaryotes and eukaryotes. In a preceding study, however, two humic substance preparations did not adversely affect coccal green algae or cyanobacterial growth even at high concentrations of dissolved organic carbon (DOC). These results contradicted previous findings, showing a clear, negative response of different phototrophs to much lower DOC concentrations. To test whether or not at least defined building blocks of humic substances (HSs) are effective algicidal structures, we enriched two humic preparations with hydroquinone and p-benzoquinone, respectively, and exposed two different green algae, Pseudokirchneriella subcapitata and Monoraphidium braunii, and two cyanobacterial species, Synechocystis sp. and Microcystis aeruginosa, to the unmodified and enriched HSs. As response variables, growth rates in terms of biomass increase, chlorophyll-a content, and photosynthetic yield were measured. The highest concentration (4.17 mM DOC) of the modified HSs clearly inhibited growth; the cyanobacterial species were much more sensitive than the green algal species. However, realistic ecological concentrations did not adversely affect growth. Aerating the exposure solution for 24 h strongly reduced the inhibitory effect of the modified HSs. The algicidal effect was obviously caused by monomers and not by polymerised high molecular weight HSs themselves. Furthermore, the maximum quantum yield (Φ PSII max) was stimulated in the green algal species by low and medium DOC concentrations, but reduced in the cyanobacterial species upon exposure to higher HS concentrations. The quinone- and phenol-enriched HSs only showed algicidal activity at high concentrations of 4.17 mM DOC and lost their effects over time, presumably by oxidation and subsequent polymerisation. This study confirms that the applied humic substances themselves are not effective algicides even if enriched in effective structures.     

Toxicity of hydroquinone to different freshwater phototrophs is influenced by time of exposure and pH

The interaction of natural organic matter with phytoplankton communities in freshwater ecosystems is an intensively studied subject matter. Previous studies showed that apparently plant-derived phenols were able to inhibit algal and cyanobacterial growth. Furthermore, it was also assumed that humic substances (HS), which comprise the major part of dissolved organic carbon in freshwater ecosystems, directly interact with freshwater phototrophs. For example, quinoid building blocks of HS were thought to be algicidal. To identify key environmental variable for the toxic action of potential quinone algicides, we tested the toxicity of hydroquinone (HQ) to different eukaryotic and prokaryotic freshwater phototrophs in terms of growth performance and investigated also the effect of HQ oxidation at different pH values on its algicidal potential. It was shown that cyanobacterial species were much more susceptible to hydroquinone than coccal green algal species were, with Microcystis aeruginosa being the most sensitive species by far. In addition, it was obvious that the aging of hydroquinone-stock solution at pH 11 led to polymerization and, by this process, to a total loss of toxicity; whereas the algicidal potential sustained if the polyphenol was kept at pH 7. Since most lakes with heavy blooms of phototrophs possess pH values clearly above 7.0, it is questionable, if polyphenols in general and quinones in particular are the effective chemicals and if litter and straw leachates are applied as means to combat algal and cyanobacterial blooms.     

Biosorption of zinc and copper from aqueous solutions by two freshwater green microalgae Chlorella pyrenoidosa and Scenedesmus obliquus

Purpose

The objective of this study was to determine the removal of zinc and copper by two freshwater green microalgae Chlorella pyrenoidosa and Scenedesmus obliquus and to investigate changes of algal ultrastructure and photosynthetic pigment.

Methods

Algal cells were exposed for 8 days to different initial zinc or copper concentrations. Heavy metal concentrations were detected by an atomic absorption spectrophotometer. Algal growth, ultrastructure, and photosynthetic pigment were analyzed by a microplate reader, transmission electron microscope, and spectrophotometer, respectively.

Results

Low zinc and copper concentrations induced increase in algal growth, whereas application of high zinc and copper concentrations suppressed the growth of both algae. High metal concentrations also decreased the photosynthetic pigments and destroyed algal cell ultrastructure. The zinc removal efficiency by both algae increased rapidly during the first day and thereafter remained nearly constant throughout the experiment. The copper removal efficiency by both algae increased slowly during the whole experimental periods. In all cultures, the quantity of both metals removed intracellularly was much lower than the adsorbed quantity on the cell surface.

