A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.     

Mineralization of Catechol by Fenton and Photo‐Fenton Processes

Catechol is one of the most abundant phenolic components of olive mill wastewaters. In this article, the mineralization of this compound in synthetic aqueous solutions by the Fenton and photo‐Fenton processes is studied. It has been found that for 1.44 mM catechol, the total organic carbon of solutions is reduced about 94.4% at best after 60 min of Fenton treatment at optimized conditions of pH 3.0, 0.2 mM Fe²⁺, 7.09 mM H₂O₂, and 25°C. A faster and overall mineralization is attained by applying photo‐Fenton with UVA irradiation. o‐Benzoquinone, 1,2,3‐trihydroxybenzene and 1,2,4‐trihydroxybenzene were identified by GC–MS as primary quinonic and polyhydroxylated derivatives. Small amounts of generated carboxylic acids like muconic, maleic, malonic, acetic, oxalic, and formic acids were detected by ion‐exclusion chromatography. The Fe(III) complexes of these acids persist in the medium under Fenton conditions, while their photolysis by UVA light and that of other by‐products account for by the faster degradation and total mineralization achieved in the photo‐Fenton process. A reaction sequence for catechol mineralization by Fenton and photo‐Fenton involving all intermediates detected is proposed.     

Humic Substances as a Mediator for Microbially Catalyzed Metal Reduction

The potential for humic substances to serve as a terminal electron acceptor in microbial respiration and to function as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides was investigated. The Fe(III)-reducing microorganism Geobacter metallireducens conserved energy to support growth from electron transport to humics as evidenced by continued oxidation of acetate to carbon dioxide after as many as nine transfers in a medium with acetate as the electron donor and soil humic acids as the electron acceptor. Growth of G. metallireducens with poorly crystalline Fe(III) oxide as the electron acceptor was greatly stimulated by the addition of as little as 100 μM of the humics analog, anthraquinone-2,6-disulfonate. Other quinones investigated, including lawsone, menadione, and anthraquinone-2-sulfonate, also stimulated Fe(III) oxide reduction. A wide phylogenetic diversity of microorganisms capable of Fe(III) reduction were also able to transfer electrons to humics. Microorganisms which can not reduce Fe(III) could not reduce humics. Humics stimulated the reduction of structural Fe(III) in clay and the crystalline Fe(III) forms, goethite and hematite. These results demonstrate that electron shuttling between Fe(III)-reducing microorganisms and Fe(III) via humics not only accelerates the microbial reduction of poorly crystalline Fe(III) oxide, but also can facilitate the reduction of Fe(III) forms that are not typically reduced by microorganisms in the absence of humics. Addition of humic substances to enhance electron shuttling between Fe(III)-reducing microorganisms and Fe(III) oxides may be a useful strategy to stimulate the remediation of soils and sediments contaminated with organic or metal pollutants.     

Quantitative Separation of As(III) and As(V) from a Synthetic Water Solution Using Ion Exchange Columns in the Presence of Fe and Mn Ions

The quantitative separation of As(III) from a water sample containing As(III) and As(V) in the presence of Fe and Mn in an ion exchange resin (AG1 X8) column for the speciation of arsenic is described. Individual and combined effects of Fe and Mn on the separation of As(III) from the solution have been studied separately. In absence of Fe and Mn, the ratio between the As(T) concentration in the eluent and the As(III) concentration in the original sample has been found to be 0.9717 under optimum process conditions. The presence of Fe(II) in the water sample increased the As(T) concentration in the eluent whereas Mn(II) decreased it. Combined effects of Fe and Mn on the percentage increment in the eluent arsenic concentration have been expressed by additive and interactive models. The interactive model has been developed by a statistical software with a 95 % confidence level. In most of the cases the error on the determination of the As(III) concentration had a minimum when using the interactive model.     

Zum Einfluß des pH-Wertes und des Calciumgehaltes auf Metall-Fulvinsäure-Bindungen — Inversvoltammetrische und chemometrische Untersuchungen

