Preconcentration and speciation of Cr(III) and Cr(VI) in water and soil samples by spectrometric detection via use of nanosized alumina-coated magnetite solid phase

A novel nanomaterial has been developed for speciation of Cr(III) and Cr(VI) in water and soil samples. In this study, a new type of alumina-coated magnetite nanoparticles (Fe₃O₄/Al₂O₃ NPs) modified by the surfactant Triton X-114 has been successfully synthesized and used in magnetic mixed hemimicelles solid-phase extraction procedure. The procedure was based on the reaction of chromium(III) with 1-(2-pyridilazo)-2-naphtol as a ligand, yielding a complex, which was entrapped “in situ” in the surfactant hemimicelles. The concentration of chromium(III) was determined using flame atomic absorption spectrometry. After reduction of Cr(VI) to Cr(III) by ascorbic acid, the system was applied to the total chromium. Cr(VI) was then calculated as the difference between the total Cr and the Cr(III) content. This method can also be used for complicated matrices such as soil samples without any special pretreatment. Under the optimum conditions of parameters, the recoveries of Cr(III) by analyzing the spiked water and soil samples were between 98.6 and 100.8 % and between 96.5 and 100.7 %, respectively. Detection limits of Cr(III) were between 1.4 and 3.6 ng?mL^?1 for water samples and 5.6 ng?mg^?1 for soil samples.     

Oxidation of Cr(III) to Cr(VI) during chlorination of drinking water

Drinking water treatment typically uses strong oxidants such as chlorine which are capable of converting Cr(III) to Cr(VI). The rates and extent of Cr(III) oxidation by chlorine are not well established. Cr(III) oxidation experiments were therefore conducted in distilled deionized water and New York City tap water dosed initially with Cr(III) and supplemented with sodium hypochlorite to increase free chlorine residual. Reaction progress was monitored using capillary electrophoresis which quenched reactions and allowed for quantification of Cr(VI). Three different forms of Cr(III) were used as reactants: a Cr(III) nitrate salt, Cr(III)-EDTA, and Cr(III) hydroxide. Rates of Cr(VI) production for all three forms of Cr(III) were rapid, on the order of hours. However, oxidation rates slowed and a plateau in Cr(VI) concentrations was reached. This resulted in less than 100% conversion of Cr(III) to Cr(VI) even at relatively high chlorine doses (10 to 100 mg L(-1) as Cl(2)). The loss of free chlorine due to a non-Cr chlorine demand, the precipitation of Cr(III) to Cr(OH)(3)(s), and the partial oxidation of Cr(III) to intermediate oxidation states (i.e. Cr(IV) and Cr(V)) were examined and eliminated as possible explanations for this behavior. Consumption of chlorine via reaction with intermediate oxidation states of Cr is therefore offered as a possible explanation for the plateau in Cr(VI) concentrations.     

Effects of clay minerals on Cr(VI) reduction by organic compounds

The objective of this study is to examine the effect of clayminerals (illite, montmorillonite, and kaolinite) on chromate (Cr(VI)) reduction by several low molecular weightorganic compounds. Batch experiments at pH ranging from 3.0 to6.0 and 25 °C showed that 2:1 layered clays illite andsmectite catalyzed Cr(VI) reduction by oxalate. The catalyticeffect increased as pH was decreased. The 1:1 clay kaolinite hadno catalytic effect under comparable conditions. Direct Cr(VI)reduction by reactive moieties associated with illite andmontmorillonite was observed, but at a much slower rate than thecatalytic pathway. Cr(VI) reduction by glyoxylic acid, glycolicacid, lactic acid, and mandelic acid was accelerated by illite,although aqueous phase reduction might occur in parallel. Theseresults suggest that Cr(VI) reduction rates in subsurfaceenvironments rich in organic compounds may be elevated throughcatalysis of surface-bound metals and/or soluble species from theclay minerals, and as a result, higher than those expected fromaqueous phase reaction alone. Such rate enhancement for Cr(VI)reduction needs to be accounted for when developing new remedialtechniques for chromium site remediation or assessing its naturalattenuation.     

