Chromium redox speciation in natural waters

Dissolved hexavalent chromium concentrations were determined in river, estuarine and coastal waters of the Humber catchment in north-east England. Samples were collected, filtered, extracted on site and after storage for up to eight days. Hexavalent chromium concentrations did not change by more than 0.05 microg l(-1) (not significant, p = 0.05) over this period. Total chromium concentrations in the catchment were less than 1.0 microg l(-1). This is low in relation to the proposed Environmental Quality Standard. Hexavalent chromium accounted for between 27% and 100% of the total dissolved concentration, with an average of approximately 50%. The proportion of Cr(III) and Cr(VI) in the rivers and estuary were of the same range as previously measured in 1993. The addition of Cr(III) and Cr(VI) to fresh and saline water samples illustrates the complexity of the factors controlling chromium speciation in natural waters. The presence of oxidisable organic matter and the stabilising role of complexing organic ligands are proposed as the main controlling influences of redox speciation in filtered samples.     

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 fractionation and speciation in natural waters

It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 μg L(-1). Cr(vi) was always below of the DL (0.3 μg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.     

Effect of contaminated groundwater on tree growth: A tree-ring analysis

A study was conducted of the effect of contaminated groundwater seepage on tree growth downslope from the F- and H-Area seepage basins of the Department of Energy's Savannah River Site in South Carolina. Trees in wetlands along Four Mile Creek began to show localized stress and mortality in the late 1970s. Extreme winter temperatures and high rainfall were ruled out as potential causal factors of tree stress. Drought was shown to affect trees in both contaminated and uncontaminated zones, but trees in uncontaminated areas exhibited better recovery after drought than trees in contaminated areas. Pollution-mediated alteration of soil acidity and aluminum, sodium, and heavy metal concentrations likely acted to predispose trees to decline, with severe drought acting as the trigger for decline initiation and tree death. Thus, a moderate pollution loading, not sufficient to cause visible damage of itself, may create conditions in which sudden, severe decline could result from natural stresses. This mechanism of forest decline may be common, and should be considered in evaluations of the impact of pollution on wetland forest systems.     

Hydrogeochemical characterization of contaminated groundwater in Patancheru industrial area,southern India

The groundwater is one of the most contaminated natural resources in Patancheru industrial area due to unplanned and haphazard industrial growth and urbanization without following basic pollution control norms. The rapid industrialization initiated in early 1970 has started showing up its after effects few years later in the form of physiochemical contamination of the both surface and groundwater bodies of the area. It has resulted in local people being deprived of safe drinking water, plant and aquatic life has severely affected, and situation is deteriorating over the years in the area in spite of some preventive and remedial measures being initiated. The focus of the present study is to understand the chemical characteristics of groundwater and geochemical processes the contaminant water is undergoing which are normally imprinted in its ionic assemblages. The water samples collected in pre- and post-monsoon seasons from forty two groundwater and four surface water sources were analyzed for major constituents such as Ca²⁺, Mg²⁺, Na⁺, K⁺, CO₃⁻, HCO₃⁻, Cl⁻, SO₄²⁻, NO₃⁻, and F⁻, and selected samples were tested for ten important trace metals like Fe, Pb, Bi, Mn, Cr, Co, Ni, Cu, Zn, and Cd. Na⁺ among cations and Cl⁻ among anions dominate the water in both the seasons where as Ca²⁺, HCO₃⁻, and Cl⁻ show significant reduction in their ionic strength in post-monsoon. The groundwater in general is of mixed type, but most of it belong to Na⁺–Cl⁻, Na⁺–HCO₃⁻, Ca²⁺–Mg²⁺–HCO₃⁻, and Ca²⁺–Mg²⁺–Cl⁻ facies. The Na⁺ and Ca²⁺ are in the transitional state with Na⁺ replacing Ca²⁺ and HCO₃⁻–Cl⁻ due to physiochemical changes in the aquifer system. The evaluation of hydrochemistry through various ionic indices, ratios, and plots suggest that silicate–carbonate weathering, ion exchange, dissolution, and evaporation processes are responsible for origin of the present chemical status of the groundwater which is also controlled by the contamination from extraneous sources that could have accelerated the dissolution processes. Gibbs plots authenticate that the evolution of water chemistry is influenced by interaction of percolating water with aquifer matrix apart from anthropogenic enrichment of elements which get over concentrated due to evaporation.     

