Determination of metal partitioning in porewater extracted from the Seine River Estuary sediment (France)

Total dissolved trace and major metals and their partitioning in porewater sediment have been investigated at two sites in the Seine River estuary (France). For this purpose, solid phase extraction (SPE) has been employed using specific chelating resins for the separation and preconcentration of organic and inorganic forms of studied metals under controlled (N2) inert atmosphere. In fact, the study is focused on the development of a method for sample collection and handling under inert atmosphere in order to avoid some potential artefacts of the extracted porewater, to preserve the samples from possible chemical oxidation changes and to determine metals partitioning between organic and inorganic forms. For this point, a separation and preconcentration method using two columns in series (chelamine and C18 columns) was used. The trace and major metals fixed on the two resins for all determinations were stripped by nitric acid (2 M) and analyzed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Zeeman Graphite Furnace Atomic Absorption Spectroscopy (ZGF-AAS). The relationship between the distribution of metals and physico-chemical parameters such as pH and Eh (redox potential) as a function of depth was discussed. Some tendency in the distributions and seasonal variability of these traces and major metals are improved. The concentrations for all studied metals decreased as a function of depth where iron and manganese were found at mg L(-1) levels and other metals were found at [micro sign]g L(-1) levels, as well as there were significant fractions of all metals (except of manganese) which were complexed by organic matter. The comparison of data for the major elements (Fe and Mn), obtained by direct determination (without preconcentration) and preconcentration, show a very good recovery.     

Adsorption and detection of some phenolic compounds by rice husk ash of Kenyan origin

Rice husk ash (RHA) obtained from a rice mill in Kenya has been used as an inexpensive and effective adsorbent (and reagent) for the removal (and detection) of some phenolic compounds in water. The abundantly available rice mill waste was used in dual laboratory-scale batch experiments to evaluate its potential in: (i) the removal of phenol, 1,3-dihydroxybenzene (resorcinol) and 2-chlorophenol from water; and (ii) the detection of 1,2-dihydroxybenzene (pyrocatechol) and 1,2,3-trihydroxybenzene (pyrogallol) present in an aqueous medium. The studies were conducted using synthetic water with different initial concentrations of the phenolic compounds. The effects of different operating conditions (such as contact time, concentration of the phenolic compounds, adsorbent quantity, temperature, and pH) were assessed by evaluating the phenolic compound removal efficiency as well as the extent of their color formation reactions (where applicable). RHA exhibits reasonable adsorption capacity for the phenolic compounds and follows both Langmuir and Freundlich isotherm models. Adsorption capacities of 1.53 x 10(-4), 8.07 x 10(-5), and 1.63 x 10(-6) mol g(-1) were determined for phenol, resorcinol and 2-chlorophenol, respectively. Nearly 100% adsorption of the phenolic compounds was possible and this depended on the weight of RHA employed. For the detection experiments, pyrocatechol and pyrogallol present in water formed coloured complexes with RHA, with the rate of colour formation increasing with temperature, weight of RHA, concentration of the phenolic compounds and sonication. This study has proven that RHA is a useful agricultural waste product for the removal and detection of some phenolic compounds.     

Monitoring of the three organophosphate esters TBP,TCEP and TBEP in river water and ground water (Oder,Germany)

