Selective separation and preconcentration studies of chromium(VI) with Alamine 336 supported liquid membrane

Chromium compounds have received considerable attention because these are used extensively in such industrial applications as electroplating, steelmaking, tanning of leather goods, and corrosion inhibition. The use of supported liquid membranes (SLMs) to remove metals from wastewaters has actively been pursued by the scientific and industrial community. In the present work, the selective separation and preconcentration of Cr(VI) ions has been studied by using a commercial amine as the membrane liquid on the porous polypropylene support. Permeation experiments were conducted on a laboratory scale batch reactor made up of perspex, with a memberane fixed amid the two chambers. The flux of Cr(VI) ions was found to be maximum (3.15?×?10^?5?mol?cm^?2?s^?1) around pH 1. Above and below this pH the flux decreases. Distribution studies show that an increase in the amine concentration leads to higher distribution coefficients at fixed pH values. At pH around unity, the distribution of Cr(VI) ions into the organic phase was found to be maximum, of the order of 56.3. The Cr(VI) transport through the membrane increases with rise in temperature. In order to check the long-term efficiency of the flat sheet SLM, an experiment was conducted with higher Cr(VI) concentration (5000?ppm) for 24?h, at optimised parameters. It was observed that in 24?h, about 1/5th of the feed Cr(VI) is left over while the rest is transported. However, minute organic droplets were also seen in the feed and strip compartments, after 1 day. This observation suggested the loss of membrane liquid. The feasibility of preconcentration of Cr(VI) by using the proposed SLM parameters, was also studied by using the hollow fibre (HF) system. Highest enrichment factor (E.F) value was obtained for 50?mg?L^?1 whereby all of the metal was transported to the stripping phase and the resulting Cr concentration was 688?mg?L^?1 (E.F?=?13.8). It was observed that while treating more diluted solutions, the enrichment factor decreases. The values of E.F equal to 8.9 and 11.3 were found for initial Cr concentration of 10 and 30?mg?L^?1.     

Exposure-response of Cr(III)-organic complexes to <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>

Hexavalent chromium [Cr(VI)] bioreduction produces soluble Cr(III)-organic complexes. The Cr(III)-organic complexes are relatively stable once they are formed, and no data about their toxicity were reported. Therefore, this study aims to investigate the bioavailability and toxicity of the soluble Cr(III)-organic complexes. Saccharomyces cerevisiae L-1 wild type yeast strain was chosen as the model organism and Cr(III)-citrate was selected as the representative compound of the Cr(III)-organic complexes. The short-term chronic aquatic toxicity tests of the Cr(III)-citrate was explored by measuring growth inhibition, direct viable cell count, dry biomass, biosorption, and the amount of CO₂ production. Cr(III)-citrate exerted a toxicity of 51 mg/L with an EC ₅₀, which was calculated from the percent growth inhibition. These toxicity data would be helpful to define the toxic potential of the organo-chromium-III compounds in the environment.     

Phytoextraction of Cr(VI) from soil using Portulaca oleracea

Cr(VI) represents an environmental challenge in both soil and water as it is soluble and bioavailable over a wide range of pH. In previous investigations, Portulaca oleracea (a plant local to the United Arab Emirates (UAE)) demonstrated particular ability for the phytoextraction of Cr(VI) from calcareous soil of the UAE. In this publication, the results of the evaluation of P. oleracea phytoextraction of Cr(VI) from UAE soil at higher concentrations are reported. P. oleracea was exposed to nine different concentrations of Cr(VI) in soil from 0 to 400 mg kg^?1. The uptake of Cr(VI) increased as its concentration in soil increased between 50 and 400 mg kg^?1, with the most efficient removal in the range from 150 to 200 mg kg^?1. The total chromium concentrations exceeded 4600 mg kg^?1 in roots and 1400 mg kg^?1 in stems, confirming the role of P. oleracea as an effective Cr(VI) accumulator. More than 95% of the accumulated Cr(VI) was reduced to the less toxic Cr(III) within the plant.     

Spectrophotometry determination of Congo red in river water samples using nanosilver

A spectrophotometric procedure for the anionic diazo dye Congo red was proposed based on nanosilver catalyzed oxidation by potassium iodate in a hydrochloric acid medium. The calibration graph is linear for 0.8–240?mg?L^?1, and the detection limit is 0.6?mg?L^?1. Most foreign ions do not interfere with the determination, except for Cu(II), Fe(III), and Cr(VI). The interferences of Cu(II) and Fe(III) could be eliminated by masking with ethylene diamine tetraacetate, and that of Cr(VI) by reducing to Cr(III) with ascorbic acid. The typical features of this procedure are that it is sensitive for Congo red, and the determination could be carried out at room temperature. It had been used for the determination of Congo red in the Ganjnameh river water sample.     