Chromium speciation and fractionation in ground and surface waters in the vicinity of chromite ore processing residue disposal sites

Chromium concentrations of up to 91 mg l(-1) were found by ICP-OES for ground water from nine boreholes at four landfill sites in an area of S.E. Glasgow/S. Lanarkshire where high-lime chromite ore processing residue (COPR) from a local chemical works had been deposited from 1830 to 1968. Surface water concentrations of up to 6.7 mg l(-1) in a local tributary stream fell to 0.11 mg l(-1) in the River Clyde. Two independent techniques of complexation/colorimetry and speciated isotope dilution mass spectrometry (SIDMS) showed that Cr was predominantly (>90%) in hexavalent form (CrVI) as CrO4(2-), as anticipated at the high pH (7.5-12.5) of the sites. Some differences between the implied and directly determined concentrations of dissolved CrIII, however, appeared related to the total organic carbon (TOC) content. This was most significant for the ground water from one borehole that had the highest TOC concentration of 300 mg l(-1) and at which < 3% of Cr was in the form of CrVI. Subsequent ultrafiltration produced significant decreases in Cr concentration with decreasing size fractions, e.g. <0.45 microm, < 100 kDa, <30 kDa and < 1 kDa by the tangential-flow method. As this appeared related more to concentrations of humic substances than of TOC per se, horizontal bed gel electrophoresis of freeze-dried ultrafilter retentates was carried out to further characterise the CrIII-organic complex. This showed for the main Cr-containing fraction, 100 kDa-0.45 microm, that the Cr was associated with a dark brown band characteristic of organic (humic) matter. Comparison of gel electrophoresis and FTIR results for ultrafilter retentates of ground water from this borehole with those for a borehole at another site where CrVI predominated suggested the influence of carboxylate groups, both in reducing CrVI and in forming soluble CrIII-humic complexes. The implications of this for remediation strategies (especially those based on the addition of organic matter) designed to reduce highly mobile and carcinogenic Cr(VI)O4(2-) to the much less harmful CrIII as insoluble Cr(OH)3 are discussed.     

Spatial and temporal variability in the relationship between cyanobacterial biomass and microcystins

The increasing incidence of toxic cyanobacterial blooms, together with the difficulties to reliably predict cyanobacterial toxin (e.g. microcystins) concentration, has created the need to assess the predictive ability and variability of the cyanobacterial biomass–microcystin relationship, which is currently used to assess the risk to human and ecosystems health. To achieve this aim, we assessed the relationship between cyanobacterial biomass and microcystin concentration on a spatiotemporal scale by quantifying the concentration of cyanobacterial biomass and microcystin in eight lakes over 9 months. On both a temporal and spatial scale, the variability of microcystin concentration exceeded that of cyanobacterial biomass by up to four times. The relationship between cyanobacterial biomass and microcystin was weak and site specific. The variability of cyanobacterial biomass only explained 25 % of the variability in total microcystin concentration and 7 % of the variability of cellular microcystin concentration. Although a significant correlation does not always imply real cause, the results of multiple linear regression analysis suggest that the variability of cyanobacterial biomass and cellular microcystin concentration is influenced by salinity and total phosphorus, respectively. The weak cyanobacterial biomass–microcystin relationship, coupled with the fact that microcystin was present in concentrations exceeding the WHO drinking water guidelines (1 μg?L^?1) in most of the collected samples, emphasizes the high risk of error connected to the traditional indirect microcystin risk assessment method.     

