Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions

This work investigated the effect of granular activated carbon adsorption (GACA) on fluorescence characteristics of dissolved organic matter (DOM) in secondary effluent, by means of excitation–emission matrix (EEM) spectra, the fluorescence regional integration (FRI) method, synchronous spectra, the fluorescence index defined as the ratio of fluorescence emission intensity at wavelength 450 nm to that at 500 nm at excitation (λ_ex)=370 nm, and the wavelength that corresponds to the position of the normalized emission band at its half intensity (λ_0.5). DOM in the secondary effluent from the North Wastewater Treatment Plant (Shenyang, China) was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO–A), hydrophobic neutral (HPO–N), transphilic acid (TPI–A), transphilic neutral (TPI–N) and hydrophilic fraction (HPI). Results showed that fluorescent materials in HPO–N and TPI–N were less readily removed than those in the other fractions by GACA. The relative content of fluorescent materials in HPO–A, TPI–A and HPI decreased whereas that in HPO–N and TPI–N increased as a consequence of GACA. Polycyclic aromatics in all DOM fractions were preferentially absorbed by GACA, in comparison with bulk DOM expressed as DOC. On the other hand, the adsorption of aromatic amino acids and humic acid-like fluorophores exhibiting fluorescence peaks in synchronous spectra by GACA seemed to be dependent on the acid/neutral properties of DOM fractions. All five fractions had decreased fluorescence indices as a result of GACA. GACA led to a decreased λ_0.5 value for HPO–A, increased λ_0.5 values for HPO–N, TPI–A and HPI, and a consistent λ_0.5 value for TPI–N.     

Degradation of bisphenol A by microorganisms immobilized on polyvinyl alcohol microspheres

In this study, microorganisms （named B111） were immobilized on polyvinyl alcohol microspheres prepared by the inverse suspension crosslinked method. The biodegradation of bisphenol A （BPA） and 4-hydro- xybenzaldehyde, a degradation product of BPA, by free and immobilized B lll was investigated. The BPA degradation studies were carried out at initial BPA concentrations ranging from 25 to 150 mg·L^-1. The affinity constant Ks and maximum degradation rate Rmax were 98.3 mg·L^-1 and 19.7mg·mg^-1VSS·d^-1 for free B111, as well as 87.2mg·L^-1 and 21.1mg·mg^-1VSS·d^-1 for immobilized B 111, respectively. 16S rDNA gene sequence analyses confirmed that the dominant genera were Pseudomonas and Brevundimonas for BPA biodegradation in microorganisms B 111.     

Temporal variation of heavy metal pollution in urban stormwater runoff

Stormwater runoff from three types of urban surfaces, a parking lot, a street, and a building roof, was monitored during four rainfall events that occurred in the one-year period from June 2009 to June 2010. The event mean concentrations (EMC) of dissolved copper (Cu), lead (Pb), zinc (Zn), manganese (Mn), and iron (Fe) exceeded China’s National Water Quality Standards for Surface Water. The degree of heavy metal contamination was related to the type of underlying surfaces. Additionally, the concentration of dissolved heavy metals peaked shortly after the runoff began and then declined sharply as a result of adequate flushing. First flush effects of varying degrees were also observed during all of the monitored rainfall events based on the first flush ratio (FF₂₅). Redundancy analysis revealed that four environmental variables (rainfall depth, intensity, antecedent dry weather period and type of underlying surface) had significant effects on the strengths of the first flush effects, accounting for 72.9% of the variation in the FF₂₅. Dissolved metals presented varying first flush effects on different underlying surfaces that occurred in the following relative order: parking lot>roof>road for low intensity and high runoff volume rainfall events; parking lot>road>roof for high intensity and low runoff volume events. The relative strength of the first flush for dissolved heavy metals was Fe, Mn>Cu, Zn>Pb.     