Conclusions

Both strains of the microalgae had proven effective in removing zinc and copper from aqueous solutions, with the highest removal efficiency being near 100%. In addition, C. pyrenoidosa appeared to be more efficient than S. obliquus for removing copper ions. On the contrary, S. obliquus appeared to be more efficient than C. pyrenoidosa for removing zinc ions.     

Humic substances

GOAL, SCOPE AND BACKGROUND: Freshwater bodies which chemistry is dominated by dissolved humic substances (HS) seem to be the major type on Earth, due to huge non-calcareous geological formations in the Northern Hemisphere and in the tropics. Based on the paradigm of the inertness of being organic, direct interactions of dissolved HS with freshwater organisms are mostly neglected. However, dissolved organic carbon, the majority of which being HS, are natural environmental chemicals and should therefore directly interact with organisms. Major results that widened our perspective on humic substance ecology come from experiments with the compost nematode, Caenorhabditis elegans, which behaved contradictorily to textbook knowledge and provoked an in-depth re-consideration of some paradigms. APPROACH: To overcome old paradigms on HS and their potential interactions with organisms, we reviewed recent international literature, as well as 'grey' literature. We also include results from own ongoing studies. RESULTS: This review focuses on direct interactions of dissolved HS with freshwater organisms and disregards indirect effects, such as under-water light quenching. Instead we show with some macrophyte and algal species that HS adversely interfere with photosynthesis and growth, whereby closely related algal species show different response patterns. In addition to this, HS suppress cyanobacteria more than eukaryotic algae. Quinones in the HS appear to be the effective structure. Furthermore, HS can modulate the offspring numbers in the nematode C. elegans and cause feminization of fish and amphibians--they possess hormone-like properties. The ecological consequences of this potential remain obscure at present. HS also have the potential to act as chemical attractants as shown with C. elegans and exert a mild chemical stress upon aquatic organisms in many ways: induction of molecular chaperons (stress proteins), induction and modulation of biotransformation and anti-oxidant enzymes. Furthermore, they produce an oxidative stress with lipidperoxidation as one clear symptom or even stress defense strategy. Stronger chemical stresses by HS may even lead to teratogenic effects as shown with fish embryos; all physiological responses to HS-mediated stress require energy, which were compensated on the expense of yolk as shown with zebra fish embryos. One Finnish field survey supports the view of a strong chemical stress, as the weight yield in fish species decreases with increasing HS content in the lakes. DISCUSSION: HS exert a variety of stress symptoms in aquatic and compost organisms. According to current paradigms of ecotoxicology, these symptoms have to be considered adverse, because their compensation consumes energy which is deducted from the main metabolism. However, the nematode C. elegans looks actively for such stressful environments, and this behavior is only understandable in the light of new paradigms of aging mechanisms, particularly the Green Theory of Aging. In this respect, we discuss the mild HS-mediated stress to aquatic and compost organisms. New empirical findings with HS themselves and HS building blocks appear to be consistent with this emerging paradigm and show that the individual lifespan may be expanded. At present the ecological consequences of these findings remain obscure. However, a multiple-stress resistance may be acquired which improves the individual fitness in a fluctuating environment. CONCLUSIONS: It appears that dissolved HS have to be considered abiotic ecological driving forces, somewhat less obvious than temperature, nutrients, or light. PERSPECTIVES: The understanding of the ecological control by dissolved humic substances is still fragmentary and needs to be studied in more details.     

Natural dissolved humic substances increase the lifespan and promote transgenerational resistance to salt stress in the cladoceran <Emphasis Type="Italic">Moina macrocopa</Emphasis>

Purpose  

Evidence has accumulated that humic substances (HS) are not inert biogeochemicals. Rather, they cause stress symptoms and may modulate the life history of aquatic organisms. Nevertheless, it is still not clear how HS interact with additional stressors and if their effects are transgenerational. We tested the interactive effects of HS and salt to cladocerans, discussing their consequences for the persistence in fluctuating environments, such as coastal lagoons.     

Synthesis and characterisation of Pd-modified N-doped TiO2 for photocatalytic degradation of natural organic matter (NOM) fractions

Introduction

The removal of natural organic matter (NOM) from water is becoming increasingly important in order to prevent the formation of carcinogenic disinfection by-products. The inadequate removal of NOM has a bearing on the capacity of the other treatment processes to remove organic micro-pollutants or inorganic species that may be present in the water. New methods are therefore currently being sought to effectively characterise NOM and also to ensure that it is sufficiently removed from drinking water sources.

