Chromium speciation in groundwater of a tannery polluted area of Chennai City, India

Chromium speciation in groundwater of a tannery polluted area was investigated for the distribution of chromium species and the influence of redox couples such as Fe(III)/Fe(II) and Mn(IV)/Mn(II). Speciation analysis was carried out by ammonium pyrolidinedithiocarbamate (APDC)–methylisobutylketone (MIBK) procedure. The groundwater samples were analyzed for Cr(III), Cr(VI), and Cr(III)-organic complexes. The APDC could not extract the Cr(III)-organic complexes, but HNO₃ digestion of the groundwater samples released the Cr(III)-organic complexes. The groundwater of the area is relatively oxidizing with redox potential (E _h) and dissolved oxygen (DO) ranged between 65 and 299 mV and 0.25 and 4.65 mg L^???1, respectively. The Fe(II) reduction of Cr(VI) was observed in some wells, but several wells that had Fe(II)/Cr(VI) concentrations more than the stoichiometric ratio (3:1) of the reduction reaction also had appreciable concentration of Cr(VI). This could partly be due to the oxidation of Fe(II) to Fe(III) by DO. It appears that the occurrence of Mn more than the Fe(II) concentration was also responsible for the presence of Cr(VI). Other reasons could be the Fe(II) complexation by organic ligands and the loss of reducing capacity of Fe(II) due to aquifer materials, but could not be established in this study.     

Chromium speciation in a contaminated groundwater: redox processes and temporal variability

Chromium species (Cr(III), Cr(VI), and Cr(III)-organic) in groundwater of a tannery contaminated area were monitored during pre- and post-monsoon seasons for a period of 3 years (May 2004 to January 2007). The objectives of the study were (1) to investigate the temporal variation of chromium species and other matrix constituents and (2) to study the redox processes associated with the temporal variation of chromium species. Samples were collected from 15 dug wells and analyzed for chromium species and other constituents. The results showed that the groundwater was relatively more oxidizing during post-monsoon periods than the pre-monsoon periods. Except one sample, the concentration of chromium species were found in the order of Cr(VI)>Cr(III)>Cr(III)-organic complexes during all the pre- and post-monsoon periods. In most of the wells, the concentrations of Cr(III), Cr(VI), and Cr(III)-organic decreased during post-monsoon periods compared to their pre-monsoon concentrations. However, the Cr(VI)/Cr_Total ratio still increased and the Cr(III)/Cr_Total ratio decreased during post-monsoon periods in most of the samples. The possible mechanisms for the temporal variation of chromium species were (1) Fe(II) reduction of Cr(VI) vs oxidation of Fe(II) by dissolved oxygen and (2) oxidation of Cr(III) by Mn(IV).     

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.     

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.     

Removal of hexavalent chromium from contaminated ground water using zero-valent iron nanoparticles

Batch experiments were conducted on ground water samples collected from a site contaminated with Cr(VI) to evaluate the redox potential of zero-valent iron (Fe⁰) nanoparticles for remediation of Cr(VI)-contaminated ground water. For this, various samples of contaminated ground water were allowed to react with various loadings of Fe⁰ nanoparticles for a reaction period of 60 min. Data showed 100% reduction of Cr(VI) in all the contaminated ground water samples after treatment with 0.20 gL⁻¹ of Fe⁰ nanoparticles. An increase in the reduction of Cr(VI) from 45% to 100% was noticed with the increase in the loading of Fe⁰ nanoparticles from 0.05 to 0.20 gL⁻¹. Reaction kinetics of Cr(VI) reduction showed pseudo first-order kinetics with rate constant in the range of 1.1 × 10⁻³ to 3.9 × 10⁻³ min⁻¹. This work demonstrates the potential utility of Fe⁰ nanoparticles in treatment and remediation of Cr(VI)-contaminated water source.     

