Enhanced degradation of trichloroethylene using bentonite-supported nanoscale Fe/Ni and humic acids

Nanoscale zero-valent iron, named nano-Fe⁰, is a reagent used to degrade trichloroethylene in groundwater. However, the efficiency of nano-Fe⁰ is moderate due to issues of dispersion and reactivity. As an alternative we synthesized bentonite-supported nanoscale Fe/Ni bimetals, named bentonite-Fe/Ni, to test the degradation of trichloroethylene in the presence of Suwannee River humic acids, as a representative of natural organic matter. 0.1 mmol/L trichloroethylene was reacted with 0.5 g/L of nano-Fe⁰, bentonite-Fe, Fe/Ni, and bentonite-Fe/Ni nanoparticles. Results show first that without humic acids the reaction rate constants k _obs were 0.0036/h for nano-Fe⁰, 0.0101/h for bentonite-Fe, 0.0984/h for Fe/Ni, and 0.181/h for bentonite-Fe/Ni. These findings show that bentonite-Fe/Ni is the most efficient reagent. Second, the addition of humic acids increased the rate constant from 0.178/h for 10 mg/L humic acids to 0.652/h for 40 mg/L humic acids, using the bentonite-Fe/Ni catalyst. This finding is explained by accelerated dechlorination by faster electron transfer induced by humic quinone moieties. Indeed, the use of 9, 10-anthraquinone-2, 6-disulfonate as a humic analogue gave similar results.     

Interlinked seasonal variation in biogenic nutrient fluxes and pore-water nutrient concentrations in intertidal sediments

The seasonal variation in biogenic fluxes of NH₄ ⁺, PO₄ ^3? and SiO₂ calculated from the nutrient excretion rates of dominant bivalves (Ruditapes philippinarum and Arcuatula [=Musculista] senhousia), and pore-water nutrient (NH₄ ⁺, PO₄ ^3?, SiO₂ and NO₃ ^? + NO₂ ^?), sedimentary acid-volatile sulfide (AVS) and benthic chlorophyll-a (Chl-a) concentrations was assessed on an intertidal sandflat in the Seto Inland Sea (Japan) from summer 1994 to autumn 1995. In spite of the large variability between sampling dates and stations, significant correlations between biogenic nutrient fluxes and pore-water nutrient concentrations were found, suggesting a seasonal linkage between bivalve-mediated biological processes and chemical features of sediments. This linkage was stronger in surface (0–0.5 cm) than subsurface (0.5–2 cm) sediments, consistent with the autoecological characteristics of R. philippinarum and A. senhousia inhabiting the uppermost sediment layer. Significant temporal variation in pore-water NO₃ ^? + NO₂ ^?, sedimentary AVS and benthic Chl-a concentrations was also found, which was related to both occasional extreme events (e.g., dystrophy) and alternating periods of production and decomposition. This study may serve twofold in (1) contributing to unravel the ecological structure and functioning of natural tidal flats, and the scale of seasonal variability in biotic and sedimentary parameters and (2) providing useful information for assessing the effectiveness of the physico-chemical and biological structure of artificial tidal flats which are growing in number and extension worldwide.     

Accelerated degradation of orange G over a wide pH range in the presence of FeVO<Subscript>4</Subscript>

In this study, FeVO₄ was prepared and used as Fenton-like catalyst to degrade orange G (OG) dye. The removal of OG in an aqueous solution containing 0.5 g·L^–1 FeVO₄ and 15 mmol·L^–1 hydrogen peroxide at pH 7.0 reached 93.2%. Similar rates were achieved at pH 5.7 (k = 0.0471 min^–1), pH 7.0 (k = 0.0438 min^–1), and pH 7.7 (k = 0.0434 min^–1). The FeVO₄ catalyst successfully overcomes the problem faced in the heterogeneous Fenton process, i.e., the narrow working pH range. The data for the removal of OG in FeVO₄ systems containing H₂O₂ conform to the Langmuir–Hinshelwood model (R² = 0.9988), indicating that adsorption and surface reaction are the two basic mechanisms for OG removal in the FeVO₄–H₂O₂ system. Furthermore, the irradiation of FeVO₄ by visible light significantly increases the degradation rate of OG, which is attributed to the enhanced rates of the iron cycles and vanadium cycles.

