Transformation of effluent organic matter during subsurface wetland treatment in the Sonoran Desert

The fate of dissolved organic matter (DOM) during subsurface wetland treatment of wastewater effluent in a hot, semi-arid environment was examined. The study objectives were to (1) discern changes in the character of dissolved organics as consequence of wetland treatment (2) establish the nature of wetland-derived organic matter, and (3) investigate the impact of wetland treatment on the formation potential of trihalomethanes (THMs). Subsurface wetland treatment produced little change in DOM polarity (hydrophobic-hydrophilic) distribution. Biodegradation of labile effluent organic matter (EfOM) and internal loading of wetland-derived natural organic matter (NOM) together produced only minor changes in the distribution of carbon moieties in hydrophobic acid (HPO-A) and transphilic acid (TPI-A) isolates of wetland effluent. Aliphatic carbon decreased as a percentage of total carbon during wetland treatment. The ratio of atomic C:N in wetland-derived NOM suggests that its character is determined by microbial activity. Formation of THMs upon chlorination of HPO-A and TPI-A isolates increased as a consequence of wetland treatment. Wetland-derived NOM was more reactive in forming THMs and less biodegradable than EfOM. For both HPO-A and TPI-A fractions, relationships between biodegradability and THM formation potential were similar among EfOM and NOM isolates; the less biodegradable isolates exhibited greater THM formation potential.     

Factorial analysis of the trihalomethane formation in the reaction of colloidal,hydrophobic, and transphilic fractions of DOM with free chlorine

Background, aim, and scope  

This study focuses on the factors that affect trihalomethane (THMs) formation when dissolved organic matter (DOM) fractions (colloidal, hydrophobic, and transphilic fractions) in aqueous solutions were disinfected with chlorine.     

Dissolved organic matter from treated effluent of a major wastewater treatment plant: characterization and influence on copper toxicity

A combination of reverse osmosis (RO) concentration and DAX-8/XAD-4 resin adsorption techniques is used to isolate the various constituents of urban dissolved organic matter (DOM) from inorganic salts. Three fractions: hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) accounting respectively for 35%, 20% and 45% of extracted carbon, are isolated from effluents of a major French wastewater treatment plant. This atypical DOC distribution, in comparison with natural water where the HPO fraction dominates, shows the significance of HPI fraction which often gets neglected because of extraction difficulties. A number of analytical techniques (elemental, spectroscopic: UV, FTIR) allow highlighting the weak aromaticity of wastewater effluent DOM (EfOM) due to fewer degradation and condensation processes and the strong presence of proteinaceous structures indicative of intense microbial activity. Copper toxicity in the presence of DOM is estimated using an acute toxicity test on Daphnia Magna (Strauss). Results reveal the similar protective role of each EfOM fraction compared to reference Suwannee river fulvic acid despite lower EfOM aromaticity (i.e. specific UV absorbance). The environmental implications of these results are discussed with respect to the development of site-specific water quality criteria.     

Microbial degradation of dissolved organic matter (DOM) and its influence on phenanthrene-DOM interactions

Microbial degradation-induced changes in the characteristics of dissolved organic matter (DOM), and the subsequent effects on phenanthrene-DOM interactions were investigated based on the microbial incubation of DOM collected from four different sources for 28 d. Partially biodegraded DOM presented higher specific UV absorbance (SUVA), lower protein-like fluorescence, higher humic-like fluorescence, lower aliphatic carbon fraction, and higher hydrophobic neutral fractions compared to the original DOM. Microbial changes in DOM led to an increase in the isotherm nonlinearity as well as the extent of phenanthrene binding. A negative relationship between SUVA and the Freundlich n values was established for the original and the biodegraded DOM, suggesting that aromatic condensed structures may play important roles in providing nonlinear strong binding sites irrespective of microbial degradation. In contrast, there were two separate slopes of the correlations between the percentage of hydrophobic acid (HoA) fraction and the n values for the original and the biodegraded DOM with a higher slope exhibited for the latter, implying that the microbial utilization of oxygen-containing structures in the HoA fractions may contribute to enhancing the associated isotherm nonlinearity.     