Methodology

Nitrogen- and palladium-co-doped TiO₂ was synthesised by a modified sol?Cgel method and evaluated for its photocatalytic degradation activity on NOM fractions under simulated solar radiation. The photocatalyst was characterised by FT-IR, Raman, XRD, DRUV?Cvis, SEM, TEM, EDS, XPS and TGA. FT-IR confirmed the presence of OH groups on thermally stable, nearly spherical anatase nanoparticles with an average diameter of 20?nm. PdO species appeared on the surface of the TiO₂ as small uniformly dispersed particles (2 to 3?nm). A red shift in the absorption edge compared to commercial anatase TiO₂ was confirmed by DRUV?Cvis. In order to gain a better insight into the response of NOM to photodegradation, the NOM was divided into three different fractions based on its chemical nature.

Results and discussion

Photodegradation efficiencies of 96, 38 and 15?% were realised for the hydrophobic, hydrophilic and transphilic NOM fractions, respectively. A reasonable mechanism was proposed to explain the photocatalytic degradation of the NOM fractions. The high photocatalytic activity could be attributed to the larger surface area, smaller crystalline size and synergistic effects of the co-dopants N and Pd in the TiO₂ crystal.     

Temperature influence on silver nanoparticles inhibitory effect on photosystem II photochemistry in two green algae, Chlorella vulgaris and Dunaliella tertiolecta

Purpose

In this study, the effect of silver nanoparticles (AgNPs) on the photosynthetic performance of two green algae, Chlorella vulgaris and Dunaliella tertiolecta, was investigated at 25°C and 31°C.

Methods

To induce AgNPs effect, algal cells were exposed for 24?h to concentrations varying from 0 to 10?mg/L. The polyphasic OJIP fluorescence transient was used to evaluate photosystem II (PSII).

Results

We show that growth media and temperature had different effects in AgNPs agglomerates formation and Zeta potential. When temperature conditions change, inhibitory effect of AgNPs also undergoes changes. Increase of temperature induced higher altering effects to PSII quantum yield, primary photosynthetic electron transport, and consequently higher decrease of total photosynthetic performance if compared to AgNPs effect alone. AgNPs has a negative effect on D. tertiolecta compared to C. vulgaris.

Conclusion

We conclude that temperature tends to enhance the toxic effects on aquatic alga and these alterations might have serious consequences on ecosystem equilibrium and aquatic plant communities.     

Sorption of phenanthrene by nanosized alumina coated with sequentially extracted humic acids

Background, aim, and scope  

Sorption of hydrophobic organic compounds (HOCs) to natural organic matter (NOM) is an important process that affects the transport, transformation, bioavailability, and fate of HOCs in the environment. Manufactured nanoparticles (NPs) such as nano-oxides will inevitably enter the environment in the processes of their production, transfer, and use and could be coated by the ubiquitous NOM. Thus, sorption of HOCs to NOM in the environment could be affected by the NP interactions with NOM. Furthermore, the toxicity of nano-oxides could be increased due to the adsorbed HOCs. Therefore, sorption of phenanthrene by nano-Al₂O₃ coated with humic acid (HA) was examined in this study to explore the possible effect of nanoparticles (NPs) on the environmental behavior of HOCs and the potential environmental and health risks of NPs.     

Co-polymerization of penta-halogenated phenols in humic substances by catalytic oxidation using biomimetic catalysis

Introduction

A synthetic water-soluble meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of iron(III) chloride, Fe-(TDCPPS)Cl, was employed to catalyze the oxidative co-polymerization of penta-halogenated phenols in two humic materials of different origin.

Materials and methods

Co-polymerization of pentachlorophenol (PCP) was followed by high-performance size-exclusion chromatography (HPSEC), the unbound PCP recovered from reacting humic solutions was evaluated by gas-chromatography/electron capture detector, and the oxidative catalyzed coupling of pentafluorophenol (PFP) into humic matter was assessed by liquid-state ¹⁹F-NMR spectroscopy. HPSEC showed that the catalyzed oxidative coupling between PCP and humic molecules increased the apparent weight-average molecular weight (M _w) values in both humic substances.