The behaviour of the three organophosphate esters tributyl phosphate (TBP), tris(2-chloroethyl)phosphate (TCEP) and tris(2-butoxyethyl)phosphate (TBEP) during infiltration of river water to ground water has been investigated. The monitoring site is the Oder River and the adjacent Oderbruch aquifer. From March 2000 to July 2001, 76 ground water samples from monitoring wells located close to the Oder River and nine river water samples were collected. Additionally, influent and effluent samples from local waste water treatment plants, one sample of rain water and samples of roof runoff were collected. All samples were analysed by solid-phase-extraction followed by gas chromatography/mass spectrometry. TBP, TCEP and TBEP were detected at mean values of 622 ng l(-1), 352 ng l(-1), and 2955 ng l(-1), respectively in municipal waste water effluents. This points to a major input of these compounds into the Oder River by municipal waste water discharge. The concentrations of TBP and TBEP decreased downstream the Oder River possibly due to aerobic degradation. TBP, TCEP and TBEP were detected in ground water influenced predominantly by bank-filtered water. This demonstrates a transport of organic compounds by river water infiltration to ground water. TBP, TCEP and TBEP were also detected in rain water precipitation, roof runoff and ground water predominantly influenced by rain water infiltration. This hints to an input of these compounds to ground water by dry and wet deposition after atmospheric transport. Organophosphate esters were also detected in parts of the aquifer at 21 m depth. This demonstrates low anaerobic degradation rates of TBP, TCEP and TBEP.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.     

Characterisation of weathered hydrocarbon wastes at contaminated sites by GC-simulated distillation and nitrous oxide chemical ionisation GC-MS, with implications for bioremediation

An extended analytical characterisation of weathered hydrocarbons isolated from historically contaminated sites in Alberta is presented. The characterisation of soil extracts, chromatographically separated into component classes, by GC-simulated distillation and nitrous oxide (N2O) chemical ionisation (CI) GC-MS provides new insights into the composition of the residual oil at these sites, the principal partition medium for risk critical components. The combined polar and asphaltene content of representative soil extracts ranged from 40% w/w to 70% w/w of the oils encountered. An abundance of C14-C22 2-4 ring alicyclics, alkylbenzenes and benzocycloparaffins is prevalent within the saturate fractions of site soils. Implications for the partitioning of risk critical compounds at sites with weathered hydrocarbons and the practical application of bioremediation technologies are discussed.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Assessment of spatial variability in some soil properties as related to soil salinity and alkalinity in Bafra plain in northern Turkey

The objectives of this study were to assess the variability in soil properties affecting salinity and alkalinity, and to analyze spatial distribution patterns of salinity (EC) and alkalinity (ESP) in the plain, which was used irrigation agriculture with low quality waters. Soil samples were collected from 0–30cm, 30–60cm, 60–90cm and 90–120cm soil depths at 60 sampling sites. Soil pH had the minimum variability, and hydraulic conductivity (Ks) had the maximum variability at all depths. The mean values of pH, EC, ESP and Ks increased while the mean values of CEC decreased with soil depth. Values pH, EC and ESP were generally high in the east and northeastern sides. Soil properties indicated moderate to strong spatial dependence. ESP and pH were moderately spatially dependent for three of the four depths, EC exhibited moderate spatial dependence for one of the four depths, CEC had a moderate spatial dependence at all depths, and Ks exhibited a strong spatial dependence. EC, CEC, and ESP were considerably variable in small distances. The spatial variability in small distances of EC, CEC, pH and ESP generally increased with depth. All geostatistical range values were greater than 1230m. It was inferred that the strong spatial dependency of soil properties would be resulted in extrinsic factors such as ground water level, drainage, irrigation systems and microtopography.     

Removal of atrazine and four organophosphorus pesticides from environmental waters by diatomaceous earth-remediation method

A new viable remediation technique based on the use of diatomaceous earth is proposed to improve the ecological system. Its ability to remove atrazine and the four organophosphorus pesticides parathion-methyl, chlorpyriphos, fenamiphos and methidathion from river and waste waters has been proven. A series of experiments including variable conditions, such as temperature, pH, contact time, pesticide concentration and adsorbent quantity, were performed to demonstrate the efficiency of pesticide removal from three different water samples. The batch experiments showed that diatomaceous earth was able to remove 95% of chlorpyriphos, 75% of methidathion and parathion-methyl and 55% of atrazine and fenamiphos from all types of waters tested. The individual adsorption of each pesticide on diatomaceous earth could be described by the Freundlich isotherm and a tentative adsorption mechanism was proposed. The Freundlich coefficient (Kf) and Freundlich constant (1/n) appeared to be closely related to the physicochemical properties (Kow, solubility) of the compounds. The actual results support the conclusion that diatomaceous earth has the potential to serve as an extractant in remediation techniques.     

