Chemometric application in classification and assessment of monitoring locations of an urban river system.

The study presents the application of selected chemometric techniques: cluster analysis, principal component analysis, factor analysis and discriminant analysis, to classify a river water quality and evaluation of the pollution data. Seventeen stations, monitored for 16 physical and chemical parameters in 4 seasons during the period 1999-2003, located at the Bagmati river basin in Kathmandu Valley, Nepal were selected for the purpose of this study. The results allowed, determining natural clusters of monitoring stations with similar pollution characteristics and identifying main discriminant variables that are important for regional water quality variation and possible pollution sources affecting the river water quality. The analysis enabled to group 17 monitoring sites into 3 regions with 5 major discriminating variables: EC, DO, CL, NO(2)N and BOD. Results revealed that some locations were under the high influence of municipal contamination and some others under the influence of minerals. This study demonstrated that chemometric method is effective for river water classification, and for rapid assessment of water qualities, using the representative sites; it could serve to optimize cost and time without losing any significance of the outcome.

Application of water quality indices and dissolved oxygen as indicators for river water classification and urban impact assessment.

The usefulness of water quality indices, as the indicators of water pollution, for assessment of spatial-temporal changes and classification of river water qualities was verified. Four water quality indices were investigated: WQI (considering 18 water quality parameters), WQI(min) and WQI(m) (considering five water quality parameters: temperature, pH, DO, EC and TSS) and WQI(DO) (considering a single parameter, DO). The water quality indices WQI(min), WQI(m) and WQI(DO) could be of particular interest for the developing countries because of the minimum analytical cost involved. As a case study, water quality indices were used to evaluate spatial and temporal changes of the water quality in the Bagmati river basin (Nepal) for the study period 1999-2003. The results allowed us to determine the serious negative effects of the city urban activity on the river water quality. In the studied section of the river, the water quality index (WQI) was 71 units (classified as good) at the entry station and 47.6 units (classified as bad) at the outlet station. For the studied period, a significant decrease in water quality (mean WQI decrease = 11.6%, p = 0.042) was observed in the rural areas. A comparative analysis revealed that the urban water quality was significantly bad as compared with rural. The analysis enabled to classify the water quality stations into three groups: good water quality, medium water quality and bad water quality. WQI(min) resulted in overestimation of the water quality but with similar trend as with WQI and is useful for the periodic routine monitoring program. The correlation of WQI with WQI(min) and DO resulted two new indices WQI(m) and WQI(DO), respectively. The classification of waters based on WQI(m) and WQI(DO) coincided in 90 and 93% of the samples, respectively.

Spectroscopic investigation of Cr(III)- and Cr(VI)-treated nanoscale zerovalent iron.

The reaction of hexavalent chromium (Cr(VI)) with zerovalent iron (Fe0) during soil and groundwater remediation is an important environmental process. This study used several techniques including X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy to investigate nanometer scale Fe0 particles (nano Fe0) treated with Cr(III) and Cr(VI). X-ray diffraction and XPS analyses of oxidized nano Fe0 showed the crystalline Fe(III) phase is composed of lepidocrocite (gamma-FeOOH). Results of XPS Cr 2p data and Cr K-edge X-ray absorption near edge spectroscopy (XANES) provided evidence that Cr(VI) was entirely reduced to Cr(III) by nano Fe0 with no residual Cr(VI) after reaction. In addition, XPS and XANES results of Cr(III) precipitated as Cr(OH)3 in the presence of corroding nano Fe0 were nearly identical to the Cr(VI)-nano Fe0 reaction product. Detailed analysis of XPS O 1s line spectra revealed that both Cr(III)- and Cr(VI)-treated nano Fe0 yielded a predominantly hydroxylated Cr(OH)3 and/ or a mixed phase CrxFe(1 - x)(OH)3 product. The structure of the Cr(III)- and Cr(VI)-treated nano Fe0 determined using extended X-ray absorption fine structure spectroscopy (EXAFS) revealed octahedral Cr(III) with Cr-O interatomic distances between 1.97 and 1.98 A for both Cr(III) and Cr(VI) treatments and a pronounced Cr-Cr second interatomic shell at 3.01 A. Our results suggest that the reaction product of Cr(VI)-treated nano Fe0 is either a poorly ordered Cr(OH)3 precipitate or possibly a mixed phase CrxFe(1 - x)(OH)3 product, both of which are highly insoluble under environmental conditions.