Results and discussion

HPSEC further indicated that the co-polymerization reaction turned the loosely bound humic supramolecular structures into more stable conformations, which could no longer be disrupted by the disaggregating effect of acetic acid. The occurrence of covalent linkages established between PCP and humic molecules was also suggested by the very little amount of PCP found free in solution after the catalyzed co-polymerization. ¹⁹F-NMR spectroscopy suggested that also PFP could be oxidatively coupled to humic materials. PFP-humic co-polymerization reaction produced ¹⁹F-spectra with many more ¹⁹F signals and wider chemical shifts spread than for PFP alone or PFP subjected to catalyzed coupling without humic matter.

Conclusions

These findings show that biomimetic iron-porphyrin is an efficient catalyst for the covalent binding of polyhalogenated phenols to humic molecules, thereby suggesting that the co-polymerization reaction may become a useful technology to remediate soils and waters contaminated by polyhalogenated phenols and their analogues.     

Isolation and Identification of Antialgal Compounds from the Leaves of Vallisneria spiralis L. by Activity-Guided Fractionation (5 pp)

Background, Aims and Scope

Vallisneria spiralis Linn., a common, submerged macrophyte, is widely available in quiet waters of lakes, ponds, marshes and streams in Southeast Asia. V. spiralis plays a significant role not only in decreasing eutrophication of water body for its productivity, but also in inhibiting the growth of blue-green algae? The aim of the paper involves the isolation and identification of allelochemicals from extracts of V. spiralis by activity-guided fractionation and column chromatography.

Methods

Leaves of V. spiralis was washed free of debris, air-dried and refluxed in 95% EtOH. The extract was isolated using column chromatography and fractionation with antialgal activity. Potential allelochemicals were analyzed by high-resolution gas chromatography-mass spectrometry (HRGC-MS).

Results

Two fractions with strong antialgal activity were isolated using column chromatography and activity-guided fractionation from the extract of V. spiralis. 2-Ethyl-3-methylmaleimide, dihydroactinidiolide and 4-oxo-β-Ionone were identified in the first fraction, and 3-hydroxy-5,6-epoxy-β-ionone, loliolide, 6-hydroxy-3-oxo-α-ionone and an unknown compound in the second fraction. They had strong inhibitory effects on Microcystis aeruginosa Kütz.

Discussion

2-Ethyl-3-methylmaleimide is a byproduct of photooxidation of chlorophyll, and five other compounds identified were derivatives of β-carotene. HRGC-MS and derivatization technology were used to identify and confirm their molecular structures. The formula of the unknown compound was C16H19NO4. Metabolites of plant pigments had strong inhibitory activities on growth of algae.

Conclusions

Six compounds had been identified in V. spiralis, among them, 2-ethyl-3-methylmaleimide was the main allelochemical, and derivatives of ionone were also potential allelochemicals.

Recommendations and Perspective

. The results of our research could help us to study further mechanisms of inhibitory effect on algae and develop new potential antialgal substances.     

Equilibrium, kinetic and thermodynamic studies on the biosorption of reactive acid dye on Enteromorpha flexuosa and Gracilaria corticata

Purpose

Biosorption is an emerging, eco-friendly and economical method for treating the wastewater effluents. Compared to many other biological materials, algae biomass proved to be the better biosorbent due to the presence of cell wall polymers in them.

Methods

Algal biomasses namely Enteromorpha flexuosa and Gracilaria corticata were dried, crushed and used as biosorbents. Ponceau S, a diazo dye was used as a model adsorbate for the biosorption studies. The biosorbents were characterized by Scanning Electron Microscopy, FT-IR and zero point charge. Batch studies were performed by varying pH, biosorbent dosage and initial dye concentrations. Adsorption isotherms, kinetic and thermodynamic analyses were carried out. The effect of electrolytes was also studied. Batch desorption studies were also carried out using various reagents.