Biodegradation of 2-methylisoborneol by bacteria enriched from biological activated carbon

One of the most common taste and odour compounds (TOCs) in drinking water is 2-methylisoborneol (2-MIB) which cannot be readily removed by conventional water treatments. Four bacterial strains for degrading 2-MIB were isolated from the surface of a biological activated carbon filter, and were characterized as Micrococcus spp., Flavobacterium spp., Brevibacterium spp. and Pseudomonas spp. based on 16S rRNA analysis. The removal efficiencies of 2-MIB with initial concentrations of 515 ng·L^-1 were 98.4%, 96.3%, 95.0%, and 92.8% for Micrococcus spp., Flavobacterium spp., Brevibacterium spp. and Pseudomonas spp., respectively. These removal efficiencies were slightly higher than those with initial concentration at 4.2 mg·L^-1 (86.1%, 84.4%, 86.7% and 86.0%, respectively). The kinetic model showed that biodegradation of 2-MIB at an initial dose of 4.2 mg·L^-1 was a pseudo-first-order reaction, with rate constants of 0.287, 0.277, 0.281, and 0.294 d^-1, respectively. These degraders decomposed 2-MIB to form 2-methylenebornane and 2-methyl-2-bornane as the products.     

Identification and ecotoxicity assessment of intermediates generated during the degradation of clofibric acid by advanced oxidation processes

The aim of this study was to identify the intermediates in clofibric acid degradation under various advanced oxidation processes, namely ultraviolet (UV), UV/H₂O₂, vacuum ultraviolet (VUV), VUV/H₂O₂, and solar/TiO₂ processes, as well as to assess the toxicity of these intermediates. Eleven intermediates have been detected by gas chromatography-mass spectrometer, most of which were reported for the first time to our best knowledge. Combining the evolution of the dissolved organic carbon, Cl^- and specific ultraviolet absorption at 254 nm, it could be deduced that cleavage of aromatic ring followed by dechlorination was the mechanism in solar/TiO₂ process, while dechlorination happened first and accumulation of aromatic intermediates occurred in the other processes. Different transformation pathways were proposed for UV-, VUV-assisted and solar/TiO₂ processes, respectively. The acute toxicity was evaluated by means of Photobacterium phosphoreum T₃ spp. bioassay. It was believed that aromatic intermediates increased the toxicity and the ring-opening pathway in solar/TiO₂ process could relieve the toxicity.     

Identification of cadmium-induced genes in maize seedlings by suppression subtractive hybridization

A maize variety, Huatian-1, had an unusually low translocation rate of cadmium (Cd) (59.6 mg·kg^-1 in the roots and 0.093 mg·kg^-1 in the grain) compared to 24 other varieties while being grown in soils with 16.50 mg·kg^-1 Cd. This indicates that this particular species may have special mechanisms that affect the absorption and translocation pattern of Cd. In this paper, the technique of suppression subtractive hybridization (SSH) was used to isolate and identify Cd-induced genes from Huatian-1 hydroponically ?exposed? to? 0.1 mM ?CdCl₂ ?for? 1 h,? 12 h, 24 h, and 48 h. We found a total of 15 differentially expressed genes in the four groups; 2, 3, 4, and 6 genes were from the groups of 1 h, 12 h, 24 h, and 48 h treatment, respectively. Phospholipase PLDb1 mRNA, adenosine triphosphate (ATP) phosphoribosyl transferase 2, and Sp17 were turned on in the maize in response to Cd stress, and it might provide new clues to explain the mechanism of maize tolerance to Cd.     

Stress response to nanoplastics with different charges in Brassica napus L. during seed germination and seedling growth stages