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零价纳米铁对大肠杆菌的毒性效应

以大肠杆菌为研究对象,通过检测尺寸为20 nm的零价纳米铁暴露下大肠杆菌形貌、生长曲线和细胞内酶活性的变化,研究了零价纳米铁对大肠杆菌的毒性效应,并探讨了其可能的毒性机制.用透射电镜(TEM)观察零价纳米铁与大肠杆菌(JM109)接触后细胞的形态变化;用0、112、560和1 120 mg·L-1的零价纳米铁染毒大肠杆...     

Comparative degradation rates of chitinous exoskeletons from deep-sea environments

Hydrothermal vent environments, particularly those associated with the vestimentiferan Riftia pachyptila, are believed to be among the highest chitin-producing systems. In order to elucidate the chitin cycle in these environments, we estimate the in situ chitin degradation rates of tube-worm exoskeletons. Our in situ experiments show that the tubes of Riftia are highly stable structures. Comparative measurements of the degradation rates of Riftia tubes and crab shells immersed at deep-sea vents show that the tubes would be degraded within 2.5 years, whereas the time for the total degradation of the vent crab (Bythograea thermydron) carapaces would not exceed 36 days. The importance of the microbial participation in this degradation was estimated for Riftia tubes. Based on previous work, we calculated chitin production by a population of Riftia tubes of about 750 g m^-2 year^-1 (763). From our in situ experiments, we estimated a microbial chitinolysis rate of about 500 g m^-2 year^-1 (496) (65% of the chitin produced).Exoskeletons containing β-chitin appear more stable in natural environments than those containing α-chitin and would thus be less available as carbon and nitrogen sources. In contrast, isolated β-chitin was hydrolysed faster than α-chitin during in vitro degradation experiments; for instance, Riftia β-chitin was degraded about 3- to 4-fold faster than Bythograea α-chitin. A stabilization process by disulfide bonds of the proteins-chitin link, rather than the crystalline form of the chitin (α/β), accounts for the resistance of Riftia tubes to enzymatic attacks.     

Thermal treatment of plasma-synthesized goethite improves Fenton-like degradation of orange II dye

Various iron oxides are used for Fenton reactions to degrade organic pollutants. The degradation efficiency may be improved by transforming an iron oxide phase to another. Here, we report on the transformation of goethite into hematite by thermal treatment at 400 °C. The products were analyzed by X-ray diffractometry, Raman spectroscopy, scanning electron microscopy and N₂-physisorption. The catalytic activities were measured for orange II bleaching at initial concentration of 25 mg L^?1, pH 3, catalyst concentration of 0.2 g L^?1; 5 mM H₂O₂, 30 °C. Results show that the synthesized goethite was successfully transformed into hematite, and the specific surface area of the material increased from 134 to 163 m² g^?1. The bleaching efficiency of the orange II dye reached 100 % for the hematite product, versus 78 % for goethite. Therefore, a moderate thermal treatment of a plasma-synthesized goethite improves the catalytic oxidation of organic pollutants.     

Health hazard prospecting by modeling wind transfer of metal-bearing dust from mining waste dumps: application to Jebel Ressas Pb–Zn–Cd abandoned mining site (Tunisia)

This work presents a modeling approach to simulate spatial distribution of metal contamination in aerosols with evaluation of health hazard. This approach offers the advantage to be non-intrusive, less expensive than sampling and laboratory analyses. It was applied to assess the impact of metal-bearing dust from mining wastes on air quality for a nearby community and agricultural lands in Jebel Ressas (Tunisia) locality. Dust emission rates were calculated using existing parameterization adapted to the contamination source composed of mining wastes. Metal concentrations were predicted using a Gaussian model (fugitive dust model) with, as input: emission rates, dump physical parameters and meteorological data measured in situ for 30 days in summertime. Metal concentration maps were built from calculated PM10 particle concentrations. They evidence the areas where Pb and Cd concentrations exceeded WHO guidelines (0.5 and 0.005 µg/m³, respectively). Maximum concentrations of Pb and Cd in PM10 are, respectively, of 5.74 and 0.0768 µg/m³ for measured wind speed values up to 22 m/s. Preferential areas of contamination were determined in agricultural lands to the NW from the source dump where Pb and Cd exceeded guidelines up to a distance of 1,200 m. The secondary spreading directions were SW and E, toward the village. Health hazard prospecting shown that a major part of the village was exposed to contaminated dust and that daily hazard quotient (HQ) values reached locally 118 and 158, respectively, for Pb and Cd during the study period. However, HQ variations in the village are high, both temporally and geographically.     