Medium optimization for the production of anti-cyanobacterial substances by Streptomyces sp. HJC-D1 using response surface methodology

Bioremediation using isolated anti-cyanobacterial microorganism has been widely applied in harmful algal blooms (HABs) control. In order to improve the secretion of activated anti-cyanobacterial substances, and lower the cost, a sequential optimization of the culture medium based on statistical design was employed for enhancing the anti-cyanobacterial substances production and chlorophyll a (Chl a) removal by Streptomyces sp. HJC-D1 in the paper. Sucrose and KNO₃ were selected as the most suitable carbon and nitrogen sources based on the one-at-a-time strategy method, and sucrose, KNO₃ and initial pH were found as major factors that affected the anti-cyanobacterial ability of the isolated stain via the Plackett–Burman design. Based on the response surface and canonical analysis, the optimum condition of culture medium was obtained at 22.73 g l^-1 of sucrose, 0.96 g l^-1 of KNO₃, and initial pH 8.82, and the Chl a removal efficiency by strain HJC-D1 increased from 63?±?2 % to 78?±?2 % on the optimum conditions.     

A fingerprint analysis method for characterization of dissolved organic matter in secondary effluents of municipal wastewater treatment plant

Dissolved organic matter (DOM) in wastewater and reclaimed water is related to water quality, safety, and treatability. In this study, DOM was characterized through a fingerprint analysis method for DOM characterization using resin fractionation followed by size exclusion chromatography (SEC). Resin fractionation was used in the first step to divide the DOM in water samples into six resin fractions, namely, hydrophobic acids (HOA), hydrophobic bases (HOB), hydrophobic neutrals (HON), hydrophilic acids (HIA), hydrophilic bases (HIB), and hydrophilic neutrals (HIN). SEC analysis was then performed to separate each resin fraction into several (n) subfractions with different molecular weights (MW). Thus, the total DOM in the water sample was fractionated into 6n subfractions. After quantification of each subfraction by dissolved organic carbon (DOC), a fingerprint graph was constructed to express the distribution of DOM in the subfractions. The fingerprint analysis method was applied to a secondary effluent sample during ozonation. Ozonation (dose of 10 mg L^?1) removed the DOC only by 8 % and reduced UV₂₅₄ of the sample by 36 %. Fingerprint graphs also revealed that the resin fractions changed quite limitedly but transformation of subfractions occurred notably.     

Molecular characterisation of the dissolved organic matter of wastewater effluents by MSSV pyrolysis GC-MS and search for source markers

Microscale sealed vessel pyrolysis (MSSVpy) was used to characterise the hydrophobic (HPO) and colloid (COL) fractions of dissolved organic matter (DOM) from the effluents (EFFs) of two waste water treatment plants (WWTPs) and several primary source waters (SWs). The EFFs showed a large range of anthropogenically sourced organics - including the metabolites of industrial chemicals (e.g., dioxanes, n- and sec-alkyl substituted benzenes and long chain alkyl phenols), pharmaceuticals (e.g., N- and S-heterocycles) and human waste (e.g., S- and N-organics, steranes/sterenes) - as well as high concentrations of alkyl aromatic and N-organic products (e.g., alkyl indoles, carbazoles and β-carbolines) attributed to the treatment biota. Some anthropogenic chemicals are potentially toxic at even trace levels, whilst the N-organics may be precursors for toxic N-disinfection by-products. Much lower concentrations of just a few of the anthropogenic and N-organic products were detected by more traditional flash pyrolysis (Flash-py) of the EFF samples, reflecting the higher sensitivity of MSSVpy to many chemical functionalities. Few of these products were detected in the corresponding MSSVpy analysis of the SWs, but these samples did show relatively high abundances of lignin (e.g., alkylphenols) and carbohydrate (e.g., furans) derived products. Their lower EFF abundances are consistent with efficient removal by the water treatment procedures applied. Conversely, the detection of the anthropogenics in the treated EFFs reflects their general resistance to treatment. Their occurrence in the HPO fractions isolated by XAD resin separation suggests a potential relationship with the structurally stable macromolecular fraction of the DOM.     

The role of humic acid in the toxicity of arsenite to the diatom Navicula sp.