Tuning the surfaces of palladium nanoparticles for the catalytic conversion of Cr(VI) to Cr(III)

This work reports the feasibility of using Pd nanoparticles as innovative catalysts in the conversion of reducible contaminants from toxic to benign forms. Cr(VI) is a known carcinogen while the trivalent chromium salts are believed to be non-toxic. The ability of Pd nanoparticles to catalyze the rapid reduction of Cr(VI) to Cr(III) using reactive sulfur intermediates produced in situ was therefore studied. Using a microchamber set at 130 degrees C, the reduction mixture consists of palladium nanoparticles and sulfur (PdNPs/S), which generated highly reducing sulfur intermediates that effected the reduction of Cr(VI) to Cr(III) by 1st order reaction kinetics. UV-visible spectroscopy and cyclic voltammetry were employed to monitor the reduction process. The results showed that 99.8% of 400 microM Cr(VI) was reduced to Cr(III) by PdNPs/S in one hour compared to 2.1% by a control experiment consisting of sulfur only. The rate of Cr(VI) reduction was found to be dependent on temperature and pH and was greatly enhanced by the addition of PdNPs. Subsequent application of this approach in the reduction of Cr(VI) in soil and aqueous media was conducted. In contrast to the control experiments with and without PdNPs or sulfur, greater than 92% conversion rate was obtained in the presence of PdNPs/S within 1 hour. This represents over a 500-fold improvement in conversion rate compared to current microbial approaches. XPS analysis provided the confirmation regarding the oxidation states of Cr(VI), Cr(III) and the nature of the reactive intermediates. This work offers PdNPs/S as a new interface for the reduction of high oxidation state heavy metal pollutants.     

Modeling nonlinearly transient zero-order bioreduction and transport of Cr(VI) in groundwater

Cr(VI) contamination of soil and groundwater is considered a major environmental concern. Bioreduction of Cr(VI) to Cr(III) can be considered a potentially effective technology in remediating Cr(VI) contaminated sites. Shewanella oneidensis MR-1 (MR-1) is one of the bacteria capable of reducing Cr(VI) to Cr(III) under anaerobic conditions. The kinetics of Cr(VI) reduction by MR-1 is defined by the dual-enzyme kinetic model which is nonlinear, transient, and zero-order. Existing transport models are not designed to simulate such reaction kinetics. The objective of this paper is to present a Petrov–Galerkin finite element model (PGFEM) to simulate transport and bioreduction of Cr(VI), by MR-1, in groundwater. The model developed is unconditionally stable and provides oscillation free accurate results for a wide range of Peclet number (Pn) and Courant number (Cn).     

中国皮革行业六价铬排放特征分析与监管建议

在分析皮革鞣制工艺现状基础上,根据2000—2013年环境统计数据、2010—2013年国控源监督性监测数据,以及典型制革园区不同类型皮革企业的现场监测数据,分析了中国皮革行业六价铬产生与排放特征,有针对性地提出了皮革行业六价铬的监管建议。     

Speciative determination of Cr (III) and Cr (VI) in dyeing waste water of Dil Creek discharge to Izmit Gulf (Izmit-Kocaeli, Turkey) by ICP-AES

Wastewater pollution in industrial areas is one of the most important environmental problems. Heavy metal pollution, especially chromium pollution in wastewater sources from dyeing and tannery has affected the life on earth. This pollution can affect all ecosystems and human health directly or by food chain. Therefore, the determination of chromium in this study is of great importance. Dil Creek is located in the eastern Marmara region and discharges into the Izmit Gulf. This water source is used for irrigation in agriculture and as drinking water for animals. In this study, a rapid, sensitive and selective method for the speciative direct determination of Cr (III) and Cr (VI) in dyeing waste water samples collected from the nearest station to Izmit Gulf of Dil Creek in May 2006 by inductively coupled plasma-atomic emission spectrometry (ICP-AES) has been developed. An analysis of a given sample is completed in about 15 min for ICP-AES the method. As the result of the chromium analysis, the limit of quantification (LOQ) for the Cr (III), Cr (VI) and total Cr were founded as 0.0111 ± 0.0002 mg/l (RSD, 1.80%), 0.0592 ± 0.0010 mg/l (RSD, 1.70%) and 0.0703 ± 0.0020 mg/l (RSD, 2.84%) respectively. In addition, the general mathematical formula has been developed to calculate the concentration of Cr(III), which can be applied to any other metal species. The result of Cr (VI) analysis indicated that water quality of Creek was IV. class quality according to the inland water classification. In order to validate the applied method, recovery studies were performed.     