A nanosilver-based spectrophotometric method for sensitive determination of methyl violet in river water

A method is reported for the determination of methyl violet in the range of 10–120 nmol L^?1. The method is based on the catalytic effect of silver nanoparticles (AgNPs) on the oxidation reaction of methyl violet by potassium bromate in acid medium. The reaction is followed spectrophotometrically by measuring the change in absorbance () at 620 nm using a fixed time method. The reaction variables were optimized in order to achieve highest sensitivity. The 3б criterion detection limit was 5 nmol L^?1, and the relative standard deviation for ten replicate determinations at a concentration of methyl violet of 15 nmol L^?1 was 0.97% (n = 10). The method was successfully applied to the determination of methyl violet in river water samples.     

Estimation of coral growth-rates from laboratory 45Ca-incorporation rates

Laboratory ⁴⁵Ca-incorporation rates in hermatypic coral skeletons have previously been used successfully as an index of physiological function. This laboratory method would become more meanigful if it also provided an absolute measure of coral growth rates. In two coral species, Porites compressa and Pocillopora damicornis, ⁴⁵Ca incorporation rates were obtained from short (0.5 h) laboratory incubations using apical (determined as fast growing) portions of freshly collected coral branches. ⁴⁵Ca exchange across the coenosarc was not significant and not corrected for, whereas diurnal fluctuation in ⁴⁵Ca in Pocillopora damicornis was significant and a necessary correction. A calculated surface area is used to express calcification rate. Typical growth rates calculated from the ⁴⁵Ca-incorporation rates were 20 and 6 mm/year for Porites compressa and Pocillopora damicornis, respectively. These rates are considerably higher than those previously obtained in the laboratory, and compare favorably with field growth rates — 24 and 14 mm/year, respectively.     

Efficient oxidation of bisphenol A with oxysulfur radicals generated by iron-catalyzed autoxidation of sulfite at circumneutral pH under UV irradiation

There is actually a need for efficient methods to clean waters and wastewaters from pollutants such as the bisphenol A endocrine disrupter. Advanced oxidation processes currently use persulfate or peroxymonosulfate to generate sulfate radicals. There are, however, few reports on the use of sulfite to generate sulfate radicals, instead of persulfate or peroxymonosulfate, except for dyes. Here we studied the degradation of the bisphenol A using iron(III) as catalyst and sulfite as precursor of oxysulfur radicals, at initial pH of 6, under UV irradiation at 395 nm. The occurrence of radicals was checked by quenching with tert-butyl alcohol and ethanol. Bisphenol A degradation products were analyzed by liquid chromatography coupled with mass spectrometry (LC–MS). Results reveal that iron(III) or iron(II) have a similar oxidation efficiency. Quenching experiments show that the oxidation rate of bisphenol A is 47.7 % for SO ₄ ^·? , 37.3 % for SO ₅ ^·? and 15 % for HO^·. Bisphenol A degradation products include catechol and quinone derivatives. Overall, our findings show that the photo-iron(III)–sulfite system is efficient for the oxidation of bisphenol A at circumneutral pH.     

Assessment of relative bioavailability of heavy metals in soil using in vivo mouse model and its implication for risk assessment compared with bioaccessibility using in vitro assay

There is limited study to simultaneously determine the relative bioavailability of heavy metals such as Cd, Pb, Cu, Cr(VI), and Ni in soil samples. In the present study, the bioaccessibility of heavy metals using in vitro assay was compared with the relative bioavailability of heavy metals using in vivo mouse model. The bioaccessibility of heavy metals ranged from 9.05 ± 0.97 % (Cr) to 42.8 ± 3.52 % (Cd). The uptake profile of heavy metals in soil and solution samples in mouse revealed that the uptake kinetics could be fitted to a two-compartment model. The relative bioavailability of heavy meals ranged from 34.8 ± 7.0 % (Ni) to 131 ± 20.3 % (Cu). Poor correlation between bioaccessibility and relative bioavailability of heavy metals was observed (r ² = 0.11, p > 0.05). The relative bioavailability of heavy metals was significantly higher than the bioaccessibility of heavy metals (p < 0.05). The present study indicated that the in vitro digestion method should be carefully employed in risk assessment.     