The potential of different bio adsorbents for removing phenol from its aqueous solution

The use of natural resources for the removal of phenol and phenolic compounds is being looked upon by researchers in preference to other prevailing methods. In the present study, different biosorbents, brown algae (Padina pavonia), fresh water macrophyta (Ceratophyllum demersum), and black tea residue, were tested as adsorbent for the removal of phenol from aqueous solutions. The optimum conditions for maximum adsorption in terms of concentration of the adsorbate and pH were identified. The results show that the initial concentration increases as the removal of phenol increases in C. demersum; in the case of the other two adsorbents, the initial concentration increases as the removal of phenol decreases, especially for an initial concentration lower than 100 and 1,000 μg/L for P. pavonia and black tea residue, respectively. Maximum percentage removal of phenol by each adsorbent is 77, 50.8, and 29 % for C. demersum, P. pavonia, and black tea residue, respectively. Also, the biosorption capacity was strongly influenced by the pH of the aqueous solution with an observed maximum phenol removal at pH of around 6–10. The first biosorbent (black tea residue) displays the maximum adsorption capacity at a pH of 10 with a percentage sorption capacity of 84 %; P. pavonia revealed a greater adsorption percentage at pH?10, reaching 30 %, while for C. demersum, the removal of phenol increases with the increase in initial pH up to 6.0 and decreases drastically with further increase in initial pH. The Freundlich, Langmuir, and Brauner–Emmet–Teller adsorption models were applied to describe the equilibrium isotherms. The results reveal that the equilibrium data for all phenol adsorbents fitted the Freundlich model which seemed to be the best-fitting model for the experimental results with similar values of coefficient of determination.     

Measurements of C6-C8 hydrocarbons at a UK rural site during January 1999. Site evaluation and correlations between species

Ambient concentrations of C6-C8 aromatic hydrocarbons and n-heptane, determined by gas chromatography with flame ionisation detection, are presented from a winter campaign during January 1999 at a rural site near Leeds. Absolute concentrations are significantly lower than those obtained from the only designated UK rural site (Harwell) in the automated UK hydrocarbon network. Both absolute and relative concentrations of hydrocarbons measured at the site have been interpreted in terms of the arriving back-trajectories. The site is subject to two main airflows during the winter months; relatively polluted air from the southwest and much cleaner air from the northwest. Ratios of hydrocarbon concentrations show evidence of significant chemical processing consistent with chemical removal by OH. Uncertainties in the ages of the trajectories prevent a reliable estimation of the average OH concentration over the trajectory. The dependence of the variance of the hydrocarbon concentrations with their lifetime with respect to removal by OH does not show the expected behaviour.     

Reactivity, interactions and transport of trace elements, organic carbon and particulate material in a mountain range river system (Adour River, France)

The background levels, variability, partitioning and transport of eleven trace elements-Ag, Al, As, Cd, Co, Cr, Cu, Mn, Pb, Zn and U-were investigated in a mountain range river system (Adour River, France). This particular river system displayed a turbulent hydrodynamic regime, characterized by flash-transient discharge conditions leading to fast shifts in suspended particulate matter (SPM) concentrations as high as two orders of magnitude (12 to 600 mg l(-1)). The distribution of SPM was accurately predicted with a "hysteresis" transport model, indicating that about 75% of the annual solids load was exported within 20 to 40 days. Dissolved and particulate concentrations of most trace elements were low compared to their concentrations in other reference river systems expect for Pb and Cr, associated with historical anthropogenic activities. Although dissolved and particulate metal concentrations were steady for most elements during low and average discharge conditions, significant changes were observed with increasing river discharge. The changes in trace element concentrations in the two compartments was found to induce a partitioning anomaly referred to as the particulate concentration effect. This anomaly was significant for Cr, Mn, Pb, Zn, Cu and organic carbon (p < 0.03). The processes driving this anomaly were possibly linked to the modification and/or increase of colloidal organic and inorganic vectors, suggested by the significant increase of DOC (p < 0.001) and dissolved Al concentrations (p < 0.05) during flood conditions. A complementary process linked to the influence of coarse particles of low complexation capacity and transported mainly during high discharge may also effect trace element concentrations. Annual metal fluxes transported by this river system were estimated using the hysteresis SPM model with consideration of these fate processes. Metals in the Adour River system are primarily exported into the Bay of Biscay (Atlantic Ocean).     