Results

Isotherm data were tested with Langmuir and Freundlich isotherm models and the results suggested that the Freundlich isotherm fitted the data well. Kinetic studies were performed with varying initial dye concentrations and the data were incorporated with pseudo first-order and pseudo second-order kinetic equations and was found that the studied biosorption processes followed pseudo second-order kinetic equation. Thermodynamic parameters were evaluated at three different temperatures 293?K, 300?K and 313?K. About 95% of the dye could be desorbed from both the biosorbents.

Conclusion

Both the algal biomasses had heterogeneous surfaces and followed pseudo second-order chemical kinetics. Thermodynamic parameters proved that the biosorption by both the biomasses were spontaneous, feasible and endothermic processes. Desorption studies proved the worth of the algal biomasses as biosorbents in industrial level.     

Algae community and trophic state of subtropical reservoirs in southeast Fujian, China

Background,

aim, and scope Fujian reservoirs in southeast China are important water resources for economic and social sustainable development, although few have been studied previously. In recent years, growing population and increasing demands for water shifted the focus of many reservoirs from flood control and irrigation water to drinking water. However, most of them showed a rapid increase in the level of eutrophication, which is one of the most serious and challenging environmental problems. In this study, we investigated the algae community characteristics, trophic state, and eutrophication control strategies for typical subtropical reservoirs in southeast Fujian.

Materials and methods

Surface water samples were collected using polyvinyl chloride (PVC) plastic bottles from 11 Fujian reservoirs in summer 2010. Planktonic algae were investigated by optical microscopy. Water properties were determined according to the national standard methods.

Results and discussion

Shallow reservoirs generally have higher values of trophic state index (TSI) and appear to be more susceptible to anthropogenic disturbance than deeper reservoirs. A total of 129 taxa belonging to eight phyla (i.e., Bacillariophyta, Chlorophyta, Chrysophyta, Cryptophyta, Cyanophyta, Euglenophyta, Pyrrophyta, Xanthophyta) were observed and the most diverse groups were Chlorophyta (52 taxa), Cyanophyta (20 taxa), Euglenophyta (17 taxa), Chrysophyta (14 taxa). The dominant groups were Chlorophyta (40.58%), Cyanophyta (22.91%), Bacillariophyta (21.61%), Chrysophyta (6.91%). The species richness, abundance, diversity, and evenness of algae varied significantly between reservoirs. TSI results indicated that all 11 reservoirs were eutrophic, three of them were hypereutrophic, six were middle eutrophic, and two were light eutrophic. There was a strong positive correlation between algal diversity and TSI at P?4-N, NO _x -N, TP, and chlorophyll a were significant environmental variables affecting the distribution of algae communities. The transparency and chlorophyll a were the strongest environmental factors in explaining the community data. Furthermore, the degradation of water quality associated with excess levels of nitrogen and phosphorus in Fujian reservoirs may be impacted by interactions among agriculture and urban factors. A watershed-based management strategy, especially phosphorus control, should be developed for drinking water source protection and sustainable reservoirs in the future.

Conclusion and recommendations

All investigated reservoirs were eutrophicated based on the comprehensive TSI values; thus, our results provided an early warning of water degradation in Fujian reservoirs. Furthermore, the trophic state plays an important role in shaping community structure and in determining species diversity of algae. Therefore, long-term and regular monitoring of Euglenophyta, Cyanophyta, TN, TP and chlorophyll a in reservoirs is urgently needed to further understand the future trend of eutrophication and to develop a watershed-based strategy to manage the Cyanophyta bloom hazards.     

Competition between alga (Pseudokirchneriella subcapitata), humic substances and EDTA for Cd and Zn control in the algal assay procedure (AAP) medium

The chemical speciation of trace metals in natural waters has important implications for their biogeochemical behavior. Trace metals are present in natural waters as dissolved species and associated with colloids and particles. The complexation of one trace metal (Cd and Zn at 200 and 390 microg/l respectively) with a green alga Pseudokirchneriella subcapitata in colloid-free algal culture medium and in presence of colloidal humic substances (HS) is presented. The influence of the nature of colloids was also addressed using three "standard" HS: fulvic acid (FA) and, soil (SHA) and peat humic acids (PHA). The chemical speciation model, MINTEQA2, was used to simulate the influence of pH and standardized culture medium on metal association with humic substances. The model was successfully modified to consider the differences in the metal complexation with fulvic (FA) and humic acids (HA). The deviations of concentrations of metals associated with HS between experimental results and model predictions were within a factor of approximately 2. The results of speciation model highlight the influence of the experimental conditions (pH, EDTA) used for alga bioassay on the behavior of Cd and Zn. The computed speciation suggests working with a pH buffered/EDTA-free mixture to avoid undesirable competition effects. The behavior of Cd and Zn in solution is more strongly influenced by HS than by alga. Metal-HS associations depend on metal and humic substance nature and concentration. Cd is complexed to a higher extent than Zn, in particular at larger HS concentration, and the complexation strength is in the order FA相似文献   