Geochemical assessment of metal transport in glacial till during electrokinetic remediation

This paper presents the chemical speciation and retention behavior of chromium (Cr), nickel (Ni), and cadmium (Cd) prior to and after the electrokinetic remediation in glacial till soil. The speciation of the metals was predicted using the chemical speciation program MINEQL⁺. The simulations were performed for single-contaminant with only Cr(VI) or Ni, and multi-contaminants consisting of: (1) Cr(VI), Ni, and Cd; (2) Cr(III), Ni and Cd; (3) Cr(VI), Cr(III), Ni and Cd; (4) Cr(VI), Ni, and Cd with reducing agents; and (5) Cr(III), Ni, and Cd with oxidizing agent (Mn). The results showed that the speciation and distribution of cationic metals [Ni, Cd, and Cr(III)] in glacial till soil remain unaffected or slightly affected during electrokinetics. This is attributed to the high pH buffering capacity of the glacial till, leading the metals to precipitate in the soil prior to and after electrokinetics. This study showed that during electrokinetics, Cr(VI) existed as anionic complex and migrated towards the anode and the migration is maximum in case of a single-contaminant system. The study also showed that near the anode in the absence of any reducing and oxidizing agent, Cr(VI) mostly adsorbed, and some of Cr(VI) reduced to Cr(III) and migrated towards the cathode and finally precipitated due to high pH conditions. Ni and Cd remain adsorbed or precipitated due to the high pH conditions throughout the soil. Among the reducing agents, the sulfide had significant effect on the migration of metals compared to ferrous ions. While in the presence of oxidizing agent (Mn), no noticeable Cr(VI) was found in the soil sample indicating the reduction of Cr(VI) to Cr(III) and the predominance of reducing conditions due to the presence of naturally occurring iron in the glacial till soil. Overall, this study provides a reasonable explanation of the speciation and distribution of chromium, nickel and cadmium during the electrokinetic remediation of glacial till soil.     

Flow injection analysis of trace chromium (VI) in drinking water with a liquid waveguide capillary cell and spectrophotometric detection

Hexavalent chromium (Cr(VI)) is an acknowledged hazardous material in drinking waters. As such, effective monitoring and assessment of the risks posed by Cr(VI) are important analytical objectives for both human health and environmental science. However, because of the lack of highly sensitive, rapid, and simple procedures, a relatively limited number of studies have been carried out in this field. Here we report a simple and sensitive analytical procedure of flow injection analysis (FIA) for sub-nanomolar Cr(VI) in drinking water samples with a liquid core waveguide capillary cell (LWCC). The procedure is based on a highly selective reaction between 1, 5-diphenylcarbazide and Cr(VI) under acidic conditions. The optimized experimental parameters included reagent concentrations, injection volume, length of mixing coil, and flow rate. Measurements at 540 nm, and a 650-nm reference wavelength, produced a 0.12-nM detection limit. Relative standard deviations for 1, 2, and 10 nM samples were 5.6, 3.6, and 0.72 % (n?=?9), and the analysis time was <2 min sample^?1. The effects of salinity and interfering ions, especially Fe(III), were evaluated. Using the FIA-LWCC method, different sources of bottled waters and tap waters were examined. The Cr(VI) concentrations of the bottled waters ranged from the detection limit to ～20 nM, and tap waters collected from the same community supply had Cr(VI) concentration around 14 nM.     

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.     

Bio-concentration of chromium—an <Emphasis Type="Italic">in situ</Emphasis> phytoremediation study at South Kaliapani chromite mining area of Orissa,India

Mine waste water at South Kaliapani usually contains toxic levels of hexavalent Cr(VI). The present in situ study was conducted at South Kaliapani chromite mine area in Orissa state, India, to assess the phytoremediation ability of three plants, namely, rice (Oryza sativa L.), paragrass (Brachiaria mutica), and an aquatic weed (Eichhornia crassipes), in attenuating Cr(VI) from mine waste water and to correlate the bio-concentration factors (BCF) of Cr. Water hyacinth (E. crassipes) showed 24% to 54% reduction whereas paragrass (B. mutica) was able to reduce 18% to 33% of Cr(VI) from mine water. This reduction was studied over a period of 100 days of plant growth. The reduction was observed through a passage of a sum total of 2,000 sq. ft. cultivated plots and ponds separately. Reduction in Cr(VI) content in mine water varies with plant age as well as with the distance of passage. Cr accumulation and BCF values increased with high soil Cr levels as well as the age of plants. High BCF and transportation index (Ti) values, i.e., 10,924 and 32.09, respectively, were noted for water hyacinth. The Ti values indicated that the root-to-shoot translocation of Cr was very high after 100 days of growth. The total accumulation rate was maximum (8.29 mg Cr kg dry biomass^− 1 day ^− 1) in paragrass. The BCF values for roots were noted to be higher than those of leaves, stems, and grains of the 125-day-old plants. Hence, paragrass and water hyacinth may be used as tools of phytoremediation to combat the problem of in situ Cr contamination.     