不同价态铬在不同水分条件下的生物有效性及其对水稻的毒性

氧化还原过程在铬的形态转化中起了重要作用,而铬形态的转化能够影响其生物有效性及毒性。通过温室土培试验研究了六价铬(Cr(Ⅵ))与三价铬(Cr(Ⅲ))在淹水与不淹水条件下在土壤溶液中的动态变化及水稻对其吸收的变化。结果表明,土壤中添加Cr(Ⅲ)时,土壤溶液中检测不出Cr;而随着土壤中添加Cr(Ⅵ)浓度的增加,土壤溶液中Cr(Ⅵ)的浓度增加,但是溶液中检测不出Cr(Ⅲ);淹水处理总体上降低了土壤溶液中Cr(Ⅵ)的浓度。而土壤添加Cr(Ⅲ)、Cr(Ⅵ)和水分处理对土壤溶液p H没有显著影响,p H在7.08.0之间变动。土壤添加Cr(Ⅵ)处理的水稻中,只有90 mg·kg-1Cr(Ⅵ)淹水处理的水稻成活,而其余处理水稻没有成活。土壤中添加Cr(Ⅲ)处理,水稻幼苗生物量随Cr(Ⅲ)浓度的增加而显著降低;除了200mg·kg-1Cr(Ⅲ)处理外,其余淹水处理的水稻幼苗生物量明显高于不淹水处理的。土壤添加Cr(Ⅲ)处理的水稻,在不淹水条件下水稻空壳率比较高,淹水条件下,随着土壤中添加Cr(Ⅲ)浓度水平的增加,水稻各部位Cr含量有增加的趋势,但增加不显著,秸秆最高Cr含量达到33.80 mg·kg-1,籽粒中Cr含量最高0.30 mg·kg-1。土壤固定Cr(Ⅲ)的能力远强于Cr(Ⅵ),添加Cr(Ⅵ)处理的土壤溶液中Cr(Ⅵ)的浓度很高,对水稻表现出较强的生长抑制。     

重金属Cr(VI)、Pb及Cu胁迫对双齿围沙蚕体腔细胞的DNA损伤

为探讨重金属Cr(VI)、Pb以及Cu对沙蚕体腔细胞DNA的毒性效应,以双齿围沙蚕为受试动物,重金属按不同剂量水平,Cr(VI):10、100和200 mg·L~(-1),Pb:5、50和100 mg·L~(-1),Cu:1、10和20 mg·L~(-1),分别胁迫沙蚕24 h,以不加任何重金属离子的海水为对照,采用单细胞凝胶电泳技术,检测其体腔细胞DNA损伤程度。结果表明,与空白对照组相比,3种重金属离子的各浓度组都能引起沙蚕体腔细胞DNA损伤,且3种重金属胁迫浓度与细胞DNA损伤程度之间存在显著的剂量-效应关系。双齿围沙蚕可以作为单细胞凝胶电泳的实验材料用于重金属所致环境污染的生物监测指示生物。     

Bioreduction of hexavalent chromium by Exiguobacterium indicum strain MW1 isolated from marine water of Paradip Port,Odisha, India

Hexavalent chromium-tolerant (1500?mg/L) bacterium MW1 was isolated from harbour water of Paradip Port and evaluated for Cr(VI) reduction potential. The isolate was identified as Exiguobacterium indicum by biochemical and 16S rRNA gene sequence methods. Salt tolerance of the bacterium was evaluated in a wide range of NaCl concentrations (0.5–13%, w/v). The Cr(VI) reduction of the strain was evaluated and optimised with varied Cr(VI) concentrations (100–1000?mg/L), pH (5.0–9.0), temperature (30–40°C) and shaking velocity (100–150?rpm) in two different minimal media (M9 and Acetate). Under optimised conditions, after 192?h of incubation nearly 92%, 50% and 46% reduction in the M9 minimal medium and 91%, 47% and 40% reduction in the acetate minimal medium were observed for 100, 500 and 1000?mg/L of Cr(VI), respectively. The exponential rate equation for Cr(VI) reduction yielded higher rate constant value, that is, 1.27?×?10^?2?h^?1 (M9) and 1.17?×?10^?2?h^?1 (Acetate) in case of 100?mg/L and became lower for 500 and 1000?mg/L Cr(VI) concentrations. Further, the association of bacterial cells with reduced product was ascertained by Fourier transform infrared spectrometer, UV–Vis–DRS and field-emission scanning electron microscope–energy-dispersive X-ray analyses. The above study suggests that the higher reducing ability of the marine bacterium E. indicum MW1 will be suitable for Cr(VI) reduction from saline effluents.     