二苯碳酰二肼分光光度法测定水中六价铬测量不确定度评定

根据测量不确定度评定与表示理论,采用二苯碳酰二肼分光光度法测定水中六价铬的测量不确定度,通过计算和评定,得出该法测定水中六价铬的测量结果为0.233mg/L时.取包含因子k=2(约95%置信概率),扩展不确定度U=0.007mg/L.该不确定度评价方法在实际工作中具有较强的实用价值.     

Effect of humic deposit (leonardite) on degradation of semi-volatile and heavy hydrocarbons and soil quality in crude-oil-contaminated soil

In order to investigate the bioremedial potential of humic deposit (leonardite), the effects of the treatments of leonardite and a commercial bioaugmentation agent on the degradation of a variety of petroleum hydrocarbons (C13–C31) and soil enzyme activities (urease acid-alkaline phosphatase and dehydrogenase) were tested within a soil incubation experiment lasting 120 days. Experimentally crude-oil-contaminated soil (2.5%) was regulated to a C:N:P ratio (100:15:1; Oilcon), amended with 5% of leonardite and regulated to the same C:N:P ratio (Oilcon-L) or mixed with a commercial bioaugmentation product (Oilcon-B), respectively. In the short period of incubation (60 days), Oilcon and Oilcon-B treatments showed higher hydrocarbon degradations, whereas Oilcon-L showed higher hydrocarbon degradation over Oilcon and Oilcon-B treatments in the long-term (120 days). Applying contaminated soil with leonardite increased urease (LSD, 4.978, *P?<?0.05) and dehydrogenase (LSD, 0.660, *P?<?0.05) activities. However, acid and alkaline phosphatase activities showed no certain inclination between different treatments. Dehydrogenase seemed to be more related to hydrocarbon degradation process. Overall results showed that leonardite enhanced biodegradation of petroleum hydrocarbons and also stimulated soil ecological quality measured as soil enzyme activities.     

Cr(VI)-DBAV-TritonX-100析相光度法测定微量铬(VI)的研究

研究了Ｃｒ（ＶＩ）ＤＢＡＶＴｒｉｔｏｎＸ１００析相显色体系,建立测定微量铬（ＶＩ）的析相光度法。在ｐＨ４５的乙酸—乙酸钠介质中,Ｃｒ（ＶＩ）、ＤＢＡＶ、ＴｒｉｔｏｎＸ１００加热形成配合物,于９５℃恒温水浴中加热析相１ｈ,即被ＴｒｉｔｏｎＸ１００相完全富集,最大吸收峰为５５６ｎｍ,铬（ＶＩ）含量在０～４μｇ／５ｍｌ服从比耳定律,采用７３２阳离子交换树脂分离干扰离子,测定水样中微量铬（ＶＩ）,结果满意。     

Effect of pH,ionic strength,and background electrolytes on Cr(VI) and total chromium removal by acorn shell of Quercus crassipes Humb. & Bonpl.

The ability of Quercus crassipes acorn shells (QCS) to remove Cr(VI) and total chromium from aqueous solutions was investigated as a function of the solution pH, ionic strength, and background electrolytes. It was found that Cr(VI) and total chromium removal by QCS depended strongly on the pH of the solution. Cr(VI) removal rate increased as the solution pH decreased. The optimum pH for total chromium removal varied depending on contact time. NaCl ionic strengths lower than 200 mM did not affect chromium removal. The presence of 20 mM monovalent cations and anions, and of divalent cations, slightly decreased the removal of Cr(VI) and total chromium by QCS; in contrast, divalent anions (SO₄ ^2?, PO₄ ^2?, CO₃ ^2?) significantly affected the removal of Cr(VI) and total chromium. The biosorption kinetics of chromium ions followed the pseudo-second-order model at all solution pH levels, NaCl ionic strengths and background electrolytes tested. Results suggest that QCS may be a potential low-cost biosorbent for the removal of Cr(VI) and total chromium from aqueous solutions containing various impurities.     

Effect of new organic supplement (Panchgavya) on seed germination and soil quality

We studied the suitability of Panchgavya (five products of cow), new organic amendment, application on seed germination, plant growth, and soil health. After characterization, Panchgavya was mixed with water to form different concentration and was tested for seed germination, germination index, and root and shoot growth of different seedlings. Four percent solution of Panchgavya was applied to different plants to test its efficacy. Panchgavya and other two organic amendments were incorporated in soil to test the change of soil chemical and microbiological parameters. Panchgavya contained higher nutrients as compared to farm yard manure (FYM) and vermicompost. Its application on different seeds has positively influenced germination percentage, germination index, root and shoot length, and fresh and dry weight of the seedling. Water-soluble macronutrients including pH and metal were positively and negatively correlated with the growth parameters, respectively. Four percent solution of Panchgavya application on some plants showed superiority in terms of plant height and chlorophyll content. Panchgavya-applied soil had higher values of macro and micronutrients (zinc, copper, and manganese), microbial activity as compared to FYM, and vermicompost applied soils. Application of Panchgavya can be gainfully used as an alternative organic supplement in agriculture.     

FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al₂O₃) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L^?1 for H₂SO₄ concentration, system flow rate as 0.40 mL min^?1, sample injection volume of 192.50 μL, 2 min for preconcentration time, and 0.10 mol L^?1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 μM, linear correlation coefficient R?=?0.9997 and LOD?=?0.024 μM. The preconcentration factor of about four times was obtained through the passage of 800 μL of a standard solution containing 0.961 μM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 μL of NH₄OH 0.1 mol L^?1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 μL of HCl 0.02 mol L^?1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.     

Effect of vehicle exhaust on the quantity of polycyclic aromatic hydrocarbons (PAHs) in soil

PAHs are formed during the incomplete combustion of organic substances containing carbon and hydrogen and are one of the first atmospheric pollutants identified as carcinogens. Most of the PAH environmental burden is found in the soil (95%). Soil samples collected from different roadsides were analyzed for seven polycyclic aromatic hydrocarbons (PAHs). The quantitative and qualitative analysis was carried out by UV Spectrophotometer. The individual PAH value ranged from 0.1 to 18.0 mg/kg. Phenenthrene and Pyrene were found to be the most abundant compounds. Vehicle emissions are the principal source of PAH in the Roadside soils. The highest concentration was found at site S2 (Hasthtnagri Roadside) which shows the highest traffic density.     

Assessing the removal potential of soil-aquifer treatment system (soil column) for endotoxin

Soil-aquifer treatment (SAT) of wastewater is an increasingly valued practice for replenishing aquifers due to ease of operation and low maintenance needs and therefore low cost. In this study, we investigated the fate of endotoxins through laboratory-scale SAT soil columns over a four month period. The effluent of rapid sand filtration was run through the columns under gravity flow conditions. Four SAT columns were packed with four different filter materials (fine sand, medium sand, coarse sand and very coarse sand). The effluent of rapid sand filtration (average dissolved organic carbon (DOC) = 4 mg l(-1) and average endotoxin concentration = 4 EU ml(-1)) was collected from a domestic wastewater treatment plant in Sapporo, Japan. DOC removal ranged from 12.5% to greater than 22.5% during the study, with DOC levels averaging 3.1 and 3.5 mg l(-1) for the SAT columns packed with different soils. Endotoxin transformation exhibited different profiles, depending on the time and soil type. Reduction in endotoxin concentration averaged 64.3% and was as high as 86.7% across the soil columns 1, 2, 3 and 4, respectively. While DOC removal was gradual, the reductions in endotoxin levels were rather rapid and most of the removal was achieved in the top layers. Soil with a larger grain size had lower efficiency in removing endotoxin. Tests were performed to evaluate the transformation of organic matter showing endotoxicity and to determine the mechanisms responsible for changes in the structural and size properties of dissolved organic matter (OM) during SAT. Dissolved OM was fractionated using Sep-Pack C18 Cartridges into hydrophobic and hydrophilic fractions. Dialysis tubes with different molecular weight cut-offs were used to perform size fractions of OM showing endotoxicity. Evaluation of the transformation of organic matter showing endotoxicity during SAT indicated that both hydrophobic and large molecules were reduced. Moreover, experimental findings showed that adsorption test data fit to the Freundlich isotherm and were affected by the particle grain size with higher adsorption capacity for fine and medium sand.     

Spectrophotometric method for the determination of chromium (VI) in water samples

A simple and sensitive spectrophotometric method for the determination of chromium has been developed. The method is based on the diazotization of Dapsone in hydroxylamine hydrochloride medium and coupling with N-(1-Napthyl) Ethylene Diamine Dihydrochloride by electrophilic substitution to produce an intense pink azo-dye, which has absorption maximum at 540 nm. The Beer's law is obeyed from 0.02-1.0 microg mL(-1) and the molar absorptivity is 3.4854 L mol(-1) cm(-1). The Limits of quantification and Limit of detection of the proposed method are 0.0012 microg mL(-1) and 0.0039 microg mL(-1) respectively. The method has been successfully applied for the determination of chromium in water samples and the results were statistically evaluated with that of the reference method.     

