One-step synthesis of bentonite-supported nanoscale Fe/Ni bimetals for rapid degradation of methyl orange in water

Although nanoscale zero-valent iron (nano-Fe⁰) is used to remediate pollutants, this reagent still presents stability and reactivity issues. To solve those issues, we synthesized bentonite-supported nanoscale iron bimetals B-Fe/Ni and B-Fe/Pd. We then used those reagents to degrade the methyl orange dye in water. Results of scanning electron microscopy and X-ray diffraction showed that the presence of bentonite and bimetal decreased nanoscale iron aggregation and increased methyl orange removal efficiency. More than 90 % of methyl orange at 100 mg/L was degraded by B-Fe/Ni (0.15 g/L) in 10 min. By comparison, only 62 % of methyl orange was degraded by B-Fe, and 35 % of methyl orange was degraded by nano-Fe⁰. The degradation rate decreased with the increase of the initial concentration of methyl orange. Lower pH allowed fast removal of methyl orange. Overall our findings show that a nanoscale Fe/Ni on bentonite-supported material is more efficient than nano-Fe⁰. One-step synthesis is more convenient than current two-step-synthesized nanoscale bimetals. Bentonite-supported nanoscale bimetals could therefore be an economic competitive candidate for contaminated water remediation.     

Diuron herbicide degradation catalyzed by low molecular weight humic acid-like compounds

Phenylureas such as diuron are major herbicides used worldwide to control undesirable weeds. The environmental fate of phenylureas is of great interest because massive amounts of those herbicides are used. It is known that abiotic degradation of phenylureas in soil–water systems is catalyzed by humic acids. However, due to the chemical heterogeneity and large molecular sizes of humic acids, the specific effects of functional groups during catalysis have not been elucidated. Therefore, we studied here for the first time the kinetics of diuron degradation in the presence of low molecular weight humic acid-like compounds such as benzoic acid derivatives. Experiments were carried out at various pH and temperature, and monitored by high-performance liquid chromatography. Results show that all benzoic acid derivatives efficiently catalyzed diuron hydrolysis. The catalytic efficiency decreased in the following order: 0.88 M^?1 day^?1 for 3,4-dihydroxybenzoic acid, 0.72 M^?1 day^?1 for 4-hydroxybenzoic acid, 0.23 M^?1 day^?1 for phthalic acid, 0.11 M^?1 day^?1 for 2-hydroxybenzoic acid, and 0.09 M^?1 day^?1 for 2,4-dihydroxybenzoic acid. These differences in the catalytic efficiency are explained by steric hindrance affecting the accessibility of reactive sites and hence influencing the rate of the overall process. Steric factors are therefore expected to control the catalytic activity of humic acids because of the chemical similarities between humic acids and low molecular weight humic acid-like compound. Our results should help predict more accurately the fate and abiotic degradation mechanism of phenylureas in the environment.     

Evaluation of the toxicity of tetrabromobisphenol A and some of its oxidation products using a micro-scale algal growth inhibition test

A micro-scale algal growth inhibition (μ-AGI) test using a common micro-plate based fluorometric detection was used to demonstrate the effects of humic substances (HSs) on the toxicity of tetrabromobisphenol A (TBBPA) and its oxidative decomposition products 2,5-dibromo-1,4-benzoquinone (2,5-DBBQ), 2,5-dibromohydroquinone (2,5-DBHQ), 2,6-dibromobenzoquinone (2,6-DBBQ), and 2,6-dibromophenol (2,6-DBP) to Pseudokirchneriella subcapitata. The EC₅₀ values were: EC_50(TBBPA) = 7 mg L^?1, EC_50(2,5-DBHQ) = 7 mg L^?1, EC_50(2,5-DBBQ) = 19 mg L^?1, EC_50(2,6-DBP) = 49 mg L^?1, and EC_50(2,6-DBBQ) = 13 mg L^?1. The toxicity of the chemicals was slightly lower in the presence of HA. The toxicity of TBBPA decomposed by a biomimetic catalytic system consisting of iron (III) 5,10,15,20-tetrakis (p-sulfonatophenyl) porphyrin (Fe(III)-TPPS) and KHSO₅ was also evaluated using P. subcapitata and Chlamydomonas reinhardtii.     

