DOC removal paradigms in highly humic aquatic ecosystems

Background, aim, and scope  Dissolved humic substances (HS) usually comprise 50–80% of the dissolved organic carbon (DOC) in aquatic ecosystems. From a trophic and biogeochemical perspective, HS has been considered to be highly refractory and is supposed to accumulate in the water. The upsurge of the microbial loop paradigm and the studies on HS photo-degradation into labile DOC gave rise to the belief that microbial processing of DOC should sustain aquatic food webs in humic waters. However, this has not been extensively supported by the literature, since most HS and their photo-products are often oxidized by microbes through respiration in most nutrient-poor humic waters. Here, we review basic concepts, classical studies, and recent data on bacterial and photo-degradation of DOC, comparing the rates of these processes in highly humic ecosystems and other aquatic ecosystems. Materials and methods  We based our review on classical and recent findings from the fields of biogeochemistry and microbial ecology, highlighting some odd results from highly humic Brazilian tropical lagoons, which can reach up to 160 mg C L⁻¹. Results and discussion  Highly humic tropical lagoons showed proportionally lower bacterial production rates and higher bacterial respiration rates (i.e., lower bacterial growth efficiency) than other lakes. Zooplankton showed similar δ¹³C to microalgae but not to humic DOC in these highly humic lagoons. Thus, the data reviewed here do not support the microbial loop as an efficient matter transfer pathway in highly humic ecosystems, where it is supposed to play its major role. In addition, we found that some tropical humic ecosystems presented the highest potential DOC photo-chemical mineralization (PM) rates reported in the literature, exceeding up to threefold the rates reported for temperate humic ecosystems. We propose that these atypically high PM rates are the result of a joint effect of the seasonal dynamics of allochthonous humic DOC input to these ecosystems and the high sunlight incidence throughout the year. The sunlight action on DOC is positive to microbial consumption in these highly humic lagoons, but little support is given to the enhancement of bacterial growth efficiency, since the labile photo-chemical products are mostly respired by microbes in the nutrient-poor humic waters. Conclusions  HS may be an important source of energy for aquatic bacteria in humic waters, but it is probably not as important as a substrate to bacterial growth and to aquatic food webs, since HS consumption is mostly channeled through microbial respiration. This especially seems to be the case of humic-rich, nutrient-poor ecosystems, where the microbial loop was supposed to play its major role. Highly humic ecosystems also present the highest PM rates reported in the literature. Finally, light and bacteria can cooperate in order to enhance total carbon degradation in highly humic aquatic ecosystems but with limited effects on aquatic food webs. Recommendations and perspectives  More detailed studies using C- and N-stable isotope techniques and modeling approaches are needed to better understand the actual importance of HS to carbon cycling in highly humic waters.     

Hollow TiO2 spheres with improved visible light photocatalytic activity synergistically enhanced by multi-stimulative: Morphology advantage, carbonate-doping and the induced Ti3 +

Great efforts have been devoted to improve the photocatalytic activity of TiO_2 in the visible light region. Rational design of the external structure and adjustment of intrinsic electronic status by impurity doping are two main effective ways to achieve this purpose. A facile onepot synthetic approach was developed to prepare C-doped hollow TiO_2 spheres, which simultaneously realized these advantages. The synthesized TiO_2 exhibits a mesoporous hollow spherical structure composed of fine nanocrystals, leading to high specific surface area(~180 m~2/g) and versatile porous texture. Carbonate-doping was achieved by a postthermal treatment at a relatively low temperature(200°C), which makes the absorption edge red-shifted to the visible region of the solar spectrum. Concomitantly, Ti~(3+) induced by C-doping also functions in improving the visible-light photocatalytic activity by reducing the band gap. There exists a synergistic effect from multiple stimulatives to enhance the photocatalytic effect of the prepared TiO_2 catalyst. It is not out of expectation that the asprepared C-doped hollow TiO_2 spheres exhibits an improved photocatalytic activity under visible light irradiation in organic pollutant degradation.     

Photo-degradation organic dyes by Sb-based organic-inorganic hybrid ferroelectrics

The organic-inorganic hybrid halide compounds have emerged as one of the most promising photoelectric material for their superior optoelectronic properties and hold great prospects for renewable energy substitutes and environmental protection as photocatalysis. Here, we report the optical properties of the Sb-based organic-inorganic hybrid ferroelectric materials: pyridine-4-aminium tetrachloroantimonate ((C₅H₇N₂)SbCl₄, sample 1), piperidin-1-aminium tetrachloroantimonate ((C₅H₁₃N₂)SbCl₄, sample 2) and tris(trimethylammonium) nonachlorodiantimonate (((CH₃)₃NH)₃Sb₂Cl₉, sample 3), which are a kind of exploited efficient photocatalysts. Samples 2 and 3 exhibit distinct photoelectric respond, which are mainly ascribed to their minor narrow band-gap compared with sample 1. For the ferroelectrics, the intrinsic of spontaneous polarization of sample 3 at room temperature is favourable for the separation of photogenerated electrons and holes within the photorespond process. Moreover, sample 3 shows the highest efficiency of photo-decomposed Rhodamine B (90.2% within 80 min) and Methyl Orange (MO) (97.4% within 50 min), thanks to the photo-excited electrons and holes promoting the formation of oxidative radical species during the photo-redox progress. These findings prove that the development of a novel Sb-based organic-inorganic hybrid halide compounds with good stability in the degradation of organic dyes paves a way to designing new photocatalyst.     