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.     

A study on hexachromic ion selective electrode based on supported liquid membranes

An ion selective electrode (ISE) for determining Cr(VI) using supported liquid membranes (SLMs) containing trioctylphosphine oxide (TOPO) was investigated in this study. TOPO, as a carrier, had a high selectivity for Cr(VI) against interfering ions such as sulfate, nitrate, nitrite, and chloride. The composition of the SLM was optimized as 0.193 g TOPO/1 mL NPOE (o-nitrophenyl octyl ether)/0.5 g poly (vinyl chloride) for detection of Cr(VI). The Cr(VI) concentration was measured in the range of1 × 10^-3 to 1 × 10^-6 M with the SLM prepared in the study. It seemed that Cr(VI) was transported in the SLM as a triply charged ion indicated by the slope of the emf response. Selectivity coefficients and detection limits of Cr(VI) in the presence of interfering ions were determined experimentally using the fixed interference method.     

Chromium (VI) biosorption properties of multiple resistant bacteria isolated from industrial sewerage

Chromium (VI) [Cr (VI)] biosorption by four resistant autochthonous bacterial strains was investigated to determine their potential for use in sustainable marine water-pollution control. Maximum exchange between Cr (VI) ions and protons on the cells surfaces were at 30–35 °C, pH?2.0 and 350–450 mg/L. The bacterial strains effectively removed 79.0–90.5 % Cr (VI) ions from solution. Furthermore, 85.3–93.0 % of Cr (VI) ions were regenerated from the biomasses, and 83.4–91.7 % of the metal was adsorbed when the biomasses was reused. Langmuir isotherm performed better than Freundlich isotherm, depicting that Cr (VI) affinity was in the sequence Rhodococcus sp. AL03Ni?>?Burkholderia cepacia AL96Co?>?Corynebacterium kutscheri FL108Hg?>?Pseudomonas aeruginosa CA207Ni. Biosorption isotherms confirmed that Rhodococcus sp. AL03Ni was a better biosorbent with a maximum uptake of 107.46 mg of Cr (VI) per g (dry weight) of biomass. The results highlight the high potential of the organisms for bacteria-based detoxification of Cr (VI) via biosorption.     

Reduction and immobilization of chromium(VI) by nano-scale Fe0 particles supported on reproducible PAA/PVDF membrane

A new class of nano-scale Fe0 particles (NZVI) supported on a PAA/PVDF membrane (NZVI-PAA/PVDF) were synthesized and the feasibility of using NZVI-PAA/PVDF for reductive immobilization of Cr(VI) in water was investigated through laboratory batch tests. The results showed that the Cr(VI) removal capacity of NZVI-PAA/PVDF was 181 mg Cr/g Fe at an initial Cr(VI) concentration of 20 mg L(-1) under pH 6.5 +/- 0.1. XPS results showed that Cr(VI) was converted to nontoxic Cr(III). Interfering ions exerted various degrees of impact on NZVI-PAA/PVDF's Cr(VI) removal capacity. Specifically, Ca2+ alone showed the mildest impact while the presence of ions (Mg2+ and HCO3-) exerted the greatest impact. An advantage of NZVI-PAA/PVDF is that the nano-scale Fe0 and resultant particles were combined within a PAA/PVDF membrane, which prevents secondary pollution. Moreover, a piece of PAA/PVDF membrane (4.7 cm diameter) can still support 6.51 mg of nano-scale Fe0 particles after being renewed.     

Sampling and analysis considerations for the determination of hexavalent chromium in workplace air

Airborne hexavalent chromium (Cr[VI]) is a known human respiratory carcinogen and allergen. Workers in a variety of industries may be exposed to airborne hexavalent chromium, with exposures frequently occurring via inhalation and/or dermal contact. Analytical methods for the measurement of Cr(VI) compounds in workplace samples, rather than for the determination of total elemental chromium in workplace air, are often desired because exposure limit values for Cr(VI) compounds are much lower than for total Cr. For years, sampling and analytical test methods for airborne Cr(VI) have been investigated so as to provide means for occupational exposure assessment to this highly toxic species. Inter-conversion of trivalent chromium (Cr[III]) and Cr(VI) can sometimes occur during sampling and sample preparation, and efforts to minimize unwanted redox reactions involving these chromium valences have been sought. Because of differences in toxicity, there is also interest in the ability to differentiate between water-soluble and insoluble forms of Cr(VI), and procedures that provide solubility information concerning Cr(VI) compounds have been developed. This paper reviews the state of the art concerning the measurement of airborne Cr(VI) compounds in workplace aerosols and related samples.     