Toxicity and bioaccumulation of heavy metals in mullet fish Liza klunzingeri (Mugilidae: Perciformes)

The mullet fish, Liza klunzingeri, commercially important and widely relished by Kuwaiti residents, and the stressed ecosystem in Kuwait Bay instigated us to conduct toxicity and bioaccumulation tests on heavy metals (Pb, Ni, V, Cu and Fe). Among five metals, Pb had the lowest observed effect concentration (LOEC) at 1 μg?l ^?1. Using multi-factor Probit analysis, toxicity tests (72 h) on L. klunzingeri reared in filtered sea water in the laboratory showed Pb with maximum effect at median lethal concentration (LC₅₀) followed by V, Ni, Cu and Fe. Their bioaccumulation factor (BAF) was in the sequence Pb>V>Fe>Cu and Ni. For fish exposed for 30 d, bioaccumulation exhibited increasing metal levels in liver followed by gills and muscles. These results suggest the potential use of L. klunzingeri as a bioindicator of metal pollution in the future.     

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...     

Assessment of heavy metals in a soil contaminated by oil spill: a case study in Nigeria

Surface and subsurface soil samples contaminated with crude oils were collected from an impacted site at Bodo City in the Niger Delta, Nigeria, after a field reconnaissance survey. An uncontaminated soil sample collected 100 m from the impacted site, but within the same geographical area, was used as a control. Trace elements such as, As, Cu, Cr, Cd, Fe, Pb, Ba, Ni, V, Hg and cation-exchange capacity constituents of the contaminated and uncontaminated soils were determined by atomic absorption spectroscopy. Trace element concentrations were: Cu, 0.5–13.4 mg kg^{? 1}; Cr, 0.2–0.8 mg kg^{? 1}; Fe, 6.2–8.7 mg kg^{? 1}; Ba 80.0–108.0 mg kg^{? 1}; Ni, 0.6–4.8 mg kg^{? 1}; and V, 4.0–9.4 mg kg^{? 1}; cation-exchange capacity ranged from 43.6 to 57.2 mg kg^{? 1} in surface and subsurface soils. Results showed that eigenvalues for the two first principal components represent up to 49% of the total variance. A positive correlation of the first principal component with Cu, Cr and cation-exchange capacity shows pollution from oil spillage, while a positive correlation of the second principal component with Cr, Fe, V, and dissolved oxygen (DO) shows both oil pollution and allochthonous inputs.     

Comparison of different valent iron on anaerobic sludge digestion: Focusing on oxidation reduction potential,dissolved organic nitrogen and microbial community

• ORP value from −278.71 to −379.80 mV showed indiscernible effects on methane yield. • Fe(II) and Fe(III) promoted more degradation of proteins and amino acids than Fe⁰. • The highest enrichment of Geobacter was noted in samples added with Fe⁰. • Cysteine was accumulated during iron enhanced anaerobic sludge digestion. • Both iron content and valence were important for methane production. This study compared effects of three different valent iron (Fe⁰, Fe(II) and Fe(III)) on enhanced anaerobic sludge digestion, focusing on the changes of oxidation reduction potential (ORP), dissolved organic nitrogen (DON), and microbial community. Under the same iron dose in range of 0−160 mg/L after an incubation period of 30 days (d), the maximum methane production rate of sludge samples dosed with respective Fe⁰, Fe(II) and Fe(III) at the same concentration showed indiscernible differences at each iron dose, regardless of the different iron valence. Moreover, their behavior in changes of ORP, DON and microbial community was different: (1) the addition of Fe⁰ made the ORP of sludge more negative, and the addition of Fe(II) and Fe(III) made the ORP of sludge less negative. However, whether being more or less negative, the changes of ORP may show unobservable effects on methane yield when it ranged from −278.71 to −379.80 mV; (2) the degradation of dissolved organic nitrogen, particularly proteins, was less efficient in sludge samples dosed with Fe⁰ compared with those dosed with Fe(II) and Fe(III) after an incubation period of 30 d. At the same dose of 160 mg/L iron, more cysteine was noted in sludge samples dosed with Fe(II) (30.74 mg/L) and Fe(III) (27.92 mg/L) compared with that dosed with Fe⁰ (21.75 mg/L); (3) Fe⁰ particularly promoted the enrichment of Geobacter, and it was 6 times higher than those in sludge samples dosed with Fe(II) and Fe(III) at the same dose of 160 mg/L iron.     

Quantitative analysis and sorption of cadmium in environmental samples with a functionalized synthetic polymer

Quantitative analysis of cadmium in environmental samples was achieved with a polymeric sorbent synthesized by copolymerization of N,N-dimethylacrylamide and allyl glycidyl ether/iminodiacetic acid as chelating monomers with N,N′-methylenebisacrylamide as cross-linker. The polymer was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and scanning electron microscopy. The sorption capacity of the functionalized sorbent was 70 mg g^?1. The equilibrium sorption data of Cd(II) on polymeric sorbent were analyzed using Langmuir, Freundlich, Temkin, and Redlich–Peterson models. Based on equilibrium adsorption data, the constants at pH 4.2 and 20 °C were determined for the first three as 0.33 (L mg^?1), 17.5 (mg g^?1) (L mg^?1)^1/n, and 12.9 (J mol^?1). Recovery of 94% of the metal ion was obtained with 0.5 mol L^?1 nitric acid as an eluting agent.     