Biosorption of Pb(II) and Cr(III) from aqueous solutions: breakthrough curves and modeling studies

The sorption capacity parameters obtained for batch studies provide useful information about biosorption system. However, such data fail to explain the process under continuous-flow conditions. The present study is an attempt to explore the biosorption of Pb(II) and Cr(III) by straw from local wheat (Triticum aestivum). The biosorbent has been characterized by using Fourier transform infrared spectroscopy and surface area and elemental analyses and found to be porous and polyfunctional. S-shaped breakthrough curves were obtained at different column heights for the both metal ions. Various breakthrough parameters and saturation times have been determined. The column data have been successfully used to study the Bohart–Adams' bed depth service time (BDST) model and Yoon and Nelson's model. It was found that BDST model quite efficiently explained the whole column data whereas Yoon and Nelson model could explain it below 90 % breakthrough concentration. The predicted and calculated BDST parameters were in agreement with each other. Yoon and Nelson's constant decreased with an increase in the column height for both metal ions. Effect of change in flow rate on the Pb(II) biosorption has also been discussed with respect to BDST approach.     

Monitoring the effects of chelating agents and electrical fields on active forms of Pb and Zn in contaminated soil

The application of electrical fields and chelating agents is an innovative hybrid technology used for the decontamination of soil polluted by heavy metals. The effects of four center-oriented electrical fields and chelating agents on active fractions of lead and zinc were investigated in this pot experiment. Ethylenediaminetetraacetic acid (EDTA) as a synthetic chelator and cow manure extract (CME) and poultry manure extract (PME) as natural chelators were applied to the pots (2 g kg^?1) 30 days after the first irrigation. Two weeks later, four center-oriented electrical fields were applied in each pot (in three levels of 0, 10, and 30 V) for 1 h each day for 14 days. The soil near the cathode and anodes was collected and analyzed as cathodic and anodic soil, respectively. Results indicated that the soluble–exchangeable fraction of lead and zinc were decreased in the cathodic soil, while the carbonate-bound fractions were increased. In the anodic soil, however, the opposite result was observed. EDTA enhanced the soluble–exchangeable form of the metals in both anodic and cathodic soils. Furthermore, the amounts of carbonate-bound heavy metals were increased by the application of CME in both soils. The organic-bound fraction of the metals was increased by the application of natural chelators, while electrical fields had no significant impacts on this fraction.     

Effect of elevated CO2 on degradation of azoxystrobin and soil microbial activity in rice soil

An experiment was conducted in open-top chambers (OTC) to study the effect of elevated CO₂ (580?±?20 μmol mol^?1) on azoxystrobin degradation and soil microbial activities. Results indicated that elevated CO₂ did not have any significant effect on the persistence of azoxystrobin in rice-planted soil. The half-life values for the azoxystrobin in rice soils were 20.3 days in control (rice grown at ambient CO₂ outdoors), 19.3 days in rice grown under ambient CO₂ atmosphere in OTC, and 17.5 days in rice grown under elevated CO₂ atmosphere in OTC. Azoxystrobin acid was recovered as the only metabolite of azoxystrobin, but it did not accumulate in the soil/water and was further metabolized. Elevated CO₂ enhanced soil microbial biomass (MBC) and alkaline phosphatase activity of soil. Compared with rice grown at ambient CO₂ (both outdoors and in OTC), the soil MBC at elevated CO₂ increased by twofold. Elevated CO₂ did not affect dehydrogenase, fluorescein diacetate, and acid phosphatase activity. Azoxystrobin application to soils, both ambient and elevated CO₂, inhibited alkaline phosphates activity, while no effect was observed on other enzymes. Slight increase (1.8–2 °C) in temperature inside OTC did not affect microbial parameters, as similar activities were recorded in rice grown outdoors and in OTC at ambient CO₂. Higher MBC in soil at elevated CO₂ could be attributed to increased carbon availability in the rhizosphere via plant metabolism and root secretion; however, it did not significantly increase azoxystrobin degradation, suggesting that pesticide degradation was not the result of soil MBC alone. Study suggested that increased CO₂ levels following global warming might not adversely affect azoxystrobin degradation. However, global warming is a continuous and cumulative process, therefore, long-term studies are necessary to get more realistic assessment of global warming on fate of pesticide.