The Influence of pH and Calcium Concentration on Metal-Fulvic Acid Bonds – Stripping Voltammetric and Chemometric Investigations. Electrochemically available metal concentrations of Cd, Cu and Zn were analyzed in dependence of different concentrations of calcium, fulvic acids and pH by Differential Pulse Anodic Stripping Voltammetry (DPASV). A statistical experimental design was the base to minimize the number of experiments and to include the multifarious interactions between the independent variables (Ca concentration, concentration of fulvic acids and the pH value) and otherwise the electrochemically available metal concentrations of Cd, Cu and Zn. At first analysis of experimental data was carried out by multiple linear regression. The main influence on available metal concentrations is the pH value especially for Cu. The Ca ion influence has not competitive effect and is only significant for Cd and Cu. It has an effect on the metal-fulvic acid-bonds. Two factor interactions exist for pH/fulvic acids and for Ca/fulvic acids too. The partial least squares regression (PLS) model was used to include the interactions between the metals Cd, Cu and Zn. For proving these two models the three parameters pH, Ca and fulvic acid were varied within the calibration range of the models and predicted values were compared with the experimental values. The approach with the PLS model is better than the approach with the multiple linear regression (normally used mathematical method of analysis of a factorial plan) with a relative error of 9.7% for modelling of Cd, 6.0% for Zn and 58% for Cu in relation to multiple linear regression with errors of 12% for Cd, 8.6% for Zn and 65% for Cu. The PLS modelling is a suited tool for modelling chemical interactions also in simulated natural matrices.     

Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio,Argentina

Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters.     

Effects of Fenton Pre‐Treatment on Waste Activated Sludge Properties

Fenton process was investigated for the purpose of biological sludge disintegration. The Box–Wilson experimental design was employed to evaluate the effects of major process variables (Fe(II) and H₂O₂ concentrations) on both disintegration and dewatering performance of sludge. Results showed that 4 g Fe(II)/kg total solids (TSs) and 60 g H₂O₂/kg TS are efficient for floc disintegration. Fenton pre‐treatment enhanced the biodegradability of sludge. For 4 g Fe(II)/kg TS and 60 g H₂O₂/kg TS, 19.4% higher methane production was achieved compared to raw sludge in biochemical methane potential assay. Fenton pre‐treatment resulted in the release of organic sludge components into the liquid phase. For 4 g Fe(II)/kg TS and 60 g H₂O₂/kg TS, dissolved organic carbon and total nitrogen in sludge's supernatant increased by 75.74 and 60.60%, respectively. Fenton pre‐treatment enhanced the filterability of sludge and it can be applied for conditioning purpose before mechanical dewatering units.     

A simple method for calculating growth rates of petroleum hydrocarbon plumes

Consumption of aquifer Fe(III) during biodegradation of ground water contaminants may result in expansion of a contaminant plume, changing the outlook for monitored natural attenuation. Data from two research sites contaminated with petroleum hydrocarbons show that toluene and xylenes degrade under methanogenic conditions, but the benzene and ethylbenzene plumes grow as aquifer Fe(III) supplies are depleted. By considering a one-dimensional reaction front in a constant unidirectional flow field, it is possible to derive a simple expression for the growth rate of a benzene plume. The method balances the mass flux of benzene with the Fe(III) content of the aquifer, assuming that the biodegradation reaction is instantaneous. The resulting expression shows that the benzene front migration is retarded relative to the ground water velocity by a factor that depends on the concentrations of hydrocarbon and bioavailable Fe(III). The method provides good agreement with benzene plumes at a crude oil study site in Minnesota and a gasoline site in South Carolina. Compared to the South Carolina site, the Minnesota site has 25% higher benzene flux but eight times the Fe(III), leading to about one-sixth the expansion rate. Although it was developed for benzene, toluene, ethylbenzene, and xylenes, the growth-rate estimation method may have applications to contaminant plumes from other persistent contaminant sources.     

Iron oxide formation in artificial ground waters

Artificial ground water containing 40 mg/l Ca and varying concentrations of Fe(II), Fe(III) and Si were rapidly oxidized with air. The ferrihydrite forming is similar to those found in natural Finish ground waters.     

Dissolved Hydrogen Dynamics Associated with Emulsified Vegetable Oil Bioremediation of Chloroethenes

Emulsified vegetable oil (EVO) is widely used as a fermentable substrate to enhance the reductive dechlorination of chlorinated ethenes (CEs) in groundwater systems. The fermentation of EVO by naturally occurring bacteria produces molecular hydrogen (H₂) which acts as an electron donor driving microbially mediated reductive dechlorination. While dissolved H₂ drives much of the dechlorination associated with CE bioremediation, the dynamics of H₂ production and consumption associated with EVO addition to groundwater systems is seldom documented. The present study shows how H₂ concentrations changed over a 4-year period following EVO addition to a sandy coastal plain aquifer underlying Naval Air Station Pensacola, Florida, USA. Prior to EVO addition, H₂ concentrations at the site were in the range characteristic of Fe(III)-reducing conditions (0.2–0.6 nM). Following EVO addition, H₂ concentrations increased exponentially, peaking at approximately 25,000 nM. Hydrogen concentrations then began decreasing exponentially, and by 4 years after EVO addition had stabilized at 4.0 nM. That pattern suggests symbiotic cross-feeding between fermentative and respirative microbial populations resulting in a Gaussian rise and fall of H₂ concentrations. That, in turn, suggests while EVO biostimulation can temporarily increase H₂ concentrations to very high levels, those higher concentrations are unlikely to be sustained indefinitely.     