Spatial-temporal variation and comparative assessment of water qualities of urban river system: a case study of the river Bagmati (Nepal).

The study presents the assessment of variation of water qualities, classification of monitoring networks and detection of pollution sources along the Bagmati River and its tributaries in the Kathmandu valley of Nepal. Seventeen stations, monitored for 23 physical and chemical parameters in pre-monsoon, monsoon, post-monsoon and winter seasons, during the period 1999-2003, were selected for the purpose of this study. The study revealed that the upstream river water qualities in the rural areas were increasingly affected from human sewage and chemical fertilizers. In downstream urban areas, the river was heavily polluted with untreated municipal sewage. The contribution of industries to pollute the river was minimal. The higher ratio of COD to BOD (3.74 in the rural and 2.06 in the urban) confirmed the increased industrial activities in the rural areas. An increasing trend of nitrate was found in the rural areas. In the urban areas, increasing trend of phosphorus was detected. The water quality measurement in the study period showed that DO was below 4 mg/l and BOD, COD, TIN, TP and TSS above 39.1, 59.2, 10.1, 0.84 and 199 mg/l, respectively, in the urban areas. In the rural areas, DO was above 6.2 mg/l and BOD, COD, TIN, TP and TSS below 15.9, 31, 5.24, 0.41 and 134.5 mg/l, respectively. The analysis for data from 1988 to 2003 at a key station in the river revealed that BOD was increasing at a rate of 1.8 mg/l in the Bagmati River. A comparative study for the water quality variables in the urban areas showed that the main river and its tributaries were equally polluted. The other comparison showed the urban water qualities were significantly poor as compared with rural. The cluster analysis detected three distinct monitoring groups: (1) low water pollution region, (2) medium water pollution region, (3) heavy water pollution region. For rapid assessment of water qualities using the representative sites could serve to optimize cost and time without loosing any significance of the outcome. The factor analysis revealed distinct groups of sources and pollutions (organics, nutrients, solutes and physicochemical).

Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material.

The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. Mössbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation.

Removal of arsenic(III) from groundwater by nanoscale zero-valent iron.

Nanoscale zero-valent iron (NZVI) was synthesized and tested for the removal of As(III), which is a highly toxic, mobile, and predominant arsenic species in anoxic groundwater. We used SEM-EDX, AFM, and XRD to characterize particle size, surface morphology, and corrosion layers formed on pristine NZVI and As(III)-treated NZVI. AFM results showed that particle size ranged from 1 to 120 nm. XRD and SEM results revealed that NZVI gradually converted to magnetite/maghemite corrosion products mixed with lepidocrocite over 60 d. Arsenic(III) adsorption kinetics were rapid and occurred on a scale of minutes following a pseudo-first-order rate expression with observed reaction rate constants (K(obs)) of 0.07-1.3 min(-1) (at varied NZVI concentration). These values are about 1000x higher than K(obs) literature values for As(III) adsorption on micron size ZVI. Batch experiments were performed to determine the feasibility of NZVI as an adsorbent for As(III) treatment in groundwater as affected by initial As(III) concentration and pH (pH 3-12). The maximum As(III) adsorption capacity in batch experiments calculated by Freundlich adsorption isotherm was 3.5 mg of As(III)/g of NZVI. Laser light scattering (electrophoretic mobility measurement) confirmed NZVI-As(III) inner-sphere surface complexation. The effects of competing anions showed HCO3-, H4SiO4(0), and H2P04(2-) are potential interferences in the As(III) adsorption reaction. Our results suggest that NZVI is a suitable candidate for both in-situ and ex-situ groundwater treatment due to its high reactivity.