Levels of Hg and other chemical elements in volcanic ash fall samples erupted from Mt. Sakurajima,Japan

Mt. Sakurajima is a volcanic island in Japan, and a big city, Kagoshima, is quite close to the active volcano. Samples of volcanic ash fall erupted from Mt. Sakurajima were collected at several locations in Kagoshima City and analyzed for Hg and other elements, including major (Mg, Al, Ca, and Fe) and trace elements (V, Cr, Mn, Co, Ni, Zn, As, and Pb). The concentrations of Hg varied from 6.3 to 124 ng g^?1, with the amounts of ash varying from 13 to 1230 g m^?2 month^?1. The Hg concentrations tended to be higher when the monthly amounts of ash fall were lower; other elements did not show such a tendency.     

Assessment of heavy metals contamination in soils surrounding a gold mine: comparison of two digestion methods

This study investigated two digestion methods (USEPA 3051: microwave, HNO₃ or Hossner: hot plate, HF–H₂SO₄–HClO₄) for heavy metals analysis in contaminated soil surrounding Mahad AD'Dahab mine, Saudi Arabia. Moreover, contamination metal levels were estimated. The Hossner and USEPA 3051 methods showed, respectively, average total contents of 17.2 and 18.1 mg kg^?1 for Cd, 11.6 and 10.6 mg kg^?1 for Co, 45.7 and 34.7 mg kg^?1 for Cr, 1030 and 1100 mg kg^?1 for Cu, 33,300 and 27,400 mg kg^?1 for Fe, 963 and 872 mg kg^?1 for Mn, 33.2 and 22.8 mg kg^?1 for Ni, 791 and 782 mg kg^?1for Pb, and 6320 and 2870 mg kg^?1 for Zn. A lack of significant differences and a high correlation coefficient (>90%) for Cd, Pb and Cu between the two digestion methods suggest that the total-recoverable method (USEPA 3051) may be equivalent to the total-total digestion method (Hossner) for determining these metals in the studied soil. However, significantly higher concentrations of Cr, Fe, Ni and Zn were found by the Hossner method comapred with the USEPA 3051 method. The soil samples have very or extremely high levels of Zn, Cu, Cd and Pb contamination, indicating very high potential ecological risk.     

Effect of humic acids,nitrate and oxygen on the photodegradation of the flubendiamide insecticide: identification of products

Flubendiamide is a ryanodine insecticide that shows a strong insecticidal activity and is relatively safe for non-target organisms. Actually only flubendiamide and its product desiodo-flubendiamide have been studied during catalytic degradation using TiO₂ and ZnO. Therefore, here we tested the photocatalytic removal of flubendiamide in the presence of nitrates or humic acids. Degradation kinetics were monitored using high-performance liquid chromatography ultraviolet–visible detector. Product identification was done using a high-resolution time-of-flight mass spectrometer coupled to a gas chromatograph (GC-HRMS). Results show that the addition of humic acids at 10 mg l^?1 increased the removal of flubendiamide more than five times. The addition of nitrate ions at 10 mg l^?1 had no influence. The removal of flubendiamide was more than ten times faster in experiments with oxygen purging. Fourteen degradation products were identified, which can be classified into three groups: phthalimide and related phthalic acid derivatives, fluorinated species related to the second amide moiety, and advanced transformation products.     

Metal levels in computer monitor components discarded in the vicinities of electronic workshops

Levels of Pb, Ni, Cr, Cu, Zn, and Cd in the glass screens (GS) and printed wiring boards (PWBs) of obsolete computer monitors (OCMs) were determined by flame atomic absorption spectrophotometry (FAAS) following standard digestion. Metal concentrations (mg kg^?1) in GS were in the following ranges (medians in brackets): Pb ND – 3100 (46), Cd 0.5–2.6 (0.8), Cr ND – 18.7 (3.1), and Zn 8.1–600 (37) and in PWBs (mg kg^?1): Pb 34,600 ± 17,000, Cd 11 ± 9, Cr 59 ± 45, Zn 15,900 ± 7800, Cu79,000 ± 22,600, and Ni 3200 ± 2500. In GS, the levels of the six metals were lower than their total threshold limit concentrations (TTLC), except for Pb with a TTLC of 1000 mg kg^?1 in 10% of the samples. In the PWBs, the TTLC of Pb and Cu (2500 mg kg^?1) was exceeded many fold. For Zn (5000 mg kg^?1) and Ni (2000 mg kg^?1); they were exceeded by 90% and 65%, respectively. For OCMs manufactured in 2001 and later, Pb and Zn levels in GS and Cr, Zn, and Ni in PWBs were significantly reduced.     