Influence of algal bloom degradation on nutrient release at the sediment–water interface in Lake Taihu, China

Algal bloom could drastically influence the nutrient cycling in lakes. To understand how the internal nutrient release responds to algal bloom decay, water and sediment columns were sampled at 22 sites from four distinct regions of China’s eutrophic Lake Taihu and incubated in the laboratory to examine the influence of massive algal bloom decay on nutrient release from sediment. The column experiment involved three treatments: (1) water and sediment (WS); (2) water and algal bloom (WA); and (3) water, sediment, and algal bloom (WSA). Concentrations of dissolved oxygen (DO), total nitrogen (TN), total phosphorus (TP), ammonium (NH ₄ ⁺ -N), and orthophosphate (PO ₄ ^3? -P) were recorded during incubation. The decay of algal material caused a more rapid decrease in DO than in the algae-free controls and led to significant increases in NH ₄ ⁺ -N and PO ₄ ^3? -P in the water. The presence of algae during the incubation had a regionally variable effect on sediment nutrient profiles. In the absence of decaying algae (treatment WS), sediment nutrient concentrations decreased during the incubation. In the presence of blooms (WSA), sediments from the river mouth released P to the overlying water, while sediments from other regions absorbed surplus P from the water. This experiment showed that large-scale algal decay will dramatically affect nutrient cycling at the sediment–water interface and would potentially transfer the function of sediment as “container” or “supplier” in Taihu, although oxygen exchange with atmosphere in lake water was stronger than in columns. The magnitude of the effect depends on the physical–chemical character of the sediments.     

Synchronous-scan fluorescence spectra of Chlorella vulgaris solution

The characterization of the Chlorella vulgaris solution was carried out using synchronous-scan spectroscopy. The range of concentration of algae and Fe(III) in aqueous solutions were 5 × 10⁸–8 × 10⁹ cells l⁻¹ and 10–60 μM, respectively. Effective characterization method used was synchronous-scan fluorescence spectroscopy. The wavelength difference (Δλ) of 90 nm was maintained between excitation and emission wavelengths; 90 nm was found to be the best Δλ for effective characterization of Chlorella vulgaris solution with or without quencher species (e.g., Fe(III), humic acid (HA)) for the first time. The peak was observed at about EX 236.6 nm/EM 326.6 nm for synchronous-scan fluorescence spectra. The fluorescence quenching of algae in system of algae–Fe(III)–HA was studied using synchronous-scan spectroscopy for the first time. Fe(III) was clearly the effective quencher. The relationship between I₀/I (quenching efficiency) and c (concentration of Fe(III) added) was a linear correlation for the algae solution with Fe(III). Also, Aldrich humic acid was found to be an effective quencher. pH effect on synchronous-scan fluorescence intensity of algal solution with Fe(III) and/or HA was evident.     

The lanthanum precipitation method. Part 2: quantification of the conditional interaction constant between technetium(IV) and humic substances

The interaction between colloidal Tc(IV) species and colloidal Gorleben humic substances (HS) was quantified after application of the La-precipitation method on supernatant solutions obtained under various experimental conditions but at constant ionic strength of the Gorleben groundwater (0.04M). The determined interaction constant LogK(HS) (2.3+/-0.3) remained unchanged over a large range of Tc(IV) and HS concentrations and was independent of the pH of the original supernatant solution (pH range 6-10), Tc(IV)-HS loading (10(-3)-10(-6)molTcg(-1) HS) and the nature of the reducing surface (Magnetite, Pyrite and Gorleben sand) used for the pertechnetate reduction. The LogK(HS) value determined by the La-precipitation method is lower than the LogK value obtained from a previous study where the interaction between colloidal Tc(IV) species and Gorleben humic substances was quantified using a modified Schubert approach (2.6+/-0.3). The La-precipitation method allows to accurately determine the amount of Tc(IV) associated with HS but leads to a (small) overestimation of the free inorganic Tc(IV) species.     