The role of metabolic nitrogen in coral calcification

When pieces of the staghorn coral Acropora acuminata are incubated with ¹⁴C-urea, the label is incorporated into skeletal carbonate. Incorporation of this label differs from that of H¹⁴CO ₃ ^- , suggesting urea is not immediately hydrolysed to provide a further source of HCO ₃ ^- . The effects of certain organic substrates upon calcification suggest the ornithine cycle is involved. Citrulline, an ornithine cycle intermediate, is found in high concentrations in the tissues of hermatypic corals. Urea, allantoins, NH₃ and arginine are also present. These compounds are barely detectable in zooxanthellae or an ahermatypic coral. The allantoins may be present as calcium salts. It is suggested that allantoins are the medium by which Ca²⁺ and CO₂ are transported to sites of calcification. Hydrolysis of urea, formed by breakdown of allantoins, yields CO₂ and NH₃. The NH₃ may neutralise protons formed during precipitation of CaCO₃ and bring about their removal from sites of calcification. As well as providing urea, the ornithine cycle may also be involved in the removal of NH₃ from sites of calcification.     

Novel approach to control adsorbent aggregation: iron fixed bentonite-fly ash for Lead (Pb) and Cadmium (Cd) removal from aqueous media

In the present study, a novel approach was used to control zero valent iron aggregation and separation problems by fixing zero valent iron (ZVI) on bentonite-fly ash pellets. For this purpose, porous low cost bentonite-fly ash (BFA) pellets with size of 2.00 cm in length and 0.35 cm in diameter were prepared and fixed with ZVI to manufacture zero valent iron bentonite-fly ash (ZVI-BFA) pellets. Importantly, unlike powdered adsorbents, ZVI-BFA can easily be separated from final effluents when exhausted without any disintegration. The performance of the developed novel adsorbent was investigated for the removal of Pb²⁺ and Cd²⁺ from aqueous media. At 100 mg·L^–1 and 1 g adsorbent, a maximum of 89.5% of Cd²⁺ and 95.6% of Pb²⁺ was removed by ZVI-BFA as compared to 56% and 95% removal by BFA. At 200 mg·L^–1, Cd²⁺ and Pb²⁺ removal by ZVI-BFA was 56% and 99.8% respectively as compared to only 28% and 96% by BFA. Further, the removal kinetics was best fitted for pseudo-second order model. The study provides the basis for improving the removal capacity of porous materials by iron fixation while taking separation ability into consideration.

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Exceptionally high concentrations of the insect repellent N,N-diethyl-m-toluamide (DEET) in surface waters from Jakarta,Indonesia

Jakarta is a booming coastal megacity in Indonesia with over 10 million inhabitants. The rivers flowing through the city district receive enormous amounts of untreated wastewaters from households and industries and discharge high pollutant loads into Jakarta Bay. Applying a screening approach for the identification of characteristic site-specific and harmful organic contaminants, we frequently found the insect repellent N,N-diethyl-m-toluamide (DEET) in river water and seawater samples from Jakarta. The compound was previously reported as persistent aquatic contaminant in industrial countries, and we present here the first data set from a tropical megacity. Concentrations in river water and seawater from Jakarta were exceptionally high, up to 24,000 ng L^?1, and exceeded by far all published concentrations in surface waters worldwide. We explained this with massive usage of the compound, lack of wastewater treatment and low average river flow as compared to rivers in other tropical megacities. The usage and properties of DEET indicate its suitability as molecular marker of municipal wastewaters. Such markers are useful to trace emissions from specific pollution sources in aquatic systems as a basis for the investigation of related impacts. We show here that DEET is in particular useful to trace the long-range distribution of municipal wastewaters in tropical freshwater and coastal systems. This application is of great value for tracing such inputs in tropical coastal habitats which are sensitive to changing water quality like coral reefs. This assists to uncover whether specific conditions in these systems could be related to pollutant inputs from land.     

Effects of gamma-aminobutyric acid on the settlement of larvae of the black chiton Katharina tunicata

Laboratory-cultured larvae of the black chiton Katharina tunicata (Wood), collected from central California in May and June of 1979 and 1980, settled preferentially on the encrusting coralline alga Lithothamnium sp. Metamorphosis, which involves the loss of the prototrochal ciliary band, occurred within a period of 2.5 h after larvae began crawling upon the alga. In response to gamma-aminobutyric acid (GABA) at a concentration of 10^-6 M, the lecithotrophic trochophore larvae ceased swimming and settled rapidly. Developmental metamorphosis did not follow settlement in the absence of encrusting coralline alga. However, when both GABA and Lithothamnium sp. were present, larval metamorphosis occurred within 2 h of settlement. Significantly different rates of settlement exist for sibling larvae of different ages; 12 d-old larvae responded more rapily and in greater numbers to treatment with GABA than 10 d-old larvae. Differences in settling rates are attributed to the onset of metamorphic competence.