Evaluation of river pollution of neonicotinoids in Osaka City (Japan) by LC/MS with dopant-assisted photoionisation

An atmospheric pressure photoionisation (APPI) source for liquid chromatography/mass spectrometry (LC/MS) was applied to determine neonicotinoid pesticides in the aquatic environment. Dopant-assisted APPI was very effective in the ionisation of neonicotinoids. Neonicotinoids generated protonated molecules in APPI with high sensitivity, while adduct ions, such as sodiated molecules, were predominantly generated in conventional electrospray ionisation. The ionisation of neonicotinoids was confirmed by ultra-high-resolution MS. An analytical method coupled with solid phase extraction was developed for acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, and thiamethoxam. Method detection limits were 0.47 to 2.1 ng L(-1) for six neonicotinoids. Dinotefuran was the most frequent and highest among the neonicotinoids examined in the aquatic environment in Osaka, Japan. The maximum concentration of dinotefuran was 220 ng L(-1). Given the toxicity of neonicotinoids for aquatic creatures, the concentrations observed here were substantially low. The change in concentrations was temporally coincident with the period of the neonicotinoid application. Although rapid photodegradation and some degradation products have been elucidated, the degradation products in the aquatic environment were not identified in the present study.     

Isotopic characterisation of lead deposited 1989-2001 at two upland Scottish locations

The isotopic composition of lead collected with grass samples taken over the period 1989-2001 from plots at two upland locations (Glensaugh in north east and Hartwood in central Scotland) has been determined using thermal ionisation mass spectrometry. Although marked reductions in lead concentrations in grass were observed at Glensaugh in the initial three years, subsequently concentrations have remained relatively constant (1-3 microg g(-1)) in all plots to the present day. The one exception was a roadside plot at Hartwood which showed a large reduction from 1.0 microg g(-1) in 1999 to 0.2 microg g(-1) in 2000 following the abolition of petrol lead in the UK at the beginning of 2000. The total concentrations at this plot were consistently lower than those found at plots away from road traffic but exposed to the prevailing wind direction. The 206Pb/207Pb ratio increased steadily at all the plots throughout the period of the study indicating the reducing influence of petrol lead but the changes were not as great as might be expected with the decrease in the use of leaded petrol. Assuming the collected lead had only two sources, petrol lead and a diffuse background "industrial" lead, the proportion of petrol lead was only in the range 17-69% for roadside samples and 0-39% in other samples. A substantial proportion of deposited lead, therefore, now has its origin other than in petrol. Mixing curves indicate that whereas the lead deposited at Glensaugh could be defined by only two end members, that at Hartwood needs more than two components in the mixture. The results also suggest that although petrol lead has been eliminated, traffic is still a source of lead and another source defined as "traffic lead" should be considered.     