Arsenic and chromate removal from water by iron chips—Effects of anions

The purpose of this study is to estimate the removal efficiency of As and Cr (VI) by one kind of industrial waste — iron chips, as well as to estimate the effects of typical inorganic anions (sulfate, phosphate, and nitrate), and typical organic anions (citrate, oxalate, and humate) on As or Cr (VI) removal. The results showed that 98% of As (V) and 92% of As (III) could be removed from aqueous phase by the iron chips within 60 min. Compared with As species, Cr (VI) was removed much more rapidly and efficiently with 97% of Cr (VI) being removed within 25 min. The removal efficiency for arsenic was in the order: As (III) (sulfate), As (III) (nitrate) or As (III), As (III) (humate), As (III) (oxalate), As (III) (citrate), As (III) (phosphate), and for chromate was in the order: Cr (VI) (sulfate), Cr (VI) (phosphate) or Cr (VI) (nitrate) or Cr (VI) (oxalate), Cr (VI), Cr (VI) (citrate), Cr (VI) (humate). In all the treatments, pH level increased with time except for As (III), the removal of which was either without anions or in the presence of humate or nitrate.     

Teratogenic and biochemical effects of a formulation containing dicofol in the chick embryo

The insecticide formulation, dicofol (18.5% EC) was evaluated for its toxic potential in developing chick embryo. Fertilized eggs of Gallus domesticus on 4th day of incubation were immersed in aqueous emulsions of dicofol at concentrations of 250?mg?L^?1, 500?mg?L^?1, and 1000?mg?L^?1 for 60?min at 37°C. These concentrations were corresponding to those used in plant protection practice (500?mg?L^?1). Two control groups of eggs were used: one group was immersed in distilled water (vehicle) and the second group was kept as untreated to study background toxicity. On embryonic day 7; recovered embryos were evaluated for mortality rate, wet body weight, gross morphological malformations, and some biochemical changes. The result revealed that administration of dicofol did not result in significant changes in wet body weight of embryo but the survival rate of dicofol treated embryos were markedly reduced as compared with controls. Among the survivors, the number of malformations was exhibited by dicofol treated embryos in dose-dependent manner. Among biochemical changes, only total protein content of embryo significantly (p?≤?0.05) reduced to 500?mg?L^?1 and 1000?mg?L^?1. Among enzymes, alkaline phosphatase and glutamate pyruvate transaminase activities were affected, which showed significant elevations.     

A comparison of two methods to observe the effects of dual metal exposure to the chironomus larvae

A study was conducted to investigate the effects of metal mixtures on the Chironomus plumosus. Two methods of preparing the mixtures were used, the Toxic Unit (TU) method and the parts per million (PPM) + PPM method. A comparison was undertaken between the two methods to observe the ease with which (1) experiment could be conducted and (2) whether LC₅₀ values could be obtained. In this study, it was noted that the PPM + PPM method was an easier method to conduct metal mixture experiments as the LC₅₀ values could be easily calculated for individual metals and compared with the LC₅₀ values of metals obtained from single metal experiments. The findings showed that the LC₅₀ value for zinc (Zn) was more toxic for chromium (Cr) when it was reduced from 9.6 to 0.3 mg L^?1, with silver the LC₅₀ value became 3.6 mg L^?1, 4.5 mg L^?1 with nickel (Ni). In the PPM + PPM method, the LC₅₀ value for Zn was observed to be 10.2 mg L^?1 when in mixture with chromium, 23.8 mg L^?1 with silver, and 13.4 mg L^?1 with Ni. Changes in the 96 h LC₅₀ value were found to be significant for all metals.     