Causes of temporal variability of lead in domestic plumbing systems

Sources of lead in drinking water are primarily lead pipe, lead/tin solder, and brass fixture materials.Lead levels in the water depend upon many solubility factors, such as pH, concentrations of substances such as inorganic carbonate, orthophosphate, chlorine, and silicate, the temperature, the nature of the pipe surface, etc. Physical factors, time, and chemical mass transfer are significant in governing lead levels in nonequilibrium systems. The diameter and length of lead pipe is extremely important, as well as the age and chemical history of the solder and brass fixtures. Analytical variability is not particularly significant relative to between-site and within-site variability. Knowledge of temporal variability at each site is necessary to define a statistically valid monitoring program. An analysis of published data covering repetitive measurements at a given site show that the variability of lead concentration at each site tends to be characterized by the frequent occurrence of spikes. Variability expressed as approximate relative standard deviations tends to be of about 50 to 75% in untreated water, regardless of the mean lead concentration. The distributions are frequently nonnormal for small numbers of samples. Monitoring programs must incorporate controls for the causes of the within-site and between-site variability into their sampling design. The determination of necessary sampling frequency, sample number, and sample volume must be made with consideration of the system variability, or the results will be unrepresentative and irreproducible.     

Network design factors for assessing temporal variability in ground-water quality

Benchmark major ions and nutrients data were collected biweekly for about two years at 12 wells at two sites in a shallow sand and gravel aquifer in west-central Illinois. The purpose of the study was to explore the time series properties of ground-water quality data collected at a relatively high sampling frequency. A secondary purpose was to determine the relative magnitudes of natural and sampling-related sources of variance in ground-water quality time series. The absence of this kind of information has severely hindered the design of ground-water sampling programs in the past.An autocorrelation analysis showed that the median sampling frequency for which the predicted ratio of effective independent sample size to total sample size was 0.5 (50% sampling redundancy) ranged from 6 to 14 samples per year. For a predicted ratio of effective independent sample size to total sample size of 0.9 (10% sampling redundancy) the sampling frequency ranged from 3 to 6 samples per year. This suggests that, for the wells sampled, sampling frequencies much higher than monthly can result in considerable loss of information, and may not be cost effective. Care was taken in the design of the field and laboratory sampling protocol to minimize the effects of measurement error. The data analysis confirmed that this goal was accomplished. In most cases considerably less than five percent of the total variability could be attributed to sampling and analytical error. Because of the relatively short duration of the study (42 biweekly sampling occasions at most wells) it was not possible to identify the magnitude of seasonal variations reliably.     

Efficacy of electrical resistivity and induced polarization methods for revealing fluoride contaminated groundwater in granite terrain

The accumulation of fluoride (F) in groundwater is a common phenomenon in India and worldwide. Its location can be identified through a direct hydrochemical analysis, which was carried out in Kurmapalli watershed (located 60 km SE of Hyderabad city), Nalgonda district, Andhra Pradesh, India affected by F contamination. The results of the hydrochemical analysis showed that F varied from 0.71 to 19.01 mg/l and its concentration exceeded the permissible limit (i.e., 1.5 mg/l) in 78% of the total 32 samples analyzed. The highest F value (19.01 mg/l) was found near Madnapur village, which is located in the central part of the watershed. Resistivity and induced polarization (IP) surveys were also carried out to reveal the zones where elevated F-contaminated groundwater exists. The objective of this paper was to highlight the utility of resistivity and IP surveys, using hydrochemical constituents as constraint, for the successful delineation of such contaminated/polluted groundwater zones in the granite area.     

a study of the temporal variability of atrazine in private well water. part ii: analysis of data