Degradation of chlortoluron in water disinfection processes: a kinetic study

The kinetics of the reaction between chlortoluron, a phenylurea herbicide [N'-(2-hydroxy-4-methyl-5-chlorophenyl)-N,N-dimethylurea], and hypochlorite, the active species in water disinfection processes involving chlorine, were investigated by HPLC-UV and HPLC-electrospray ionisation mass spectrometry (HPLC-ESI-MS). In particular, the concentrations of the main chlortoluron by-products were monitored as a function of time by HPLC-ESI-MS and a kinetic model was developed to fit the relevant curves. The results showed that chlortoluron degradation starts with two parallel pathways, namely, chlorination and hydroxylation of the aromatic ring, which are then followed by consecutive chlorination reactions, and after almost 2 weeks by ring opening and partial mineralisation, as confirmed by head-space solid-phase microextraction gas chromatography-MS (SPME-GC-MS) and total organic carbon (TOC) measurements. Kinetic constants for the first reactions of the overall process, under pseudo-first-order conditions (hypochlorite excess), were estimated by a fitting procedure.     

Mathematical Modeling of Column and Field Dense Nonaqueous Phase Liquid Tracer Tests

Mathematical models for the simulation of dense nonaqueous phase liquid tracer tests (DTTs) in laboratory columns and in the field are developed and examined. The DTT technique is a means of estimating the quantity of dense nonaqueous phase liquid (DNAPL) in a domain of interest in an aquifer. The two-dimensional field DTT model uses the Method of Principal Directions and an asymmetrical upwind algorithm for describing advective transport. Both models include diffusion transport of tracer into and from low-permeability porous structures such as clay lenses, as well as the mass transport kinetics of partitioning tracer to and from the DNAPL droplets. The dependence of the effluent tracer concentration curves on the parameters of the models is explored, and conclusions are drawn regarding the applicability of, and several possible problems with, the DTT technique. Model results indicate that the DTT performs well at locating distributed droplets of DNAPL, but is unlikely to be useful in the assessment of pooled DNAPL.     

Quantifying the phenolic content of freshwaters using simple assays with different underlying reaction mechanisms

Five different assays, Gibbs, Prussian Blue, Folin-Ciocalteau, fluorescence quenching of added phenol and precipitation of phenolics with bovine serum albumin (BSA) were investigated for their suitability in measuring the phenolic content of freshwaters. Phenol and a hydrolysable tannic acid were used as standards for monophenolics and polyphenolics, respectively. The individual and simultaneous application of both standards in doubly distilled water and filtered freshwater samples showed no matrix interference for the Gibbs, the Prussian Blue and the Folin-Ciocalteau assays. The quenching of phenol fluorescence and incomplete precipitation of added tannic acid in the freshwater samples were thought to originate from complexation. The Gibbs assay was specific for monophenolics, monohydroxybenzenes, with a Criterion of Detection (CoD) of 0.027 mg l(-1). Evaluating the assay using twenty-two monophenolics of lignin origin showed, apart from phenol itself, the phenolic acids vanillic, isovanillic, ferulic and syringic to have a linear response between 0 and 10 microM. The other monophenolics were not responsive in the Gibbs assay. The oxidation-based assays Prussian Blue and Folin-Ciocalteau had a CoD of 0.169 and 0.025 mg l(-1), respectively. The ratio of response of both assays for each sample was taken as an indication of the degree of polymerisation of the phenolic content. The Folin-Ciocalteau assay was used directly on the samples, on samples spiked with tannic acid at 2 and 4 mg l(-1), and after precipitation of phenolics with BSA. The difference in tannic acid equivalents before and after treatment, assayed the amount of protein precipitated phenolics. The results of all assays allowed differentiation between monophenolics (Gibbs), polyphenolics (Prussian Blue), total phenolics (Folin-Ciocalteau), complexation of added phenol and protein-precipitated phenolics. The reaction mechanisms underlying the assays were matched onto those occurring during humification. The assays were applied to six filtered freshwater samples and two humic and two fulvic acids. The results showed a different pattern for each site and illustrated varying reactivity of the 'phenolic content' of freshwater.     