Uptake,distribution and loss of Cr in the crab Xantho hydrophilus

Uptake of ⁵¹Cr(III) is faster than uptake of ⁵¹Cr(VI), but it occurs mainly on the surface of the animals. Steady state is attained after 28 d. The resulting concentration factor is about 200. Although the uptake of ⁵¹Cr(VI) is slower, it is more intensively distributed into the organs and tissues of the animals. Steady state was not attained during the experiments (35 d); the highest concentration factor reached was about 10. The uptake of both ⁵¹Cr(III) and ⁵¹Cr(VI) seems to be passive. For both chemical forms of chromium, the loss rate is inversely proportional to the exposure time. When the uptake lasted longer, owing to the distribution of Cr(VI) into the organs and tissues, the loss rate of Cr(III) is somewhat faster relative to the loss rate of ⁵¹Cr(VI). The opposite is the case when the uptake of both forms lasts only two days. On the basis of the distribution and loss experiments, we argue that hexavalent chromium in living organisms is reduced to the trivalent form and then complexed with organic molecules.     

Acute toxicity of 30 pharmaceutically active compounds to freshwater planarians,Dugesia japonica

Pharmaceutically active compounds are produced worldwide and consumed in large quantities, so these chemicals are frequently detected in limnic environments posing potential ecological risks. Thirty pharmaceutically active compounds were selected for examination of their acute toxicity for freshwater planarians (Dugesia japonica). Among the 30 compounds tested, diclofenac, mefenamic acid, naproxen, propranolol HCl, and diphenhydramine HCl had a 48-h nominal LC₅₀ below10 mg L^?1, and for 18 chemicals, it exceeded 100 mg L^?1. The 96-h nominal LC₅₀ was below 10 mg L^?1 for diclofenac, mefenamic acid, naproxen, propranolol HCl, diltiazem HCl, diphenhydramine HCl, hydroxyzine HCl, and triprolidine HCl, and for 15 chemicals, it exceeded 100 mg L^?1. Among different therapeutic groups, analgesics were most toxic to planarians, and antibiotics were least toxic. Antihistamines and beta blockers varied in their acute toxicity to planarians. At the current environmental levels, none of the tested pharmaceutically active compounds may have acutely harmful impacts on aquatic invertebrates. To answer the question whether chronic, long-term exposure to pharmaceutically active compounds may entail ecological risks for aquatic ecosystems, further investigations with different end points in multiple species tests are needed.     

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.     

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.     

Carbon paste electrode modified with chromium thiopental for the potentiometric flow injection analysis of chromium (III)

A chemically modified carbon paste electrode for chromium (III) based on the formation of ion-association complex of chromium with 5-ethyl-6-oxo-5-pentan-2-yl-sulfanyl-pyrimidin-4-olate (thiopental, THP) as electroactive ion-exchanger (Cr-THP) was prepared and investigated. The electrode has a linear dynamic range of 1.7?×?10^?6–1.3?×?10^?2?mol?L^?1, with a Nernstian slope of 19.6?±?0.5?mV per decade and a detection limit of 9.0?×?10^?7?mol?L^?1. It has a fast response time of <15?s and can be used for at least 7 weeks without any considerable divergence in potential. The proposed sensor revealed good selectivity for Cr(III) over a wide variety of mono-, di-, and trivalent cations and could be used in the pH range of 2.3–6.5. The proposed electrode was used in batch measurements and in flow injection analysis. The Cr-CMCPE was successfully applied for the determination of Cr(III) in real samples (wastewater of hot dip galvanizing unit and alloys). The present electrode was also used as an indicator electrode in potentiometric titration of Cr(III). The results were highly satisfactory.     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min^?1 when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min^?1 were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.     

The role of root organic acids in the tolerance of Festuca rubra to zinc,lead and cadmium

Abstract

Festuca rubra L. plants are pseudometallophytes colonizing abandoned Pb/Zn mine areas, successfully employed in phytostabilization. To study the contribution of low-molecular weight organic acids to metal tolerance, F. rubra plants were grown for three months in hydroponics with Cd (1.8, 18 and 36 µmol?L^?1), Pb (50, 250 and 500?µmol?L^?1) and Zn (0.3, 3 and 6?mmol?L^?1), separately, and in ternary combination (18?µmol?L^?1 Cd + 250?µmol?L^?1 Pb + 0.3?mmol?L^?1 Zn). The roots retained most of the metals but their distribution from shoot to root was altered when the plants were treated with the ternary combination. The main organic acids in roots were citrate and malate. At the lowest concentrations, the metals caused small reductions in biomass, had no effects on photosynthetic pigments nor on malondialdehyde, but led to increases in root organic acids. At higher concentrations, phytotoxic responses were observed, associated with a decline of citrate and malate in the roots.     