In 1988, the Iowa Department of Natural Resources, along withthe University of Iowa, conducted the Statewide Rural WellWater Survey, commonly known as SWRL. A total of 686private rural drinking water wells was selected by use of aprobability sample and tested for pesticides and nitrate. A subsetof these wells, the 10% repeat wells, were additionally sampledin October, 1990 and June, 1991. Starting in November, 1991,the University of Iowa, with sponsorship from the United StatesEnvironmental Protection Agency, revisited the 10% repeat wellsto begin a study of the temporal variability of atrazine and nitratein wells. Other wells, which had originally tested positive foratrazine in SWRL but were not in the 10% population, wereadded to the study population. Temporal sampling for a year-long period began in February of 1992 and concluded in Januaryof 1993. All wells were sampled monthly, a subset was sampledweekly, and a second subset was sampled for 14 day consecutiveperiods. Of the 67 wells in the 10% population tested monthly,7 (10.4%) tested positive for atrazine at least once during theyear, and 3 (4%) were positive each of the 12 months. Theaverage concentration in the 7 wells was 0.10 µg/L. Fornitrate, 15 (22%) wells in the 10% repeat population monthlysampling were above the Maximum Contaminant Level of 10 mg/L at least once. This paper, the second of two papers on thisstudy, describes the analysis of data from the survey. The firstpaper (Lorber et al., 1997) reviews the study design, theanalytical methodologies, and development of the data base.     

Microbiological characteristics of multi-media PRB reactor in the bioremediation of groundwater contaminated by petroleum hydrocarbons

A multi-media bio-PRB reactor was designed to treat groundwater contaminated with petroleum hydrocarbons. After a 208-day bioremediation, combined with the total petroleum hydrocarbons content in the groundwater flowed through the reactor, microbiological characteristics of the PRB reactor including microbes immobilized and its dehydrogenase activity were investigated. TPH was significantly reduced by as much as 65% in the back of the second media layer, whereas in the third layer, the TPH content reached lower than 1 mg l?1. For microbes immobilized on the media, the variations with depth in different media were significantly the same and the regularity was obvious in the forepart of the media, which increased with depth at first and then reduced gradually, while in the back-end, the microbes almost did not have any variations with depth but decreased with the distance. The dehydrogenase activity varied from 2.98 to 16.16 mg TF L?1 h?1 and its distribution illustrated a similar trend with numbers of microbial cell, therefore, the noticeable correlation was found between them.     

Fluorine contamination in groundwater: a major challenge

Fluoride in high concentration in groundwater has been reported from many parts of India. However, a systematic study is required to understand the behavior of fluoride in natural water in terms of local hydrogeological setting, climatic conditions, and agricultural practices. The present study is an attempt to assess hydrogeochemistry of groundwater in parts of Palar river basin pertaining to Kancheepuram district Tamil Nadu to understand the fluoride abundance in groundwater and to deduce the chemical parameters responsible for the dissolution activity of fluoride. The study area is geologically occupied by partly sedimentary and partly crystalline formations. A total of 50 dug cum borewell-water samples, representing an area of 2,628.92 km². The results of the chemical analyses in September 2009 show fluoride abundance in the range of 1 to 3.24 mg/l with 86% of the samples in excess of the permissible limit of 1.5 mg/l. Presence of fluoride-bearing minerals in the host rock, chemical properties like decomposition, dissociation, and dissolution, and their interaction with water are considered to be the main causes for fluoride in groundwater. Chemical weathering with relatively high alkalinity favors high concentration of fluoride in groundwater. Villagers who consume nonpotable high fluoride water may suffer from yellow, cracked teeth; joint pains; and crippled limbs and also age rapidly.     