Determination of airborne anhydrides using LC-MS monitoring negative ions of di-n-butylamine derivatives

An air sampling method for simultaneous determination of organic acid anhydrides and isocyanates is presented. Air samples are collected in impinger flasks filled with 0.01 M di-n-butylamine (DBA) in a mixture of toluene-acetonitrile (7:3, v/v) with a 13 millimetre glass fibre filter in series. The amount of anhydrides and isocyanates are determined as their amide and urea derivatives using LC-MS. Four anhydrides, maleic anhydride (MA), phthalic anhydride (PA), tetrahydrophthalic anhydride (TA) and cis-hexahydrophthalic anhydride (HA) and 11 isocyanates could be separated in 9 minutes using gradient elution. Anhydride-DBA derivatives in standard solutions were quantified using LC with chemiluminescent nitrogen detection (CLND). Anhydride-DBA derivatives were found to be stable for at least two months when stored in acetonitrile or toluene in the freezer. The yield of DBA derivatives of anhydrides in the 0.01 M DBA in toluene-acetonitrile (7:3, v/v) was in the range of 70->95%. Using MS and negative electrospray ionisation (ES-) linear calibrations curves were obtained for the anhydrides with correlation coefficients ranging from 0.9970-0.9997. The instrumental detection limit for the anhydrides ranged from 10-30 fmol, based on a signal to noise root mean square (RMS) ratio of 3. Monitoring positive and negative ions simultaneously, both isocyanates and anhydrides could be determined as their DBA derivatives in the same chromatographic run. When air samples were collected during thermal degradation of different coated metal sheets both anhydrides and isocyanates were present in the same samples and all the studied anhydrides were found.     

Biosorption properties of Cd(II), Pb(II), and Cu(II) of extracellular polymeric substances (EPS) extracted from Aspergillus fumigatus and determined by polarographic method

Extracellular polymeric substances (EPS) were extracted from Aspergillus fumigatus using cationic exchange resin technique. The EPS were mainly composed of polysaccharide and low quantities of protein and nucleic acid. Biosorption of Cd(II), Pb(II), and Cu(II) of EPS was investigated as a function of pH using differential pulse polarography and the Ruzic model. Results showed that the EPS biosorption capacity determined using either the direct titration curves i?=?f(C _M) or the method proposed by Ruzic (Analytica Chimica Acta 140:99–113, 1982) were coincident. Cu(II) had the highest affinity with EPS followed by Pb(II) and Cd(II). The total number of binding sites for Cu(II) and Cd(II) increased with pH in the range of 4.0–7.0. Similar trend was observed for Pb(II) at pH?4.0–5.0, while precipitates were observed at pH?6.0 and 7.0. The conditional binding constants of these three metals displayed low levels of fluctuation with pH and ranged from 4.02?±?0.02 to 5.54?±?0.05.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

Optimization of pulp mill effluent treatment with catalytic adsorbent using orthogonal second-order (Box-Behnken) experimental design

Novel catalytic adsorbent (ruthenium on carbon) was employed for the treatment of pulp mill effluent in the presence of hydrogen peroxide. Mathematical model and optimization of the process regarding the most favorable COD (%), TOC (%) and color (%) removal rates was developed and performed with experimental design taking into account catalytic adsorption process kinetics. As the initial experimental design, 3(3-1) half-fractional factorial design (H-FFD) was accomplished at two levels to study the significance of the main effects, such as catalytic adsorbent (g l(-1)) and hydrogen peroxide (ppm) concentrations using the response surface methodology (RSM). Finally, a four factor-three coded level central composite design (CCD) with 28 runs was performed in order to fit a second-order polynomial model. Validation of the model was accomplished by different criteria including coefficient of determination and the corresponding analysis of variance. The achieved removal rates for TOC (up to 75%), COD (up to 73%) and color (up to 68%) were observed for the defined optimal conditions: 1g l(-1) of ruthenium on carbon, 7 ppm of hydrogen peroxide, pH = 4 and ambient temperature. The proposed method benefited significantly improved TOC, COD and color removal efficiency, regenerability and reusability of the catalytic adsorbent and unaltered initial pH of an effluent in comparison to traditional adsorption or oxidation processes.