● Higher concentrations of PS, PS-NH₂ and PS-SO₃H inhibited seed germination. ● PS, PS-NH₂ and PS-SO₃H influenced seedling growth in a dose-dependent manner. ● PS, PS-NH₂ and PS-SO₃H reduced essential nutrients uptake and plant quality. ● PS, PS-NH₂ and PS-SO₃H increased antioxidant enzyme activities and MDA content. ● Nanoplastic toxicity was related to surface charges. Nanoplastic pollution has become a significant problem in farmland systems worldwide. However, research on the effects of nanoplastics (NPs) with different charges on field crops is still limited. In our study, NPs with different charges, including unmodified polystyrene nanoplastics (PS), positively charged polystyrene nanoplastics (PS-NH₂), and negatively charged polystyrene nanoplastics (PS-SO₃H), were investigated for their impacts on seed germination and seedling growth of rape. The results showed that seed water uptake (after 12 h), seed germination, seed vigour, and relative root elongation were all significantly reduced under exposure to NPs (200 mg/L). Similarly, remarkable decreases in plant biomass (root weight, shoot weight), growth (root length, plant height), photosynthesis ability (chlorophyll a, chlorophyll b, carotenoids), essential nutrient uptake (Fe, Mn, Zn, Cu), and plant quality (soluble protein, soluble sugar, crude fibre content) of rape seedlings were also observed after exposure to NPs. Among the three kinds of NPs, PS-NH₂ showed stronger effects. Moreover, superoxide dismutase, peroxidase, and catalase activities of rape seedlings were changed, and the content of malondialdehyde was significantly increased under exposure to NPs. Furthermore, positively charged PS-NH₂ showed stronger effects on the phenotype, physiology, biochemistry, nutrient uptake, and plant quality of rape. Notably, a comprehensive toxicity evaluation revealed that PS-NH₂ had the strongest toxicity to rape. The present study provides important implications for the interaction and risk assessment of NPs and crops in soil-plant systems.     

Improvement of the assimilable organic carbon (AOC) analytical method for reclaimed water

Microbial growth is an issue of concern that may cause hygienic and aesthetic problems during the transportation and usage of reclaimed water. Assimilable organic carbon (AOC) is an important parameter which determines the heterotrophic bacterial growth potential of water. Pseudomonas fluorescens P17 and Spirillum sp. NOX are widely used to measure AOC in drinking water. The AOC values of various reclaimed water samples determined by P17 and NOX were compared with those determined by the new strains isolated from reclaimed water in this study. It showed that the conventional test strains were not suitable for AOC measurement of reclaimed water in certain cases. In addition to P17 and NOX, Stenotrophomonas sp. ZJ2, Pseudomonas saponiphila G3 and Enterobacter sp. G6, were selected as test strains for AOC measurement of reclaimed water. Key aspects of the bioassay including inoculum cell density, incubation temperature, incubation time and the pH of samples were evaluated for the newly selected test strains. Higher inoculum density (10⁴ CFU·mL^-1) and higher incubation temperature (25°C) could reduce the time required for the tests. The AOC results of various collected samples showed the advantages of the method proposed based on those five strains in evaluating the biologic stability of reclaimed water.     

Effects of iron oxide nanoparticles on phenotype and metabolite changes in hemp clones (Cannabis sativa L.)

● Fe₃O₄ NPs increased the biomass and chlorophyll content of hemp clones. ● Fe₃O₄ NPs penetrated and were internalized by root cells. ● Fe₃O₄ NPs induced the alteration of metabolite profiles in hemp leaves. ● The psychoactive compound THC in hemp leaves was significantly down-regulated. We investigated the effect of iron oxide nanoparticles (Fe₃O₄ NPs, ~17 nm in size) on the phenotype and metabolite changes in hemp (Cannabis sativa L.), an annual crop distributed worldwide. Hemp clones were grown in hydroponic cultures with Fe₃O₄ NPs (50, 100, 200, or 500 mg/L) for four weeks. TEM and ICP-MS were used to determine Fe₃O₄ NPs uptake and translocation. LC-MS-based metabolomics was employed to explore the deep insight into the effect of Fe₃O₄ NPs on hemp plants. The results revealed that plant growth enhanced gradually with increasing concentrations of given NPs up to 200 mg/L, which improved the fresh weight and dry weight by 36.13% and 74.68%, respectively, compared to the control. Even at a high dose (500 mg/L), Fe₃O₄ NPs promoted plant growth, including increased biomass and tissue length. NPs significantly increased the iron and chlorophyll content in plant tissues Increased catalase activity and reduced hydrogen peroxide content in hemp leaves suggested that the Fe₃O₄ NPs activated the defense system. TEM showed that NPs were abundantly attached to the cell wall and dispersed throughout the root cells. Metabolomics revealed that Fe₃O₄ NPs induced metabolic reprogramming in hemp leaves, including the up-regulation of carbohydrates and organic acids, and down-regulation of antioxidants, especially tetrahydrocannabinol (THC). The significantly up-regulated metabolites, including peonidin and 2-hydroxycinnamic acid, could be involved in photosynthesis in hemp plants. These results demonstrate the potential of Fe₃O₄ NPs for promoting hemp growth and decreasing the THC content at low doses.     