Hepatic effects of yttrium oxide nanoflowers: in vitro risk evaluation

Yttrium oxide nanoflowers were prepared by a hydrothermal technique, and X-ray diffraction and scanning electron microscopy were used to determine their structures. The cytotoxic and genotoxic potentials of aqueous dispersions of the nanoflowers to cultured primary rat hepatocytes were examined at concentrations up to 500 mg L^?1 for 72 h. Cell viability was determined by monitoring the reduction of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, release of lactate dehydrogenase, and uptake of neutral red. Genotoxicity was assessed by the liver micronucleus assay. Exposure to Y₂O₃ nanoflowers at concentrations lower than 100 mg L^?1 did not lead to any cytotoxicity or genotoxicity. At higher concentrations (200, 400, and 500 mg L^?1), cell viability decreased and induction of micronuclei increased (400 and 500 mg L^?1).     

重金属胁迫对日本对虾(Penaeus japonicas )胚胎发育的影响

以受精1 h以内的日本对虾受精卵为实验对象,采用静水试验方法,研究了Zn、Hg、Cu、Pb、As、Cd和Cr 7种重金属对日本对虾胚胎发育的影响。结果表明,在实验浓度范围内,7种重金属中Hg、Cu对日本对虾胚胎发育毒性最大,其次是Zn、As、Cd,Pb和Cr无明显影响。Hg、Cu、Cd、As、Zn对日本对虾胚胎LC₅₀值分别为：0.0177 mg·L^-1、0.1070 mg·L^-1、1.6057 mg·L^-1、3.3682 mg·L^-1、8.2644 mg·L^-1,致死效应最低可观测效用浓度（LOEC）分别为0.0037 mg·L^-1、0.0166 mg·L^-1、0.1302 mg·L^-1、1.1572 mg·L^-1、2.1522 mg·L^-1;抑制发育LOEC分别为0.0062 mg·L^-1、0.0176 mg·L^-1、0.4002 mg·L^-1、1.9497 mg·L^-1、0.0617 mg·L^-1。随着Hg、Cu浓度的升高,胚胎孵化率不断下降,无节幼体死亡率不断上升,在Hg 0.0256 mg·L^-1浓度组中,胚胎48 h死亡率达到100%。以上结果说明,Hg、Cu等重金属的存在会延缓日本对虾胚胎的发育速度,随着重金属浓度的增加,滞育现象愈加明显,在Cu 0.32 mg·L^-1浓度组中,未见无节幼体孵出。     

Enhancement of extracellular Cr(VI) reduction for anammox recovery using hydrazine: performance,pathways, and mechanism

● N₂H₄ addition enhanced and recovered anammox performance under Cr(VI) stress. ● N₂H₄ accelerated electron transfer of Cr(VI) reduction for detoxification. ● N₂H₄ enhanced anammox metabolism for activity recovery from Cr(VI) inhibition. ● Extracellular Cr(VI) reduction to less toxic Cr(III) was the dominant mechanism. The hexavalent chromium (Cr(VI)) would frequently impose inhibition to anaerobic ammonium oxidation (anammox) process, hindering the efficiency of nitrogen removal in wastewater treatment. Hydrazine (N₂H₄), which is an intermediate product of anammox, participates in intracellular metabolism and extracellular Cr(VI) reduction. However, the roles of N₂H₄-induced intracellular metabolism and extracellular reduction in nitrogen removal under Cr(VI) stress remain unclear. The addition of 3.67 mg/L of N₂H₄ increased the anammox activity by 17%. As an intermediate, N₂H₄ enhanced anammox metabolism by increasing the heme c content and electron transfer system activity. As a reductant, N₂H₄ accelerated the reduction of c-Cyts-mediated extracellular Cr(VI) to the less toxic Cr(III). Extracellular Cr(III) accounts for 74% of the total Cr in a Cr(VI)-stressed anammox consortia. These findings highlight that N₂H₄-induced extracellular Cr(VI) reduction is the dominant mechanism for the survival of anammox consortia. We also found that N₂H₄ increased the production of extracellular polymeric substances to sequester excessive Cr(VI) and produced Cr(III). Taken together, the study findings suggest a potential strategy for enhancing nitrogen removal from ammonium-rich wastewater contaminated with Cr(VI).