Photo-/Bio-degradability of Agro Waste and Ethylene–Propylene Copolymers Composites Under Abiotic and Biotic Environments

Composites were prepared by two methods, (i) graft copolymerization (GFC) of isotactic polypropylene (PP) with maliec anhydride, (MAH) followed by esterification with coir fiber and (ii) by direct reactive mixing (DFC) of polypropylene (PP) and ethylene–propylene (EP) copolymers with MAH and peroxide with coir fiber. These composites, after molding in films (5×5 cm, m thickness) were examined for susceptibility to biological attack by measuring the percentage weight loss in compost upto 6 months, periodically, and fungal colonization on surface of the samples, when kept as sole carbon source for the growth of Aspergillus niger in culture medium upto 40 days. Photodegradation was evaluated by monitoring the variations in FT-IR spectrum and crack formation after successive treatment with UV light (≥290 nm) for 0, 20, 50 and 100 h at 60°C in the presence of air. Specimens of virgin PP were taken as a reference during all period of photo and biodegradation studies. Significant changes were observed depending on the preparation methods during photodegradation and biodisintegration of composites. DFCs samples were disintegrated faster than GFCs during the composting whereas, in culture, GFCs were covered highly in well uniform way by fungi. It was observed that photo-oxidative ageing directly enhanced the biodegradability of composites as the increase in fungal growth rate and decrease in weight during composting were found. It was concluded that extent of compatibilization had a profound effect on photo-oxidation and biodisintegration of composite material; consequently ester bonds were main units during fungal consumption. Composition of monomers in copolymers was also showing significant effect on the degradability which decreased with increasing content of ethylene in ethylene–propylene (EP) copolymers.     

Simulated photo-degradation of dissolved organic matter in lakes revealed by three-dimensional excitation-emission matrix with regional integration and parallel factor analysis

Simulated photo-degradation of fluorescent dissolved organic matter(FDOM) in Lake Baihua(BH) and Lake Hongfeng(HF) was investigated with three-dimensional excitationemission matrix(3 DEEM) fluorescence combined with the fluorescence regional integration(FRI),parallel factor(PARAFAC) analysis,and multi-order kinetic models.In the FRI analysis,fulvic-like and humic-like materials were the main constituents for both BH-FDOM and HF-FDOM.Four individual components were identified by use of PARAFAC analysis as humic-like components(C1),fulvic-like components(C2),protein-like components(C3) and unidentified components(C4).The maximum 3 DEEM fluorescence intensity of PARAFAC components C1-C3 decreased by about 60%,70% and 90%,respectively after photo-degradation.The multi-order kinetic model was acceptable to represent the photo-degradation of FDOM with correlation coefficient(R_(adj)~2)(0.963-0.998).The photo-degradation rate constants(k_n) showed differences of three orders of magnitude,from 1.09 x 10~(-6) to 4.02 x 10~(-4) min-1,and half-life of multi-order model(T_(1/2)~n)ranged from 5.26 to 64.01 min.The decreased values of fluorescence index(FI) and biogenic index(BI),the fact that of percent fluorescence response parameter of Region I(P_(Ⅰ,n)) showed the greatest change ratio,followed by percent fluorescence response parameter of Region II(P_(Ⅱ,n),while the largest decrease ratio was found for C3 components,and the lowest T_(1/2)~n was observed for C3,indicated preferential degradation of protein-like materials/components derived from biological sources during photodegradation.This research on the degradation of FDOM by 3 DEEM/FRI-PARAFAC would be beneficial to understanding the photo-degradation of FD OM in natural environments and accurately predicting the environmental behaviors of contaminants in the presence of FDOM.     

Potential environmental fate of elsinochrome A,a perylenequinone toxin produced in culture by bindweed biocontrol fungus Stagonospora convolvuli LA39

The photosensitizing perylenequinone toxin elsinochrome A (EA) is produced in culture by the bindweed biocontrol fungus Stagonospora convolvuli LA39 where it apparently plays a pathogenicity related role. We investigated the fate of EA with reference to its stability under different temperature and light conditions. EA remained stable when boiled in water at 100^∘C for 2 h. Similarly, exposing EA to 3–27^∘C in the dark for up to 16 weeks did not affect its stability either in dry or in aqueous form. However, results from irradiation experiments indicate that direct photolysis may be a significant degradation pathway for EA in the environment. EA either in dry form or dissolved in water was degraded by different irradiation wavelengths and intensities, with degradation plots fitting a first order rate kinetics. EA degraded faster if exposed in aqueous form, and at higher quantum flux density (μmol s⁻¹ m⁻²). Sunlight was more effective in degrading EA than artificial white light and ultraviolet radiations (UV-A or UV-B). Exposing EA to natural sunlight, particularly, during the intense sunshine (1,420– 1,640 μmol s⁻¹ m⁻²) days of 30 July to 5 August 2004 in Zurich caused the substance to degrade rapidly with half-life under such condition only 14 h. This implies that should EA gets into the environment, particularly on exposed environmental niches, such as on plant surfaces through biocontrol product spray, or released from shed diseased leaves, it may have no chance of accumulating to ‘level of concern’. Furthermore, a toxicity assay using Trichoderma atroviride P1 as biosensor showed that photo-degraded EA was not toxic, indicating that no stable toxic by-products were left.