Microbial iron reduction during passive in situ remediation of an acidic mine pit lake mesocosm

Ferric iron reduction was studied in a pilot-scale enclosure experiment for passive biological remediation of an acidic mine pit lake in Lusatia, Germany. The metabolic properties of prokaryotes involved in Fe(III) reduction may be important for the outcome of biological remediation, as chemolithotrophic Fe(III) reduction can counteract the desired pH increase, but heterotrophic Fe(III) reduction will provide the necessary Fe(II) for precipitation of sulfide minerals following sulfate reduction. Therefore, vertical profiles of sediment parameters related to iron and sulfur cycling were determined in conjunction with viable counts of different ferric iron-reducing micro-organisms using selective media. Findings were compared to an untreated reference site. The addition of organic matter stimulated ferric iron reduction and sulfate reduction in the enclosure and led to elevated pH and accumulations of ferrous iron and reduced sulfur compounds. Numbers of neutrophilic heterotrophic Fe(III) reducers increased during treatment, those of acidophilic heterotrophic Fe(III) reducers remained similar, and those of acidophilic chemolithotrophic Fe(III) reducers decreased. Zones of ferric iron-reducing activity corresponded well with microbial depth profiles; however, viable counts of neutrophilic or acid-tolerant Fe(III) reducers must have been underestimated based on the corresponding observed activity levels. Ferric iron reduction by chemolithotrophic acidophiles seemed to be of minor importance, so a lowering of pH values due to Fe(III) reducing activity is unlikely.     

Arsenic Cycling in Hydrocarbon Plumes: Secondary Effects of Natural Attenuation

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe‐hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude‐oil‐contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe‐hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe‐hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.     

Effects of reservoir stratification and watershed hydrology on manganese and iron in a dam‐regulated river

The presence of metals, including manganese (Mn) and iron (Fe), adversely impacts water quality. In seasonally stratified reservoirs, Mn and Fe can accumulate in the water column due to reducing conditions in sediments and be released to downstream rivers through dam discharge. In addition to reservoir stratification influences, the release of metals downstream is influenced by hydrologic conditions in the river. We examined the seasonal and spatial variability of Mn and Fe concentrations in a eutrophic, hydropower reservoir and the downstream river over a two‐year period. Overall, we found that reservoir stratification was a strong predictor of tailrace Mn and Fe concentrations but that tailrace Fe concentrations were also influenced by dam discharge. Downgradient of the tailrace, river discharge and suspended sediment were the dominant predictors of both Mn and Fe concentrations. Using our data, we develop a conceptual model of seasonal and hydrologic drivers of metal concentrations. The model can be modified for other systems aiding drinking water utilities and other water users in forecasting under what seasonal and hydrologic conditions that Mn and Fe concentrations in river systems are likely to be elevated.     

Stability of arsenopyrite and As(III) in low-temperature acidic solutions

Arsenopyrite is one of the most important pri-mary arsenic mineral. In the Eh-pH diagram of the As-O2-S-H2O system, if the total arsenic concentration (TAs) is taken to be 0.75 mg/L, the total sulfur con-centration, 32 mg/L, the temperature, 25℃and the pressure, one atmosphere pressure for the discrimina-tion of arsenic species, it may be found that under hy-pergene conditions, arsenopyrite is a moderately stable mineral. Only in the strongly alkaline and reducing environment can arsenopy…     

Evidence for Enhanced Mineral Dissolution in Organic Acid-Rich Shallow Ground Water