Gold modified microelectrode for direct tetracycline detection

The residues of tetracycline antibiotics in water have attracted many concerns due to their harmful impact to human health. This paper reports an electrochemical sensor for the determination of tetracycline (TC) by the microelectrode, which was fabricated by electrodeposited gold colloids on tungsten tip. Cyclic voltammerty was used to study the electrochemical behavior of TC on the microelectrode. Well anodic wave was obtained at about 1.5 V in acidic solutions. Electrochemical determination of tetracycline was investigated using microelectrode by cyclic voltammetry. Under optimized conditions, the calibration curves for TC were obtained. The oxidation peak currents were linearly related to TC concentrations in the range of 1–10 mg·L^-1 and 10–100 mg·L^-1, respectively. The detection limit was 0.09 mg·L^-1 (S/N = 3).     

Technical feasibility study of an onshore ballast water treatment system

To fulfill the requirements of Guidelines for approval of ballast water management system (G8), a set of onshore ballast water treatment equipment utilizing micro-pore ceramic filtration (MPCF) and UV radiation (MPCF&UV) system was designed and set up with a maximum flow rate of 80 m³·h^-1. Technical feasibilities of MPCF&UV system were evaluated in three areas: removal efficiencies of indicator organism and oceanic bacteria, perdurability of a ceramic filter, and application on native seawater. The results showed that no indicator organism (Dunaliella) or oceanic bacteria was detected after treatment of 20 L MPCF and UV radiation at 1.3× 10⁴ μW·s·cm^-2. A 20 L ceramic filter can run continuously for 5.3 h at the flow rate of 15 m³·h^-1 before its pressure drop up to 0.195 MPa. The removal percentage of total plankton amounts were 91.9% at a flow rate of 70 m³·h^-1 by 80 L MPCF and UV radiation at 1.3× 10⁴ μW·s·cm^-2.     

Hormesis-like growth and photosynthetic physiology of marine diatom Phaeodactylum tricornutum Bohlin exposed to polystyrene microplastics

• Polystyrene microplastic caused hormesis-like effects in Phaeodactylum tricornutum. • Low concentration of microplastic promoted growth, otherwise the opposite was true. • The change trends of pigment contents were opposite at two initial algae densities. • The chlorophyll fluorescence parameters were more sensitive at low algae density. The effects of pristine polystyrene microplastics (pMPs) without any pretreatment at different concentrations (0, 10, 20, 50, and 100 mg/L) on Phaeodactylum tricornutum Bohlin at two initial algae densities (10⁵ and 10⁶ cells/mL) were assessed in this study. Hormesis-like effects were found when microalgae grew with pMPs. The results showed that pMPs inhibited microalgae growth under a high concentration of microplastics tolerated by individual algal cell (low initial algae density) (up to −80.18±9.71%) but promoted growth when the situation was opposite (up to 15.27±3.66%). The contents of photosynthetic pigments including chlorophyll a, chlorophyll c and carotenoids showed resistance to pMPs stress under a low initial algae density and increased with time, but the opposite was true under a high initial algae density. Compared with the low initial algae density group, Qp received less inhibition, and NPQ (heat dissipation) also decreased under the high initial algae density. Under the low initial algae density, OJIP parameters such as S_m, N, Area, Pi Abs, ѱ_o, φ_Eo, TRo/RC and ETo/RC were more perturbed initially and returned to the levels of the control group (without pMPs) over time, but they remained stable throughout the experiment at high initial algae density. These results show that microplastics in the marine environment may have different toxic effects on P. tricornutum at different growth stages, which is of great significance for understanding the impact of microplastics on marine microalgae and aquatic ecosystems.     