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.     

MODELING NITROGEN UPTAKE AND POTENTIAL NITRATE LEACHING UNDER DIFFERENT IRRIGATION PROGRAMS IN NITROGEN-FERTILIZED TOMATO USING THE COMPUTER PROGRAM NLEAP

Readily available nitrogen (N) sources such as ammonium nitrate with excessive irrigation present a potential hazard for the environment. The computer program Nitrate Leaching and Economic Analysis Package (NLEAP) is a mechanistic model developed for rapid site-specific estimates of nitrate-nitrogen (NO₃-N) moving below the root zone in agricultural crops and potantial impacts of NO₃-N leaching into groundwater. In this study, the value of NLEAP was tested to simulate N uptake by crops and NO₃-N leaching parameters in large lysimeters under the tomato crop. Three seedlings of tomato variety of H-2274 (Lycopersicum esculentum L.) were transplanted into each lysimeter. N fertilizer at the rate of 140 kg N ha^–1 was sidedressed in two split applications, the first half as ammonium sulphate and the second half as ammonium nitrate. The lysimeters were irrigated based on programs of C 0.75, 1.00, 1.25 and 1.50, C referring to class A-Pan evaporation coefficients. Parameters such as leaching index (LI), annual leaching risk potential (ALRP), N available for leaching (NAL), amount of NO₃-N leached (NL) and amount of N taken up by the crops (NU) were estimated using the NLEAP computer model. To test the ability of model to simulate N uptake and NL, measured values were compared with simulated values. Significant correlations, R² = 0.92 and P < 0.03 for the first year and R² = 0.86 and P < 0.06 for the second year, were found between measured and simulated values for crop N consumption, indicating that the NLEAP model adequately described crop N uptake under the varied irrigation programs using an optimal N fertilization program for the experimental site. Significant correlations, R² = 0.96 and P < 0.01 for the first year and R² = 0.97 and P < 0.01 for the second year, were also found between measured and simulated values of NL, indicating that the NLEAP model also adequately predicted NL under the varied irrigation programs. Therefore, this computer model can be useful to estimate the NO₃-N moving beyond the root zone under conditions in which the present experiment was carried out. Also, the NLEAP-estimated NAL values and other parameters can also be used to improve N management practices and N fertilizer recommendations that will help to decrease the adverse effect of N fertilizer on groundwater quality and farm profitability.     

Fractionation and potential mobility of trace metals in Danube alluvial aquifer within an industrialized zone

Thirty-five alluvial sediments of the River Danube and 12 groundwater samples were taken within the Pan?evo Oil Refinery (Serbia). The results for groundwater samples exceed European primary drinking water standards for Fe (obtained results, >200 μg/l) and Mn (obtained results, >50 μg/l), while the levels of the trace metals are below the thresholds for drinking water quality. Sediments were treated by sequential extraction procedure with five different solutions, each having a higher extraction capacity than the previous one. We also wanted to determine the possible relationships among trace metals and between sediment properties and elemental concentrations. These solutions partitioned metals into CH₃COONH₄ extractable (F1); HCl carbonate extractable and NH₂OH·HCl easily reducible (F2); (NH₄)₂C₂O₄/H₂C₂O₄ moderately reducible (F3); H₂O₂–HNO₃ organic/sulfide extractable fractions (F4); and HCl acid-soluble residue (F5). The sum of trace metals Ni, Pb, Cu, and Zn associated with the first two fractions (exchangeable, carbonate, and easily reducible) is significant and extremely important because it represents the proportion of heavy metals that can be easily remobilized by changes in environmental conditions such as pH, redox potential, salinity, etc. Sediments located nearer the groundwater flow are exposed to stronger groundwater fluctuation and had a higher quantity of amorphous and less stable substrates of trace metals. Principal component analysis was used to understand and visualize the associations between the trace metals and certain geological forms within analyzed sediments. The observed association between Cr with total sulfur and Mn from the acid-soluble residue could indicate that Cr is in the form of reduced, less toxic Cr(III), which is from the ecochemical point of view very important.     