Dissolved organic matter (DOM) affects arsenite [As(III)] toxicity by altering its sorption equilibrium at the cell wall interface. A better understanding of such mechanism is of great importance to assess As(III) ecotoxicity in aquatic systems. Batch experiments were conducted to study the effects of DOM on the regulation of As(III) sorption and toxicity in the diatom Navicula sp. The influence of humic acid (HA) on As(III) toxicity was assessed by measuring algal growth, chlorophyll a, and reactive oxygen species (ROS), whereas As(III) mobility across the cell wall was estimated by determining the concentration of intracellular, cell-wall-bound, and free As(III) ions in cell media. Results showed that the effects of HA on arsenite toxicity varied depending on various combinations of As(III)-HA concentrations. EC₅₀ had an approximate threefold increase from 8.32 (HA-free control) to 22.39 μM (at 20 mg L^?1 HA) when Navicula sp. was exposed to 1.0–100.0 μM of As(III), compared to an overall low complexation ratio of HA-As(III) in a range of 0.91–6.00 %. The cell wall-bound and intracellular arsenic content decreased by 19.8 and 20.3 %, respectively, despite the lower arsenite complexation (2.10?±?0.16 % of the total As). Meanwhile, intracellular ROS was decreased by 12.6 % in response to 10.0 μM As(III) and 10 mg L^?1 HA vs. the HA-free control. The significant contrast indicated that complexation alone could not explain the HA-induced reduction in arsenite toxicity and other factors including HA–cell surface interactions may come into play. Isotherms describing adsorption of HA to the Navicula sp. cells combined with morphological data by scanning electron microscopy revealed a protective HA floccule coating on the cell walls. Additional Fourier transform infrared spectroscopic data suggested the involvement of carboxylic groups during the adsorption of both HA and As(III) on the Navicula sp. cell surface. Collective data from this study suggest that cell wall-bound HA can moderate As(III) toxicity through the formation of a protective floccule coating occupying As(III) sorption sites and decreased effective functional groups capable of binding As(III). Our findings imply that As(III) toxicity can be alleviated due to the increased hindrance to cellular internalization of As(III) in the presence of naturally abundant DOM in water.     

Quantifying interactions between propranolol and dissolved organic matter (DOM) from different sources using fluorescence spectroscopy

Beta blockers are widely used pharmaceuticals that have been detected in the environment. Interactions between beta blockers and dissolved organic matter (DOM) may mutually alter their environmental behaviors. To assess this potential, propranolol (PRO) was used as a model beta blocker to quantify the complexation with DOM from different sources using the fluorescence quenching titration method. The sources of studied DOM samples were identified by excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration analysis. The results show that PRO intrinsic fluorescence was statically quenched by DOM addition. The resulting binding constants (log K _oc) ranged from 3.90 to 5.20, with the surface-water-filtered DOM samples claiming the lower log K _oc and HA having the highest log K _oc. Log K _oc is negatively correlated with the fluorescence index, biological index, and the percent fluorescence response (P _i,n) of protein-like region (P _I,n) and the P _i,n of microbial byproduct-like region (P _II,n) of DOM EEMs, while it is correlated positively with humification index and the P _i,n of UVC humic-like region (P _III,n). These results indicate that DOM samples from allochthonous materials rich in aromatic and humic-like components would strongly bind PRO in aquatic systems, and autochthonous DOM containing high protein-like components would bind PRO more weakly.     

Chemical characteristics of chromophoric dissolved organic matter in rainwater

Proton nuclear magnetic resonance (¹H-NMR), UV absorbance and excitation-emission matrix (EEM) fluorescence spectroscopy were used to define the chemical characteristics of chromophoric dissolved organic matter (CDOM) in whole and C₁₈ extracted rainwater. The average total recovery of fluorescence determined from the sum of extract and filtrate fractions relative to the whole was 86% suggesting that 14% of fluorescent CDOM in rainwater is comprised of very hydrophobic material that cannot be eluted from the column. Half the fluorescence of rainwater was recovered in the filtrate fraction which is important because it suggests that 50% of the chromophoric material present in precipitation is relatively hydrophilic. The average spectral slope coefficient was smaller in extracted samples (16.3 ± 9.0 μm^?1) relative to whole samples (18.9 ± 2.8 μm^?1) suggesting that the extracted material contains larger molecular weight material. Approximately one-third of the total dissolved organic carbon (DOC) in rainwater exists in the extract fraction suggesting that a large percentage of the uncharacterized DOC in rainwater can be accounted for by these hydrophobic macromolecular species. The fluorescence of extracted samples is strongly correlated with total NMR integration and is most sensitive to aromatic protons suggesting that molecules in this region are the most important in controlling the optical properties of rainwater. The lower removal efficiency of CDOM in rainwater relative to surface waters or the water-soluble fraction of aerosols during solid phase extraction (SPE) suggests that rainwater contains significantly more hydrophilic chromophoric compounds which are compositionally different than found in these other aquatic matrices.     