Temperature effects on the toxicity of four trace metals to adult spotted Babylonia snails (Babylonia areolata)

A study was conducted to determine the median lethal toxicity of four heavy metals on the marine gastropod Babylonia areolata. Median lethal toxicity tests were conducted to observe the sensitivity of this gastropod to metals and how variations in temperature might affect toxicity of test elements. Four heavy metals were used in the study. It was observed that the 96-hr LC₅₀ (in mg/L) for the different metals was found to be nickel (Ni) 33.53 (35.22–28.43), copper (Cu) 44.59 (46.43–41.53), cadmium (Cd) 21.53 (23.43–18.37), and zinc (Zn) 27.34 (28.81–24.24) at room temperature 24 °C. With temperature as a variable, median lethal concentration (LC₅₀) values were observed to increase from 22.41 mg/L at 10 °C to 27.34 mg/L at 28 °C and reduce to 18.43 mg/L at 30 °C and a further rise in toxicity was observed at 35 °C where LC₅₀ value was 12.7 mg/L as seen in the case of Zn. It was also observed that at 40 °C thermal and chemical toxicity overlapped as 100% mortality was observed in controls. This trend was noted in all metals for Babylonia areolata indicating that temperature played an important role in determining LC₅₀ values of toxicants.     

Interaction between peat, humic acid and aqueous metal ions

Analysis of peat samples from four regions of the British Isles indicates that the concentrations of Al, Pb and common transition metals tend, as expected, to be higher in regions subject to industrial pollution, but that the concentrations of the nontransition metals Na, K, Mg, Ca and Zn tend to be higher in regions remote from industrial pollution. Humic acids were extracted from the most polluted and least polluted of the peat samples and some characteristics of these acids were compared with those of two commercial acids. Values for stability constants of complexes formed between humic acids extracted from peat and Cu²⁺, Zn²⁺ or Pb²⁺ have been obtained by an ionexchange equilibrium method. Of the three metal ions examined, Pb²⁺ was found to form the most stable humic acid complexes, followed by Cu²⁺: this order agrees with the findings of Irving and Williams and of Bunzl. Implications to the binding of actinide and other heavy metal ions in aqueous humic acid are discussed.     

Geochemical distribution of trace element concentrations in the vicinity of Boroo gold mine,Selenge Province,Mongolia

The environmental impacts of Boroo gold mine project in Mongolia was evaluated by chemical characterization of trace element concentrations in water, soils and tailing dam sediment samples. The results showed that concentrations of B, Cd, Ni and Se in the water samples were within the accepted levels of the Mongolia water quality standard (MNS4586: 1998). However, the concentrations of Al, As, Cu, Mn, Fe, Pb, U and Zn were higher than the maximum allowable concentration especially in the monitoring and heap leach wells. The average concentrations of As, Cd, Cu, Ni, Pb and Zn in the tailing dam sediment were 4419, 58.5, 56.0, 4.8, 20.6 and 25.7 mg/kg, respectively. Generally, arsenic and heavy metals in the soil samples were within the acceptable concentrations of the soil standard of Mongolia (MNS 5850: 2008). The chemical characterization of As solid phase in tailing dam sediment showed that the majority of As were found in the residual fraction comprising about 74% of total As. Assessing the potential risk to humans, simple bioavailability extraction test was used to estimate bioavailability of arsenic and heavy metals, and the concentrations extracted from tailing dam sediment were; 288.2 mg/kg As, 7.2 mg/kg Cd, 41.1 mg/kg Cu, 13.5 mg/kg Pb, 4.7 mg/kg Ni and 23.5 mg/kg Zn, respectively. From these results, the Boroo gold mine project has presently not significantly impacted the environment, but there is a high probability that it may act as a source of future contamination.     