Assessment of phenol infiltration resilience in soil media by HYDRUS-1D transport model for a waste discharge site

The movement of contaminants through soil imparts a variety of geo-environmental problem inclusive of lithospheric pollution. Near-surface aquifers are often vulnerable to contamination from surface source if overlying soil possesses poor resilience or contaminant attenuation capacity. The prediction of contaminant transport through soil is urged to protect groundwater from sources of pollutants. Using field simulation through column experiments and mathematical modeling like HYDRUS-1D, assessment of soil resilience and movement of contaminants through the subsurface to reach aquifers can be predicted. An outfall site of effluents of a coke oven plant comprising of alarming concentration of phenol (4–12.2 mg/L) have been considered for studying groundwater condition and quality, in situ soil characterization, and effluent characterization. Hydrogeological feature suggests the presence of near-surface aquifers at the effluent discharge site. Analysis of groundwater of nearby locality reveals the phenol concentration (0.11–0.75 mg/L) exceeded the prescribed limit of WHO specification (0.002 mg/L). The in situ soil, used in column experiment, possess higher saturated hydraulic conductivity (K _S ?=?5.25?×?10^?4 cm/s). The soil containing 47 % silt, 11 % clay, and 1.54 % organic carbon content was found to be a poor absorber of phenol (24 mg/kg). The linear phenol adsorption isotherm model showed the best fit (R ²?=?0.977, RMSE?=?1.057) to the test results. Column experiments revealed that the phenol removal percent and the length of the mass transfer zone increased with increasing bed heights. The overall phenol adsorption efficiency was found to be 42–49 %. Breakthrough curves (BTCs) predicted by HYDRUS-1D model appears to be close fitting with the BTCs derived from the column experiments. The phenol BTC predicted by the HYDRUS-1D model for 1.2 m depth subsurface soil, i.e., up to the depth of groundwater in the study area, showed that the exhaustion point was reached within 12 days of elapsed time. This clearly demonstrated poor attenuation capacity of the soil to retard migration of phenol to the groundwater from the surface outfall site. Suitable liner, based on these data, may be designed to inhibit subsurface transport of phenol and thereby to protect precious groundwater from contamination.     

Comparison of Groundwater Level Estimation Using Neuro-fuzzy and Ordinary Kriging

Water level in aquifer plays the main role in groundwater modeling as one of the input data. In practice, due to aspects of time and cost, data monitoring of water levels is conducted at a limited number of sites, and interpolation technique such as kriging is widely used for estimation of this variable in unsampled sites. In this study, the efficiency of the ordinary kriging (OK) and adaptive network-based fuzzy inference system (ANFIS) was investigated in interpolation of groundwater level in an unconfined aquifer in the north of Iran. The results showed that ANFIS model is more efficient in estimating the groundwater level than OK.     

Statistical source identification of metals in groundwater exposed to industrial contamination

Levels of selected metals Na, Ca, Mg, K, Fe, Mn, Cr, Co, Ni, Cd, Pb and Mn were estimated by flame atomic absorption spectrophotometry in groundwater samples from Kasur, a significant industrial city of Pakistan. Salient mean concentration levels were recorded for: Na (211 mg/l), Ca (187 mg/l), Mg (122 mg/l), K (87.7 mg/l), Fe (2.57 mg/l) and Cr (2.12 mg/l). Overall, the decreasing metal concentration order was: Na > Ca > Mg > K > Fe > Cr > Zn > Co > Pb > Mn > Ni > Cd. Significantly positive correlations were found between Na–Cr (r = 0.553), Na–Mn (r = 0.543), Mg–Fe (r = 0.519), Mg–Cr (r = 0.535), Pb–K (r = 0.506) and Pb–Ni (r = 0.611). Principal Component Analysis and Cluster Analysis identified tannery effluents as the main source of metal contamination of the groundwater. The present metal data showed that Cr, Pb and Fe levels were several times higher than those recommended for water quality by WHO, US-EPA, EU and Japan. The elevated levels of Cr, recorded as 21–42 fold higher compared with the recommended quality values, were believed to originate from the tanning industry of Kasur.