Hexavalent chromium removal by a novel Serratia proteamaculans isolated from the bank of Sebou River (Morocco)

The novel Serratia proteamaculans isolated from a chromium-contaminated site was tolerant to a concentration of 500 mg Cr(VI)/l. The optimum pH and temperature for reduction of Cr(VI) by S. proteamaculans were found to be 7.0 and 30 °C, respectively. The Cr(VI) reduction rate decreased with the increase in Cr(VI) concentration from 100 to 400 mg/l, suggesting the enzymatic chromium reduction. Resting and permeabilised cell assays provided the better evidence that chromate reduction in S. proteamaculans is enzymatic. Reduction by cell-free filtrate shows no extracellular chromate-reducing activity, revealing that this activity may be associated to membrane fraction and/or cytosolic fraction. Assays conducted with cytosolic and particulate fraction of S. proteamaculans confirmed the role of membrane-bound proteins in Cr(VI) reduction. Furthermore, chromium reduced by heat-treated cells suggests that membrane-associated chromate reductase activity of S. proteamaculans is preceded by its adsorption on the cell surface.     

Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions.     

In vitro Cr(VI) reduction by cell-free extracts of chromate-reducing bacteria isolated from tannery effluent irrigated soil

Four efficient Cr(VI)-reducing bacterial strains were isolated from rhizospheric soil of plants irrigated with tannery effluent and investigated for in vitro Cr(VI) reduction. Based on 16S rRNA gene sequencing, the isolated strains SUCR44, SUCR140, SUCR186, and SUCR188 were identified as Bacillus sp. (JN674188), Microbacterium sp. (JN674183), Bacillus thuringiensis (JN674184), and Bacillus subtilis (JN674195), respectively. All four isolates could completely reduce Cr(VI) in culture media at 0.2 mM concentration within a period of 24–120 h; SUCR140 completely reduced Cr(VI) within 24 h. Assay with the permeabilized cells (treated with Triton X-100 and Tween 80) and cell-free assay demonstrated that the Cr(VI) reduction activity was mainly associated with the soluble fraction of cells. Considering the major amount of chromium being reduced within 24–48 h, these fractions could have been released extracellularly also during their growth. At the temperature optima of 28 °C and pH?7.0, the specific activity of Cr(VI) reduction was determined to be 0.32, 0.42, 0.34, and 0.28 μmol Cr(VI)?min^?1?mg^?1 protein for isolates SUCR44, SUCR140, SUCR186, and SUCR188, respectively. Addition of 0.1 mM NADH enhanced the Cr(VI) reduction in the cell-free extracts of all four strains. The Cr(VI) reduction activity in cell-free extracts of all the isolates was stable in presence of different metal ions tested except Hg²⁺. Beside this, urea and thiourea also reduced the activity of chromate reduction to significant levels.     

Responses of kinetics and capacity of phenanthrene sorption on sediments to soil organic matter releasing

Soil organic matter (SOM) releasing with dissolved organic matter (DOM) formed in solution was confirmed in a sediment/water system, and the effects of SOM releasing on the sorption of phenanthrene on sediments were investigated. Inorganic salt (0–0.1 mol L^?1 NaCl) was used to adjust SOM releasing, and two sediments were prepared, the raw sediment (S1) from Weihe River, Shann’xi, China, and the eluted sediments with and without DOM supernatant remained, termed as S2a and S2b, respectively. The FTIR and ¹H NMR analysis indicate that the low molecular weight hydrophilic SOM fraction released prior to the high molecular weight hydrophobic fraction. As a response, phenanthrene sorption kinetics on S1 showed atypical and expressed as three stages: rapid sorption, pseudo sorption with partial desorption, and slow sorption, thus a defined “sorption valley” occurred in kinetic curve. In all cases, partition dominates the sorption, and sorption capacity (K_d) ranked as S2b > S1 > S2a. Compared with the alterations of sediment characters, DOM solubilization produced by SOM releasing exhibited a greater inhibitory effect on sorption with a relative contribution of 0.67. Distribution coefficients (K_doc) of PHE into DOM clusters were 2.10?×?10⁴–4.18?×?10⁴ L kg^?1, however a threshold concentration of 6.83 mg L^?1 existed in DOM solubilization. The study results will help to clarify PAHs transport and their biological fate in a sediment/water system.     