Spatial variability and temporal changes in the trace metal content of soils: implications for mine restoration plan

Trace metals in soils may be inherited from the parent materials or added to the system due to anthropogenic activities. In proposed mining areas, trace metals become an integral part of the soil system. Usually, researchers undertake experiments on plant species selection (for the restoration plan) only after the termination of mining activities, i.e. without any pre-mining information about the soil-plant interactions. Though not shown in studies, it is clear that several recovery plans remain unsuccessful while carrying out restoration experiments. Therefore, we hypothesize that to restore the area effectively, it is imperative to consider the pre-mining scenario of metal levels in parent material as well as the vegetation ecology of the region. With these specifics, we examined the concentrations of trace metals in parent soils at three proposed bauxite locations in the Eastern Ghats, India, and compared them at a spatio-temporal scale. Vegetation quantification and other basic soil parameters accounted for establishing the connection between soil and plants. The study recorded significant spatial heterogeneity in trace metal concentrations and the role of vegetation on metal availability. Oxidation reduction potential (ORP), pH and cation exchange capacity (CEC) directly influenced metal content, and Cu and Ni were lithogenic in origin. It implies that for effective restoration plant species varies for each geological location.     

Spatial and temporal variability of metals in inter-tidal beach sediment of Mumbai, India

Nine metals were monitored in the beach sediment in Mumbai from May 2011 to March 2012 to evaluate the spatial and temporal distributions. The average heavy metal concentrations exhibited the following order: Fe > Mn > Cr > Co > Ni > Pb > Zn > Cu > Cd for the four sampling sites. The mean concentrations (± SD) of Fe, Mn, Cr, Co, Ni, Pb, Zn, Cu and Cd were estimated to be 31.15?±?10.02 g kg^?1, 535.04?±?76.42, 151.98?±?97.90, 92.76?±?14.18, 67.52?±?11.32, 59.57?±?15.19, 54.65?±?15.01, 32.24?±?8.07 and 18.75?±?1.76 mg kg^?1, respectively. The results indicated that the sediments were polluted with Cd, Cr, Co and Pb due to high anthropogenic influences. Spatial variation of metals revealed that most of the metals were high in Dadar beach and low in Aksa beach. Cd was the highest contaminant metal studied with a mean contamination factor of 93.75. The pollution load indices of the studied beaches ranged from 1.63 (Aksa) to 1.91 (Dadar) and indicated that the beach sediments were polluted with heavy metals. The heavy metal contents increased in relation to monsoon, and most of the heavy metals showed significantly high concentrations in November during the post-monsoon. The statistical analysis revealed significant effect of study site on all the metals studied. Further, there was a significant difference on metal accumulation on bimonthly basis in relation to weather pattern in Mumbai beaches.     

Factor analysis and linear regression model (LRM) of metal speciation and physico-chemical characters of groundwater samples

An approach is described for viewing the interrelationship between different variables and also tracing the sources of pollution of groundwater of north Chennai (India). The data set of 43 variables which include major ions, minor ions and trace metal speciation (Cu, Pb, Cd and Zn) collected during the pre-monsoon and post-monsoon seasons of the year 2000–2001, was subjected to R-mode factor analysis to comprehend the distribution pattern of the said variables. It was found that first factor measures salinity and hardness which explained 19.12% of the total variance (comprised of variables EC, TDS, Na⁺, K⁺, Ca²⁺, Mg²⁺, total hardness, Cl⁻ and SO₄ ²⁻) during pre-monsoon, while it was 25.08% during post-monsoon. The second and third factors were attributed to speciation of zinc and copper ions during both pre-monsoon and post-monsoon. Although there were two more factors, loaded with speciation parameters of lead and cadmium, the variance of them were less than 10%. From this study it is seen that sea water intrusion, municipal solid waste disposal are the identified sources of component of pollution. The importance of metal ions is taking a secondary role and the anthropogenic origin-industrial activity, is the reason in the evaluation of pollution status as they come in the second, third, fourth and fifth factors. As the trace metal speciation was grouped in separate factors, linear regression model (LRM) with correlation analysis was applied to check its validity for prediction of speciation and to apply LRM for rapid monitoring of water pollution.     