Total concentrations of formate, acetate, and isobutyrate varied from less than 5 to greater than 9,000 μmol/l over distances of < 3 m in ground water from a shallow hydrocarbon contaminated aquifer. Laboratory incubations of aquifer material indicate that organic acid concentrations were dependent on the amount of hydrocarbon loading in the sediment and the relative rates of microbial organic acid production and consumption. In heavily contaminated sediments, production greatly exceeded consumption and organic acid concentrations increased. In lightly contaminated sediments rates were essentially equal and organic acid concentrations remained low. Concentrations of dissolved calcium, magnesium, and iron generally were one to two orders of magnitude higher in organic acid-rich ground water than in ground water having low organic acid concentrations. Carbonate and Fe(III)-oxyhydroxide minerals were the likely sources of these elements. Similarly, concentrations of dissolved silica, derived from quartz and k-feldspar, were higher in organic acid-rich ground water than in other waters. The positive relation (r = 0.60, p < .05, n = 16) between concentrations of silica and organic acids suggests that the microbially mediated buildup of organic acids in ground water enhanced quartz/k-feldspar dissolution in the aquifer, although it was not the only factor influencing their dissolution. A model that included organic acid microequivalents normalized by cation microequivalents significantly strengthened the correlation (r = 0.79, p < .001, n = 16) between dissolved silica and organic acid concentrations, indicating that competition between silica and cations for complexation sites on organic acids also influenced quartz/k-feldspar dissolution. Physical evidence for enhanced mineral dissolution in organic acid-rich waters included scanning electron microscopy images of highly corroded quartz and k-feldspar grains from portions of the aquifer containing organic acid-rich ground water. Microporosity generated in hydrocarbon contaminated sediments may adversely affect remediation efforts that depend on the efficient injection of electron acceptors into an aquifer or on the recovery of solutes from an aquifer.     

Arsenic — a Review. Part I: Occurrence,Toxicity, Speciation,Mobility

In natural waters arsenic concentrations up to a few milligrams per litre were measured. The natural content of arsenic found in soils varies between 0.01 mg/kg and a few hundred milligrams per kilogram. Anthropogenic sources of arsenic in the environment are the smelting of ores, the burning of coal, and the use of arsenic compounds in many products and production processes in the past. A lot of arsenic compounds are toxic and cause acute and chronic poisoning. In aqueous environment the inorganic arsenic species arsenite (As(III)) and arsenate (As(V)) are the most abundant species. The mobility of these species is influenced by the pH value, the redox potential, and the presence of adsorbents such as oxides and hydroxides of Fe(III), Al(III), Mn(III/IV), humic substances, and clay minerals.     

Automated Ion-pair extraction and Ion-pair chromatography — a versatile method in water analysis for the determination of highly polar micropollutants

An automated HPLC method is presented which combines on-line ion-pair extraction on small exchangeable RP-C18 precolumns (RP-IPE) with ion-pair chromatography (RP-IPC). Weakly acidic herbicides — carboxylic acids, phenols, and the N-H acidic bentazone — and strong acids, e.g. aromatic sulfonic acids, can be determined simultaneously. Performance data are given. The tetrabutylammonium ion pairs of all investigated compounds are readily transferred from the RP-C18 precolumn to the analytical column by a phosphate buffer/methanol gradient. This is also true for the chlorinated phenoxy acids which, in earlier off-line extraction experiments, could not be desorbed from the RP-C18 material by the lower polar acetone. The RP-IPC is carried out at neutral pH where weakly acidic compounds appear in their stronger UV absorbing dissociated form. Compared to conventional reversed phase chromatography using an acidified eluent, the sensitivity of UV detection is markedly enhanced, especially for the phenol herbicides and bentazone. In addition, phenols can be detected more selectively because they show a second intense absorption band in the wavelength range between 280 nm and 290 nm, where there are only little interferences with the matrix. Due to miniaturization and automation, the online combination IPE/IPC allows a large sample throughput at a lower consumption of solid phase material and organic solvents. Time consuming manual steps are totally missing. The IPE/IPC technique is well suited as a screening method for fate studies of polar micropollutants, e. g. for monitoring the efficiency of different water treatment technologies. An example for balancing an activated carbon filter is presented.     

Distribution of dissolved and labile particulate trace metals in the overlying bottom water in the vistula river plume (southern Baltic Sea).

Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.     

Peculiarities of annual variations in the concentration of iron compounds in the water-bottom sediments system of the Mozhaisk Reservoir

Annual variations in concentrations of Fe forms in the bottom water (0–70 cm from the bottom, by layers), pore water, and in solid phase of silts (25 cm, by layers) of the Krasnovidovo Pool channel area of the Mozhaisk Reservoir are studied. A drastic increase in the concentration and ratio of Fe_susp/Fe_dis in the water layer 0–20 cm from the bottom is detected. Fe(II) dominates in dissolved and suspended forms. The concentrations of Fe(III) reaching 2–3 mg/l were for the fist time revealed in the pore water of silts (Eh ～ ?120 mV). The factors responsible for this phenomenon are discussed. Fe flux from sediments is tentatively assessed as 0.2–0.6 mg Fe m²/day.