Chemical properties of dissolved organic matter derived from sugarcane rind and the impacts on copper adsorption onto red soil

Dissolved organic matter (DOM), as the most active organic carbon in the soil, has a coherent affinity with heavy metals from inherent and exogenous sources. Although the important roles of DOM in the adsorption of heavy metals in soil have previously been demonstrated, the heterogeneity and variability of the chemical constitution of DOM impede the investigation of its effects on heavy metal adsorption onto soil under natural conditions. Fresh DOM (FDOM) and degraded DOM (DDOM) from sugarcane rind were prepared, and their chemical properties were measured by Fourier-transform infrared spectrometry (FTIR), excitation-emission matrix (EEM) fluorescence spectroscopes, nuclear magnetic resonance (NMR), and molecular weight distribution (MWD). They were also used in batch experiments to evaluate their effects on the adsorption of Cu(II) onto farmland red soil. Based on our results, the chemical structure and composition of DDOM greatly varied; compared with FDOM, the C/O ratio (from 24.0 to 9.6%) and fluorescence index (FI) (from 1.4 to 1.0) decreased, and high molecular weight (>10 kDa) compounds increased from 23.18 to 70.51%, while low molecular weight (<3 kDa) compounds decreased from 56.13 to 12.13%; aromaticity and humification degree were markedly enhanced. The discrepancy of FDOM and DDOM in terms of chemical properties greatly influenced Cu(II) adsorption onto red soil by affecting DOM-Cu(II) complex capacity. The FDOM inhibited the adsorption of Cu(II), while DDOM promoted adsorption, which was significantly influenced by soil pH. Maximum adsorption capacity (Q _m) was 0.92 and 5.76 mg g^?1 in the presence of FDOM and DDOM, respectively. The adsorption process with DDOM could be better described by the Langmuir model, while that with FDOM was better described by the Freundlich model. The impacts caused by the dynamic changes of the chemical properties of DOM under natural conditions should therefore be considered in the risk assessment and remediation of soils contaminated with heavy metals.     

Effect of mycosynthesized silver nanoparticles from filtrate of Trichoderma harzianum against larvae and pupa of dengue vector Aedes aegypti L

Mosquitoes transmit dreadful diseases, causing millions of deaths every year. Therefore, screening for larvicidal and pupicidal activity of microbial extracts attributes could lead to development of new and improved mosquito control methods that are economical and safe for nontarget organisms and are ecofriendly. Synthetic chemical insecticides occupy predominant position in control strategies. These hazardous chemicals exert unwarranted toxicity and lethal effects on nontarget organisms, develop physiological resistance in target, and cause adverse environmental effect. For vector control, fungal-mediated natural products have been a priority in this area at present. In the current study, effective larvicidal and pupicidal effect of mycosynthesized silver nanoparticles (Ag NPs) using an entomopathogenic fungi Trichoderma harzianum against developmental stages of the dengue vector Aedes aegypti was investigated. An attractive possibility of green nanotechnology is to use microorganisms in the synthesis of nanosilver especially Ag NPs. The mycosynthesized Ag NPs were characterized to find their unique properties through UV-visible spectrophotometer, X-ray diffraction analysis, Fourier transform infrared, and surface characteristics by scanning electron microscopy. To analyze the bioefficacy, different test concentrations for extracellular filtrate (0.2, 0.4, 0.6, 0.8, and 1.0 %) and Ag NPs (0.05, 0.10, 0.15, 0.20, and 0.25 %) were prepared to a final volume of 200 mL using deionized water; 20 larvae of each instars (I–IV) and pupa were exposed to each test concentration separately which included a set of control (distilled water) group with five replicates. Characterization of the synthesized Ag NPs were about 10–20 nm without aggregation. Susceptibility of larval instars to synthesized Ag NPs was higher than the extracellular filtrate of T. harzianum alone after 24-h exposure, where the highest mortality was recorded as 92 and 96 % for first and second instars and 100 % for third, fourth instars, and pupa. Lethal concentration 50 values of 0.079, 0.084, 0.087, 0.068, and 0.026 % were recorded for I–IV instars and pupa, respectively, when exposed to Ag NPs at 0.25 % concentration. Toxicity was exhibited against first (1.076 %), second (0.912 %), third (0.770 %), fourth (0.914 %) instars larvae, and pupa (0.387 %) with extracellular filtrate at a concentration of 1 % that was three- to fourfold higher compared to Ag NPs; no mortality was observed in the control. The present study is the first report on effective larvicidal and pupicidal activity of Ag NPs synthesized from an entomopathogenic fungi T. harzianum extracellular filtrate and could be an ideal ecofriendly, single-step, and inexpensive approach for the control of A. aegypti.     

Study on the spectral and Cu (II) binding characteristics of DOM leached from soils and lake sediments in the Hetao region

Introduction

Dissolved organic matter (DOM) is the most active component in environmental system and its chemical and structural characteristics most likely influence its biodegradation. Four surface soil (0?C20?cm) and three core sediment samples (0?C10?cm) were collected from Wuliangsuhai Lake. The objectives of this study were to investigate the spectral properties and humification degree of DOM and to determine and discuss comparatively the complexing capacities and stability constants of DOM by Cu (II) in the Hetao region.