Determination of redox potential of sulfidic groundwater in unconsolidated sediments by long-term continuous in situ potentiometric measurements

This study was undertaken to investigate the redox potential (Eh) of sulfidic groundwater in unconsolidated sediments. The Eh was determined by long-term (several days to several weeks) continuous in situ potentiometric measurements using a platinum (Pt) electrode. The Eh values measured in two monitoring campaigns were ?259 and ?202 mV, respectively. Chemical analysis of groundwater showed that the redox species in the groundwater were sulfide (S^2???) and iron, respectively. The saturation indices calculated from the chemical analysis results indicated that FeS_(am) and mainly mackinawite were close to equilibrium in the analyzed waters. Comparison of the measured Eh values with those calculated using different redox couples revealed that the Eh values measured in the first monitoring campaign were nearly equal to those calculated using HS^???/SO $_{4}{^{2-}}$ , S^2???/SO $_{4}{^{2-}}$ , FeS $_{(\text{am})}$ /SO $_{4}{^{2-}}$ , and mackinawite/SO $_{4}{^{2-}}$ redox couples; on the other hand, the Eh values measured in the second monitoring campaign were almost consistent with those measured using the FeS₂/SO $_{4}{^{2-}}$ redox couple. The good fit between the measured Eh values and the theoretical calculated Eh values suggests that the sulfur system is related to the Eh value of sulfidic groundwater in unconsolidated sediments.     

Comparison of stochastic and deterministic methods for mapping groundwater level spatial variability in sparsely monitored basins

In sparsely monitored basins, accurate mapping of the spatial variability of groundwater level requires the interpolation of scattered data. This paper presents a comparison of deterministic interpolation methods, i.e. inverse distance weight (IDW) and minimum curvature (MC), with stochastic methods, i.e. ordinary kriging (OK), universal kriging (UK) and kriging with Delaunay triangulation (DK). The study area is the Mires Basin of Mesara Valley in Crete (Greece). This sparsely sampled basin has limited groundwater resources which are vital for the island’s economy; spatial variations of the groundwater level are important for developing management and monitoring strategies. We evaluate the performance of the interpolation methods with respect to different statistical measures. The Spartan variogram family is applied for the first time to hydrological data and is shown to be optimal with respect to stochastic interpolation of this dataset. The three stochastic methods (OK, DK and UK) perform overall better than the deterministic counterparts (IDW and MC). DK, which is herein for the first time applied to hydrological data, yields the most accurate cross-validation estimate for the lowest value in the dataset. OK and UK lead to smooth isolevel contours, whilst DK and IDW generate more edges. The stochastic methods deliver estimates of prediction uncertainty which becomes highest near the southeastern border of the basin.     

Hydrogeochemical processes controlling the high fluoride concentration in groundwater: a case study at the Boden block area,Orissa, India

The present investigation reports the assessment of hydrochemical/geochemical processes controlling the concentration of fluoride in groundwater of a village in India (Boden block, Orissa). Boden block is one of the severely affected fluoride-contaminated areas in the state of Orissa (India). The sampling and subsequent analysis of water samples of the study area was carried out following standard prescribed methods. The results of the analysis indicate that 36.60% groundwater F⁻ concentration exceeds the limit prescribed by the World Health Organization for drinking water. The rock interaction with groundwater containing high concentration of HCO₃⁻ and Na⁺ at a higher pH value of the medium could be one of the important reasons for the release of F⁻ from the aquatic matrix into groundwater. Geochemical classification of groundwater based on Chadha rectangular diagram shows that most of the groundwater samples having fluoride concentration more than 1.5 mg L⁻¹ belongs to the Na-K-HCO₃ type. The saturation index values evaluated for the groundwater of the study area indicated that it is oversaturated with respect to calcite, whereas the same is undersaturated with respect to fluorite content. The deficiency of calcium ion concentration in the groundwater from calcite precipitation favors fluorite dissolution leading to excess of fluoride concentration. The risk index was calculated as a function of fluoride level in drinking water and morbidity of fluorosis categorizes high risk for villages of Amera and Karlakote panchayat of Boden block.