Performance and kinetics of iron-based oxygen carriers reduced by carbon monoxide for chemical looping combustion

Chemical looping combustion is a promising technology for energy conversion due to its low-carbon, high-efficiency, and environmental-friendly feature. A vital issue for CLC process is the development of oxygen carrier, since it must have sufficient reactivity. The mechanism and kinetics of CO reduction on iron-based oxygen carriers namely pure Fe₂O₃ and Fe₂O₃ supported by alumina (Fe₂O₃/Al₂O₃) were investigated using thermo-gravimetric analysis. Fe₂O₃/Al₂O₃ showed better reactivity over bare Fe₂O₃ toward CO reduction. This was well supported by the observed higher rate constant for Fe₂O₃/Al₂O₃ over pure Fe₂O₃ with respective activation energy of 41.1±2.0 and 33.3±0.8 kJ·mol⁻¹. The proposed models were compared via statistical approach comprising Akaike information criterion with correction coupled with F-test. The phase-boundary reaction and diffusion control models approximated to 95% confidence level along with scanning electron microscopy results; revealed the promising reduction reactions of pure Fe₂O₃ and Fe₂O₃/Al₂O₃. The boosting recital of iron-based oxygen carrier support toward efficient chemical looping combustion could be explained accurately through the present study.     

Suspended solid abatement in a conical fluidized bed flocculator

With the random movement of silica gel beads in a conical fluidized bed, micro-vortices resulting from the fluidization promoted the collision and aggregation of suspended fine kaolin powders. The abatement efficiencies of the suspended fine solids under several hydrodynamic conditions were studied, and a suitable control strategy for operating the conical fluidized bed flocculators was identified. The suspended solids abatement efficiency was found to increase with increasing Camp Number and flocculation time (T), but decreased with the increase of velocity gradient (G) within the range studied in this research (165.1–189.6 s^-1). The abatement efficiencies were all more than 60% at the range of G = 165–180 s^-1 and T = 15–33 s at an initial kaolin solid concentration of 150 mg·L^-1, polymer aluminum chloride dosage of 60 mg·L^-1 and sedimentation time of 20 min. However, the formation of flocs was influenced by the liquid backmixing. Excessive backmixing caused the breakup of flocs and resulted in difficulty for the fine powders to aggregate and sediment to the reactor bottom. The results of the calculated fractal dimension and measured free sedimentation velocity of flocs obtained at different runs showed similar flocs properties, and indicated an easy control strategy for sedimentation of the flocs.     

Bioleaching of copper from pre and post thermally activated low grade chalcopyrite contained ball mill spillage

Bioleaching of a low grade chalcopyrite (ball mill spillage material) was tested for copper recovery in shake flasks. The original samples (as received) were thermally activated (600°C, 30 min) to notice the change in physico-chemical and mineralogical characteristics of the host rock and subsequently its effect on copper recovery. A mixed culture of acidophilic chemolithotrophic bacterial consortium predominantly entailing Acidithiobacillus ferrooxidans strain was used for bioleaching studies and optimization of process parameters of both original and thermally activated samples. Mineralogical characterization studies indicated the presence of chalcopyrite, pyrite in the silicate matrix of the granitic rock. Field emission scanning electron microscopy coupled with Energy dispersive spectroscopy (FESEM-EDS) and X-ray Fluorescence (XRF) analysis indicated mostly SiO₂. With pH 2, pulp density 10% w/v, inoculum 10% v/v, temperature 30°C, 150 r·min^-1, 49% copper could be recovered in 30 days from the finest particle size (-1+ 0.75 mm) of the original spillage sample. Under similar conditions 95% copper could be recovered from the thermally activated sample with the same size fraction in 10 days. The study revealed that thermal activation leads to volume expansion in the rock with the development of cracks, micro and macro pores on its surface, thereby enabling bacterial solution to penetrate more easily into the body, facilitating enhanced copper dissolution.     

Kinetics of oxidation of dimethyl trisulfide by potassium permanganate in drinking water