Materials and methods

In this study, fluorescence spectra and fluorescence quenching methods were used to evaluate the humification degree of DOM and calculate the complexing capacities and the stability constants between DOM and Cu (II).

Results and discussion

Two defined peaks, at wavelengths of 260??300?nm (peak I) and 300??350?nm (peak II), could be identified for soil DOM at a ???? value of 30?nm. In sediment DOM extracts, a third peak (III) was observed near 364?nm. The results show that there is a significant difference in the structure of DOM because of different sources. The humification degree is significantly higher for soil samples than those of sediment samples. The FT-IR spectra of DOM show that structure in sediment DOM is more functional groups than those in soil DOM. DOM has a stronger Cu binding affinity in soils than in sediment in the Hetao region, which may lead to potentially significant influence on the migration and transformation of Cu (II).     

Fluorescence spectroscopic characterization of DOM fractions isolated from a filtered river water after ozonation and catalytic ozonation

Fluorescence spectra were applied to investigate the structural changes of four dominant dissolved natural organic matter (DOM) fractions of a filtered river water before and after ozonation and catalytic ozonation. The ozonation and catalytic ozonation with synthetic goethite (FeOOH) and cerium dioxide (CeO(2)) were carried out under normal conditions, i.e. pH 7, reaction time of 10 min, and ozone/DOC ratio of about 1. The fluorescence spectra were recorded at both excitation-emission matrix (EEM) and synchronous scanning modes. EEM results reveal that ozonation of these DOM fractions causes a significant decrease of the aromaticity of humic-like structures and an increase of electron withdrawing groups, e.g., carboxylic groups. The catalysts can further improve the destruction of the humic-like structures in catalytic ozonation. Synchronous spectra reveal that ozonation of hydrophobic acid and hydrophilic acid (HIA) yields a significant amount of by-products with low aromaticity and low molecular weight. Catalytic ozonation enhances substantially the formation of these by-products from HIA and improves the destruction of highly polycyclic aromatic structures for all examined DOM fractions.     

Growth inhibition of bloom forming cyanobacterium Microcystis aeruginosa by green route fabricated copper oxide nanoparticles

The cyanobacterium Microcystis aeruginosa can potentially proliferate in a wide range of freshwater bionetworks and create extensive secondary metabolites which are harmful to human and animal health. The M. aeruginosa release toxic microcystins that can create a wide range of health-related issues to aquatic animals and humans. It is essential to eliminate them from the ecosystem with convenient method. It has been reported that engineered metal nanoparticles are potentially toxic to pathogenic organisms. In the present study, we examined the growth inhibition effect of green synthesized copper oxide nanoparticles against M. aeruginosa. The green synthesized copper oxide nanoparticles exhibit an excitation of surface plasmon resonance (SPR) at 270 nm confirmed using UV–visible spectrophotometer. The dynamic light scattering (DLS) analysis revealed that synthesized nanoparticles are colloidal in nature and having a particle size of 551 nm with high stability at ?26.6 mV. The scanning electron microscopy (SEM) analysis shows that copper oxide nanoparticles are spherical, rod and irregular in shape, and consistently distributed throughout the solution. The elemental copper and oxide peak were confirmed using energy dispersive x-ray analysis (EDAX). Fourier-transform infrared (FT-IR) spectroscopy indicates the presence of functional groups which is mandatory for the reduction of copper ions. Besides, green synthesized copper oxide nanoparticles shows growth inhibition against M. aeruginosa. The inhibition efficiency was 31.8 % at lower concentration and 89.7 % at higher concentration of copper oxide nanoparticles, respectively. The chlorophyll (a and b) and carotenoid content of M. aeruginosa declined in dose-dependent manner with respect to induction of copper oxide nanoparticles. Furthermore, we analyzed the mechanism behind the cytotoxicity of M. aeruginosa induced by copper oxide nanoparticles through evaluating membrane integrity, reactive oxygen species (ROS), and mitochondrial membrane potential (Δψm) level. The results expose that there is a loss in membrane integrity with ROS formation that leads to alteration in the Δψm, which ends up with severe mitochondrial injury in copper oxide nanoparticles treated cells. Hence, green way synthesized copper oxide nanoparticles may be a useful selective biological agent for the control of M. aeruginosa.     

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.