Alterations in serum electrolyte levels after dimethoate exposure and recovery in the freshwater air-breathing catfish,Heteropneustes fossilis (Bloch)

Dimethoate, a moderately toxic insecticide, has a wide range of agricultural and domestic applications. Like other organophosphates, dimethoate has anticholinesterase activity. Fish are non-target organisms, inadvertently exposed to pesticides and their metabolic products. The present study includes short-term (96 h) and long-term (36 d) effects of dimethoate exposure on some serum electrolytes Ca²⁺, Mg²⁺, and Pi in the freshwater air-breathing catfish Heteropneustes fossilis. The concentration of dimethoate for short-term exposure was 2.24 mg L^?1 (75% of 96 h LC₅₀) and for long-term exposure 0.75 mg L^?1 (25% of 96 h LC₅₀). The study includes the recovery pattern in serum electrolytes after placing the fish in pesticide-free water. Fish show hypocalcemia, hypermagnesemia, and hyperphosphatemia after short-term and long-term exposure to dimethoate. When placed in pesticide-free water, these electrolytes exhibit recovery towards normalization, indicating significant (p < 0.05) recovery.     

Application of water extract of slippery elm tree leaves as a natural reagent for selective spectrophotometric determination of trace amounts of molybdenum(VI) in environmental water samples

A novel spectrophotometric method for the determination of molybdenum(VI) by using a natural reagent, water extract of slippery elm tree leaves, is developed. Molybdenum(VI) reacts with this natural reagent to form an orange colored product. The formed product shows maximum absorbance at 418 nm with a molar absorptivity value of 0.57 × 10⁴ L mol^?1 cm^?1, and this method is linear in the 0.4–10 mg L^?1 concentration range. The detection limit value was found to be 0.0350 mg L^?1. The proposed method is simple, clean, low cost, selective, and sensitive. It was applied to the analytic samples with satisfactory results.     

Adsorption of phosphate ions from water using a novel cellulose-based adsorbent

A novel cellulose-based adsorbent, iron(III)-coordinated amino-functionalised poly(glycidylmethacrylate)-grafted cellulose [Fe(III)–AM-PGMACell] was developed for the removal of phosphate from water and wastewater. The scanning electron micrograph showed that AM-PGMACell has a rougher surface than cellulose and the adsorption of Fe(III) on AM-PGMACell made the surface even rougher. Infrared spectroscopy revealed that amino groups on the surface of AM-PGMACell complexed with Fe(III) played an important role in the removal of phosphate from solutions. X-Ray diffraction patterns showed a decrease in crystallinity after graft copolymerisation onto cellulose. The effects of contact time, initial sorbate concentration, pH, agitation speed, dose of adsorbent and temperature on the removal process were investigated. Maximum removal of 99.1% was observed for an initial concentration of 25 mg·L ^?1 at pH 6.0 and an adsorbent dose of 2.0 g·L ^?1. A two-step pseudo-first-order kinetic model and Sips isotherm model represented the measured data very well. Complete removal of 11.6 mg·L ^?1 phosphate from fertiliser industry wastewater was achieved by 1.6 g·L ^?1 Fe(III)–AM-PGMACell. The adsorbent exhibited very high reusability for several cycles. Overall, the study demonstrated that Fe(III)–AM-PGMACell can be used as an efficient adsorbent for the removal and recovery of phosphate from water and wastewater.     

Effect of humic acids on the Fenton degradation of phenol

We show that the degradation of phenol by Fe(III) and hydrogen peroxide is faster in the presence of humic acids. This is most likely due to faster reduction of Fe(III)-humate complexes by H₂O₂/HO₂^·/O₂^–· when compared with Fe(III)-H₂O complexes. The fact that humic acids, a major class of naturally occurring compounds, favour the Fenton reaction has great relevance in the field of water and soil decontamination, where organic compounds usually have a negative effect. Furthermore, it adds insight into the self-depuration processes of natural aquifers.     

Toxicity of metals to tadpoles of the common Sunda toad,Duttaphrynus melanostictus

Tadpoles of the common freshwater Sunda toad, Duttaphrynus melanostictus (Amphibia, Bufonidae), were exposed for a 4-day period under laboratory conditions to copper (Cu), cadmium (Cd), zinc (Zn), lead (Pb), nickel (Ni), iron (Fe), aluminum (Al), and manganese (Mn) at various concentrations. Mortality was assessed and median times of death (LT₅₀) and lethal concentrations (LC₅₀) were calculated. LT₅₀ and LC₅₀ increased with the decrease in mean exposure times and concentrations for all metals. LC₅₀ (96?h) for Cu, Cd, Zn, Pb, Ni, Fe, Al, and Mn were 0.03, 0.3, 4.2, 1.5, 8.8, 0.4, 1.9, and 39?mg?L^?1, respectively. Cu was the most toxic to D. melanostictus, followed by Cd, Fe, Al, Pb, Zn, Ni, and Mn (Cu?>?Cd?>?Fe?>?Al?>?Pb?>?Zn?>?Ni?>?Mn). Duttaphrynus melanostictus is similarly sensitive to these metals as other amphibian tadpoles.