Metabolites of algae such as geosmin, 2-methylisoborneol etc. are reported to induce pungent odors into drinking water and attract additional scientific attention. Recently, in China, taste and odor outbreaks in drinking water supply have become increasingly common. In source water affected by eutrophication, dimethyl trisulfide, speculated to be produced by decayed algae, was found to be the source of taste and odor issues and can be removed effectively by usual oxidation agents. In this experimental study, batch scale tests were carried out focusing on the removal of dimethyl trisulfide. Reaction kinetics of dimethyl trisulfide oxidized by potassium permanganate in water had been studied; influence factors such as pH, organic substrate, other existed taste, and odor contaminant in equivalent concentration were also discussed. Results showed that dimethyl trisulfide can be removed by potassium permanganate efficiently; the ratio can reach more than 70% with oxidant dosage of 4 mg·L^-1 and contact time prolonged to 120 min. The dimethyl trisulfide decomposition followed a second-order kinetics pattern with a rate constant k = 0.00213 L·(min·mg)^-1. Typically, the degradation rate of dimethyl trisulfide was increased with the increasing KMnO₄ dosage, but dramatically dropped with the increasing levels of humic acid (1.8–4.5 mg·L^-1) and other odor-causing compounds (e.g. β-cyclocitral, 0–1886.0 μg·L^-1). Solution pH (5.2–9.0) and initial dimethyl trisulfide concentration did not significantly affected the degradation. This study demonstrates that KMnO₄ oxidation is an effective option to remove dimethyl trisulfide from water.     

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb(II) and Cu(II) ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 mol·L^-1 CaCl₂ as background electrolyte. The desorption isotherms of Pb(II) and Cu(II) were similar to the adsorption isotherms, which can be fitted well by Freundlich equation (R₂>0.96). The soil in the three sites had greater sorption capacities for Pb(II) than Cu(II), which was affected strongly by the soil characteristics. In the binary metal solution containing 1∶1 molar ratio of Pb(II) and Cu(II), the total amount of Pb(II) and Cu(II) adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared (FT-IR) spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.     

Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane for enhanced micropollutants degradation

● A CNT filter enabled effective KMnO₄ activation via facilitated electron transfer. ● Ultra-fast degradation of micropollutants were achieved in KMnO₄/CNT system. ● CNT mediated electron transfer process from electron-rich molecules to KMnO₄. ● Electron transfer dominated organic degradation. Numerous reagents have been proposed as electron sacrificers to induce the decomposition of permanganate (KMnO₄) by producing highly reactive Mn species for micropollutants degradation. However, this strategy can lead to low KMnO₄ utilization efficiency due to limitations associated with poor mass transport and high energy consumption. In the present study, we rationally designed a catalytic carbon nanotube (CNT) membrane for KMnO₄ activation toward enhanced degradation of micropollutants. The proposed flow-through system outperformed conventional batch reactor owing to the improved mass transfer via convection. Under optimal conditionals, a > 70% removal (equivalent to an oxidation flux of 2.43 mmol/(h·m²)) of 80 μmol/L sulfamethoxazole (SMX) solution can be achieved at single-pass mode. The experimental analysis and DFT studies verified that CNT could mediate direct electron transfer from organic molecules to KMnO₄, resulting in a high utilization efficiency of KMnO₄. Furthermore, the KMnO₄/CNT system had outstanding reusability and CNT could maintain a long-lasting reactivity, which served as a green strategy for the remediation of micropollutants in a sustainable manner. This study provides new insights into the electron transfer mechanisms and unveils the advantages of effective KMnO₄ utilization in the KMnO₄/CNT system for environmental remediation.     

Effects of Nitrate Nitrogen Additions on Physical, Chemical and Biological Parameters in Lake Enclosures

The effects of nitrate additions on the physics, chemistry and biology of lake water were studied in 5 × 10 m polyethylene enclosures installed in Lake Kastoria, a shallow eutrophic lake in Northern Greece. The water physics, chemistry, chlorophyll a and nitrogenase activity were monitored from July 10 till October 17 1985 at 2 week intervals. The experiment included a control enclosure.

Water confinement in the control enclosure resulted in ammonia accumulation, a slight decrease in chlorophyll a, a significant reduction of nitrogenase activity and an increase in phosphorus release from the sediments at the end of the experimental period.

The addition of KNO₃ resulted in higher than the control accumulation of NH₃, chlorophyll reduction, increase in water transparency and reduction of nitrogenase activity. Large losses of nitrogen added were measured which were attributed to denitrification, organic matter sedimentation and ammonia volatilization. Anaerobic but not aerobic phosphorus release from sediments was inhibited at the end of the period. The reduction of nitrogenase activity and of chlorophyll a concentration are attributed to changes in phytoplankton composition from blue-greens to small-sized species grazed by zooplankters.