Biosorption of Cr(VI) by free and immobilized Pediastrum boryanum biomass: equilibrium, kinetic, and thermodynamic studies

Background and purpose

The biosorption of Cr(VI) from aqueous solution has been studied using free and immobilized Pediastrum boryanum cells in a batch system. The algal cells were immobilized in alginate and alginate?Cgelatin beads via entrapment, and their algal cell free counterparts were used as control systems during biosorption studies of Cr(VI).

Methods

The changes in the functional groups of the biosorbents formulations were confirmed by Fourier transform infrared spectra. The effect of pH, equilibrium time, initial concentration of metal ions, and temperature on the biosorption of Cr(VI) ion was investigated.

Results

The maximum Cr(VI) biosorption capacities were found to be 17.3, 6.73, 14.0, 23.8, and 29.6?mg/g for the free algal cells, and alginate, alginate?Cgelatin, alginate?Ccells, and alginate?Cgelatin?Ccells at pH?2.0, which are corresponding to an initial Cr(VI) concentration of 400?mg/L. The biosorption of Cr(VI) on all the tested biosorbents (P. boryanum cells, alginate, alginate?Cgelatin, and alginate?Ccells, alginate?Cgelatin?Ccells) followed Langmuir adsorption isotherm model.

Conclusion

The thermodynamic studies indicated that the biosorption process was spontaneous and endothermic in nature under studied conditions. For all the tested biosorbents, biosorption kinetic was best described by the pseudo-second-order model.     

Effects of pulp mill chlorate on Baltic Sea algae

The long-term effects of pulp mill chlorate on different algal species of the Baltic Sea were studied in land-based model ecosystems simulating the littoral zone. Brown algae (Phaeophyta) exhibited an extraordinarily high sensitivity to chlorate and pulp mill effluents containing chlorate. All brown algal species ceased growth or showed major signs of toxicity at all concentrations tested, down to microgram per litre levels. EC50 levels for growth of Fucus vesiculosus were about 80-100 microg ClO3- litre(-1). Blue-green algae (Cyanophyta) were not deleteriously affected nor were green algae (Chlorophyta). The perennial and annual species of red algae (Rhodophyta) were also unaffected by the effluents. Diatoms did not show any sensitivity and phytoplankton (fresh- and brackish water) were particularly insensitive. A phanerogam, Zostera marina was also unaffected by the treatments.     

Influence of humic substances on the toxic effects of cadmium and zinc to the green alga Pseudokirchneriella subcapitata

A method combining (1 h) algal photosynthesis inhibition tests and tangential-flow ultrafiltration (TFF) technique (cut-off 1 kDa) was used to determine the effect of humic substances (HS) on acute metal toxicity to Pseudokirchneriella subcapitata. Three "standard" HS (soil and peat humic acids and Suwannee River fulvic acids) at two concentrations (1 and 5 mg/l) and two metals (Zn at 390 microg/l and Cd at 200 microg/l) were studied. Toxicity of Cd and Zn to P. subcapitata was significantly (p<0.05) reduced in the presence of humic acids (HA) but not in the presence of Suwannee River fulvic acids (SRFA). Metal partitioning between colloidal (1 microm-1 kDa) and truly dissolved (<1 kDa) fractions was found to match a decrease of metal toxicity in the presence of HA, but not in the presence of SRFA. The results suggested that HA reduced Cd and Zn toxicity in two different ways: (1) HA decrease the amount of free metal ions. Metal-HA complexes are high molecular weight, relatively stable with regard to metal-exchange reactions and consequently the metals were less bioavailable. (2) HA adsorbed onto algal surfaces, shielded the cells from free Cd and Zn ions. Several possible explanations can be postulated to account for the observed SRFA results: (1) Cd- and Zn-SRFA complexes are thought to be labile (i.e. undergo rapid dissociation); (2) SRFA coagulated, presumably during equilibration, and that coagulation altered metal complexing behavior of SRFA; (3) FA has a lower ability to adsorb on cell membranes at pH>7.